Interpretation of Mass Spectra

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INTERPRETATION OF MASS SPECTRA FOUR TH E D ITI O N

Fred W. McLafferty

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Frantilek Turetek

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Prin ted in [be L:" j,O<1 Sr.' "
Preface 10 the Fourth Edition

Molecular ma" "f!" Clmm~ry o:m hnu e' to , Jo nw an ' '' f'''ncnti. 1gm ..,th. "'ilb a .u ~ta u tlal l'<"poTf icu of it, apple fin' «!iti on ." Ih', bo ok ..". publi......J more th n 2.\ }~~ n ~ go. whell m'.... in.uuulcnL, could "",aWf< oll il ~ fe..' unh " wn rna.. 'f"'I.1ta per b"ur T he Pref:au; 1o the I~ H IJ Tbird L.ili" on e' tirna«:d worid wi'k: imtrumenl .~ 81 flCarl}' 1,1))) ,' ,,"" .pe.:tro melo", ~t ~""t, the p"' '''nl . ale i< """" , ,,I lirn., \h.lf. wilh m,,' o than a ....PCn n, . jot m" n,dllclu, c"''' The'" ;",1"'· aT<: ~l "" far more riflei"nt, lhe ~ ""' t m"jorily f>eing computerized sa,enro nu' <>gTap h,ima" ·. l'C"llOmeIC' IUC/M SJ ,).tcm, thal ...,n tum ......1 up to lOt) unl M ",'n ma>! ~p' el ra in a In-minute GC/MS ,,'n. ...lt ho ugh . ulomMed e" m pul",.m,nclm,,, f'1"",..edUl'e ~ nf , """ 'f'«'lta are "0" _umeient ly f.!t to b :q ' up " ' lh thi' oUlp" t tChapl "" ~ l " ter p re t a.l i " n 01 M ~ .. Spectra lOT T e~ d," ", <:>t Intnl",' " tion Cou, «,' at .he 1'ilI! Conl"t"C ""'" of ' he Allle",,, n Sociely f"t )vi" ", ~P"'''''''I­ met.) a lLr" etod JO a Uc'1\dees. Ib e MOSt lmpoltant addItion to lhi, bool , in Ih" opi ni,m of lhe " ."ior "uthor . u. iI' co·a uth" r. F ranl TUJ'eCel, .. ho is Ilm'" at the IIni"" " ity (II W" , h il\,i;l<:m a _ . n ,,""' Oei. l. Profe.,,,,, hM had ~ d, ot l,,~ u i , h c d rost a, w. ""'e, aU-a_ "S mo" , pcetJ"''''lr ) CTili",,] to 10;' bocl. He loa' made ~..p«iall)' imlX'l tJn[ "" ntribulion, 10 Ibe med ...' ''<",•. Our e' le,I>' '''' ,evi,; on. ~ " .. haJ lhc o~ ;ect i " c " I wr ,. l ~ l' n~ ;Oll d;_...~ " t i o n mec h ~ n " t'" o n a m ~ cb broaJ,:. "",It. .... ith <mplw .i .t",,, tbe'" " "-",h. nlSrr,, ~re apphc:ml~ to the unim,>k· ~lL l~ r di....x:iolll O'" or i o,, ~ r d by an y i"n;zaj ,on method , ; "" l uJi n~ t h~ ~'; li n~ v....., y .~ new m,: lhod, for ot>I. ' ning nla"" 'lJ"'Clra of 1. ' ll" Jncle<.uk '

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Contents

Pr.t."" to ltle F_

1h Edilion

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f

Intr04\lctlo n

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1

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"'P P""OU1oCd uctl on S• • t. ",. 11

1.6 ' .7

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St. M a,d Inl. 'prel ' ''Cln P'OO@d Uf' ~ e 'A " "' _ 15

1.1 I .~

I' 14

""lyOi' ' Z : 01. ' $ trun.,. Infoo.... oon

:l I Elem.nlal Co m position 2.1

2,2

2.4

2.5

13

11

Sta b- . l.o!cI>e. Clus,fi" ICl n "'coo,aing tCl Na'", ,1 " O . S,llu ' . Cb lo' '' e• • r
2. ~

IZ

20

" A +" lo, on,.ot• . C., bc><, " nd N" ' " gon 23 .... '. EIe "'...."' · l'ydlov" • . fl uo ' ;.... .... _ " '.... . no:! 10'h _ fli"91 pi" " 00" " 9 8
25

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C O" I"'"'IO(" ... .. A1I ~ _ a ... _ ..... Oed.J C,,,,, Element,1CompO." ion . :r.J

J , Tile MolecUlar Ion 3 .1 3.2 3.3 ~ 4 3.5

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om

35

11""""."'''''10 '0< (h. _

Ioe", ,..-I"" J6 Ot!I'· f lec t, .,., "' '''' 3ti Th. NI I'""e n f><J le 37 R g l. ~ _ Imoo .... noe 01 P10Ih 3Il L O~ ic . 1 Ne" t,.l l o, . . . :9

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4 , a.&ic Mech .niwns 01 Io n Fragmentat ion

81

41

LJ.'''OIeeu'a r loti D"""",po. ;(,ono

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52

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OI""eli"" lo" ,a lion '" A""" a l or Cha rg. Si..,. 501 Re a cti"" CI. " ihe.,on" ~ 4~ Sigma _ o;sooc ial i"" I ~ ) twtl 4.6 ~ oo
5 I POSlulililion 01 Molecular StTud u res 5. 1

5.2 5.3 ~ .4

5~ 55

o.. "" ra l Appe• ••"". ol th. SpeWLJm II'; Low 1oA~" " Ion SOOr.... 91 6m.H.....""a' l o... . 97 a..ra""', i" 't Ion. ~ Poo1ulat '"," poss il>le 5h\1 du..... t OO ""'''g n''' OOI of the ""'" PrDb
6 , A Ullllillry Te c hniques 6 .1

6.2 (; 3 64 6. ~

ee

61 6 .S

IS

103

Soft lonizaho o Me\hod . 103 Ion':ali "" of La rge .....1"""'... 105 b a cI Mass Io.! ou u , e _ rtts fHign "' ~ ' a l u l io n ) T ' '''' ~m M.". 5p00ct,o me lry (MSiU SI 109 Co roltl<...... Tecnniq" . .. 11 ~ Th ~ St.;" l ... hnique 11~ c""..i... ro.o ri vat i Y~ " " . Genera l ~ ~ 18"""'"'' 114

109

7 , Theory 01 Uni~u l e.r Ion Dec omposillon, 7.' z. a 13

F"",9'o' De po;iliM a M Rille F.-.cn"" " 11~ TherMOdYna mic _8 , IV",,"c E" ~ c " 117 Ou""" -e q u i t i b ri ,,mTh _ ~ ns

14 T~

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'e 7.7 7.8

120

C" l c " la ~ ..... ol ~ I E I

FunOIl"" . US The rmo
8 I ()@lailed Mechanisl'Itt a nd Ion Fragmentation e. 1 6~

8.3

115

u.. "' '''eeu'a , "", D. c omwsilio.... 138 Sto , ic fa OIO'. IS'

Prod,,", $l . bility

1:15

135

127

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RUeI,on I_ Ii"" .o' Rad iCa l ", Chio r!1"5O'e. Re llCl''''' C '~ t i c.\ i "". 185

86

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Initi.tioo (~ -e l uv.go ) 111 Imt,a tio
aI Cyclic S"uo;t~r .. liyd rOOl'" R"'''...gements 111 1 Othe r R.....' . _ _ m. 213 GeM ' .. ' PeI...... ..",.. ~ 1

113

\ 7~

9 / M. .s Spectr a 01 C om m on Compound Cle nes g, ~2

9.3 9.4

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200

10 I Computer klenlltW;"t lon 01 Unknown M . .. Spectra 10 ' 16 ~ 100a

The O."'bftSe DI Aa'.renee ~I Mass SpoocIfe 2601 l: Tfle P, ob.bi lity llaoed .... 1Ching 8 y. tom 2M l ", oW ~ " . ' i o n : The SeIH h>1orp,eli, e a nd F1olr i.vel S""te m 2e7

10.4

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290

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11 I Solut io ns to U"'nownI;

203

Il ll>liOO"''''''' 311 ' _ nella 339 NLJees 339 N. "" . I " llo.Jnd .",:<,. '" Combin . tio ,," '" 8 mmi.... SilieOn. and Sulfur J40 h b" " 3 loni,.""" Ene 'll Ya nd Pm'"" ""'lilly V. ,.... 343 T80I. " 4 11I061>0 " '" Ion Atlund. nces ,," , ComJ'o."'d Type 346 T8OIe " S Com rnM No"" ol F' ra y ..enllo 34& l a_ " 6 Com mM F, a ~ . ", I"... 351 Tat>le A 7 Co mmoo E1e.........1(:(>m_ " ioo . of M o lecu l. r Ta ble A. 1 Table A..2

CIllo"""',

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361

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" 8.4 8.S

RUeI,on I_ Ii"" .o' Rad iCa l ", Chio r!1"5O'e. Re llCl''''' C '~ t i c.\ i "". 185

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Initi.tioo (~ -e l uv.go ) 111 Imt,a tio
aI Cyclic S"uo;t~r .. liyd rOOl'" R"'''...gements 111 1 Othe r R.....' . _ _ m. 213 GeM ' .. ' PeI...... ..",.. ~ 1

113

\ 7~

9 / M. .s Spectr a 01 C om m on Compound Cle nes g, ~2

9.3 9.4

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The O."'bftSe DI Aa'.renee ~I Mass SpoocIfe 2601 l: Tfle P, ob.bi lity llaoed .... 1Ching 8 y. tom 2M l ", oW ~ " . ' i o n : The SeIH h>1orp,eli, e a nd F1olr i.vel S""te m 2e7

10.4

,",pplic otlO n 01 P1l ~ ;III d STI llS

Fl<>",,,••

283

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10,5 Go"" ' o l "'. ~~

290

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11 I Solut io ns to U"'nownI;

203

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n'

,

] nducliv'e initi", ion of a Tcad ion thro ugh electr on ",ilhduwa l by lhe e h a r ~e ,M , inL

Relat ;v. intemil)' or a peal,

or

the ,ame oominal compo,m ons,

n",,, bul or diffe,enl clemenlal

Peal who,e elemental composition contains an i,, 'lope no l o[ lhc hig hc' l nal ural abunda",," I'hc funclion de'crihing lru, change ill Ill' rate eonstan!. Ie, with eh""ge in lhe internal energy, F., or lhe preeutw r ion [Ot a panic"lat ion-deco'lJpo,ition rcaclion. LC ,MS

... li4Uid chro rnal og ra ph interfaced 10 a rna" ' pcot, omoloc La",,]' desorption [Ot ionization of non-volatile ",mple,

I'hc ma" of the ion in dalto", divided by ilS charge lusuaUy unity), a Thom,on: mie ha, al,o been used li n ion d ecomposin ~ between lhe jon source and deteclor of the mass spectrometer, M ' , mok cular ion

Tb<,; iuni ,,,,,! molcoulc, "'doe moleoula, ion" i, I ho peak represent ing the ioni zed molecule thai cOllta;ns only the i, otope, of grea le' l nalUral abundance.

(M - 11+

The ion formed by lhe los> of one rna" unit from

M'

.\le

MelhyL CH "

.\IW

Protonated mok culc" (M + H ) ·

.\1I ' pectra

Ma" speclra formed by mcta., I;iblc ion di, ,, ,,,-iat ion,

tmn u, millima" un it'

0.001 alo mlc ma" unil; a millidallo n,

'"

.\Ia..,

MSi MS, M S"

~ t l'Ometr)'.

.\fS do~ in tandem .,ith mult iple (n) rna" analy', cr<; "'p:uatod ion< Im m one analF",r arc ,lj' '''lC;ai<xl or rc~cd to form lie"" ion, rna" >epara led by the next ana lyzer, m ~"

Non ho ml; n~ ct""(r<>n<. A pea l whooe elemental wmpo,ition hI' only i""topo , of highest " ' lural . bu" da" "". N en In Ii...1i000-r.ionizatio".

xviII

OF' ,,,,,ld-,,Io"I"'11 >00

I"n in which an outer-sh"1l electron is llnpaired; a radical ion, Pascal (l Pa _ 0.0075 lorr; I atm _ 1.013 x 10' Pal. Proton affinily.

P""u"or, p'lrcnl

The decomposing ion in any l"action.

Product id'l\lghlcr)

The ion formed by dissociation of a p,"cnrsor ion.

'"0

!'{I;J

'0

Plasma de'''rrtion ioni/alion, such a, thaI ulilizing

'''CL Oua,!rupnle analyzer

Q 1',

rhe dislrihulion funclion ,Io,enbing Ih" prob"bilit), ror parlicular value, ofinlem"1 energy of an ion.

rearrangemenl

A reaclion in which lhe m"koul"r conncoli,'ily of the atom, in either the ionic or neutral product i' not the same as thai in the precursor ion.

r I
Number of rings plus doubl" bonds.

rI'.rJ,re,rH

Remrangement, involving cyclization, displac"ment, . Iimination, and hydrogen transfer. re,pe,li"e1y

RDA

RCiro-Did,-Alder reaclion,

rolati;-e ahundance

The abundance 01 "" ion relalive to tbat of the most "bundanl ion in tho sp"ctrum (or, if '0 staled, reiali 1'0 ro L~.J

sigma-el"ctron ionizallO!\ reactlOl\

A simpl" cleavage r.aclion vi,uali""d as taking place throlLgh i[\ilial ionization al the sigma bond clea\'ed in the reaction.

0,

rolal ahunuance of all ion< in the , peclrum, rotal ahundance of all ion< in the 'pc<:lrum 40 and alx,..".

"I"",,,

An ion-decomposilion reaction which in\'ol\'es cleavage of only a ,ingle bond

"M

Selected ion monitoring,

srvs

Secondary ion ma" sp.ctrom"11'y.

Thorn,on

An miz uni!. Volts: speciflc use, accelerating I,ollage. The number of charges on an ion ("e' was formerly "'"d for thi' definilion).

1 Introduction

1.1 App • •

r.nee 01 .. . m." specttllnl

(.....n;n' ho", to identify ~ ";mrk onolicr lhan fw m othe r t~ of . ""CUI . The ,na,'. ' r«.,u~, ,,!low, II", ""... nf ,It. m.)/tr ul, I", J /Io<....usn ,,! pi"C~ 1 ./r"'" i1. 11,,,, ,Ill: " homi, t doe. 10'" ha,'. to l. " m . nyt bing "'''' - 1'''' appro"ch \1 siml1.u 10 an Mit!> ",,,' ;c trno in " ~ a"' t_ TTy on. ,,0<1 "'"

_ ....... 1.' ""' ~

..

L

J

In 1"" b.ar-~rap" ' m m of a l pectr um t"" in that lor Un kn " ",'''' 1.1 ~ the ~",,"i .. a IndiClllC'l Lh< nLaM laclu" lIy " / : . the ratio of " "•., 10 the 01 charJ'.~ o n II...· JUT" cmplolcd). and tbt o rdi "~tc lndicaln the "-... ti.... Intensity_ If yo u need a him. •"_ mber that lhe l " 'm ic w.i~h t, ,II hr
"""'ber

n

t

a

1 I '• ..."...110.

No", Ir)' another ,imple 'pectrum, Unknown 1.2. Your stnletUfe wiD be correel jf the molecule and it, picce, have rna,,", co"nl'onding '" th"," of Ihe ,pectrum. (\1" ke a ,eri"us attempt to ,oh-e each llllknown before looking al lhe ,,,luLion. rhi, is a vilal pan of the book-, in,lruciion.) Unknown 1.2 100-

t.

Unknown U contain< ~aTf>
Th. tabular d"la lor Unknown, 1.1. 1.2, and l.3 include additional lowabundance peak> lhal run Ix: ;mportanl ("lnL" is Lhe peak inlen,;ty rdali"e [() the most intense peak as 100). The mass speell'ome!., has a dynamic range mud, greater lhan the lloree ordeT< "I magnilude ,h",m; lhal i" ion ahundances

' .1 _ ,.... 0< ......

_

a

or « O, I~~ can l-.. mca'un.'I! "'rrodlleil>l.y, Fo. th.: m.... ' pectr al data "f (l>c unknov..m in ,hi, a re pr oclu ~jb i' i l.l' "r ± l~~ ffl Qliw or 1-0.2 ~ b ",l u l.e, whi<:hc"". ;. ' M ~,.m.r. will be WIth m od ' I n ''', Irli monl'' ' ucll ff prod ucihili.y l~ <>eblt \'abk wil h fd .. l.i ,~ ll W1~D . ample and fur measu",m" n , limes.

"'.>k,

""Ono ... , ,1

miL

,",

, "" ' "00 o •" " <0 , i

Ii"'"

,i",

linO..... 1.Z ~

, "

"" """

"

.."

..""

' 00

"

U.k.._H ~

""" ,H

"te

"

,. " "

" " "' "

-o

~

•• •aa " ""

~

"" " "" "

<0

T!>< .., buL" ,,",I,, "I' lJnkno,"ns 1.1 to L3 abo .,]\0 ," sm a U p
r1U ~

aIJ<JH , h~ , """ •• ponding to the: 'n"k..... I ~r ,.. i~ht. T ho, c aT"lO d ue h' rhe' ...._ ....."" " I 1...,·~bu o,l ant iwt" p"" tht .:.aroot>- 12 f" und ill nato ", rom! be ac" " "" p9t1J<'1'l"lam for d.d uc ing the " I ~fntfltal compo:;;li"" " r the mo l,cllle ami ii, r ;""'t'> dis played in the m a" ' rc<'lf um (O apt er 2). FI<.'Tl\c " I ~ 1 compo,,;tiQO,...... alo~ "'-lU l>e unil nla... resc lunon {~ ..... i,~ " bK' o.ring t~c lad that i, otopic ma.~

,"0"""...lh

d iffer from iOI , gor "al ue, [T al.>lf A.I, ~,u m i n ~ carbon "" 1 2 .()()()fO)~ The m. a,urcd spect ra o! (Ill;,.. romJ1d. cont,,;nc'd add jtiooal J".- ..h (nUl show nJ d"" to lhe "b"c k ~o .. nJ ~ in 110< instr ume nt. Thi$ ! rion (rom com pounJ s lhal a re delolbin~ fm m (he ...,lIs of tho in'trn nlMt o r ;ore IcaLing in f",m variou, ,~uTU."', To a void ctm fu, ,,m , ~ u c h a "ba, k gm und Sp"C1fllm " i, " sp a Ul ru n tx: r~ " 1I>e U l1>p1e " a,luaHy in t ro:>d uocJ. into l he i.... IUmCnl. Suc h a 'peo· (rum is rJ><>.. n _ I )nLoo wu 1.4, Can )'nll .denlil)- any of l he co mpo n, nt, '

"

•

__

Uok'lO". 1.4

", '"

_._-

..

001

,,,

"" "oe "" Mr .e " " •" '"" " "

. •"

s: •

00

~

•

"e.c

,,,,,, _

0.10

O ne "I the compo nent, in il, p ure , la lC Can you iden tify it'

~ i,e ,

00

' be 'p"c lrum ofl nknown 1.5

Un' " ". ,.• ml<

"re ,""

."

,.

I" L

"a.s " U

,•e

'00"

•

i•

"

0-

•

00

u _

00

•

1 ! i, ~n aClu,tI m~ " ,pcClrun, of the "l artian atmo, phe", (after or co a nd CO, ) from the US- ",'...SA Viling mission,

F i~ ~ r~ tL"",,,,'~ 1

TIl<: inlctprrtalion of rna.. spectra i. baS«! 011 the ,-hemi'lr}' "I ga>ro u. ion >; !~ c.1n no'" be t,,,mcd by • wi,lc ""-Tictj' of met hod•. ~nd CJD be m "",,anal y",d ~n J dc'''''ted "' ilb ~ ...-id< ,'ar~t y of i"'!lllmolltat;on. Of nc, >:." . ily t ni' boot ~i,'C< a limned d",cu . , ;un \ hc""" m mplete det ail' a", .v~ila bl . in tho ~,.,.I1
<*

, ....

,,-' ..

_AT~ ""~'

...

... ~ 0,. , •. ""' .. "" ~ " T

,

" <>.II<"""

'"' """...-r--rr-

"

"

"

.

'" "' ","." , "'........

1 19 ,,' c."

'"

,

...

-, 500 ag

"

!

,'"

100 ag ,"'

-

"

,~-

~I," ,. U . G .. , h' '''''-'l<'i''''' '" 10 " \~ l~ " i llOO,UOO "",kc", I.., of "",..n"",crt. phth. l."", dotO
'00

" ~il "<,,, ,< , 1992 ~

''''Ilo'';''''

m. "y <"'e m;"" l nollcti" n, ~"'" f". ,m. I ~ ,i . _ I he b ~,ic pu rpo.., of!h. rna" >f' lu oon ••n lh~ ....mple int~ mea..... bk pr OO ll<:lI l b.1! arc indicat""11 k>< mcd ~r~ _I><, ra Lhco- un u.... al: I'a><;<,.... l" " ;\;' c i{On" .,1".... m. -..e<; .00 re1a tj~ ab unda,,= . re displa )'ed in the mus . pe<'t rll'D. ~..~.Il'e ,,;to I>i"" ~;I'~er "e""d i, ;ly file ~(.;x,tront:gll.. Ii..., "" , "",~ I<; . Wi!",'" I . 2~ lIo we. c, . lllcir rt otmenlations ( Budllk....io:z 1981, Il<,..'ic: 19 /1'}, Hild 19M1 a re nO( ulC'd mu,h for "'ructur.: d etornllllllti Oll,. OO '" "-e will 001 dlSCUSl. them. T M Iy!'"" uf io niut;Qf1 u1li<.'
io,"

•

1I ,,,,,"",d"o

..-..., .. . IX

'

, _ . U . M"" -' pc<1rom<; lcr iun "'"Cc<.

cla,""" ~ H , m l- ; 'm; / ~\; " n . " L~h a. with 70 -. V . 1. Cl eo"" P<()(!
l, ,,gmeut before lea v;n,l lhc ion ,,,uf"", lh. rna, ,,,,. of the.. rragrnont ion. " rc lhe ha,ie , ub, lm c!urc ;nf" IlM, ion uled iu im erp rct ,,\i,ln. "sor," i" ni....w n, Oft 1M other hand, minimize, lu, h j1llthn rr"""",M~linfl: thi . i, particularly us.rut lOf example, for

ch'iT ~ "t c d , ;n l' m i ~ I U",S

£Iec/con ;on;:atio. ( FI) , h ." 1 ~ ", w ~ . rd ~ iOUllatwn method Wig..,c 1 3 ~ lhe "reagent " pr,,oik d "IT'" in in ;"c~ nde=nl IiIiIm cn i. a nd ' T. .. I t h rou gh the io n c haml\c r tQ an a" ode ("elecllo n \l4 P"')rm ' OC ""pooile ,"doe. The ,IITam f.I " no ,-~ n al, o m trodu ce , ample, or larj<:l-"- mol.cnl.,

n ,.,..,

im olt
~ l ~) ~ ,rn ~

11>0 p;lMJd t-btarn tt
- ~M G I (- ~

~I

imoi:tllitHl. By incr~~loi nl' 1M p, ~"' ur~ in , be iDnizauOJl cLim b.. 10 - lOll I'"~ (0.15 lm . l. ""'" ""n en h UBd redf. of roHi"ons bofor~ if EIocIron bomb.lld.... " l 01 me l ha... 0' 011><. 1."""''' ~I ""h " " .."" U"" in a d " d Irrn'~1cd pUm Plnll .~11') ' ou 1'. 0d uces 8 11 a bundance of ft..... ~ l~ ions ....eh 8S C H , · . I h= will ", ~ ,1 wil h added ...mpk m ok<1~ .. th' Ollllh a vallely 01 ~>J~ , eo<:/"",-" ..,.... a ~ ~ '>Oft, y ",l d i o ~ Sl a bl ~ prOOIl<1 ion• ...."lTo,enling Ilnofu.""';~ l ed ;.;"rnplc m o l.,. col"". W ith Ih.. ehem irnl iOJlI2J.t'o n lei: ,.,. M '''''''II aIld F i~ld 1%6:. Hamoon of ""''''''III"" ""n ht- ",I""livelv ilmi...,.) ...il h """,.;oc "'... 1983). d ilkrenl ";1I'c. and ... It''n v ~ reatttD1 roos. H el ~roal om -<:OD1 aillJ n~ m olt0 molecular ",. lj!hl. btcau.. tMy a~ oft.n pr=nl in 1bo CI ' pecI,a or rompou nds " h<,.... U '<J"'ClTa ,ho", no m " locllhu i"..... MO'O t i<m ir..I;.... ""'hnM.j ...... lm " " '-"" molocul.. imolecu la, " e,gbt s ."... n > I ~; """ SecliDn (d)...uch as Fa.. Alon. "' .... b:lIIl>..., nt 1t"i\R; """ IkIrbcr t1 ,,[ 1'P1l 1. ca n hi: m ade , ~l a l "",l ! -ooft- 10 , Jrid stlIblr j ",,~ m,>l<cuLo.r 'fI«."'"

.""'pes.

"""CC'

W

I,,,,,,,

i"".,

I .J lilian _

lysis of Ions

I he ion bea m fw m l he .... UTCC <:an hi: ""I"'r:an:d a
ma.... laduaUy '" 'I, l be ran<> of tbe roas; 10 l he n um ber of ch.1'g<'S. ror which

i.

i,,,,.

the term WT h, om"",,· ~1"" n.oo) of Ihe by ~ , ~rict , of l' -" " M.j l&e'O , "" J. ~ net · ic ddlot.1 io n, q uadru pole tilt«, io u l nlf', time-of-fllf-ht, a nd cycl ot ron ..,..,na...,. a rc the """"nd ing lu:hnM.j 1lC" m """ ... .... ""ml, """" in ",,,,,"""";al rna '" ""'"'" 1ro me ters. E,reI k-" t detailed d i." 'II'oS"''''' ' " IIt= me th<>d, a~ ha ~ahle in the geoen l

"*= .

•Wq,tIrlk .....,..,. The ilin ilie-focutill&(f"""'c ~ rqJ<; ll er" and ftitl n _ foc",,~ electm.k< are adj'h ted I" ma. , im i.oe the ion CUlY"-"T. all" ,,';" g a ..ti .<.~ n g hl:am ' M enlt"Tin !'. in " , 'M I ll<: ", me ma,,-to-d>a' ttt rali" ,mil) I" be focu soJ on the . naly.." ""it . Iit. 11Ie mag nctio: f>eld lOt:l . ~ . tho: ro.", analy'..,r. "Tbe "'il nIne in Tho m",ns nf Ihe wns which rn n pa" th (o ,, ~h the n ;t . Iil depend. QA I h ~ , ad ,,,, (r . ......l ' Mtoc i" n "",Ih in tlte n..gne tic lield. (be field stre llf.(h ( U, ~atl .. ~ and the in" · acceJenling 1" >lenliJl.I I l-'; "li t,) a . de fined b~ the fa nd " mcm ,,1 ""'n "" .... (Beynon

"",,

•

"

_-_.

...

"

". "

.....' a u . S.ingk- I"" , ,, n' ~ _ fi\1lgnotL'·'<eto , m. .. 'I"'C', om
( 1.1)

-I hi. ~~" "" derived on th. b.1Si, that the io", of elementary "hafy " • (a. ,(i, l;n_ sl ,i, hed from : . lh. numb" of ,M arg e, <>n Ihe ion) ha l-o a ll bun gi,, " II><: .,' me l ;JlI:I;< t the rn. .. analy, i, of , uch ions, the pressure j . maiotaioe
""'=

",un jilt•• 111<4 ion rrllP. W olfgang r aul .hared the 1'I~'1 N" hd in Phy , ; ~ , ti " hi, conccplkln of tfoi" nMel i"'tr unlellt' liotl, For the qua · u,up" le (!'is" r. I.S~ ions from l lIe roure. dli ft .. ~tll\< bet'.,,,,,n the fmu ",d <\1 alS sep'tr " llo n j , "~ll~vo(l b)' ~ ",,,,, bin:tlilln of radi tl. f""l.""""Y ( RI') a md (} . ~J'~r u~

!' flle

' .j

. . .,-1_-

II." .......'....... Tur....." _ '

•

."'_ 0'..,. '" ,u ;"(\ ,,.=-n~=FF==:r=-' "" ,,,.......,.,,.i

,

~ I 'I - [1--{~'

~_ , ~ I.~~.

,

, ,-~=----~

~""~~, _~iL~ j_~ "'" f"","'..... .'............. 'I '

m .. "9

","""", . _

,--

"::;~"." \ Cs" ;ang. "

C:-I'". ;"", ''"I'

-.. U ul, 1'l'J1

m .~~ ~J'Kl "')Ol "''' ,

,"...."'" '..... ..... m

(Mepri",od ..-;tn ro,n, i..ioo from C""h or

f ""'J- .~ ..... 69(11, 211-,. oory r i ~h ' ' ''''1 by ,0< Aln " i
di. .....-<."Un crJl (DC) J>cld. wilh 0l'l""ile p"l ~ril ie . un the p.i" of oppo, i" & rod " Palh osciJIali<>J" cau.. <1 by til< cll,prial< r~ q lL. n CY . Til. ion trap (Figure 1.6) i, b",ieally the throe-1itme"";" n.1 analnjl, of the qu adrupole ICook, N at. 1'I<)(), 19911, An adu fllnlle of Ih""" " Ye, "",,,nclie in'!r lLmonb i. thaI the fields requi red to f,,,,u, II ""nk ulil. m,,,, <:.In be ch.njl,ed vel)' rapidly « 10-" '1, which i, e,peeially ,.Iu;.blc lot com pulcr-eontm lk d mea,uremen " , ueh a, ",elected ion moniI,>, ;,,! "' !>•.,., X
i"".

J

. ;j, '

Ii ., r"

i

•

r

o o o

,,

, L __

,,. .-

"ro-

r:'

'! !.

r

-

•

•

, I t .: _ •

-== .. ~--LJ11

'-- t

1!

I

"'

, • s" ,, o'

.. :I:

1.' ..",...

-Jo~od,,"""

.,oto",.

J10" at mi. 100), and capabilities for ionmolecule rca"ti"", and tandem n",,, ,pc<;trometry (MS').

1.4 lon-abund..nce measurement

The po,ili I'e iom 'lriling lhe colleclor produce a flow of neutralizing electron> proportional to the 'on abundance. and thi, curren! "an h<; mea,ured accuralely and with great ,en,itivily h)" modern ekctronic leehniqu",_ Amplification of lhe ion ,ignal by an electron multiplier can mal. possible the deleclion of a sin"le ion arriving;n Ihe collector. AlthouEth t.he effi"ienc)' nr ionizati"n ~nd l",n,mi,_ ,ion in the ma" 'peclrometer may yield only one ion al the collector for _10' sample molecules introduced, usoful spoetra can be obtained from subnanogram ,ample,. and ,pecific deleclion of .\uhpic"lJ"am {< lOng} _,ampb i, po"iblc (Figure 1.2)_ Thus the method can be used;n a variety of research and analyti"al problems for which mo,t of the u,ual "tru"tur~l to"l, do nol h,,,'c ,uITiL;'-"Tll ",n,ili"ily_ Changing tho magnetic or elenric fields thm effect separation cause, ion, of difl"eITnl m.. . z ""Iues 10reach the eolled"'_ On_line eompuler 'y,tom, prod uce sel' of mass and abundauce values directly b~' moa,uring tho field and ion "unenl corre,ponding to each po"k. Thc," 'l"lem, e~n 1"'-"emd complete ma" 'peclra ",,,eral lime, per =o1\d, which I, e,pec;ally v'aluable for GC/MS (see below), However, the sean rate alleci. Ihe accuracy of ion-abundance mea""ement which is imporlam for deducing elemeotal compo,ition> from isotope ratio", e~eek the perform,,,,,,,, of your imtrumem wit.~ known ,~mplc, t" h" ,ure you have not sacrificed lhi, accuracy unnecessarily_

1.5 Sample-Inlroductlon systems

For conventional EI and CT, the sample must be vaporized '0 thm the molecule, will b" ,ep"r~t"d from each other h<;r",c ioni,,,ti,,n_ Dired int.roduclion inlo lhe Ion ,ouree i, pref"red for the 'lUdy of compounds of low volatility; samples are inserted with a prob . through a vacuum lock inlo the ion source,

,,----

"

. 'he, e ohey 2rc "apot" .,d by lKaling, Wit h Ihll ' y' tem, " n. caL ~ n \ll i n 'P"C" It.. o( no np"la, m"l ocule, Di molecular ...'. j~ht ~ 1(0) in llJ.llogmm I moun,S. W~rniH" " i. " ..~ ~""~ I.<J Use "'" lu~ch "" nplc in the di re<:-lIll",d " Cli"" Sl " rnt: ope cr;....al lhal is I~,g. e" ., ugh \" ..., ' hould be ,umClcnl. T he hC~l ;n~ T~te ' hould a lso be conTrolled C.1rd ully lQ """ id "Ol"lili, jng Tho ""mplf 100 rapidl y, "Iore vc>l;« ile ... mples ca l' I>c itltro;l...-td thWUf.h a fC•• ~1" l<.~n_ A !a' 1l" ., """" " f """pic I ~ 0.1 "'tJ '5 1'ap<,,,zed m to An cv~,u~'ed. lJcal.d """n"iT. from ",h ' h lite ".-lm p ;~ now. thro ugh J ,mall orilk " (ruolo"ula r leakl , ~ ' o the i o~ . o nTOI' n l . ne"l y N ni, m a k e••!"Xlnl "'''''iUrt'mlOlll$ ftlo e. {cpC<.>mro""'" Sf......... as .. elf 3' 10f malchm K"[ unkn,, wn and ""krcncc _peeln , 'Ille rna.. ' peel",m. l. r C~n SilO be d il ~ C lly coar kd (0 l g~ . , \romawgrap/'l (a Ci l,..l ~ , see Scc1lon 65) "" Ih lhe " on fOUr= .. he", ~ hei. \'.m1J'kfe _('«Ira a ' c "blam' d -u n lho Oy." 8~- ·.d~ct< d jon m" ~J1 <mY'~ ~ r.", ~" u ' ln 8 Iwo or 1t,,"~ !",.,h " ~ lle n li all}'. b<>lh h;J!,h _r.." ,ificily aud high sr n.oli" ity of d.tect ~m "'"'I n "" :>chi.<,c.J for co mr<>uD1her ",,,,,,rm in! do' -,en. , uch ~. rho high_pcrlon naocc- li,,"i ~ chcomal0gca pr. ( 1.t:("1:S~ hd>O aho be. n 'k_ 't!,h<;d (. ... !)u:lion 6.5).

J""

,.""ir

r ile an..,lylica: ~ 1.'l"" "f't<'(rm Jl ",a;o a pplif l ilt com",.. nen'.. ,n the .. me W;t~ lhat lb....'. Jaw 1I'''-nn, >J"-" lropbol,Y""lric m"ture ~ n ~ IYJj .. 1-.... Jo,. -rr~"""" "lJ">olil ium fot el«1nm in,a z. lion cau", eac h m ,X!a ' c cOlllpnIlent ttl com rib .,,",, illd.pen,lcn lly to the m. u ul<>d ' pet;t,"m <)( -ample.•0 lh..,t the s.t->odm m '. aoo" J~,..,... ""n toe r:l'h1o:d b) a ""r ltS 01 ..... ~'l~nc­ om ~ 'l"'riolU "";ng d.~ t " n:""...."" ,~ .. or the fKIr~ cOIl'I'"nenh, fha' , j f Y" " COil iJ,,,,,jf)' coer"", I;' " oc c" tn pcmenl of an .,n~nowD mi'l ll", ' pc<:tru m, yOll caDlhe n . ub tr act out lhe ,of' I...", tIll ' onmpolKnl ,"'>ptcllv.m 'Iril'Piu8"~ uJ " ' telllpl h>;ut..-p"'l lho raid u.J "P"'·1Jam. NO\<, howe""" t ba! 'l'f:'CIr ~1 , upt."po, ilion wllt J1' ~ 'le<::oI""aril}' ~ !i""ar fN Cl anj Olher ,!'C"tTa ob\~'n"d al p'e•• ur .s l1 igl1 . no ugl1 fol' i<>n·malecul< r ea.cli<>n. , To>,b )', most MS "" ,'!,,~ ~"" I1"is " hl l"" oorrboru:d ,n.l JU<1\""tl li,m ~b "" G Ci M:. ,K~ ,a ... ~ ~ n d ~ I ~ M : I1vr " f>N 198": C ~ ! k> w ,,0<1 Roso 1 ~~9 ) ,

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1b< main purp<'l~ " f ll" . bc><>k i. 10 ' how hew mol •• ule, ~ a r, be , tructUI;,J!y characleri , cu from Ihc ,n.,,,,,, of their i"" iU
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rompouml mn , ~i n , _ 2" bit' of duta. the rna.. and abundance """,,11m! from .fe mb;ltdmc nl "r "' o~~. Tbc:",
t""

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mol= I<" muelurc; ~hc intorprota tion P"""""' Uti"",,,... lo conv' J1 l ho ;,potlr.•l in/m m:lc ", possible. Tho 7O-eV "!ectron cnc rgiL.. used U. \Ii'Uaoovc ' he _ 10 ± 3.V r~qu; l'Ild ror til< i" ni, ,,~ i"n of molo< ""gli~ l ~le , Th.. ,niti.1 r",~ l t or Ill, . !«trOll IIllcT" anll""" furrbn '0 ) 'cld lh<: (rag",.,,! ion;. 01 11><: ,~1 mm _ For .
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11", JiH will ~ u"~I I,, inJ i0 t h ~' ' he t)ml,,,l· · '
all tOa wilh only pai red el«:tnl ns If a n -ne r>- c ke ~ ", n" (ll(!) ion. N<>Ie ;n Fl'\'l;ng 11>0; H rna" spectrum, iO M · · i, pre, onT. ",1ft i"nwuj on ( ~ I' on 6.1) ""an oftell , upply 11115 i d" ,m ~ l; on_ T h. cl rrngllKD' k.n. inJicu,c If", ~ s of ",·hiol1 the mo"-""ulc i. el..-npo",d, and lh, illlc"f f'l" el<:t aU""'p'. to cltdu<e h" .. lhe.. pi",,. iii 'o~he, in the original " w lerular ' IN " " , e.. ~pc"" ltaim uct ur~ OOlt ellllio"" """" no ..' heen puh li,hed for a ..,ok ~a ""1 y '" co>rnpkx mol<cule, _

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.01 - 1" c"f11y 'lu" lion' · th, mo>,1 e/fl'; 'cnl "I'1"l"" h u.u.illy 11 to> rUIl bc:twoen maj or "'leg",i" e,g.. - Is ' '''' person male', Mo l<cu"'r .. ruct ~re cJw; id"li" n i, , imllar : - !>lind al"ys~ ClIo b,,,l b<: rninlmi-e d uo~ n O"' n

..

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il ""!'l ain t yp'" of d~l~ in the ' I"'ctr um arc "sod hd",. oth en, A' 3ppro"ch, informa'ion ll ac<jui~ . f1icictltly In the following ,,,dor,

J i:<""f~1

(al "'<>I..,~l " "'~ fh,. ""m,,.,101 com",,,, " i"n, ,;n ~' · ~lu,-dO'u".~·bon d'l; (h) Sllb' tr \&nntn,y;tic""

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a,.i",'

(d ) P,,,tulated p<>MIbk m"'..".. lu. "'''''p'' rlnlcacll m uet,..., all ..vaij· a!>le <4L•. Relor(I'ltt H m. " 'f'<et ra of 22O,o:xl dil'r= lll com!""" ,," "'~ collecte
To.> Jearn I"..... I"" '. "~'Y ct i"fo,m"' "," ,h,, '" a>~ ;I:I bk- ; n ,.... rna... ,.,....,. .h(>U ld loiJO'o' lh. cm lLO<' " r !hil "'~) k .' I .p b) 'llep in inte,protiQlI ' pectrum This "Slandard IDICT'p retat ion Procedu,," i. ,", forLh i"sid<; M e:' em'" in t l>c r"'tIl (If a d "",kW I" be U9W ",'her. yo " an:: inter_ lwelm!' an IInk""" 'D. This i. ~ wcnc"fa L ..... pfi 6cd """",,"eh app!ic" hIo 10 th" "i '-era gc" l.! l mas> 'rcclnlm, Wilh e~ pe ri<; nc e lhe Ii,,, <en ral ,tel" wlil b< fa' l ' nd larg_Iy " "I" m' tic, While you lin: ~a,nin lj. howen " ~" c h ' tep , hould \'C d" ne i.. rhi<. ''fJer, a nd you, f'O"lul.:lllO"" a~"""""" aud "",,,,1...;0... ''''''' ea~h .1<-1 ' ,~o<,ld "" re.;" ,o,kd ",,*,~hly Oil "'" If. m,," lholl OJlt "planat ion _rrean p"""ible 10' apanic" l" r ' l'-'l:lr al !e,nute, be " " " h' no t. i""wbililic"" l rUIn.

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'b"

'peel",m.

an

Otlor, _ ph "" "'lfHttiNo. II '. import.lnl III i"corp " alt aD :>ll>k , In"l ural informalion l.e"" m;'a!, ' pc"I,al, 'ampl" hi>!ory) in!" 11K> i nt~ rp r el a . Ii,,,, ..here,e, ~ ppropti ~te When " ...~m pk i• • ubmitled b~ anot "" r rese"cn ..orker e" tht 1lU/»"" pe<: tro," cLcr b l>o",w ry t:>r an "'., ,,,,, ,t i' ",,,,nl"'" re.l· , on. to ha ,'c the re, car ch. , interpret the m. " 'p. ~tra "f hi. or her o•.-n , am. pic. ;, Ihe impo ,rT . ,1Ct of Ihi, infCHm.' ion. for "" hich that I".-t "',, will h.... the I,,-,..dn t aoc m<>st 1h.'''''Ulth uoo..~t"l>d ;nt· T his. ;. ~I>O .:0... of el\e main '".,.,, ' ;h .. lOr , b. r n-r . rn' " ,,, "r Ih. hn,'k: Ina.. SJX'.1., o m 'l r ~ >h:,uld mOl be j"", fOI rna" , pe<;tm met, i' h.

".<4'"

Oi><" i"'", SI'«"'Htt. T he jnr~rp""3I iom pr....clur.. rot 1" :5 book ..'Ill ...... rl" unknown E l , pecuum '" !Ie eha' "r ~ p"l<; "'>rI1J'O u~ J. ll f ~""ra l com p" und, are pre..ent i' lht la mpk, the I" uh j,, ~ , peel' ,lm will ,e p!li",nl a lillu r ' " per1",,;,(00 of ' hr co m!,,,,,,,n r 'f'<" era,l b en ...-ith ' '''>d llOuld he ",bTIJ..1.cJ from ' l>c ""n' pk 4' Ih.. .. mpte can ~lTec t b~ d.:so,ptilm ral, "f the bac kglountl ma"ri,\. t )n ~ ' l ,,-"a~ lime, mll well aha •• the

,..

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"

" ' p h...... "" U ~ene",lIy . IMI al ""i! 12, , in", l he'" i , li,.," u",ful infor ma t;"" beIo-..' that , .I ~ e ;n rna." , ,..,...1 ra of of~.nio; m ol""" Ies.l 1f " . of, io n""''''''l l« hni4ue i' ~, .i1" b1 ... u'" il 10 obMlll a n i"",,,,,·nd. nt mea 'lll c"",nl of tbe rnot.:.:ular we igh t. 11 II illlpe", ti,'c lh l tilt n" ,,"uJoo m,/; ,'n lu o, h" C<'H'. ...... I ± < ll. ~ mas, unJl'~ C'omm"~ h~ck~round pea k... ' \J'Ch as lh o ,,", ,,f oir (UnkDOl'!n 14), can "I"" a. ,m ental .rand,lI d,. [f [ lot.,." i:l. Qny do uhl, add. on iOlCmal rna" "andMd. " ..." , a, per fluofD. lkan.... C.F::"." . " d I.k•• OCCODi~ "",m" The reprodue-;!>ility 01 ))Oak.ink.....ty ..... ' urom en.. Ih" uk! al.., "" checked, A mult>-(1,,'B, contpound .....::II I" C ,(1. »" w ide. ~ ""n... .......1 u ~nd" rd , sin"" il> i.Olo pie abun "a n,~ are a",;",al.l:l)' l'fedietabk: (Ch " rlet 2~

))0""

M~lrif'IJ ..I' Mrt eJ .... . MOlt in " .1\IlSS $pectr urn I J>rear, c<m" :,, ienllJ , . 1 inl egra l rn"'" num hi>n (fo r rMc exact rna .. dill'e..""""'" , ee ""eli" ,, f> J). H_ eye.,., mult;pl) char,w io n' call arrear at f. ~< [i o " al rna" ,, ; 1m t '4.,mpk, in Vn. "","" l.3 Ih, n: i, a pe. k at Itt! ' 1 ~5 01 o,r~ i ~l.l: n ";[ )'. rcp,ncntOn! tr.. do ubly d "n gc,1 i""" of rna" 31 (1jOC Cha pler 61.

..-N,,,,,,,,.

1,8 G_ r..1

Wil h IHttIlz in~ " i, io n, Sir J J. Tloom" ,n , 19 13) wr Ole: 'T""no an fn;l.n)' problem, in chtm" lry whieh coa l<:l te r bJ th i' lh;,n by a n y ,~ h"r me tho d~ There is now" b ' $e . u ~ fa'eina\in$ blernlUJc Ihat ;. hi ~bl j' n:ca
t'"

HtJtJIo . , o"ynofl lW'-' lIeyn"u et w"" In ?, 1984; I\ULi u na h 1987; I\udzikiewia '" Qt 1% 7; n" rhn~"mc I Yll~ 1'ilI5; Chapman t ~6; C" mli,n' in "I " I, 19'10; n ",i, and Fr eam m 1 ~1; l>a....,n 197(,; Dd "n @h 197 5: Dtocklo. o n h l'r 01. 1'I>t6; r~ CC h. tli [9R5; G ""-ell 1 1I ~ 6; Oro., 1971l; H a nlm i n ~ and F" m,. 1911; Hill 11l72; Ho"", eI aL 19&1; Kara ,,' " nd Clom""l 1 ~ ~ ~, Ki'e< 1% ~ I eh"""n ~ nd Dursey I n h; le'WD 191 H; \I " c" ,, 11 1<)11; " b rch 19 ~Q ; M a"'hall [91lQ "!o:C Io, ke) ( 9\lO; "!cO..,....d l 1963; McEwen ~f>d La " en 1990; \kLalTe")' 1% ." 19n M el ~ (f.,l\ y hnd S," uITe.,. 198'l, 19'11; \ol cLMlmy " nd \<~ l al am g h a" an 1982; \l i,j,lIct1ilch / 979i Milt" rd [1178: Milu" 197 I: r orter 198 5; R,"'" and J ahn, w n" 1 9~1; Selbl 1970; Spilel ler 1%6; Sud ler and W~ ...,n l \>-)(j; Wall" 1972; Wallet ,' lid De n ner 1911O; W. I"'" ' ~H5; Wh ite 19~(\, Wri, hl and Woo d I Y ~li: Vino n 1'-'117; lare tstii [97t1.

JOI•.-q!> oMJ , tri. I,. tJ"~a njc -"to" Spn:,,,,",,,,,,y, Wiley IChlCloes\cT, I n ,l a l1 d ~ In"''''OIU>tull J our",,1or ,\.1 W .\'f « " """,rry ~'lSfJ, FI"", it' (Am' ter_

"

. . .- . 0....

(~"" ~

lh."""tCP.... I I", MS.l Spectro",oPl ~"-~ )' of Japan (Tokyo); MaS! Sl'ff,n,,,,..,,) l!ulI.ri~, R ~ l"~ ~ ,,"i c \}' or C hemistry IC ",,· b, idge, Ellglu" ,U: Rud ingame el ai, 19W I'W2. "lIio"nial Re, iews of M.", SI"'Ctlo rnc lr~'. "; n ,1""1..,,,,, 1 ChtltllS/, )"; S pecial",", l'Ui M l<',oJ R ~/I"mJr : \ 1"", Spe<;Uo""""I, R" yal SocieTy , of (' ",-.."",\,y \Camb [i d~e. Fn gl.. ro/"'<'11 ~~: M m" SI'I"·t,,'mrtr y. ChL'ffi ; c~1 "ho.-rac~ Se, v;c.: if .\,lum bm, O HI. Uo;to re OOlllm uing lo C hApter ~ tr y tlnk ........o> 1,1> 10 1.9. "Kain ignOTing I'" ' 11'011 ",a" adjacent to ~,, ~ "n ~.... Wi ll u nt ~ }'Oll ar e n;;o lly ""uck- bolore Ibcnins h ' Chapter 11 for hd p .\f=

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A firSl kel' rO=tt of iol" , ma,;on ro, id.." lif}';ng a u unkno wn OC'l"l",und .. molecul. r ron""I. , Ih. " " mtx:. of o. , h of j l> con.>lCe lin l ~ ; ' j , UI U;' UV rna.. "I'lI\ w-aJ abunda nce m . ~<:o possible a ",oful aoo ;lI"O'" as ,mo m.lo u, m ","in~ {he nn kno ..',", of ( 1uple, 1, Even If }Oll "".. high-n; .,,1.,(jon info. ....tion on clemen tal u mtp<>S\· liom .,·a~.ble to Y"~' it i, ;ml""rt ~m 10 nndeuran J thoro"gh.~· Ihe "'"' of i" ' '''r k abuodam.~. whkh ;, ba";,, " . a n tinde"l "ndi,,~ of rna" $ptClra and of eq>erim.", ,, lh m "" 13.i'l<'linjt wil h 'lable ;,,' 101""" F IP.Uv. l he eleme nta l . om· p"""1;,rn 11 also important inf" , n"" tio" f,," the Ir_~' ",,~h

e,e,'or p""ihle.

i"""r<'

i\ I.'he",~·,'ll;' P"" " ' Illinic com l'" und .... ill I've a ""(IU ~ or m'" ;l""1 '~ heca~ ...

lhe eIen"...,. ,h. I con'!",''''' il are not ;"'lopically p ure, Roc. ll l h,: ca.. of ,he cl.: me,.. ne o n. " 'hich Sir J. l . T hom$o" t l~ 1-') sho wed p •., nol """ I""'..k at it. " ... nital . ~"mic wlU>ll8n
"

c"menlo aTe ' ho", n in "I able A.I (it1 lhe Af'l'Cndi , ): howe,'O[. thi. bool< OO"Cr> Ihc 1JL~" ,[>Cella onll' of co mpound! c(>nl" ; ll i n~ 11'1< "k,,,n" Ie""... " "f T~"" :U _ ""• • 0" . 2, 1

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The etIca or ;'>OfollC< on a rna.. 'J'C'-~ r ...m i. iIl....... ~I ..1 il> U"l"o....n 2,1, \....hich ".... .tai... m" I"""h .. io... ~ , Jl> ~ nd 3&. Th elf ct..\r,,.;r.ri9l1 c i.otopie ratio or l: 1 ;/wold Dl3ke lhe rltmenl u " ly rocolfTI;,,," lu fr,,'" lho.: .l ~I" "r I ~ ble 1.1. :>rOle that the interpnobl,i,m . of "'.." 36 a> ~ l' aSlnml io n (Iou of tWO II] fro m m-/I ~ R .. o uld he to' aUy m isl .."d jn~ . It i> hlghl)' im potl" nt Ih"t Y" ~ " ,,,,,,m,, Iauuliar ,.,nh 1'" data or T ~ b1c 2. 1. " Ole l h ~ l ~ ho.: i .,mop. tif (1J ~·._'1 ", ~." ,. r" lh • ...".., Q/>uMlln' fOT all 11>0.- .. d en"' ''l';, q uite forrunJ rely, Note also th"r the Il"t" · p,c abuooances or the "an be cla"i flCd inlo Ihrce lI'-"1\cra l cBtt~o rie;, ..... ~ IboloC clemen!> .. ith nnl)' " ne nal ura l ",m o t'" ," nprJl'eci.'oJt abundance: . ,\ -t I ." lh" .... c1emenu (hat haw two isOlOp", th e so"o nd of which i. ,,~" maR 1In ll hea vier Ih" n tl'l< m,,,t ah undanl i,,,lnpc, an d "A + 2," t h~.., tl~ mtJlt ; lh. ' ha w ~n i,,, tope thaI i' two ma" unit ' heavier thall the ......"t " hu n d ~ n l ' SOtope. Th e ~ A -l T d em ent, arc Ihe ea,ic,! In Tce"J':IIize; '" ynu < fi r" _We ",ill uSC a ' imilar clas,ificat ion fnr ma. n pectr al reak " ~ ~ '" ~~k il one who.. m ain element" l formula i, eom l'" ,ed of ,,~I y Ihe m,,,,t ~ h u n · (\Mn t IK'l Opeo; ih iA + I) I',,,..k i, Ihe JlCa k one mo" unit hi ~ hc<: ; . 00 '" fo rrh

,''''ow:

A ","clInd Isot Ope ma h . an "'flC'.-"ia llj' I' m m j""n t :lp pea.."'" in lhe .pc..1 TUM if tt il mOIli th Ull n I\C u" i, hj ~h<-r in th. n the most ab unda nt "",[I'pi" . !"-Ua.

tn."

ll ro mme and chlorme. aoo to ~ I~","" " I he pre..nce of Ih..., elem~nt, in an ion i. of' '''' ea.dJ Te ",, ~ nj ..,d trom Iht ~ i S O! C>i'I ~ cl",,~ I'm dll<.U:l i n lhe "J'OClrnDL Thll. okmenrs or L: Dll1o ,"'n, 2 2 a~,1 2..1, M e Onkllo"' n 2.1. "" 0 be I~ Im m ' he

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"rlit<: ion, , opn a lcd h)' I..." m"-'C' u" il<- (h ..- n....,

.th~ 1I I"'~k , tl .~\ l~

the l",t" one<... ..' n i" ilial in,peaion of tlle oor \l,"ph il OftOll nn c".~ ."" y 1(1 id" nt i r~' '\l"~ ;\Qlo,.i<: d u\lcf'l , For ..mplification. ,mly \he m"' c"ula ' k' n J~L K ore md udcd.

Lin,u. lup" posill.... of Ilolvpk ,." .,,,. . If Th ;" more l h~1I " nc al"", " I 1"""" c!eme"t' pre",n l in II><- m"I." " lc. ' he "", ,,11 i ' ..n m"'" ,I n king }"m b~ tlml"-"" bro m; d~ the i<(ll<:> pi.: molecular ioll.< at ....it lI{l and S2 (11"'8 , an d H"' Ill) a re iJ:t the relat ive pl o por11on , 01' foo, hl) I: I , Tile rna>l _pel.1I um uI D. J . ........ prrumne D! j1l ~lllC u l:tr iOnl a llU ~un I ~ ll, 1((1, ~ nd tl>l. <>f rc l~ l i~c aoonda"",. . I ] : ',

due III lhe i"." '" liT, . " U,·' II, and " lIr '·Or, a M · ' 9r , . rnpei l f" LIT pc;, k, at ;n lc",al. "f l.." """'. uni h in l hc '~l i" 1, .1 } ; r , ~..,j t ho 3: I i'UlU)'!;" rat;" of "0."" 0 yodds lhr« pea k. ill IIIe rauc 9 :6 ,1 fOJ j"n ' p<'Cie, c(lflt:l ; " i ,, ~ t""H-f>I", ;,1C ... "", I"" f il" ~ 2 I } """""'" u ~,

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The Ch~T~"'""'. ti c pattern. =< ~-h l"" .... b,omine. . ,,]fur. 6nd , iii con i,,,!o!,,,, k~ , 1I"i\ '~ tcJ by T" hie 2J (lu,id e fronl coyu). atran!!""l in 'n,T< "" ng ord " of 11'1<' ."I~".c abl.ooa...,.,. Ilr (... + 2\ a nd 1-' + 41 ' um" rica' . aJIOL" cnmtHna tiom of~ A + !" ....-men.. M~ ~i ,"n in Ta ble 1\.2rho,", ",n. akttlaln1 1m", Lhc binomJal eXI'~n";"" ." _ bY' ~ a" + n~' - ' h + n(n - l)~ ' ' h'i !' t- nf ~ l ~M - 2)0" ' h'...n !) I .. . • T b... ro,. Ihc pc~k> cont~i l1 in~ rour chlo rine al,,"''' ,"" into"" ;I)' of thc t" + 41 rdan~ h' !' ' "l' UI
f,,,

O. un> t1~tI ub.~J~~,·. ~,"t:Ji"u'u.. n... IA + 21 rela l;". ab andan..-e 01 "' ~~ .. II "NY low t(l ~\J. 'I(KI th us high An.u" d4...." .,'I;\lJ ~ CY i> necessary l" dc" IJQw ble u l.>m . <" 0 ' or .L 11):,; 0 1 al>I ± 0,2 (on th. <ealc t hat the a h,m," nu: 011 '" bi!,h" l l"' ak - 1(0). "hictl"'"e( ,. ~re-41C" in th. ,'alue or [(A + nll ,!:A] "ill oc a ..... mo«!, ", ! ~ I (i njl. m an unom., of t ho "A + IN......."'n• .".. OOn MOl l""..:nl, p, od oci0."", " k nl,f>ed ,

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+r The ,alu" "r - "" l!"-U'" infolm3t ~'"" . ",mld not ,"'crlooked. .~"o t l l( , ,~ ~ ..o n lor ch< c kin ~ fi", f,,.. the P1C5'ffiCe 01 ~A + 2" . I.m~ n l , i , tha t one « ,..., find.. ,hLm ' 0 hoi " b,.nt , C" n, idL~ ~n ~ pe<>k A (fragAb.nw~ of ~ A ~

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,. _ --_...-

"

""nt ;"D ~ ~ well ... M ' ) in '" m",,, ,peel,um And tilt pU k two rna.. unib. ~e, L' hc: (A + ~ p:ak ] : if [ (A + 2)l.'TA] < 3:~;~ the !'C al. A cu" ", >l """' ai,, Ihe mo'" """"dll ~' il.Ol01'" of thc ckmcnl' Si. S. or Hr III A ront~in. m" , e ' ....n one ion form ",la. thi••",ti" dolerm i"" , 1he proportio n "I i" n. free " f th= e1.mL"'''l- Ta ~l. 2.1 (i" lid. fro nt cover) "'''W'< th l if I""' ~ A oonl~JnS "no "Si Atom. fl." oj ZlJi[Aj ;> :\.4 :.~, t..·\OO u"" in nat u", 3.4 ' oS, at om _ mil"' "" riti..... al""mn ln hule 10 lhe IA + 2)po_k

Cl.

Th<: lim.'" - A + I demenl\ ill Til bl~ ! 1 i'1'I: h}urogen. ca,bon, an d mtroi"ft, I>uI IM ' I V H rati" i, '" ~.>'" I ~ KI "'" ,ball c" m ide, hydrog. n to be an WA" elC'm

n ~lom in lb. C'H"Br molc",lIe ,,( Unon""'n 2.2 oonm \'l ut"" U ;~ 01 ,..... ,ntensuy of H'. miz lJ4 pcak {J ' C H, " Ur- l to the ",i: ~5 pe~k ( " C H , " 111 -). ,nd "f th~ ....: % (" CIl J " Br ') 10 the ~ 7 I L'C H, OJ fll ' ~ C n kno..'D 23. wbich ~on· taius no " A , 1" clemen " , , how' [m,..-: 6~1.'(...iz 641 d ooe 10 Ihal e'l'f)'); lh2t gi,n lIS ~n"' h.r reMO " why"""" f. 2" clement< . h" ulotopo;; Lt-' + IJ] 1A] fo, a C Je ion will lhm exhibil tOll ti m ~.,. ,he I"'..... bil il~ 01 <:" (>r 10 . l.l~_; , '" ll /~. Thi, racl provide, ;< Y,-" ) 1.<, o.. of "'!~ 43 aOO ~~, 'The r""IIl< , ind i~·"l ~ tha I m/: 43 peak is fe,med fiNn tl><; ",j: ~ by Ihe I,,,,, "r ""'hal gw uj'J' ~ or. th l mllny ""all 1""'00 in IIn k"" ",,, 2.4 ",ere ",Iat i\'ely unimport ant for d<Ti,'int n. , tr ucm,e. ptah . :"'cb clln be Imm~d fwm llb"n,l.n l l"-·. ~ ' by 111 0 I"", (~ ~ yd"ogcn OT ",hi~h "'r ......" 'l d" ubly charg. d ions , In other un· ~ noL_ ullIn'p<>r1anl peakl ..·,n ollen be omirted, For U nhd"'" 2, ~. nnd fhe ......... "1;0] fonn uLt or ih~ m"lc~'utur ;"ni Ihi, ;, Ih. kl' ge
r

""..,rj

»c "I<"""

'·C

=

"""' ;U;

,.

".. .. .....". """rs •,

"

sc

.. .... "

"' ,",-, "

." ." ""es

"",

"

'" " " " ,ro

." "."". •

~

.""... .."".. ",. ".. ...". ...."

•"

"" ""

u. . ... .. " 1.1

,,,

""" ""

"•

•"

"" ~

ee sa

"

.,. ,.... . ". " a

" "

""

r

"

.'""

r •

'-

•" """ " "" "" '"" " "eo

ee

"

""z. o

'.

" "ea

"

'oo

,.

•

"

!" I•

" "

"

•

" •

o,,~h1" C_D. T he li nknown 2.5 ,pectrum "15.0 cont ,; " , a mino' . hut ' ml"" u nl. p""k al m,,.'; 80 or O,2~-; inkn,;l}_ A"igning Ih;, '" tho "0 romrilK,I loli or Ol>e IO n alom in mi. 78 would mean that til' l~lter rontain' nO m" ", tha n li... u rl><m at"m,. wherca, \he m.. .z 79 Hbundanc< indicate s Tn" peak at .n ,.'. li'Il a<:tu a ll~' ~ri",s from C.[ I•• ' ions containing two J ' c: "t.om, and four ' 'e aWm . 11", a bun J a n ce " f , uch (A + ions rolat ive to the A-i on de~lId. "" (he number of car bon a'oms,ju" a, [( A + I)' J..'lA' J 111 . .. Kb llM . lICC. a ~ ~ I ",) ta l1 ulalcd in Table 2,2, 0 1 coor.., (A ~ })- isotopic c''''lril1uti''n< "an aho from "A + 2" t lt roc~ l<. .".rtcr Oil< 11 " , " <signed til. num~r or t.rfx m and ~ l l lOlI.n JlOID~ from

"t.

2r

,1<"""

",i••

•

...•.._--_. - .- .--

"

'

the I.". + 2)' n lue m u, L h< "'ctIt:Ckod fo' Ihe dClCc'\i<m " f ,.. ,~cn: ~ l lh"u8h tile " 0 /'·0 v" l"e of (l.r·~ i' , m "n. lh" ahundulllX 'l ""uT~,;i<:, . " "mcd ill Lhi' book (th" 8reat" r 01 ±U.l aOO(1 luL, or :!: I ~'; ~ 1 ~I ' v~) u,u.. l1y ,In" .. 'm<: T<1 , alcul.t. Lhe ",}'ge n 10 withi n I " IOn" fo r lhe M"" I"'.~ If inf,. ",d or N~1R . peclrJ of the unko""'n ,,'" " ,';o.ilahlc. Lhe"" run pro >lde definiti ve e" idcncc tor Lhc p",,,,n ,,, "r , pccir", o' n en fUllcl;o"alilie,. F"r l.' ni< n",. n 2 . ~.
+

U-

a b u nd~n ~ e v "l u~ ,

=

u. . ..... u ~

ae

ee

" ". "

., ea

se c.e

" "" """ "" """ ".•• ".e.s "" ec,. " "..., •" a.e "" '00"" " "" "

.. .

"

00

1 , " f•

I

00

I

00

-. ..JJL. "

"

..

- - --

..n", Ihe n am h
"

hI' hecn fi , o.-l h>r ..ti--

On Ih. c' rn "' '''''', 1 ' '''Ufllq~ th " to-olaDC< "" the rn a,.. "" the

",,"k m..., he d"" '" Ihc mo n" "" " " .,;.. " I\" "':;men" . The " " ill"m""l " fl lIc ,,,tal elemental co mpotuion I" r of tit" ..' o ral plS'ibl. rom l'O"itiOQ , j is th. " oomh~ """ 'II n u"'t.;.... of 'hc...: clement, oo n, l>t<:n' with r ulev of ho OOing. llIus tra Ling Ihi' ..·il h Lite p"'.....u, , ,,",,, ra , , "" 1><1... rra k al m/% J6 .,.. C nl no"' n 2.1 m~" <;<>nla ' n o O>C "" IIlI '''''' No""'" on Ihe abotnd anco: 01 i1>; A + 2 Sul>t , ...1in, lite m""• • of , " I" rinc. U . ' ro m Lhe """" . of , hi. """~ . J6, lea, .,. 3 rgm;"" """ " nc carn.m;

"Ie",,,

""""al'"

t""

" 94 - 79 - 12 ~ 3. '0 the e!em."la' ,ompoSlli" " "r ' h< 00'1<' penk is C H.1 " ' Fur Unk n,,",,'n 2.3. Inc ~, . . , 64 I""lk ",a ' ~" ignc " tht elem 4. '" lh conlai" ed C , and C" r"' f'<"' , i . d ~ ; Ihn, 43 - 36 and ~ ~ 4lI ind i«t le th< n um oc r of ~}'dro~u ' lOrn, in each . :-" 010 .h~1 "nl~' ny d ,oj!."" a'<>m< CIln he uoW

n

lu account ['I' ,,, .. diller""". until tb••'alue ~ a. large ,., 19, tl>o n.....' ,,( Ru",i"". ,"ddjlion all~ . t he O1.ml>ol' of hy<.l",gcn. COD ollu be infeTTed fwm 1M p roTon N M R _peel'III " , and l ho: minimu m !l urnn." . of e~.hon al om , fr" rn the C· 1l NMR ' r"C. lruffi, Try III", r;lfli. 1'peclrum r.I',,-.. ,:nliD~ a " u ~J~ fra~m<:nt ion: mIz

Int

'"

100

126

"0

12'J

0.0

N o ~ A + :r OJ ..... + 1" no . ale nt (A) . lom<"nl (...h;,.. h~'1. <>r " p.1ir, 0' a wmb"'a ' il>l1 (I( th.", with pn."phO"'~ (thus H , r.. ~.,.i gn mC ll t ). r he r,,,gmcn t iQn~ of I"" l u, lh<; , exam ples Invor,c Ihe ,"line moIlof:<'

i' """'leei,."'"

,. "'" "

.. ..

~

,~

"

WI1 " t il the "'H imum num hcr of " A ~ T' den...... ' . ·, or " A + I " .le m...I'-' •
' '"t'

I' ~', -

1f}'

, """" J'f~d lLre'

" irll lJ nk n,""". 2.7 and 2.8.

U

_

~

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s.e

,.

•" " se"

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----

I'•

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- ,. ,oo

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00

O. C.•

•"' ' ""oo ro •• "e.e" " " "

~ ~

.

..",

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-r... >0

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I

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I " '"

,. , .,..Io~,-T", • ,. i ' i

2.5 Ring. pl us double bOnola

Because of Ih. ,'al enees or Ihe e lem.:"I. ;" .., I. ed, lhe l<>1al nl,mbe, of nns , and d<>\l bl. Ixmd, in a "',,","uk of tbc f~rm ul, ( ' , H, ' ,0 . ",ill be c~ u"l \0 .• + i. + I (pellegrin 1983). For «Ins, IhH" ]<.1JIiII<:d u luc """ end in "j;" (ind il;"hn ~ . Il "e. ec-ek elro n i",,: SccLi" n J ': ~ , ,,d lhiJ fract ion , houk! he , uhlracted 10 l>hf lhe eu mpies in Bo~ 2.1 -n .., •• 1"" J '..." ,Iln
t,

"" , "Ie

"r

• I • _

''''I"''''. , ~ \10""'" ''''''''' '' C,H,N,O. ",,"c,., <0• • I,IJ.III,IV" ""."

I.H, F, 0 , 6 ' , '; h O. S; Itlt N, T",. I ,i"ll" pi", double bo'd • • • - ; 1 ~ ; I"

_

em, ,."

P;."" IV- C, s..

Ole ,)

'O' "" . ,",_. ,.0>'0' I"" (••• ,0:;.,.",,,,,, ~ .2 1, tn. ' ''' " ,oJ"" ,,,".....'_ "" ";""

Ex.mpl•• G .~,N

" '0' pic. _

b1Q """",,,

,

l"

Q ~ , , _ .

' 0, . .. mpl•. oyridi, .' (""",, _ , 0) G,H,O' ,Ing. oJ .. """"' ''' ","H" . 7 _ 15 _ , • S ~ '''' 0'""'ll '0, C. ~ .CO', \ _","",,0 0)

t>enz..,

the car bo nyl ~"".L!". C.ak ul... Ille nu....ee r of Ijo~ ~ Ild d" uble t>und. ror IN f"m ,u La, tlul you loun'" r.",~ : 4,1 on'" S~ in L'nl llowlI 2.4 If other f u .ban a ' ~ m s. 1M ,,~mbcr , ~ halOll"n "t" m, l<' ,he hum"". of hy IMl lhil IS bJ,cd on tll<: low"",, . alcno.c , [;de " r II\<: ~ I ~m tn l ~ 3l.,j J on D<>l ccent do ~ hlc h;,nd, {(mnoJ lO d r:menlS in higher val~n"" >lat"'- Th"... rhe iom' ul. iod><:i,e\ ~ ne double bOl.,j no CH ,'" O, (" i, mm L1 h ~ ft c). nO t. _ O,~, in H"O ' , Such . ,.,.,go,i, c ,~Iuc .hould be nolN, be<;au~ it uri....... h" m , eurm nl"' ", ent M cbemicaliomzaticn. Va h.., m o rt JM:;;;t!>vc th a n Ihi. ~ ,e no t po"ib1•. ~ lId '0 m",t be due to \nC"TT" c' 8N "'.,.., "Fe1e...ental "om position M inwlrcc! ""ku l,,~ion or ,i o1'" ~I u ' doubJc ho ~ ~mI'i ric.1

°'" . .

"""liN

pm",,,,,

F. r " c "'f'CO;"""" ha, , hown that i, n. ce" ,,' y '0 dc,'cl,'f' ,,,,,,' , ab'l· i, ) \" "'.. I "l ~ e1'lm m~1 com po, ition, from i,,,1opic a oo ndan"",. ! P~,h . p, Ih" i, because 1M eh ' IU"" lrum sho wl his/n cr carel'ully p uri~ "d """,pound to bc a mixt ur e of i"'tOJ'ica llV di(k:. om m o leclLle•.) It is importa nt I'h " I yo" undc"tand Ihi. l'rocMlll'e, , iooo it iI the t el' prim 'lI)' , ' ep in in terp rel ing all lLnlnow n ' p""lr um , To ".oW ~,<ml". 1' 00, lhe ,\~p ", i", p""redlLl'" beio'..., ...' hik you arc "'lUniog. I lIble lJ illu, tralel I h~, pr ~dul" wit h dal " (rom ,nc M" ,eg inn of Ihe 'peet, um of ",,·tlLllyl' hin phonc, C, H •• S. N Ol~ lh " l lh i, i, '>01 do ne roc the nth 10111a b..... J ~n " c. bu" ~, .. e the 10':.~ accum cy in a bllndance i, rcla li ,,,, 10 the allU nda nct of that !",uk.

'"II"w

=

e~f'C rlm~n l ~1 """, or "~"''' " n tloc u riginal dal3. in 1M "J," eOlJlf ' co h,mn lon' " n l"" "",n.. I,,""] d o... of Slep ,i).

iii lo",,' r! tile e . f'Cc,O'd

. ................. ~.

,.

'...'".,,

~

0'

es,

<., - G.2!I 1.> ..: 0.<

0. 1 = 0.2

-

"

_

malin

O.

'00.

00 rie < 5 + 0.8 0,' J. 0.8

"s

....

' 00

. .,

•

"

'

'.

c,

0,

"0, ,

-,

0,

.. .. . ' . .. "'

,.

00

'00

eo

00

0. '

o'

IIi) N Olm a!;1C . 11da la (~ld oo m ll "' I"'Tin,etllaJ a< r.~ l"r nel'd.d to ""I l A] "<:lual lO JOlr;' (i,;, r ,nd ~1l p""';blc "A ... 2" elerncn1< ILl>< u l"" 1<11 O ~ l'Bu tion. in "'paratc coi\l mnl (S, an d (J , in the u a mple; "", ,,,,,II, . at Ihil $t. ao; up \0 thre e ol Yll.nl ~.n be co m i de l'ooJ ~ Ii,') i'd""e t h ~ . lornent ,}'mho [" pJ.ce lheil ma., value" \0 guord . ~. i n " lhe

ffi'"

tot,,1 nc.."m ;n~ 1<1<1 "' ~h (,'j A" ign tnc po <s,bIe own bcr ,,' c"" ~llS. 111 ow in~ IOC'OC in ,im;l.u ""IIImn.. Subtw :t lOn of Ill<; 'OS contribution to 141 places the caf b" n-;. C>I01'" ront( ibuu. ,n in Ihe J~nIlC 8,2 lo IO.n .. leadiDIl to C. and C. :)$ PO''''

'"i.

hilili"" 11" "' e' er. 5 1and C. [oto1 140 nw", Uhi\'., ""... I IOlho1l o! pc. k .... e.g i, a 1>;",1>1) unli ~.ly ion for mula. m"l i", C. IlK f~\'"rro ~ .. jgnn'~b1. The L" lumll headed A I I . S, W t ,w, ~ ~ ~ of "c, ' ·'c " s "'111 bo accompanied by .l...l.~.;, ~ 8,8 = 0.4 i"n< of "C,>" C ' · S. pn:d; "t i n~ ~ . o rrc, po nd ing conln l:>u,," n lo ",h J43. (, i) ..... ign lhe (AI 01" '......... I>y d,lf".nc. , T!>c p" .lulot.d C ,S f.. , mula ,'CCollnt, f,,< % + ~ 128 of 1"'= 140 <no" units 01 po " ~ ..., H 12 IS 1'" " hi,,", choi"" 1m Ihc T<:tna;n
>.ho,,'.

io""

n

L " ng thi> p<, u dutc, can you . ";s n compositio " , a lld .~l ..'" ' a , , ing, pj"" <1, ,,,hle ....."ds 10 1'" rr"~ffiL'Jl \~' )' 'pectr a shown ;n U n~ ... """s 2,9 thro ugh 2.141 ns. 1"'3 h of l 'nh own, 2.9. 2, 10. a nd 2 12-2.J 4 conJoi" II>< m" l"cular jon tM' ~ jII:~ ~ i in U nkn OWl1 2.11 ~f ;" 1:»' k>$s f,om M ' u, ind icat ed. No,," "f

U,"",,' wnU mi'

" ,."

''.. '..."' ' 00

'" ,

............ . .10

"",

,,,

.." .,•.. . •" rs

n

•. 0 1

" mlz

"'"

ee

""

~1

"

. . ......... ""'

'" '

0.0

~O

r~ ·

I i)'

,.'" ,.z.z" ,.'"'" "" ," ,

1.'

1.0

.',,' ---------

00

Un""'". 2."

Unkn own 1.13

M, 11 ~

se

,.,m

113 110

'.1 100

no

111

0. '

11 ~

e.'

llA

0 .'

0'

,,' oc

• " '" '" " "" """ '" no no '"0

'00

00.

,"'

lhe, . contain nitr ogen, it. idenlllicatioll is discus sed in Ch ~pl" J. Untnowll 2. 10 m nlai",. me" , " ",,,,,,,,l 01 hi~h"t .. b,ol ule ,"ccmaC}' than tli< 'Imed ±O.2.

2.7 Com po sit ions 010111 p.. aks where possible

1'". ~h< 1'"'-='

" f lhu mole"" '" di,pln}'M in ie, ma., ' P"Clru m, knowledge of til<: de me"t. 1com po"l;an, as "'ell " ' II>< i. "1\.0 very valnable in str nctural rna.. mc~,ur"mcn t, unc can " flOll ' ''''riet lh e elucidaliOll. E,'en w,thOllt •. po:..., ih,li\i¢> f"r u' . mc n'al.." m p",ilio" " " ignmem for impot'l. nt pea l> by using i Wh'P ~ ·a bun d ~nct dall II ... the chid difficulty i. lll . t tll<: .b undancc mea.u red at R pa r\icular m.., ..J" e can . ctually rc PfC"'~t "Ofl(ril>uli() ~, (rom more th" n (l"" ck mcnlat ~~""p<"i lion Such interference. ~re ""..ible e'en for ;'01"1'M; pcah of tnoloc~l ~r ;0,,"

,""t

"f'"

m.".

Uu j","", ~.",I>n' '1 -''''''' ~l,.,.,_. In cok ulu ing the . lemem .1 rom po ;,;l;Oll (It ~ reak . . a bo., •• we . .. unled rh. t th" QDlyrona ibuti<m, I" t nc ( ," + I) .nd ( A. • : 11"",b wet<: fro m ' oc rc... ~ ho.!nJ . nl iM:llOp,. of tile elements in A, H" .. ~·,"', ' hi. i, not n=s<.o."; ly I.Ue; lhere could be ; ml"" b nt . rldi t;"n~1 "" n _ t n b a llOll' tQ Ih. (A • I) ~ nd (" t 21 ",: 0.1:. (a n " . ,,,-,,,,-,, on,,lIl , W (leak Al for ,,"' , ~ h C<>f!W'""" m L " t he m ~ Jc h ,c I he ( il. + Il oRd(A + ! l peak.. the.. 00'J1d

HC_._.. . _._....-

"

ari"" r. um ul....., r•• ~"""'l1 i",,, (or impurities. backif DUlld. QI i' >n_m" lccu'" n:r." l he I!l, + ' Il"'ak these could "1' 0 ari", rn'", I>c h y ,....t"p" oonlrihtmons of ~ A .j. ~ M elemflll•. , uch a, from the ( ,-I. _ I, l'u k. W u1tolJ, ....,h emlhe c a k" lu li ,,~ , l!lu' ~ i ,' e til_ ma .,i",u~ , numN' ;U<,)m, " ,f "",eh I}',,", i" ,10" d enl«llal c o m ~ os it i o ll .

aet~m,~

r«fi,,,..,.

er

/.ruf~".a j,,,m "I."" fr-,_IOI 1M.. In UlllrOO.... . 24 ,,,kub 'in, the o"mber " rcarhon atoms or mit 4 1 lw m t!>c «:I", i.., a hundllllce of ]nn, in "'iz 41 Ili' c, a ridiculo", ly high number ,of ul '''''n arnm,<; [ 41')/[41 ' 1 '" J.?/27 _ 44~~, Corresponding W 41) carh..n a luffif, ill TJble 2.2, Althw gh lhi, i. curT"l.'Cl lor rhe m"ximwm n am ber of C aronu, " " h;oI(I!) • ~ " Irru l calc ulat ion; lhe reason IN th il .'aloe i , tloal m",t or I,," ....: 42 """,l Mi",s frem "C / H o " . aM I...... Iragmo;M ~ m th l m nlaill'. onl y 1 ~ Ill"'l J bu lldont i,o tofl'l'" Th i, re ak i, j)llrt of. ~n'.p or peak<, ......... "'P'" . U:d r",,,, il' neighhor h}' Olle lOa. , un,t, of I h~ ron nu lio, C ,Hn~.' ltnl n" wn 2.4. which i. the Ipe. lr Um of bma",,- C . H •• • I13s "",·~ ,~ I " I....r f'l'al gro ups wh ich correspond t" lho rrag"""'l ""'" C, H. _•• C , lIn ,_ ,11'" C. H" _", , The on ly (A) peak . to, ", hi< b Ihe co m ,r.pondin& IA + l) an d lit 1 2) ""ok< do nol contain inted« lnJl II U a~ 1 ion. a "" mfr l ~ 29. 43an d 511. c~ ",e"l' ondill g to CH.< ' . C , H , . ( :, H, •. ~nd C. " ,. ~'. T hul !he m""t u",rul i,ot()p;e-a bunda"u CJk u-'110l\ll an: 8'...." ... 1Iy th o.. that """ 'he ,i~" ilicant pe~h whictl a re ~ t d.., hi~h.ma'. end ,ll I"'ak group' , Can ~' ou dedu ce the eleme nt" l coml'"";li,,n. of ~ '" ",,," io ns in l'nkn own, 2 ,~ and ~ . 6 '!

Inte'f " " ":' f'- ~ " + r . ,, _ ..... '" ft,,.,.,...-... 1""'1<>. Th. full lna'-' ,,," otTUm

of mothyi hm midc tCnk"""''' 2.2l alio coOlai", f,a~mcn l i"". f,om tilt I"" d H a[<)I1'" COr· . J~~ C Hllr' • 2~;'; and CH, Br ' . 4~'; (Wilh CH, llr· . lOO:.Q, Tloc ",. uln o, ""''' ""","' . " m i . a lin eu , uper position of the'" " m mnln b. li"", \= Fi~.", :!.2). E;fd. ~e. mu,t gi'C a I: I pa ir of ' "Or, " Ilr peab . and t locn: m llS1 N ~ 1 . 1% " e I"'a k rot each 12C peak, SI.ltina IlI'ilh lhe -t'z 9 1 C ''' Rr ' """ie>, i" J'>f.... nce dem ands a similar inten, it}' at -t"'~ 9' ~nllLl rty. Ihe C H'"B,' p"a k at ,~i. 92 dem~nJ , an "4 Ual. inten "' t}' pcok a t WI/: 94 . f'I..... ;" e'al~ a l inl: Ille con tTilluti'm or ('H , " ar~ a nd C li , ' " Dr" at ..... ~_ \H ~nd 94, 1>1I" mu,t r.r,t , uhtrac! the ccmll ,l>uno n 01 t!tc . , Dr ;""I'>JI(: of Ihe l" ..... r-m,'" ' p<Xie,: so on e find, a 4';';' tn" t ~~ I "",nu i"'"',,,,, from Cll ,o ' Or' al "'i~ 9S, Thi. fiiu re n"'Sl then Ilt s"hl riIL1c.J [,om , he mt3.~red Jnlenmy .al"" to c,hm~lC the " m ,'~n l due [0 lhe "c conlribulion flom ...;1 94. H" wcyc", il ia much Ilnlpler (an d !lc,e more acooratt) to c.ak U"'IC lhe "'\ + I~ eleme nt s fro m !hc ["',.'1 Q7JI r'~I: % ] n,h". , ine<: "'-ir 94 .....1 W, "' ..., oomnin the . " me ~urnbcr "r carbon a'" m , . Deal • .e l~ I""CI -IDd" has ''''''. 1 ~ .," ""n no t con tr ibule to Ihi, I:A + II p" .\~ .. II", l u. + II JiV\ J m li" cr U ?-~ co rro.:tl}' indicmes the prcsce oc ol o ne ClIrh. >n 110 m . "pi... 1he mo<sl ~ ..Iul ;,otopi c .... kulalio.' generally .~ l b"", Illal ~ .. Ihe sitnilicant pca h at the !li~h.m~" end or peak ~roul'"- Ha c a pea k', "an ;~", n"" i, delc,mined hy lbe inten"IY YAluo, """, ,,
, ,

G B" ~

'"'"'~ r ... ..,

I' I'

LJ

- f':d

oo:"',, II

-~

11

I

102

9/

"

Sp. clrl>1l

"iI."

1.2. Linea r '''perpo, ilion

i.<"o ~ c

. ~J (J.(J9t~

c.r

pc, b in tbe 'pc<trun, <>l CH,ar

_

..-

~

. 00

•

10

00

,.

aa

"

lU U

u r

" " • 1 7 3.'

0 07

' 00

"

00

-... 00

J

~

' 00

,.

,~

",

......= .""'''Pi<: j"OI h l",m or(., 11 0 ,

'" " "

'l'C""

I U ~' '''''''''' 2. 1 4~

2.0 0 • • " " ,

aa

_

~ "" c, ....r t' for lh< calculauon In UnknoYt'D I. 14 the ne.dod '" ': 1J1 poak ha s aD intr.,.ily of 0 .0 ± o.~,;. ..' ,"'" L"'i: I J71Tm,i: 136l = "" ~'/~ <\f .o 5 c.o,b" n at, ,,,,,,, If JfCJ" "".." ..1 ",, ( .' ~1 tile ove, lapping i, a topic ""n l, i h"I ~,n«. lICe tbe brraLdo" 'n in Figm e I ..lIn summ;o , y. if " "A + ".. clcmCtm a re present, the fA I II pc;Ik LanoJ "'......bly " lhe. 1,\ - 2n + I I pea k<J will conMn iWIe..pi<: <:u n lrihulit>n< from r be IA · 1) P<'~ L rand po"ihly other IA - ~" - II peah). ln ca lrulatinJ: the .. urn!..,r "f ' '' loon " tni'll ' h)' usinE' [(A + I ll if At "Itt slI<'uld currcct rm >ur-h " "h' p' C iut., feTel' c",. Ahernativ"ly, u"," [(A .. 211 + Il l:[" + 1,,)] co rrt ' )X1 ndlng to lhc pc.k~ oJf high"S! ma , ... ,i OOl: lhe (A I] ""ak ",m o<>1 make Oil i.otopic . " nlri· butioll to th o.."

Errbl''''''oJ, ,,,... .-.J... .... J,,,..,,,, ~ 'l o n" l1 y a , i ~ n i fic a nt proportH>n of

I he !"'~~ A " llenSlly w~1 be due t" ,I>.; j"'L"pi' .ontr ihlllian of aD " ,\ + I " .....""nl in 1M 1"I) ""o\;, Of an -A + 2" oJom eDt ill the ( A - 2. pea\; . r Ot c, ,,,,,plo:. 11M: 'f'I«lrum crf hmylh
""

.. ~,

•••" •"

e.t

T he ratio r"'i! 'l JV['" '; 9 ~J - 1. 1~," c q ~h' a lo nt te ~ .4 c.a ,h~~ a L", ,,,. allhough M,/! ~2 is ma inl)' <:, H, " ACl ~a ll)'. l. r ; of miz 92 "nd n.25~" ,,f 9J ore d ue to vc:..." eH ' • + and "c >,,. ~ , H,•. ,,"'~·c ,'- ,i ,'d,.." thu, " c • u'"H '- . • = 1M'" " ' .• ~nd " C , Il . + = 41. 3~·;" ~r"l lhe; . r~t;o i, 7,7~·;, as expect ed r" , "",,~.. cubo.>ns.

2,. D.cIuc ln9 e le me nta l compo5ltlon . Abo~ e W(

detiwll

p<:~ k

iDten' ;t"" in (he mn hyl tnomi
~ n ow l·

cdllC or .h ~ndaD ce, of particular ion c"",,,,,"; li,ms: however, lor aD unkntlwn

, ,,,,ctn,m wo f.oc the opIX"';1c p, ,,I'I"'m , ,.he l ugge" ions that r"I1 " ,,' . ho uid i nc " ~ $11 j'OHI clf" " .- nq in ani,'in" al all rea"'D.,bk , ,,lulio", Lo 'uch • pro bk-m. I, 11ilt" " -.-, ~.1< .. 11.., r, ,,t lhose l"'J Ls "' b i ~ h , hould yield "" m po-f hi$.h . ""ufac y a, woll a, hi~ h ulilily. '!lie loa.. i,olopic <:0 ,'" tamm.. liotl l" thc l l\ ~ (A + I ~ cl<,., peak< .houkl 'oe tounf hit!..... ,nasr. (.. ~. cioUy if n <" " ta ll" M - J F LlrLhe" ror aDj' partl( ular pe;lk IW"", lhe high-rna.... peaks ,h~ul d c"n la;D 1oc least i, oto pic oonl""" n..i..... ~,,; gnm. n l'

1, H~I>tSl ;',nuity ,.. Ir.•, Will'; D, ''''''' linll1>, , '''' ..." ," acy or ck",e"'al com-

pm illO" ""Icul.llou, oh,i uLLll y shouill improve " ilh

I nc re a,i n~

pe.o k imcm ity

J......~ qj'" .\ puIt. . 1he Je.in:<1( " ('<'-il k .... l"" p<'a k ~ruUf il; Ih.e 0"" .~ hitbW """"' '"'t~,b ",ml~i"$ onl, Ihe mO»l abu nd. ul'1OI 0P'" ,such . , " c , ' ''0. HClr, it i' also ""lied lhe " ~ '",i'01C pic' r<~ k. A, the r, ""l c8 ndida l" fM A, II)' l ~ large. t peak i ~ ' he lI' OUp; if the leo<md larj!.e, t i, ~I a rna" hi g h ~ r tban (1\ + 2), II)' il in, te:ld al pc. l A [ no le iT T-ilbk: 2.3 the r arily oi M " poa" for . "i~ n ' ""'Pl. ~ """'" IA ~ ~, po:ab]. Not, d" IIA - 21J.!I A] > ,l~;" chc.,.i lhe pu'>:ri ble 11/,,, irol o pOc r i tl e,n, IT ~hlo, :.3 an<.! .... 2) 1<> 0;0:; i f I ll ..., xre " " ~'I"" pc~l< . o)f the ,,\ n1e dem"'l l ~l fornwlJ , F"e exa mple, lhe lary M !'Cak of th l Elr. i,otOP1C c!u' lcr is oe\uaUy I he (A ~ 4) f'r . k, Hen: . " ",,[ul c"'!'dation i' In, flOCl \h al the 1M - ~ , ' i> u... . lly much leu . l>und'l nl lha D cilher ~r' Dr (M -I)', t",ca · S!o... lly. ho,...,',r, (M - JI' i • .,,,,,,, .. bU...... Dl ' h,'I\ M -'. N<Xl, ".lLwale 1"" po" ibk . k m c N ~ 1 comp",il;"'m ror thi, IA) peak; i f~" assi~n~ " nl <:'l nno l be round l h l :>ceOl\nh fm Ill. iu,.",il"''' of 111" higher· mo" ]:"'. L" " llhm c, perlmenIal error, ul Ira.ou, P"~". Bee"U", m/, 91 conn,,' co n!;l\n n\ O~ th an ,,",ven ' " roo n " lo ms. no c lcm em .1 co mpt" ltio n [Of Ini, (A) peaL can a«oun l for the I ~UI1J """" 0/ "'" ~2; ;1 la lls 11' " '' be u>cd 0' A

pea.

4. 0,,, ,,

( A) J'f hyd r ~ " I
m""

5. C~"";'Wtq "J <'" mpM;' ;n••" W,1ttLII'." '>'n("th e!' ""~'C ll to ' \':t.lk. SimiLotl;t. tile fl ,,~me"\ ion ~"m ",,, il ion' " ill ll, ual!y , ho", '01\l(: mu tual conli",,,c;,,,; UIlC the "" l" infer tlh~hl, oomp'",ili"n(,) i f n" ,ro \lla1\ one ag ree' ",il hin e'rcrimenlc "'~" I""' il.i o". 01 a.. tl(r,l~m""l ionu rc ~'<1l in h hlc IL ~ and an: disc for IIlOlecular LOI" .:on t ~. n; ng th' elc..-n •

"'''1'"

,,,,,lee""t

.........,.... aU """"lri hue:s.

3 The Molecular Ion

T he m()l"c ul~ , ;0'1, M +', pro ,'jd<:, t1>c m' ..... ~ I Wl I>Ic inlQrmalion m lh. rna" ,pcel,um; it< m"l1 an d d.mC ~ lal com Jk"ilion show the mo""ul"r h() u nda r~ , into wh ich th e , I T lI<-,~r..1 f' ll-nlems IIllhcaled iJl 11>.; m . .. ' I"'Cl, urn m ust b. filled. Un f"rt un ately, IOf "",," C l fl'C' of ",,,,,,,,'tind. th e 'Q ole~\I l ar ion i, n o! ' LLlfoci. nlly st.ble to Ix '''uno.! ;" 81'1'reciaNe ~bu od " nc~ ;n \h e F J ' pectrum. All jn"rc~,;ng!l la'l"l' ""'01»"'00 of ma"' -'poc(romet r~ fa~i hl~l also hJ\'c " " ",fI io nitd I ~ . ",,,I,,,,,,!>, ,.~,~ h' """l:I'm~""l w"."," ~r ~Slblc , How",'c r. e,en ,",' ;lll ~,'Of h"'" ...... l(ln; ,~l;"m. l h~ ~,,~ncwll spectrum , h" uld 'lill be n .minecd in .hi. ~hM r>ler. "''''''' t hi' ,hould k....J I" u' efLLl ~t ruetu r. inf(l(rn oli" n ..., ..wcU ~I <el lflt;, oj I ll< M ' - ~"i g"rn "n' Il ~ ~omeD l i on , rna" ' pun.b nl i, ,;,t opt of eKh of tho ok mon" pre""n\. F" . ""'"",ne (('.. I I. ). ..lOCI> b' . u l> w n , idered to be ~\ rna" n (C "" 12, II _ t ~ M' for ' M mDl<>cule HI, j, ...... 'side«d 10 b< l~ ~, Iwice the rn a" "j lhe m",\ . ~n "mla"l i""to pe. '" Rr. allhoo,h Ul ' h~ rn ~ ... . pectrum of RT1 Ihe mo stabunJ . "t lOn IS at ...:; ltll lSa.1 i<>n 22). Wi\h ill lh<Sl: com l"';" " . in tbe EI m. ", "!'OCtru", "t .. !MIn; <'Ompoun ",,~ ). d.... not rCpT"""m tht m('>k"'u lar iOl~ alt oo ugb I""",, 1""'- ,;;onn,, ' J<mo",UJ le tlte con,"r,"" W

'i""

3.1 Require me nt. ..... Ih. m olecul • • IOn

"".k!

The foll<,..'inll a, e Ileces.... .y, bw "0 1 "u!.l'kl<,.., " '1ui,..".,nt. 10' Ihe m" k " ula, ion in tht ma" ' peI....' ''m "r " pu" , ample. f, ~ ot cs tno n,:" ". 5uch as 11...- fro m b.lcl S"'u..u and ion-molecule ' c;"'tkm'l Ie must b< Ihc illn or j,il'iI<:st n....... in the SPC<~ f1,'l'll ::. It mu, 1 he an ,l" 1Sc<.~i.m J, ~~ ; . It l'll U
~ jtI0 "

If l he io n in q lJ<'Sl ion fail. any "f th.,. tesl>. i t ca n... ' t toe , lie m olecu lilI iOn: if 'I p" ~ lan the ", I",t" i t nlay or may no l lle t1" mo~ l ." ion

For Fl ' 1"'el, a, lhe "" mplc m" lr:c ult bt<:om. , io nizec! b,' I O $i n~ ~n .1<':lI<m, leaving one .1""11<'1\ unl"" red. and lh. " w", the mo l. cula, i"n .... rtJJk al ' l"'cie., Suc h an k' n. c" her moln :" I'lf dd -dtcl ,,, n~ IO F) ion, and i' d ~"i ll "l cd b)' the ,}·onb.>J· .ne .>fl en u>d'ul and ron ~Qlcnl on o, plaining and cl""if)'(" S io" -Jecom"""iti " n T~aolio", 10 d ill"D ~ ui,h kh. 'ecn sueh ' odical ion ' ~" d -c. eu·cl",: "'m~ n eE) iou., t ho .~ in ", h i ~ b ,he () ul.r-s ho1 • will be u""d ,m ly 10 m~ , 10 ovon·electrOll iOn! f hi, ,"~m c o pt can be ,·i, u. Ii....... in il ~ >impk' l lor m "' ito , tmcmre, (Equali" ...

'- I to lJ) that ind aclc

tlo
rile ease or

(11 1 1l,(:":CIl, '.

,~, c , : c ~,

0' H,c ....,... · ·

(, ,2) (3" ,

io nizat ion or Ihe"" eln.1 roll. ill ~n~rall, in the oro ., n 0> ~ 0> ~ K hol .,..,·, 4~ L , uaU)' ,..",al ",,"onic;d tu<'n~n"" form' call b~ dmwn to ar l"" . ;nli l' , ''' el.Clwn di,trib'~"m in ifni , Not~ th.t th ~ iymb<,li",," i' n"""-O I 10 iOOlo:at. only "" km .. ith 'Q "~,,,"<J ~kctwn, nor a" ~1e.."'Nn ift tJd4iJ~", 10 ,he (" , milia ..p,nenh ; aJcli ,, ~ an dcuron tD CH. """",1<,1 tlI , ~ lleling lh.ir n"utr~ l eoun '" '1'"rt<, ioo ' coQlamiOi onl)' paired d " ot r"'" ~ (r E ' l ~ ~ gene,,"lly mOre 'l~ h le . • "od th are m"," ....' cn 1M abnndant fr"~mcll l l~n! In ~I m" " 'l"'ctra, For n am pk. d<. ,~ ~ of a C II bond in CH . ,. form.

t'"

t"'...,

.he 'table EF." i ~, ," n'UrlOlI an d fa,;!-atom Mlllhardm. m lend wI'''' 1,;[ ' nl(>l « ~ la , K)l ' ~ $"""~' MH 0, r<' ulling in the !n\>Ch .m ~l lc( tkl!rttOflr~iW
3.3 The _ _n rule

1""'<

. '" m,," deme" " enco~ nt' fc" in " Trani<; oompou,>d" i., a fottullato belween 'ho rna>, of ~ n dem<:ot·. mr»t. a bundant i,otope and iI' . aJe nce, ellh< , f+t),h ~,. e e"" n· o ~m "'·. ,"" . ' " bolh ~ ro ood ' nllmben:-d, ...i,h oi'm"",n 8' the mojo< .":<:.,t... n I hi' lead, W lh. ",-""lied ",, ; t 'o~ rtol",W which ca n l>c ' t" ,,~l ~, (" Uows: 1/ " (.'(+. '1"""'.1 " "'. "" ( Of' "" " to,." ,"um"<' nirr"Rt'" O .>d ~ll<:C

"n

"" ,a ,,"

11,0, CH. , (", II" CH,O H,

"';~ 18: "':: 16;

"'iz 2~;

.../~ 32:

c..H ,OH.

~" . .. 1114; rniz 94;

C n H ,,('(J O II,

mi~ 2~ ,

O :U , .

; H, N N H" miz J2; a od ~m 'n"l'y r;djne. C ,H. N,. Hf!~ 94 An <+<J d num"," " f niIw,.,,, "I u"" ""'''se, M - to Ix at an odoj mas , n"rn he<: NH , .

C, H, NH, . q..inoli .... C,H,N.

m,.... 17; "'1z 45; and "'i z LN .

Thu s if Ihe ion ,,' hie""" "'.it j.." M ' ·; Ih'" ll>c n' tmg." "'Ie c~ o abo be sl" ted '" f"ll" wo: ~ " ,,Jd••ledP'On ion "rlJ "" 41 " """"" mil." numh'" i{ " ,'o" ,o;n> "" ~,,,~.....-.Joe,

"">fb

..... '~':'='--_'::'---== '4 N,

N. ,

N" N._N"

".

~ .

,,{ n,'roye" alom,_S'mi\" ' •.• . an e~d--eltc1rOll

IO n ~u n 'ai nin g an e,,,,,, I\I>m l:>n 0/ nitrogen atom, wil' ...pt'ar al 8n 00,1mil" n um ncr, Ym, m.y find lh'. n.n....;,,! at fir- I, unti l you ~et .....-..1 h' " ", king with thi" it ""n pm ha bly be •• $Ier 10 e ThlJ from lllc fit>l ..mem. n!, re mcmlx:rin g II.." M - - IS all OOd--clccl'''n ion. •n ."", mary. _ T Ilw.. .1, t,

"'.... _ .... J .1. Imhca ' c wh. lher IOD. 01 lh. fol l""'lJg lomllll,,' an' odd_de cl' on Of O\" D~k:~"" n' C,II•. C, H,O. C. H."'. C.H,N O. C, H, ClB" C, H. O !>, (">o F,• . H,C , . lId C,H ... " -' hiell oi lhe'«: ion' "' ,I] appear al ~.,-"" rna" lIumt..,,·;'

"'o.

oe-: ions h.;l~C a ' ped a l "'''''hani'tic .;,nif""... nce. a. <1;""",,,,<1 ;n ""clio n 4.4. "r

fkca llS< lhi.' yon . ho uld indk,de all ; "'l"'f1" ~' O f: ' ion.I, mak ing IIl""e di· rc..11y e n lhe specl rum (in Ihe r itlur", 0/ 1110,. ,IIo11pl.:.. an: ,irded), T hi' i, Iho ...." Ile p m the "'Sla" Ja ' d In le, plOlatio" Prou d lln:- IInlOde ~",,: k e",· c, ). The ~iml"" la n ,,,,- . .. ... peak, afle, o n~ ha. cor,ec ted it. a hun d4...." rOt COlll rib ,,' " '''' "f i,,,,,, , o ll.a minil k"",,omnl on 1>010....... ll""""'11, ;.... r.a~ " 'ilh;

(" i d ",, ~'; n ~ intensily; Iii) ,ocn:u ing m" " in the ' I"«t' "lh; (iii) illC,e a! lnH m ~" in II" puk i!(>lI 1' '1"' , liL',da, ly the mO, t or the = ndm, ,,1 numt.., of hydrogen ~toH ... IOJ ~n OF ' pea.)

'0"' . . ",

Iml>ort. 1l1 OE- ' ",en k"" pr obll bl. in thc I""'·,.,·m. ......d of lhe ' pectrum; lh ;n " """" .' dd numbe' oj' nino£en alon". ",,~h as C H.N ' . .111 (MUll, . !)Il l t. S imd.o. J "~"," i n~ lead' Ie a com ll. ty 01 t~ " n;I,,'I\'-"" Ill," ' A srardty 0/ ,mJ'' 'r/ ,, '' t e"eII-Ina," "",,",'." .,..-ckJly W...., "'i: 0'''1..... . I"Jlca'~_, mol,('"I~, .'",gl,,_ lhe ' ",'en ", i , no t alway, Iroc, the I'IC'oC",,-" of ~ hunda"1 e" en·mo .. io'" doL... ....1 nc.:eo•• n ly iDdi~"t. "" "dJ .ma" M " , rhi, ", Ie i' helpful lOf l h~ "'~"' """,,l,um oIMopenlanc, molocu la' "''t''$.IIoI which , how, no mok",,~la, ' Of) (Fj ~m . 3.1),

"'i'

.... nm-"''''' n.

Hm".,u.

tI'

" "

,oo

!

r

.' "

•

•• •

•

~"" ~ft <>lll~ • •"'l~in number of nentm l ff'I ~"""nl' (Or I"... mas, ' ....1 u e "..",,,,....1) 1,,,\ In .keomp"" ition, or m() l e " ul ~ r The p",,,, nu: of an '":i"""... "'''I ;"n "'J'd lnted Irom t he highe'l.n,a" ion by .1ne n<>me 1ou , ,,.. .,. ," <:knlt.. _ l~l f",m ula " ill ; 'oJ1 ~ate lhat Ihe latter ;" n i. not I'" m"le<:ul~J j "". Pre"", ,,,,. of an abundant (a, oom r llr«1 '<> ;" ",-~!,h b..riIll\ io "'1 j"n S '''''''' unit. ~ l"w the ion of highe" mil "'"ukl h.. ~ lo "'pr=.nt lhe 1o,,, <>1 Ii"" hyJ",~n ~toms " high ly unli,el l' d c""mJl'O ~ i l ''''' . Sm.a1J ncutnll rflljl:mm l' lot, fro m l~ . mo lecular jon a", com mM ll' tl,,,,,,, ~tl ....iocd by . <Jnj.le bond. For Clan1pk:, if Figu"" J.l hact l>ccn ' )/,l ~;"'-..t ("'m a•• unidt mified r UT< "" mpo und, "', . 57 mj~ht he Cnre of a ,,<>n""10~1C Ion mi' 4l i" dicate ' that Ih~ "'i: S7 I, ... ""Ill "" l I'<' , he mol;o he dU<, I>u~r. lo t he m, ,1o;.'U lar i,,,, of an un, xpocted itn p" l;t) ..hi,:h i. a hom ol", 01 the " n ~ "",. 0

j",..

M

"';>n-

c.r

compoulJd, M"" 1u.. <> ul 4 Lo 14 al.d 21 .... 2~ , h~, ,i~< lml"" I"nl po:ak , a '" h\ghl ~ u n l .~ , l y, N" m"mlx'<" , hose u ngos: Ta ~ A. , ~ pn:....,.,I' " more comp lete liit "I" lh. m, and of neulral fn ~'ncn" .. h"' h a n: cOln "."nl}' 10'1, Maximum e'l'C"tod r. lati..... Ul" 'n d ~""'... no l'i ",n hy ~J'«k 1l!l78 ~ for ex"mpl ". (M - 21+' i, "."a111' mud . k a t>u" da..' IIIan m her \f ' '" IM - II " (Section 2,6, If 1M ment,,1 c.m>",,,,ili,m or Lh. fmgme,,' lost ~; m lx: OCrlu=.l, thl< gi.... an ~ ~ ro..-erf" llesl, For e",,,, plc. thc p' o",: n" e ofa major 1M 151' ion is common, l>ur " (M - NH t· ion j , prob..N)' an . "" malou. ion; 11M: loss of35 i>; l o ~ I ' >n l)' ,1" ch10 rj". i, present. Ca 8 lh. ion 01 h l ~h~'1 m"" Ix: lh" ltI
"'''J'''

~I T "_ '"

Un"""""

.~ , 2, C , ~H , .O,

(' " ,H,.O, C. H" I>. c ,0H " . <.:. H,oO

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"r

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H

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f, "J •

j •

oo -

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I

,L L l.

oo

•

•

•

,

U'.-_ ......,

"

" ....nO... U

miz

,, '

"' "ee ,•" "

", "o s

."•..

U

,s

"" " " •" '"»" •" "' '" " ", "" '" '0; ,. " '" "

i] I _

.

"

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•

IJ(I

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..

f he ~ bU lld;l n"" "r I h~ m~ looe"l" r ion, [ M " J, Mpend' m oinl)' ~Il III stabilit}' ~nJ Ihe '''...... unt .". enef g~ noodo<1 to ioni.. Ihe m"lco:ul. lTabl e " .3). P~rliroL1.r .tmctura l fe~ll"C' tend tn sh~", Clo J"~"tCJW lc >at't.. or thc," pm """., 50 Ihal lhe '''''~Il;' u,1c "f [ M"l Jl'I " ,i
"r

3.1 TJJ>i<* """.. IlMeI,.

r'l"'''''

3.2 tn .l :~ p, e... m ' f'CClr~ ,b~, ..I.... . bow , uoh tf,n<1•. I' be90 ligllTt:> ..;!t , .ftc", he , eferr. d 10 I~ I "' in the book. Tlte ' fl echanistio .~mh< ,1s helow will he n pl.llncd in Cha pte, 4. (])

E

•

, •

odd·d."" ""

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I" t OM I«l. the chem ical S '.b1 ~IY " I lhe m ol~ u k f'iI .~ l ld, the sta bihty of !.4 • ~ and '" i" , .flec:TM in i.OC all' LN ,l tlC< of M ' "; [ M · '] UI ~ " U y inc , c&>e> ""nil in-

"re"sed unI ring>, as ,Uu""."" t by lbe >ottikill' " hu~ · dance of M ' 1ft slr)'chni" , {Figure l !8~ l1>e d l'cd "r mol... ul«. "";8'" ;" I~~ d , ,,!; incr...,,,, ng Ih" chain l"l~l h up l<J C . or C, g"nq ;~ll de;n LM' " increa""" ~!"Ii n f... longer ' l,"i glll ebai" . (Scc1 io n> g,4, 9 ,SI_( 'b. n.-br8tlch in g i \lb, \an tiaUy d..., e.t' co M' 'labilil y _"... 11\ "1 its "bLIn d """,

If lei S eno'IU' "' ""l"'~ 10 ion;' " lnc 'Mol..:.,I. (t h;" i., if i' hal a 10...... "'" i"' I;"" cl>er¥y~ 1Jl(>I< m" lc.. ular iou, olio,"" , inlernal ell" gy t -~''' ,j ;,m, -, can be r". ","(l. an d [ M ' J ,,'ill ' .,Id 10 be h ,~"",_ '•• •hown in T.llk ... J. I"" eJSc or iO<' l.l3J ;OQ "' Inc o uler -.hcU lw n", mding ck etrOll i ,>n h,:tcro.ato m. m Cl~ u "" in ll' ';''1'' d " ...·n 0 column or til , '''' k rr in a rm. of Tb. pt, iOOK; la bl•. T his ".",,,,, nlS for th e dramal ie incJ ..."", ' " lM' ") for mCf<". p,a", m oo mpar i, o n «, ,lie " ' rrc, po nd ing k!ooh<.I. 1~'i g u "" ),8 on,l ~. 2 1~ (>rima.,. ~ m i n •• (Fi g u, o l l61 a , mallc[.lh, ... ~h . igllJr",ant . inc " :.. ...· in [""'1>."""' tho: c<m espond"'M .It:ohol•.

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4 Basic Mechan isms of Ion Fragmentalion

(Jlll imt la l .l~ l.m.nt (f " ' plcr 1) Ihat " l be m~", ' I"' ctr um . how. rio. m. ' 1 or Ihe m" l<:c uit ;\nd t l'>< ma~ "" picce. b ~ ... jC i, o,-,,,impbrl«l , in that it n< abull ' rl~nr;. " r • ,;pc ,.,. 110;" ,n(orm ation, we m"'l Ut>d < " l ~ nd ,b. ,,,,1.or , lhal "",,1 '01!ragmenH OII abunda " ces. A I" climJnary, ..,,,,,,...'h~1 <.",p j rjca~ J ..........Oll of I h ,~ fa.... " " ,,'ill be giw n h, ,,,- A mN . dCla,!«l ll. " tl'l,ent 01"'cclu "" ml " prea", in Cha p ter ~, ~ n<J \oc !>a,i. PI""C' ''''" in. oJ-al '" forming rna.. ' p"e'".....'ill be cumined iD ( 'hIlp""" 7. tt<'wcvcr. if " omportant tn ~ PJ'~h'l c tila t n",.. ,pectronwl ' ) " ~M ",m itiw to .11 .u" clu ,~l feal '" C''' " tid 1l1 at t il~ rom p]e. and com rL1 ,I;'" intera cti"" , of ii, ~ hcmi m }' limit io.';e f,lCIO" . T.. ~ o ~ ni , c fo r more: ""n' l' le~ molec ules wha t ~ I t em ali.-c ,I n.a.. , al !X,,,ihilitie<. co uld gi,'e , i... I.. the ob>e' vcd rn"" " l"' ctral k " luros, ..e n l",1 "ud~ l!loe spectra 01cl""",,y ,..1... <1 m<>'""u\es, Such " nimok ..,... l~r ion -<mi",y. ~" 1' 'l1 U n.l t ~ly roo mMI , " emi, t< >t ll(l ~n,-, this b""le lhen M' ~ "", ny do ,. ,im il" ril;'" to pyrol>'tic. pIk'tnlytic, nl,J; . d in ea ch ","ct;on in 1"0 rna.. sP<'"t",metcI, ~ nd lheir C{lmtH neu effectl ",,,,,d imes "1'1"'" ' ~ nn .u al to tile o rp nic chemi. I, C n.m_ irn; ""'~ also ~ """" i()n the rcl'~bi"ty of , tT""tura l rcJ,.,t;on, hil" hued 011 'c. ~.,an gerntn( """ctlclJlI, Hm••c." r, many nf tn. ~.", ba,ed on "d1-flI ~h ii, h ed che mi' t')' an,J Can pm . ide t~ mnleculu inr." ",ati<m

.,,,,In...

"""'f"''''

"

·,

_-

_

~la ...'

pK! r.ll r~.~I ...m are ""im"I~,·ul",: the , a mp le r'~""'"'' in Ille EI ion ker ' ."lTkic"ll111 In,.. Ih" t himoi«:ulct ...';' h , ~ . ~~""'\" "'''' I>!c m o lec,,1es al widd)' ," ' yLng d.. ld" ,,"' . ", Ihal lhe mok a , lac un" rM· 1 I ' e (,,,mal ...-i(h a ",iok t;,nlll' vi 'Q'ern~l energies, T ho," rhat are ll ,lfL,Jelllly ··"",,1" "'Jl1 no l decompu... I>l1 . in Ihe IMma lio n of .n ion and ~ "" utr,,1 , pecic" Ihi, prima' y r " ......." ,n" m ~ y h ~ • • , ulficie lll en", ~)' to dc_ompo, . furt her, In the m. <S ' pe«rom or "' bCU ll'q ""li",. " .It ,I>c ah..n_ .u,,' ce (II IICD ' will de pen,l on L'''' a~Cf '~ no. f~" or IhlolDLllio n and docompo · !.ilion. ",he,."" [ BC' ] will d' p""J ,," ("" rclali,,, <;dc, of .e.-er~I rompo; lll i~~ ~n,l <~'nse!l (r ) or tl ton.. oolld ".~ rdauoflSbip; of A lit: D " , ", . ~ t<:C ....

"'OC D

---"--

", e GO' ·

-

-

A" ' ~ C D ·

,. , BCD'

-

L..

8 C' + 0

(4. ()

D· ' ''' !C·

L • ... , ac-

- -'- "'0·', e-c • .2

1I . ~ e "' ~1 o ' .

tba l inll"ence Ion abund..,.; .

Tht: I" n(>'l\'; "~ i"no!';,1 guidolllLe, Ii" p n: di ~\i " g IW' II ~ .. ~ . " ho';"- d ",mioal principle<,

" n Lln "l oc ~la r ~ m

tkcon.po";.

..{ 1M I"~ ;IHI. T I.. mill;\ rr"p" rIUl1( gell""ll foetOf a"",,!i ~8 lilt; ..r a prod uct ion ill ;,. , u h,h\) Ke;- t;-re' ~f ion , 'abiliza !io n i"cluJ. , 1'(1''''1 , I"",;"'} i.. m l~i .. ~ ~ no"b...n ,l m ~ orbita l of 0 hOlomal" m, . ucl1 . , . ill tl", ~ od }' 1 'on CH , -----e --o _ C Il , (;=0 (lhe latter i, i,oe!j/;z..,;PIl. , nell a, i" th. allyl ca li"n . C ll , = CH CH , .... CH , -('H - CIl , and , ''' De,..,;- I ca l ~1l1 C, H , CH ,("ow. ,'«, the ph. n}'l cati(ltl i. m....·h ~,,,. la ~or td . b«.llL"" i, Ita. on ly"'·" ,, _d ed "'''', hOI' a,. tCq'Llred for arrH'Latim .. ~I. In 4) ClI" be ""'''' " " ble 111<1 " their cln.. ic~ l W Lln l0'l"'rt" C H , CH , C H ,CII= O' ... ·ClI ,C' H, C H, C H 0 ' H. C H, NH, _. ... 'ClI,N +H, ~ .MIfIJ

~h ~"'lll ,1Ct:

,i,

. , ~"" "o<." _"' ''' ''_'' To pIod;,.. Prflc rrctl d~ O ln po, i ti OT l pa.th.. ~ ~ " wtO "'til llse the ,in,pliucll a ,i lt i. " ;" ~ a. pr",id int- the d ,; . in ~ fon. lor , ped;, c lypes 01 , ,"c,;,,'" which .'e , 1\;"'oc1cli, tic ~ f the ~hc m ica l " ~l\1 r ~ " t· lhc ,itt , .4. lt" (><>!!h lhi. gives only, al best. "n _ppl'o xim" ti. ,n "f lhe aet u.u clc' lro nic dj,pl.u:mem " it p"" iJe<, a OOO\'<:n;"nl wal' to cu " d ,,' t Mnd for you I" ~rlIelllbcrl ~ I_r~ llumOcr "f the 1'e, oom,non cl. " if,ca lion, of O' P "'" ch. mimy (McM urry J9 lt4} 'The mo'l fHorod , "'"",1 300 char~c , ile, ill lhe "'" .....ular ion ar e " .",m~ 10 arise fr~m k_ "r lh. mok culc'> '''''''roll "r l" ..... t ic nll" lion ~ l iF. Table .>\ ,I I II d . h.. ~... ~y ",~uiT<menh a", ';,niJar 10 tho".; (0' lhe elcf:l"'''ic lfllm;lio n< a/leeUn! uh raviolet ipo<:ll'll; r..>o. a\>d,ly f", it,ni zal lOfl ICJlorall)' il

"" 1Mo.dc, "r
-_.......- - ... ,,""

.,...-.

- -

T h. sym h< ,l , . II lbe end "r 1M molecuk ' itniflos a n ",lJ-<;lecl ron ion ",;lho Ul ~ t,i~l1 "t ing tl><' r'lld;",,1 . il•. U sc " f "ill>
Dccon' f'<"j\loll< invol.in~ M ly th. cle" " !,,, of a .... ~l" ,,""'d in the ,ld.!",ln.u on (( lE •. ) mo"",,,la, >O m f1 LUII p Wd LlCC "'" eH Q-dul",n (EE') fragmenl ;"0 ~,od a

,,","!fa l ."di"" l 'fI"cie<:

(4. II l'h e . ...·0 flaprt. " ts eo n1flClc fo< tM d lil.ll" " nd lhe ullpain..-.lde<:f mn; l h ~ IIhunda ll"'" "f t ~. t wo ionic l"" oo.UCl. r.. ,m Ihil t ypo of ",....1 iOl' would be c4ual onll' hy
"'3<:1"""

_

.. . . ... ...

..

(4.4)

Again, the tw" fr~,mcn'-' "''''' pele for the eha r~e and radical In a ,;milar f. , h\(In. clcH ago . of thn'\' b(",d. of VI ' pr<>t!" c,,, an EE ' ion:

..i '· CH,CH,+-C"'~

'-

CH,CH.. + C"H, ' • H;>

14.51

" The tl«rnn p,-,"ilion' "I c"cn.d cct Nln ion• • re " ",ngly inn...nc:cd by ' he poc_ b e"'"" /" , for ma lio n of .n EE + ion and E E~ ~ .u t ... l ll~e "ev<:t>-clect ' " .. ",It," Cumm ing, and Bleakney 194'J. F, .."'"", n .ntl Lc"'8 1953, Kmni and 1\!dclb aum 1990J. ProJ ucdnn "f an o r · ' io ~ from an EI: " ion mu,( I:w: ~c c" m p . n i o d b )' formati on ~f . rodieA' MI'l r ool .~ ;n~ " I . i n g the o"" rgot;•• lly unfm'om blc .. parat i,m "f an do......"'n ~ j , ( a;q ua t,o lli 4, ~ ~

CH,CHr--O==CI1,

::%1:,

-:

<,

<

" " , ,'

.='"

CH,.--------;(;ot, + H6=CH, " " , ,'

• o=c..;'

("'a~

"'iI7&l'Oll)

(_rong."'o 'll, ""~"JO retentoo) (una...",)

CH

•

CH,=CH, I·....~ ' .._ l

C>1, = CH

•

Cot,

CH,

CH;'

/4,6 ,

I"""""""

; uW'. T.I . ( 1)72). In EE + ion de~ompo.iho", !Q[mi~ thc ....mc 1;[ - (l1"Odocl. ' he tendency of" \loulr al to k a vc n'ilh" " l tilt d lMJ!'l' is &""~ter I", m ollll: uk . of 10....« pr o lon affi nit y (pAl. In Eq uation 4,6. the fOl1Wll JOD of C"H, ' wilh o C H, (PA - 1.4 t V) ",,,uk! be ~a l ly r.. ...,rtd 0....,. I"" I,,,,,,,,,[;()l'l orC , H, • "'Jlh S=CH , (P A ,. 8.9 .'.-"1 !."m ( :, H,S ' -( ' H, _ Tho .."en main tyl"" of (:31100 f [~ ,mc n l;l1i """ ,1...""",J in lhi, chapt"1 lIr rho," not in brackct . ;n Ta hk 4 ,1, f>'inj1 tho clca,'a,'c of",,", noM art d ,~Uf:lotd ,n Sections 4,5 ro 4,7. of 11"0 bon,l. in 4 R ~nd ( .9. 3nd of mitt bt>nds ;" ( \ 1: f E ' <:le<:" mpo , itio", clca .-ing " "" and two

___..... ,'""._--

..

., ..

-

~'

W

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ce-

-

N,"""',,"

~ tHl ••,••• ed

,,, ,,

[M - ')

". " >

"......,--

EE'

1'1

"""1'"1 H "

I·' ",

IOE-r

"

"

,;

GO"""

, oten tion

mOll'"otl""

EE' ('1 0 [" lai l

IEE-I·,.'II'

'"

[OE " )"

"" "11<'. ,,,,,,,,,-.

'''''• ..,01....... ' , " """ ' , " .... 010" .... ~ dox' ; >< , ,~ • ....., " .......1. r"" , _ ,_ I. ... " " .. '""'" , huQC

_

" " . ", ,,,,, '"

~ ~ollonl

.. "', •

" = ~ ,,

,""'''''''. '',,,."1i'"'' 'I.,,,...., In " _ .

B, ock" .

""' ~ ".

·N"'''....'

h<m J, aro co ,-.red ill S.C!;cns 4.7 " nd 4.10, r. specl; vel}', Note (hal OF' f<>Tma_ lion u fa vorN " " '.' for lh. ck" v. g, of [wo hon,[, in an OE ' pr""."'or; this is why you . h" " IJ ma rk impmlan l o u- ;om (Seclion 3.4),

$umm"". Th.

i o n·d.~ompo,it ion mecha nism' di, cu,,,,d in the r<,1 of thi, chap/ or a r
(4 .7)

......oes:

If The oJe<:tr o n lOS! in ; ,, "il ~11P" ""me", frum the ". lurated bo nd f'Jlne,,'ork, will {,f OO U,,", be favorod; ionization of ~ hnT>C inc""'''''' lhe b<."J k ",.th by _ )0';.; and h;,lvc< it< I>o nd di","''''I;'''' e~rgy (Bellville I'l R2). TIle more...burx' "llt ionif",.j rt _b'1l10nt ".. ,Ube til< 0tabiIll<: Ih ~ pu. il;YC ~h ~rS" _ r ", ' a1ura ted h)'droa u bon, ' ud! ;" n;,otion f,o'" lhe ...!><,,,J ..>-l<m " Ih~ lo" ,""t ~ 'ler'j' V"""""" ; ,~i>. c:m then :t=l<,,,t rOt' r. "or«! ~lb'Je h ~ ,nl<''' t" uon "I ~.,.. i:><,~ ~, ,,"" th l a n: nl'" '' hi, hlj' , ,,bsl ;tulw , "nd wil'eh , ~<" ....,,'" .h.,~ (d m" ", ",adily a rry tho cha
e (;

ti."

sp«ll unL I

--".

... •

IH_

"

""" cs,~ Se<,1 i"n .~.2 1 in H g ~ , e ~ :l.2 10 3.4, and in the 'pectrum 01 pl i. l«no:, Fi ~ u"" .. I. Ho wever. 101 Ttt. ~ _ I>t , ~ lhe fo' mation of tbe ke y mi. 113 II{' 4 3 and 57 r',""od try- ",,"on1 in 'lcco<m .~. I.

hyu. liom ...~ !O 4,1l SlImm...-i, . Ihe ho m" I)·tic di uo
19~4)

dj s~", ~

~.rYR

~) ,r-;;¥ R-

,t,h "" (ally i<

c".vage )

--"-

CH,

' ."{1"' CR

-"-

"

y

,. •

CR, _

TR

" . O<. =CH. •• • CA=-:V

R-Q~ --"- • • •

r• • (410)

(4.1 1l

CH,=c ..........e>\l (4.12)

Rca"h() ~ i~; li . t ion I I Ille radi«ll .;te aTN-" 1m", it, 'lron~ te llden~y for <'i,cIron pairinq ; th" od d ~I",n " J' ...a" J I" f"r", " new Ixma lo " n " dj"", nl al"m. T his i. " CC()fllI'"n ictl " y d eu at" or aOO1hc' 00 00 to tha I ~_a!nm; Ihu~ Ihll II ,()fllm'jllly ""-lied I"," ~a ~, ,, te , e".'(i on-;

r: <,

,,,0. .

' O<.-. D-l,--"---
..

< '

. C>i, + CH.= OC, H.

( ~ .•

CH,_ OC.... ~

(41 ) .

50'10 ICOH,- - 100'l\.l

.pc'Ie'

ll« r " " "" ~.~~ N,u l ,"1 ' adi c.1! u n~l;c", . na l"!,,>,,, ~-dea..... &.. IO re. n I<)A(); Ci J lld Whilt CD In9J. A " fi .h h oo k ~ bJ lf·3m , .. mlhc'dlC> lTaJl,r.,. 01 ~ ." n~l. e J~ e l! oJl ' , ueh !lomo!y' i<: d CH _ge " ,U$I IU O'~ lhe ";Ic ,,r ,1>< unp:tJr"d electron. A d"uhly ha rbed arrow " . 11 b¢ uoe<J 1<' iM;""", the tran, l", to an cJ,~l",m 1" '" ' ueh holerol)'I i.: dca.'al:" ",nO(> tM c"a.~" ' il" I:~ct; on 4.7;

Sha nnon 19(4), The dC" lllg f" eu: i.> ill. tbat u ndcc, ... .urn. a~ d ll....,; ...l1oo and h) t1mgc-n ~ botra c ll O II Th. l,,"d eney IOf th" rJdi.~l 'UC'" inil' .'., a reaction in comp" tit ion wlth th~ ,h "T~C ,i le j!.""" ally I'aralk:b. tho radiea l $Il~'$ lend" ncy 1" d"n~le de" ~,,,n ,, ~ > S, 0, ~, R ' ;;. III ,~ H . "'heu " WlUI,r. .. In Un, aIUT;ilec! ' ;lC and R ' an alkyl rodi«l l ITh i.

a.

~.,

e

-,

•

,

• • ,•

r

,i , •; •• j • ;

• ;,

- -:" t ,a ~,~

e-,

-

•

,

, , , ,,

, ,e ,I• •> ••

, -• • ~

•!

.-rf ' _

-.

~,

...'d

"

oed" , irlg doe, no t mean, howcur, that II chlorine alom c_nn nt initia te _ nJical· ,it. [",\Cli on in the "h,"~c" , (",nsoTuri d n, r" rc••.) The dOllat il' t abihty of a parti cular , it ~ ,,' nff"C t~d by it. molerul.rr en,'iron ment, for prod ; ~ tin~ thi>.. "" n_ \'entin nall'esonOllC<: and ; nd \1ct i~c cff""t. urc 1'<"", . 11) _llf'li"",ble [oDil atio n or an a l iph~ l; " ether (Equi l;on 04 Il l ihooid O«Ur p~ ntia U J by 1o", of an n-e l~ c tron of the Ol}'gon_ DOOallQrl .: unf'ilirod d~u o n \0 the adja cent C-O bo nd i , f"ll m. 'cd hy lr~" ,I"r (If ... elKlron from a" o lM r bond or lhi, 2·carho!l alom. The r""'ltjn~ cue-e lectron bond then o;k~~ to all)'l radical and the re, cnanc" . ' tabi li""l •••" n;um [~ble· l:>ond "",,,,,c w, or ~hi, j"n , , he I" "ff .. ,il l he lhe ' "l icJI (ac l j"~ lIon l ener~ of 1M ",a u io". Note. t h ~{ only the nd ic.tl ~ lI e mo, '« ; fhe ehu lle " h,' .... .... i... ,m Ihe oxygen .

"r

io?"" .""

[htk""w" 4.? ]" cdi<.:t which will he lhe "" " ,... hu nd~nl p ,, >..aluN . imila,l)· wnll f">nn miofl "f the , [ahle a cylium ....." as in Eq l18M" 4.14 (Stt Filu~s J II) .>nd ~ . l l ).

~ CA · " C,I\--e=O

(4.141

,=

_, "' ;M.~ "'" ;mtJalc"d by 3JJ ,,1.-1inie
,

CH, ' .. CH,= I t --GH, {..... CH,-

CH= CH;, )

100%

, ._

CH, ' +

(H.' l a c~ "OO IlY) do..hk h
he""""" "'>oM n c" , tanil i"a li"" or (hi, 1'""I"cl ""lui",",

p<>" t i,·~ I;h~ " o locJ ~z.'tjon On a mmlO"al,nl a ll'gen. Wilh (be Qlh" ca no nicnl . l, uchlT"<;. ~ n ",ll~mcly unsl "N. a-a
wherea v the t'l ' alent o,,,,,i,,m

C H ,...£~).iC {C,fio;-~· 0

i"" j, lhe m""·[,,""rOO , ilc/ Fq ual'" '' 4. 1h~

-:*-

C....' + CI',=CID,t<,r--O -

~--c(G,H,l==O (4.16)

.,--_..... _.....

'"

ee /! . 1;..,....• ~ j 1011 01 11 is ~ll t: ,,1<110"' '' 4.3

...

"",

I ~ " I" ... ", ,lie l~tl""l ",I. yiN t~ l. l""dic'1' tha l ,hot "'..... ndanl fra gmenlatio n path""ay'. Po,h,l. t. a muclnr. 10< r", "hi<,.-h ' U" ~ • k"' , .. ll n ~Om m On

." .

_.~

" vZ

1,,\

•" "" "" ••

""

""""n",h!<,

,

"ee ""ee •• "ee

ee

., '.' "•••

.... ".•••. ..... .... .."

" "" " "" ""

.,"

.""

"

i"

I•

.

..

"

-. '"

..'.

" " "c.s ee " "e.e

.... ,. ..

..

n. 'z

as r .c

se

"se

' 00

se

" "

'00

,

~

--

" " •

•

•

,.

'fl,,'

L<>,. "! '''' '"",,,, .lkyl ..,di,-.I. r ule lSe<:lio1l 4.2) ;, ~,,,,ully ' W !icuhlc (" ~ ....* ,..'.t<' 1="~U,,n,. Not. tb, ! th. ", uro two . -oon d' for Ih" "" ' OOIly! RfOU P

, " -«:

I

. ' ~ fff fur , " akOO ol HOC- or I"''''''' ' . m",.

. n ~ h", - C-·· O

I

I

C

I

I H , NC · - . ux for

I

. and ,lin. lor a "'fl ;nt} ' am ine N$C

!

' , . This rule

I

prfll" " ' ''''-I II>< 'flC''1 r un' of :l-n"'tllyl·:t.-hcU llUI (tigun: 4.21 should , ltow 1<" ;' 1", I"'uh at "',' : 73, U , anoJ !(II. ""ilh .. hunJ ."""" deccea..m, io the orOO ~bo·.m in F
.'1>;"...

i"""""""

u • •• ,

"

l*

I]I _..

..,

""

..

' 00

• .,

> ." .8 ? ~ {I""

fC,H,ClC,H,I==6+rl "U'OI , IO% 14 ,17)

'. f,...."U. 101 . .. "t"<" um ~r Im 1>uI,a.m"", The "Yor",' hcl min~

dll~"'~ 10= pm'id«l by the nilro~n '.Qlll·~ ol..nm n· abilil}' rna. "" ,t.... ..."lta va ~e Ieacti"n J mnilla nl in t ~ "!""'Ira of ali~hJtlC MlillC., T he t>nly "'81<>~P' in rl"l.hutl lamine a«: "'"1." yls., 3"d th i, 10"' yield. t l>o; majo. peal of lhe !"".'rum (Figur e 4.~ ~ II>... represent s SS':-; or all LOll' ""I I.-.:ted. Th cr< ~rc (..." 3-melhyl, and r..... . ·bydI<1le,,, in dieth) lJ millo (F i ~ u " 4.4t mdh~l l o ss i' . till d'lfn iTUlnt, )'idd ", ~ Y1; ~ ,orIll. lolal ion. , "". 6~.~ rOT ~ ... of II (the large mi " )(l p".k .. ,ti""u."''' In S..,lion 4. W~ For UDhranrtied all yl;I[ninc, (R N H , . R = C:H., to G 1.H 1.1. to" mi. JO is Ihe .bundant ion I ii., ,.,pla"",meDI ur . l","n\lnal h}'dro w;n >h"" ill dod....,,"" by a ll d , ,,, ~\in g

/''''''1_

.,

sa

- --.

..

_.,., ~-_.. .

"'Ii"" '.4. M~" ,pc"'um '" olCth yh,m;OI: ami" e grollp cause, the profound , peeua! change Ihown

b.tw~~n

FIgures 3.2

and J,16

Te' l your undeN an ding of the," . " ncoph with L' " klloW nl 4 4 to 4~ . wllkh Hre 'pectra of i, omeric C. H 11:\ alk ylam ine,.

Unk"",," 4.-4 10 U

~.

" •," •

•"

....." •• •" "n n n

"

.. .. .."" ..""" ". "" . ...."" .""" ., " ., " .,.. .. ", .. ... .,.." '.~

er

' 00

o.

2 .~

..

"

..

.. ."

lOt.....'"

..

." "" .. "" . .." ".. " ...." """ ".. " .." ..".. "...,...,., " "ae

00

"

"

""" ""ee "" • •" "

.~

"

.~

" "

"" "

'00

4,' . _ "'''"00 ,,_ _ ,

"

""kno""' ,

•

'OIl..,

, ! I <

I

.j

"

,.,

•

,

_ ~

....

,.-

iI

~

•

" .."

ij

, ..,1,• •

'.

•

-

-.

,

,

•

•, •

•

, I I, 1

•

"". . ...nU

•

,~

,f .-j

I ~

1.,;j ,," ~

"

•

f]:

LL •

•

• ,

, ~

•

•

f' irs! .. nlc J ""in ,,,- ~ il'hl pOlsihlc am,.l\tS ol mol" uL.. ",,-~ ght B , 5",rt ,"' jlh the four 'p"clra l b a l I>• • c a base ,...." k al ' x; " hoch ot your str lKtuJCSlIilll ' h"" ;, tcady I",. "r 15" (Thu.. ",lu ch hoye un ·, · no
.',i,

.

' _

••00

".' ·

•• I h~ ~[>eCtr" of II"" <1 ~.~, TIl<: nther i' om m C' C. Am inel (If II nh" ' '' nf 4.4 th '-(lHgh 4, ~ oonra in \I>c rcma inilll: Ih' '''' , -mc thyl"m "",, : y0 m"j or i. TI>c ' ,,",,' ru m of
'il"

'>""i',,

4.7 Ch.'--'M Inll l.tla n (I"d",,!lve

Fq ua l"_ 4. 18 In 4.2 1 ' U1nmal itt [he Uio.cusserl '" lhi. , eclio n,

OE "

,,'

,

-

r··

1I - ' ~ -fI

, ,F

,

-

R~ R-'-Y=CH,

;

•

'h" oaiUio' .. [M "M Uffl 1984)

~

44 18)

-'-

••

,

.

•

"OJ .' I,'('m", pair.

(4. 1~)

14.10)

(4,21)

V= CH,

aU,,, ,·,i,,,,

'''acl",n ~J lh. po , ili ,'c ch a' F LO)'OJ-'C, The [,""oc'''' y fo, ' be lilfmatior' of 1\ ' fm rn RY is:

tr",ial Lo n of " d ,'u ,'u!!"

uf

A---(;,----y

VH"

R' +

-•

'1

~ . \. r ol y l lC

(-)-")

0

r-:

".... ~_,

h ~ lo­

tM' " 0, S ~'~, C. f' lf d em. nt ' of 'he ""m. /'010' of , 1>c ptriodic table ' hi, tend ency .... ' a lk l> ,he illd lLet i" o elfuc[ (" of 'I, H o",nt l'. lt ~ bili uli".. of [,... eh" ri:< i, 1L' '''MlIy mnrc im!"''' ' ''l ' .....n ' hal .,( Lhe unp a in:d ,i<...1 ton J;) , doter. m;n" " fe'~ C1~m p'0 d llClS [Sc<;t;,." 4.1) in bolh th e forma lion and Ih" Jccompo_ sinon (Or ,he l"I'ocu, >or; hcoou,", \ J..", hel,ro ly\ic .-It a\ 'ilfC'> Tt."le' fe' mj ~ ", 'i(," l~~ """,,rg,\ lhe) " Ie !!': nc nl Uy I~" /w,,,,,·J Ih. " 1. rtnct ionl, O , ygen i , in lc, ,, ledJat. in it- ~h dlly 10 in!h.c....-c .,1"'" ~ o r i rc :«-1 ,,," ,,- In ;on ,11Ip h" ' ie et he ' ,'ll'~' Itm, "r all . I«:lr<> o I... i. inil~'l ed b ) ' t he l o<~IiH4 p<>c al k"A~'l to d icaL in Cnse [he ( Il;org< , i'e .. mo ved (Fq wru <>" 4,12: ",e F i" ur. 3.9). l>;" ", [h~ 1 Iii< h Ol1 d c1ca,,,.,J l it· CH, - () )(J ;' _,..I l h.l ,1ca vt
"r

'.1<1''''''....

,h"

es CA ' • •oc.... (4.12 )

~

..

~

CH, C H, C H,----et<,----Gl

~

(CH,),.Ctf-CH,---c.

--, ,-

t"'-----t
-'..

("'-

rlCl)

"

C,H,," , C, H,'

(4.23) ~

C, I-Io" ,

,~

C,H,

,., ,-

i4.24,

t il " 1 ( H, - -OK Eq ua tion 4, 13\, Th e I fa~tl o n

j , .1", ~,,,,,po:lili.e for 1nIl"~' "'lr oallla,,", al~)'l iodi de" , c"ondacy and lorhary . 1< >'1 bron,ides. aDd Terti a.) alk yl chl".;"k, _ hul nol for Re B, Y ro ml'OuM S of h'J"" C- Y hor>; u",,,,-: . h ~ lou at C H.C1 is mu,h large r in F~ua(j Qn • .H t ha n in 4.li. Tni , , "ad i< m will "ot d ..., ., a m ultIple 1>oDd ,,, a 1>; 1 on}'] ~j O UP IEqu.hoo 4.2 S~ d ,,<:c mn-Jl'U' ~m a cl i~ 1l to the c h~rl!t' site yield' the canon; , _1 ' .....'n;ln"" ", ,,,,,, lIt<:; ;"d lJC1 i ,~ c1ea\'a~ or thi$ then ~ ;'c, lh<: a lkyl ion and aql radl,>~l H....."e\"er. l bC'><' prOO"ds "'" 1he "","pl"m"",, of
O;m";de ri n ~ Equa li" n< 4.14 and 4,2! , O" e would e1pt'Ct alipb:lt>c kclOn,.. 1" oJ",w j" ur maj or iom Fmlll clea\'J~e or the t ...o bond. l" the ""m.m yl ~ m u" the I;\>'ored Heyburn ;" n ,"oL11d be o.hc " ....' f"'mN l!m' uV! 10M 01 the largot oll yl ~wup , " nd Iho Fav ored ,a rboniuon j"n Ih ould be the mor e st"hle one. ltllkn"w lls 4.9 and 4.10 'I e the l(>eCtla
.

-

,I j

_-

.,- _ .. _.. ..... ....

_

•

•

, "1

,!

•

·i,~.~J~ -'" ... ""

I

I

•

""

.-

1.,• i,.. ••

•

~

r....

f""

"

-

•

"r....

En«H:/ec.l" '" " ,.." . " , d""",,;at in Sec,;".. 4.4. ,"" d e<." ",,,,"'; ' i,,n F E ' i"n )'ield. "~"' '''T FF ' i"" lUId ;a m<>lc<;,,1e ~. the ne" t,al prodUCt F'rod lJCt mo lec u..... o r Iu,., 1''''''''' affinit y a t<: f•• " n:J., . " ,h ", l hooc '" fq u~"<'0 1 4.2l> 4.111 U'A = 1.4. 6,2. a lld 1.2 t V. .....p. ':tl vely, r ,eld ', Il ule. 4~ !-,!u.8 I" ,n. 4.26 and • . are I.. ",..,.",p I"' l h"""l"' fu t r" ...." ..s Ihe 'an,. I'I<'duCt1 prod ,O«
Snol,,'"..

n

Eqlla' ;"'" 4,22 a nd 4.25. ""'f'C'-'t,,<:I, _ H " w~ Y<:r, 1M""

" ""blo:; by 0 ,<

:t
~~ ~

,=

·\ w

,~

- R'·

•

'".

-, , -'-

C

-, - ,f< • ~

-

W

a

~~ •

'",0

--• ,-. , ,-. -

•

,-

IU t.)

'0

(4,17,

. ,0

\ 4. ~ ~,

The injlial jon, prod llced h;' chen,;c..' j"nj,,,Ii,," (0) " re ma inly fE ' IOnl ' uch ", MH + ""d (M Hj": other ' Ofl ion;",,';o.. mcll"" b , ud ' a. r''' '-at"... lx, ,,,b",J lIJe,,1 call ,,1>0 PlOO lLC'C " ... 10 .hLL..d a n l F.F + in... (.SOOT;, Ne (F ield ', Rule , Stolio u 4.4). The EI m" " 'Jl<'ct,u m of ephod ,;"" (f:ign rc " 5) , ho w, n" mo lwullir iun: tOe 'f'C.lrum i, '0 domin" ted by the ~-cle" V"jl.O renctio n Ic. dm g to CIl ,N +II=CHC lI , (m /: 5~) ' h I th e'e a, . only "'cok peaks ind icati ve of tM rc' l ,,[ t h. rn"kc uk H OWCW[, tile CI ' pec tr u m tFigu re 4. ~) ha, . hu nd8nl ion, at m/~ 1M , MH ' _ indi ca ';ng lOe nm l""ul"t wci~h t, ;md al 148. (M + 11 _ H 2 0 )' , Th. btleL for me d by indueli~o cleavage (tquali,,"" 2 ~~ lhLl' ;Tl
~ .

•.

~1

i I

!

-

"j ',

~

- --- "

. .1 , •, •

I '

•

if? ,-

>, ,,",, , ~

"

.. '.

" ,~

J

,.I "

•

~I

t

"

, ",,

"

,. '

-t

-.~ ," ."~,~;,_,,~,;,_:,~ , JJ.' -j "J

.... :II>

._

'"

..

U . Eht _ inouza""".ad

OIl

_

~

' lD

•.,.

.....iDll..... 10 1.

,on

~_"""'I m-.

""'"'_ of

"rod""'"

ono.1 ..- of tb~ ~m,""

J[r..... p.. , he rno..H p... l ,ro ,..., a . poc1......1 _ : 1) 5 11-<1""00.. ... 291 ;.. ..:ry ,.••:1.11. IlnaI It m.kates 1_ /11--00) 1 f.rOIIp. "."'" IN t the ~'ft<1O " " loa. 04 H ,0 II . " CI-I , Iollo-n Fitld", .~ IPA ~ 1.1 ' 00 '1.4. "", pa:ti~el ~ ~ Il" bra ~ "'"""'tiool of an " )0:' rtUd· ...1. ;., .., hJp.hIy
.i,...

........

,..

c....-<.>ot---Q< "'.-"-#< ..p<,

---L- 4tl.~+ ~". \4 2'>1

. , _ _. . . w .. ... . '

_

In U uk _ n ~ . II 1'" ""0 1_10 ptIl k ... ~ 1'" d t mtm al t mO'd>ani, m, in tl"cidal;DK1'" "roeWre of IbIS molec ult, (I I ",,. l'l>e molecula r i"" ,nfnrmal;nn f,...... T a... l. A.4 is ab." 'al.......I"-I

U~

.... .. " _~

~

,~

"• •so "• • •" •• •• "• • "ra •" ,m '"

" """ "

..

,oo

!

••• •

"0'

..,.

ea

J

" " as

~

..

-.

• •

"

~

..

_ ._---

•

• "•

,.

• ••

••

' OO

""" " "0' 0' 0'

2.1

cJt •.Q

4.' De<:orIlpou*GflU ofeydc a _ .... The cle a,' a~e of Iwo bond. in a rin K ;' n=,",,'1' 1" [1« Ktuu:: a. r....@mcn. ioo IE,! U-a, ion 4, .\(1~ Clea."a.gc of o ne " u nJ """',..,. nu ,'hallt<" in pr od 1Jci n ~

.lI3."'"

0

.zs.:

C (; .," --'--

o,'u ~

--'--

. , l--. oWz !l'l>

j O lll

" nil' a. di , I,,,,i< r:wi",,1in n (RaJom ~I al. 1 9 ~ ( . <:O m", and McI .,.ITc, ' )' , ~ 7 ' 1- "'"'" with a J r"woec bet,,'een ie, radical alld c ha r ~ e >lIe> , The unpaired tlec1ro n in Ihi, i,ome ric ;on i, doo med 10 for m a new bond to the adj. cent caroo n .I o ,, ~

.0 0 _ 0

.

i _d

-

.~

I

..

,..

t .JLj,tL "'" 20

.,

..

""

. ..... ' .1. M",. , p.,", u,n ." ")'< Ioht"' n.

"..it h con,~"";' a n l cleavago « a no' '''", bond to thaI ZrC.1n on lh. chargM ll~ " nl>proo ucins "n ,>dd. /'. 1' '' " ion. T ht ma.•• ~rum "I cyd " lItxane i, , h " ill Fig",. 4. ~ (...,., al.., H gure 3.6), ,,"Ptc I....t ,he importa nt O F ' ion C. II, ' ('~i: 56) ha, 111<. m....' h;' d l' O ~C '" (S<Jcl;,,,, ) ,4) ~I . ny " on.i, ol;."", C . H : inn. N"'j) ·~/p.AiJdu......-,; a di,t" llle radic«l· iCll\ "", mOl" by ~.., lca.·.l ~ a _ ond >!Ie h reocri"" d,mina,e, neutr al C 1H. NOle Ihm the " Ih", prod oct n i" ni, . d U-bu tad ~:pc> ... !~ . t thi, corr c""l" or>ds 10 a '"t ", .Dicl ,· .~ l" n 'ragn"'nt~ti on tcllCiions, Ihe l'\:" " . () i, I, -Aldo, ,t~"""'''' will b< iml'''',a,, ' ouly' il no l" c!t ll ble frarncnta liO!,! dre P'J'S"Mc. Th" l the ",h11' ;,,,, of a fUl'Icti,mal gro up Can " .am.tl lically red,,,,, the abnndan cc " I kim from lhi, ' . action. Con, cr"dy . funcliona] g""'l"S ' hal can 01 tlx rin" ..u ylir bond, la m, tilt reuo- f)t . l..AI!l~ ~ Un!",,,,,,n, ;ol, , he struel nn:. a nd ' pe<1ra, an ,l j ",,' ily ) '0'" clt" icc.

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C. arK~ migrali"". Tht final ~I~ P oJ Eq I" " 0l14,31 i. , I.own a, a hnmnlyt;" hOlld cleavage, with ead of ", p.o '~l i ng frapocll" rt ,aining OIl< of the electr ons. HQw",'el', heterclylic cl. ~ t " I iJ I ll<> l'O'l,i blc (FGualio n 4..121- mm'ing It.. po,it i,'e cha rge 10 prod _ ' he i",.;;.,<1 al ~ " n e ( H ~U T C 4.8). In the tr an. ilion il l t. Ihe .:tIl """ ~»d olefin a,., rompt'n n, r~ r an .leetron; according to "St,'-'«I"'" " Ita l ~" ,he produ<:1 mon li~.ly 10 10M tht electro n is ,he one ",';In ,fo<, w..~ 1 io.>nil.3110n . n.rn. llE, T;
t""

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'lite", a re a l'" im!",,'. " ' ""'' '' 'f'<" u,,1 r....~li"n ... h :h r" ~I ..,:,, ,«1 the OOnll<'<'(;\'lt y ",tallo",h,p'" of rM ...rr~,na l m" l«u!e; r " f1 or ,1>c 1' 1,:<,; ut~J r ion ha. ruo"l';,J with ~ 1I0t h.l r art I:>efOrl (>f d u nll ~ dK<'mpo ' ition. s..'!tl<'t i,,,,,, ,,,,,h rear... n!",,\em, . re .... ". "....-i ....' ,h., Ih., ," . ~e the prod\lct '<:In u..l<"" Co. m ,,1;"l'Uly F"r"' n Ol.I~'. man~' "" "" "i<''''e"" {...." ul ~~' ""'.." of ">P<"'f"'" ","'halli'ln' ",f,;en a rc " m'" "'ell urK!et>\'K>J, .nd I n~...., p,.."Ia.;t ;<>n' ;lft rh u> 'a1ua t>k for deducing mu clnr•. 1I)'d w~e tl·. tom realU ntnnem, 'nai al od >I a r.di~J I Iii., lOC mai n .,ub;",,\ hi, = \i,,'l , " rc a n 1mP<'rt"nt d ill Sof re,,'tiMI eth lbltfd t,~ a ..'ide ,'arj ol}' "[""\I\-'1LL'O•. A, with 01 ', - [,,'mo',,'" from . cye'li<: m'.......... I" c ion. the initial , o. l rangemem pr ool,cf il a dm oni' radI cal ion (IInmmen'm

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,..H rr" " " tWemn tr l<>.~ ~~" .f~r.fe4 1C"JMp ",il~ 1-..t'.'"J" An unpnJfed tltct>c d"naled I" f"rm " new b"n,1 I" lin "'\.i llC"11t atom IhW\ll:h In m can ' pace: as in Eq ua lio n 4,14, the sec<>nd tl""ll'on of fhi. JXI ir I, , upplied by tran , fer f", m ,m"l hcr h" nd to thi, ",tj .",m "tom, r ~, ult inl: ill its d e,w age rEquatloll 4.33). rlanerin gly. this i' u ,u all ~' relocrcd 10 ""' Ih" MMc L..Il l'n y n;"rc"n gcmC"I" 1\-lcLofTerl y 1956. 1959: King' tm, "I "/. 1974; T urc~c k d " I. 1'Nf1. ) ~ llr pound s containing an unsat ur ated fUnCllOna ll1y sucl> u the carbcn~l.d~ ~ tran'itiml , lal e. nowever. in lhil prore" the initial clt avagt d~ 1 net le' ull In

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llle I"" "r pa,' " r ' nc inn. nut only in a cb. nge in lhe posinon of ll>t radical ..", 10 form tl~ i'omeric d i'IO ll i~ rad ical Ion. Th e JK'" lud"",, 1,i lc <;;tn nm.' inilial. "ll ~-de,,,'a~c "'"ction rc, U1\ing in rcalC"'cnlali"n ,,( I ~ . ea rbon-a rbon t>ond wbicn i, b in~ lhe se.:on;! ' 1q> i' the "'ilOll"nCC " d ,;l;' ali" n nf the ra;!<.:.at ;p, "nd lhu' n~.n &lC$ , · 11 tt~ M!" IU prod "'" t he , cac, i>e inl1.'1"rtICj ~"" ",,,,, ,,, d J~ ,"" lhM I ~""' I'" ".,,~ ~,akk h)des. l ....o ne< \Fi &ures 3.10 :md 3.\ ''' 'e ro , ~"illl"''' 3 I l 10 J, 15 ~ acid. (F if:ure 3. l 7). am.del; (rigme> 3, I'I ~,..J 3. 2Cl~ ca'bon~ ' ell, phosph"n;lt<><. . ulfit"" l ctiminc.. o ..md., hldr.orono< IEqnation 4, J ~ \' u l ~ ,,'e,. ~I k ylll. .... and p1k-n)·Lall a.l<S , E'IUalion 4. :16; F i~ urr 3- 7~

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Note thaI Ih..e j", m. r< ",-0<1""" the ",,,ne h} ~ ~ H a go 1"' /' 4J ~nd on<,! hy H:leo- age (",.it 15 a lld H ~ wh ere.. tile /I-cloang< r . " r r~n~",m c"l mol es ;! pos,ible !<:> di, t i" Ku ,fl;\""nl, " n tho ~'f'<"'l; o n_ T1Ic ' e" d ency for re~ ,r ,""" me ll t ;, great"" !()[ hy(tru~1I Oil brand.N . all l1ic. OXygOll, Of o t1>e< labile ~ }j

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hLlL Iho l. lL<:r rn~} h ~ ,. . " ". b ' _Again, the , ,,rn or the;,. complementary rna,,", cq"all that 0[ \1· ': in Figure 4,9, j ~ + \04 ... 161.

to .. _. atJl,u f~d hd11 4..\7 A$
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00 00 t<J I~ ~ t hvd rogcn. Howe''Cr, a """'''d radical- ,, '~ "'ac ti" " i' not f. "o.ed, ,inoc , w bd lZ.)u <>II of t ~e unpaired el«u o n ;n I ~ c ",,><J ut l -CH.CH , 0 ' H , .. Il(I belt'" ,.... 0 l"" t I" the imermedi" ,c ( ' H ,K llo I, O ' H, _ l,, 'l<:.J. ~ charSe--511C """,li" " is HOW po.. ib k . fmmin~ i" ' hi, C<' $C 111 . (M - H , 0 ," P<" ~ by '*"'>~~ "f a bond to the hc t,-",aWftL (Wal• • 1...., i ' m uch mar< fa'ftr~ hIc f.... pr im a ry " k" h ,-~ , lhall [", >a.'O", ",in giyc >eco"dary pTod<><1. b )' d ea OJlle of. n.mcred.ting ; "termedl at~ i , n" t requlredt f u rt"cr. the rL... uJ,,"g bel. ra . ' <>m-c"n tain ;,, ~ fl ~f"'C"1 ;.. "' turated. Jlld '" "ompct.... lm -0 1"" the ChaT!!' ITa ble A. )~ m ~ ~ ;n~ charge migration lI''l ual i""" 4,:J&, 4.40) "' ''cl> 1M I'e COmm on. 11>< cl> ~'Se ·nll$,a tJO ll rcacl;"n fa,'()1'1 tlr<:t ronc ~a li,'c 'fl< -

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if l,i.. k.. ,. .... 4.N invo l"C. ""me imp. orlUI 1"';"1' Ihal have ken ""w....... p"'" . <m , ly. Fl<: "" e Y" " .. ,,14 nd ;l' ......';on belOit 1»,.......-..Ii" 1I- 111<: "1 ~i l y of l h• ....i• ..... 5 f"'.. L r<>rmed b)" rneu., able ','n ,\<." ""","'U"" ..·,11 be
Soc1w" 10•••

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fJi.,.l~u_ U- ( ) -..i u nlio.m W"" nlio.m 4.42) I" a di, .."'m chl,,,,' ",um io n with di<J1l.....-menl ,.. an ~ Ilyl po ul' &CCOlLnll 101 the \;\r(/'l'SI peak III - and l · br o m o .~ k . ll ~ ' ( F' ~ ( ll C ' .1. 2.1, ~ , 2 4) This redctlOil is m uch h..,... imp."'lan l in f>o-and ...lIl ~ al. ", l h .........nd rnr rUt1 Cli"nahh"" .... lh .. ml' h.... . len J ",,") for radlcal·. ice ~ ."llOd. , Th e "" l ~S ~l-'t' <:t ro m of .. -dOlieryl lTJe1'C;ill'lall (Tipme 3.l l) ,ho w, thoc r"lIo "' ; l'~ (:. H ,.>,S ' ; on~: .. ~ I. 2~~ (CH, su r""" ~ -.;lcan..'Ci; .. _ 2. ~ :;; .. _ .l. l ~~ : n _ ~ II ~; (fh emcm l-crud . ing); and n _ 5. r·;, N oco tho ' imila' ~io n ..r ies" (So, tio n ~ .l ) ' 11 dodocylami"" (Tigm o J. l ~).

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re~rr~ngem en1s

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froon an ~ncfll!C,ic ••~"d"",ut. in volve r""IT~"I\L"mtnl (Se<:hOll 4.4), ik =u~ Tilt .h. 11I" " ' e d" .... n<>l nlO"'. lhi\ . " " he l< lCII.<edon It»·ot~tr"ncgali v " fUOCllO""I· it«-.. own . " ami"" N. an d m"Te~leootronq:.ol;-' < f"nC\~lnal itie • •,,fed if I,,,, of a m "l ~ r; \l lc " I I" .., ptoton . llinl1 y i, in,,"h'ed; • <:om"",n m•."h~ n i , m of th= p" " inJ. in>'ol>"" a l'J<>t"n. k<'ulld imOfmwi. tc I t - H' Z: Morroll ,9X2, Il" w~ n and William, 1%0: McAdoo 19S5. t The .... ullin. prod u. l inn' can h" \'~ t hci < a,,'m_ ..crambl< , tTu<: J'foOl' Cl ions mu,1 he ; nt"pA:l~ ..,l h ca ution . ll o.... n .t . tho;

F F ' ion ''''~JJan~""", nl 01 hyd ra~n 10 an unsacumted gro up ~o ntaln LTl g a h<1.c:r.,., l mn ",; ,1> di mm ~ ,i , m "r ~" un" ,tuntl.d 11 . ,,1, "1, ~"n prov ide \'llluable informalion. Th i. ,ea ction gi\'h th" ",",ond l a,g~" I"'ak in ,h••""etrum or dit.1h~lam",c. Fi~",c 4.4 (F'I"" hon 4.4}), Tile t,.ml liou-nate lize req ui"el on em yl or !'f" U" "" l he nit"'I!"n lhi. '"" rt" ~ ll< n1 elll. T11 " , thi. nwction prorides a specua! dJStinclion bel" """ (("H, ,-, CN H , \ ~i gu," J. l), ((:H,j,(:H NHCH,. a"" ( ~ H ,e H,'ICH , I. IUnknowl1l 4.5 and 4.bl. Although the ", 110 "", . 1"'"'1.... also . h_ a ""'" f"~'Jam "le (.", te llw t h~ ' re Sh U a Pflreci8hle. '10 Ih.al , ""... da la ", 1 he ulili,c" " " 11> ca u\kml.

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V"l.lki.... t !O I' rodi<.1 the " "'''; f'ill "" ah in Ihc rna", """el r on, of N ' IN t h) I·N·iI.oprop~ I·N·buIyl.lmille. r ven-elceu on '<>n_ ' a n " I.,. undc'co H rc..rr.n~n><"" ..hiel> do """ wvoive , h•• hargo '''0 ("", a" un... lu'ated ....1C'''. lom~ _h ". ,c;Krion 4,44. Tl>e r mtl ll n~ peaks s,h ould be- used ",·jlll n "llO" lOr aW ~n Jn8 f.. nc:tj,m ~l group

•

locat ions,

h ow e ' ~ r' ll ot ~

~ ic h lv ", b u l ane

tlla l (Figure 4.111)

c',,,,j,·tJ ioni",fl ill" .

I~i:

55 is til. 00.", peak in h<>tb 1,3- and U -

Ilccau,," CI produce, ma inll' e"""-ctcctroll ions, for such , ['Col' a it ;, "'1'«';" Uy iml'Ortam Co reco gnize tha i r e " [n n~:m cn l i. "" mmon _ pla,e in EE+ di, ,,,,,ia liom (Ha rr iwn 199J; Kings.ton "t al. 19 83: eron,ble and Ha" i, oD 1988). Alt hough 110 . , ite or CI """",," tio,, in a molecule . hould be th dt or hig hc
"

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K~"""It/(,,,,,,,,t uf ...u lIyw"l(' " .,""'" (t he MM cLo ffert}' I 1" t<:iIIU~ ~"MI i. a ,,""[00 h ) dl<'~~n by r, moch. "i,m allnk'gou, \0 re actio n 4 .4.1. An :tct,kd ,If;Y,"!,, fu te" i, \he l" ..u na".., >1 al:>ili, al ion or f nc E F ' I'md uu ion ( Inn.'" 1>0,,<1. are cka,'Od ,n th" t'O"IKt Lon). I, or propy1 . " d higher .,u's, a Olable aU}'lj" mdi"a l . an b< prod U«>d; h O WC V~ f . ';gniroc.lnt C , H , an d C, H , 10.' ''''' 00<\l1 r",m Cln ) , an d i" ' I'"" yl ",1<:" to pruduce ,-inyl ,adioal, _ AlthoLLgh thi, (M C.II , " , )- ion i. oflen rO'm"ndanoo. ~."" , hould be a\>k; to, "-'C<' gni,,,,, it h om lh<: un " , " a l rna,,,,, 27. 41. 55. clc.. 1",\ (Ta llie ....5) in it' for ma lio n. Th" pro,jdes a useful cham"tori' tic or ..te,. (Figure, ~, 14 aDd ~. 1 5 ~ tni"" , t,-.-" amide, (Figure 3,20\ phosp h. t". ( Fi ~"rc ~_ n ) . " 1>d C,'C1> ",Ifonc, (I(, SO " H g\Ire :l.n~ lhi, j , why ~..ou , h" " IJ mark importan t (M C.II , . , )- iom of o~y­ gen. led compound . (Slep 4, Sta ndard J lllerp rciali nn Pmcedure)_Hc ,,"c>cr, I" r _ mation 01' the 0 c, ' pmdu
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The . ~m"'ary imido; \l"K: bac ~ co' . r j,. intended to \lnd"T "" <>~ the ", L. ';" n, hip, " I ,he romm,m ' }I'"' of react,..."", .. hk b i"m undct ~o. "';ng example. fl"'m tlti!. "h artCT. You , houlJ u'"' t lus ~. u "" "" kli' t .... h." y"u a. e J lt.mp lin~ 10 pnod iCl llle , pc'Clrum of a moln.,.lc; to uSC It e rl';~',c l y. h" w. "", you .... ill h• •" 10 " nd. "I" nd , n., ma rc" " l ,>I 'he preced m ~ _ , i" "s, The loll<,,..inl com..ntio" , ha ve been cmph'l" '.J. II. indicate. on . Ikyl ~fOI lP, bur Ihi, ,-,' uk! also e" nl;ed in, "h ain of two <>r ""'.... al<>m l~ U indicald. a ""ble q dic or " n... ' al cc~ lc. In n:aetior" In ,," ieh an al ~yl group ;" 1".1. ,h. 10;' ot t1>e la<ust is l"' neT~lIy r. voroJ . ~01C ,,1... lha l III thl.! JU mm ~ J~·." well a, ;n l h ~ ~ St of 111 . h",k Ihe J..i"", tinn 01 a hom o.l ~ I c ....md cl~ J\' J ~c " I\l'' ' " milS lh. "'e,md fi,hbool; II . .... .uld be ~ l1d.r · " "..d '..... , tM second electro n of , he bond r.ccomc, Ih. tlnl"' in:d el..n on " f the radical prod u. '.

",In

5 Postulation of Molecular Structures

T he, e ar e ..,,·.. ,,1 ......jut krnd. of ~. lle f; 1 1 ' [m otll....1 ;" IOI'n;lli,m ayailabl . \~ th. rna" spc.:tn.m f hes< are p" rli cul~, I) hel pful if ) " U "";'~ no jnform au " n h om "ther ""ore"" c o ~ " "m iT1 g tilt llnkc(>wn m,*"ul<. Tho ,,,,,_all appear_ a".,., of "",,;c leu m and Ibe 10...' m.. ... ~h can give a. l!-CTIC' roJ indicali,m of the lY r< "I c"mp"un~ ; ~"" the 6l.'~ "" ill ( ' ha pleT 3 a , t U lTlJ>ln l<" 'l1.uJy. h rl h.·rmo re, the nCLl lr. 1 r... ~menl' 1os1 in f" rming the bj~h m... pea h can prM j~ mfonn ~ !i "!l t>n .peafi, oln.clural featurea, Tl>o fragm..." a,Oon bere, a, outlmed in th" Sl4u,h rd Inte rpretati"" r rO<;/;d u", insHle l he ",",ck "o ver.

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In unbranched alkan.s. tho most ,,~sily cleaved fxmll< (lhe ,,-hond, belween second,,,} e,,,boml ~rc ncarly "qui,-alen[ in I>ond strength, The [.sulting mass '[JCclm trigu,"' 3.2 and 5.21 haw mally peak, of regularly varying abundanc",_ Study the,. typic"l "pi","\ fence" '[JCclra triki ",ccpt M' an: e"en-electron io",. Th~ rale, of the initial decomposition reacliom of any mok~ular JOn i""olving dea,'ages of the dillerem ""rbon-carn",, "o",i, are campara ble to e,""h oth"" a, arc the ,ccondary decompositions of the primary product ions, This account, for the TegulaT incn,a," in abundances witb de",ea,;(OJ ",," or the alkyl ions. The possibility of rearwnge,l product, or grea ler stability becomes higher with the ,e~onJary "'"Clion" '0 that the structures of the ,man"r io,,", ,uch a, C.1H,+ aranched carhonium ion slrllctures, Thus th" di"n bUlion of inn, " maximized in the C J and C. region of higher alkanes Furlhe' ,uh I>ond" compare Figure, 3.2 :lA and 4.1. Aher you reread Sectiou 4,5. try Lnkno"'", 55 lo 5.7. which are C j611,. i,omers, Don'! forge! th,,1. ,,_bond cleavages give EE- C,H, ._,' io"" nor OF' C.H,"" ion,. In tbese unknowns ignore such important OF' ion" which arc di"'u"ed in Section 9,2,

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W IIlp<'und, ~ onl ll i " i nit Ih.,.., d~m" n t; an I&,,,,,,"",i. rin g , /low ~ \&h a l ,,;n,ik , mi " \'. l u ~ plu, addilionAl peaks al "'i> 411, S3, 66, aDd 19 I' '''' ""h igh" arom~ lj~ .. rio." or rabl~ A,6l OOoau"" "r . e'J'lno.ment ef CH Itt' "0, '" CH , by O. Altl ", u ~ o lhe Ilromohc ,~ r;"", i, Men of ulllli,'d y I"", I b~ nd.l n "., Ih. uniqaelie"" <>I" It. rna" ,·"1",,, (l"ah le 5. 1l 1l,u an~' make< it q une ~",gni zal>le; note iI. al>oeoc<: In I 'nkne wm 5,') and 5.11) compa..d tc 53, 5.4 and S.8. U",,,,, H ll u,," )2 ,,, .1 27 n< ullkno......... """ if yO ll call ded LlCC ...""'" comail' ~I omul ic .....,i.tie, .....ng this seri,.... A! " an he ""'II In F"i~\I r"' .1.231 ...:1 3.1 4, l~ O cepla,-emenl of h}d r" l"'n alom, hy halop 1&10111" X . e h a ,, ~ ", (It< h"",...J,,! (}u> , ori 05 Sp.:Icin!!-, h )' CHX o r ex " cau' ''1l:a m a r~ed "h al1~C in lhc ~ f1l"'~ r a llO< of the . pectrum, Ad,li{i"na ll) , the clc"t1' Outf.m i, 'e hal o1" " al""'. a,e m""h mt e rs. ~ F luo ri...., an d iodine ha , c ' 'Illy one nJlU I ~ 1 ;"'''>]"1< .~ ,h · , or and .. ·T- ~ul the," oan u'u alJj' Ix: """'9,,;zed by th" 'c' y unusual ma " diffc... , t = l he)' . " u,c.

NftCo>(.....; nx ion >UiN. o..,," i' l' qUlrkl}' """'>JIlt aille to Kk'll ify """ t>o uy'l pea k< in lin inf,anod . po.'lrum or C H, iu a prol" n N',{R . p"':lm m. Simila rly, you ...·,11 led much mOtc "al h" me' with rna" ' p«'tra if J Oll can ~,li ( l~ recoglliu ,he J'OS , ible ,i llnll'i ,'llnce 01 rna" _alue. , t;.... lhc C. II ••~ ,· ",ria 1'2 ~, 4J. ~ 7, ,~(" ,11 yo ur rck... nee ",ak Note tha' in ,he I()()o; r<{li,m. , oj, i, onI, ,,,,,, inS"; umt, i" " e, ( I B, 127, 14 1, 15\ . tc , ~ "'"aulo< (CH , ), cnrmpond. ,,, ~8 on,' " " nil< (F ig" ... S.2 ~ the 200. f C~i,,,, ;,; thea 211, 225. 239, 253, and .., fort h, ,\ l>(', tl.:caus< C H, 114) can be rcpla,," by N H 115) or 0 ( 1 6~ one <:a n ostimnt<' the t ot ~ l numbe, of C. N, and 0 ~'(l n' . ny' dividinll 1'» 14 iF the ' I'<:0l, " m contain_ . ";gnifi,,"" l 'a'u rs toJ ion ""ric., For u"""w' alion, . nch a, ;nd ICa ted oy a n aromal ic jon .. riM,add lwic. the , +- do ,'alue U"" ~"y l. add 8, t>cf' .... d1 \'idmg h)' 14. A, a h ~ndy ,,\1. of lhumb. 100 lila'" unit, n . "f' prn. im~ l~l y [("+ ':': + 0 )" In L nkn" . ,nj, '-I I ;lIld 5.1 2 notl<>: in l"'rltculJ r lbe go.......l ap""" ,,, nce of the ' l"-"t1ra an d jon "rie..

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5.3 Small neul,allosses

Perhaps the simplest and most specific assignments that can be made in thc ,pc~t,um are for the 'mall ncutral ,pecic, lo,t in the formation of lhe fragmenl IOn< "f bighe'l mass in the spectrum, especially those formed directly from the molecular ion. For ex"mplc, important io", at ma"",' (M - n-. (M - 15)' (M - IHI', an<1 (M - 201- alnll'" alway, 'epresent the losses of Il, CIl " ]J ,0, and HF, respectively, from tile molecular ion. Becaus. formation of such larb'C prim~TY ion, involv", lbe I"we" pTOb~bilit}, of a randomizing ,earrang<.'Ilwm, ;ucll ",maJ]-ncutralloss" peaks fife of major 'ignificance in deducing the m"l""ular ,Irucwro, Tbl,L' an abun<1anl peak corresponding 10 (M - 1)- indicates a labile hydrogen atom (and the ab'ence of olher labilc substituent'). A list of common small, n.utr,,1 fragmenl' 1"'1 in Ihe formalion of important speclral peak< i' ;et forth in Table .'1.,5: lheir use as Ie'" for tile molecular ion was discussed in Section ),5, As di,eusscd in S""h"n 3,4. lhc,e high-mass peaks are oflligh relati,' . imporlanee; ",'en Ih"se "f < I~,; inlen,ity can be u'eful fDr ,truduro determinalion. Tile specillc loss of" larger neutral Cilll al'o be ,Iruclumtly characterislic. but ih i'knliricati"n "flen 'equire, di'lindion rrom adjacem low-mas> ion 'eries, Thi, is I", a problem with low-mass odd-electron iOllS, since OE" ion 'erie' an; relativel}' ," ro, However, carefully examine any FE I ion repro",ntinEl a peak mo,c impurlanl lhan an)' "lbe, in ilK ion serie,. especially if il is nearly tile Ilighesl mass in its peak group; repiacem.nt ofCH, b}' NH or a rai'es thc rna" ",'d u,ually lowe"" Ihe i"niz~lion enc'g}', In Ibe '[J"dmm "f bexyl formate (figure 5.3), you sllould easHy idemify the c"n' .~jo· ion series al mi: 31. 45, 59,73,87. and 101. However. Ille tiny peak at miz 47 i, e,pcci~lly irnpurlanl, became it i' althe higb",l rna" or it' peak clu'ter m,i. 36-47, and tllere ar. negligible peak, in its ion serie' at miz 33, 61, 75, and 89. Examining T"bk A,6, we "an 'CC tha l lbi, ,trongly ind;,,~l", the pre",n"" of a 'ccond o,ygen or a slilfur alom. Jf you knew the molecular weigill. }'OU sllould haw also marked mi~ 47 as an important 1M - C.H"_lJ" iOll of an untllown tll"l could cOnlain @

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'" Yl'<-'fl· t he "'/~ 47 1'C'l1 ~~lUa.I'· aI. - 1»- ,110< d ooble ·h yd, o*",11 IU lla"$. ,nc n t I"" of <-\H , ,. a d ,ara«en ' h< <1;",....;• • ;"11 . of (," ma'e.. l"cc illm 4. W •. II t he - 1"b"",,1n"ut..1 ",,", . I.... ind lCateJ l l1.11 1ht peak of hi,ILe;, ,n.", " n" ,

the moleru la r iOIl. thi\ ill <~l m",,' di lk.......," then ~ I' ~senl, t be (lLft"... nce het"",", 111 . ma , ses I"". from tlte n~.le<:ula , ~ m in r"' m;n~ 111,. .., ' " '' fT. b""cn h . For example. if l!>etc i, on imf\orlaOl p<'•• k ltu « IlUlfSoe$ blelow 1110< rea l 01 h i~h .'t mass, thi, could "'I'~nl ,t..: ~ _ "f H ,I I f,,,," . ny bl a "",IecuL" ion lhal '11'0 easily 1o"", <:H" An "npona n t r u k I J 1113 it- ",1",. the JlC"k of higM ' \ m,,-,, ""uld hc <1"" ,,, lho; I,,,, ,of ( "l H. ..., CO f, o ll1 a rnoJtcUla r ion thai a l", I""" C H, c .,;I ~ N" ,,, th ai il l'" n'a_' diflerft>OO " an odd ..umber, an d nitr o gen is no t pre .em , t h." " II<' or Ihe , .. " r' ak"",,n\ po:;I k. m.... ' . "'.....nl an O L ' ion.

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... ~--- In C lllr.n,'''''' ~ _ J:l, ~o~m iUn'lll<1llS sh.,.., lIal m,'; Il ll i, f,,, mcu by the jo" of C, II , from tlle molocular ion: " och neutral k>sscs are i ndic"r, v ~ " I 111 ~ , tm clurc. Dw )t>u iden ti f)- burlt '''' IIOn . ut 'o n "'tic","

._11

5.4 Charact8ri st ic ions D"duClion of tl>< m ucr" .., inf"nn~l i"n ' Will a larger 10 0 i, more diffIC ult. becau' " ,,( tno largO( " umber otl l>eole1 ime of tMs<, liko ~lIc '" ': .1\! rr~ ,n a mi...... m,,~ 71 from r hcnyl and 11I/= 105 from mcth}lhcn/,yl '" bon~oyl (Uni ".,...-" U~ 'f Fi ~UTC 5.4 ~ . c a n un1 ........n. l~ experienced interprcrcr ""~", "'l'~u ~m~ 140.1 );10 ,lilT,rcnl n,a, ,, 'pew a r\fd .... fl: rI~ ;011l tit CJ r efu ll ~ checked. PII( n> i n~, ca p ti",," . ga, l 't, 1and cll,-omawgm[""" Cf~ umn f",,:Lingo.. Thus Ih.. nOlf It ~p in \"" inlo'l''''la Lion oflhe ' pc-le ,lruoLural . ilni r",a,,'" of ~ II imporla nl f'C<'h. \Ii,""," mot ' lhan 0'" poSlihlc inlcrpretalion ~ XJlts. be , "IC I" nole an " f lhem: ff Ollie!' ev id .nc ~ ;11 10" '1"-'" trum elirnil1" le, " "",,, ....' "' ,.h t>c.c ~bil i tie ,_ thcsc TemainiT1 g will be much mote me.nin!:f"L r ,"";hlc ~ ";If", ... nu lor 10m are gin n '" P'lrl of tOe ion ..ri.. ofTahl..· A.... .W..." S,'<" -l'''/ C""''''lio'', (McLa lTcrty and Vonl atlrl,III"an

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'" 19821 shows what elelllemal compositions a"d ,Uutlun:" arc p""ihlo for a pcak, and what the "elari". prohabilit}' is for oach of these postulation,_ The Important Peak Index of Ihe Key;,,,")' of Ma.'," Spe"lral J)ara (Md.un.rty "nd Stauffer 1991 i pro\'ides a listing of compounds which give a particular m,/' ,',,-Iue 'lS the mo,l imporlant- 'econd mo,t important, etc" peak inlheir spectra,

5.5 Postulating possible structures Oflen [he 1i"1 '" ,Lep' or I~" Slandarc,lw concentrate 11,,1 un the ,truclural features indicated tho most clearly. Review (or 'veir" down) the general type of fragmcntali"m ,,,po",od (imide had oo"er) for the indioared substnlOlur"S 01' compound classes. These product ion' will appear in ion ",ric, wh"", ma"e' depond on the size and kind of sllbstituenrs: such ion '"ries ditTering by CJJ, groups were discussed in Section 5.2, hut an ion ,OTic, oan "lso contain high mass ions from sl'ec!/k cl"avag"s typical of functional gm~p'. Now chock tho unknmm ma" 'pcdrum for il' m"'l important Deaks belonging to "aeh of rhes" '"ries, and use their po,ition in the series to lin'it tho number ofmuotnn~ possihihties for eaoh correspouding Sll bstrllctur" or compound cia". For e,am_ pie, in L'nkn(}w" 3.1:1 there aro strong indication, th"t thi, i' a chloroalka"e' th" alkyl moiety accouuts for rhe peaks at mi. 29, 43, 57, 71. and ~9, and tho ohloroalkyl moioty acooum, for th. peak, at mi~ 63/65, 77i79, 91i93 and 119,/ 121. Mechani'tically, ,igma-bond ckavagc at alkanc bT"nehe' ,hould be the mo,t I'\cil" dissociation pathway: the important [>Cab in thc'" ",n" at mi. 57, ~~. and [I 9il:' 1 thus ,hould repre,ent the ,,,h,titueuts C.1I 9, CII,CI (loss of 49), and C,II" Placing these on a tefliar~ CH Can aomunt fnT the m/z 14g m"koular ion, making thi,,, possible ,tructure of the unknown. In rigure 5.3, the "obtcd mi= 47 peak indioalCd that this might be a formate ester (S"ction 5,2), 'vI"chanistic.ally. the alkyl functionality w()~ld produo" an alkyl ion ;erie,; both C.H'.+lO+ and C.H'._jO,- product.' at m.'·. 31. 45, 59, 7J. 87. 101 would be ",pcoted, ", ob,er"ed, ACak< in thi, C.H,.' "'ri" ,h"w, the higher ma", ""d thu, the potentially more important C"II,: peak. Charge migration i' favored ",or charlo'c rotonlion (ScOlion 4.9) OCO"U'" the ioni"niOll . nergy of formie acid. 11.3 e\', is larger than that of alkene, (9- 10.5 eV).

"'nOS

'" 'lk ab,,,.., '1C'p$, ;,,1<1 ~ II ulher H a il~blt mlo nnali" n, .h oul d be u lod fim to w,l . 11st, uctUJ<." , ,,,,<>-,j.a bly possible , r-or """h "", io", candid"te ' 1' ....1 "''''. predicl ;t. , ,..:d rmn from the app,,,...-ialc di,"","allOll mcchani, """ =d compar. Ihi, " Ah lh. unk now n '!"Xl, . m tarrlullJ . Th e d im; na l;"n of all bu r OPe r><,>.i l>i lity Icr I h ~ molecular m UCl ur~ don nol, of cours e, p'OH tha f !hi. 0'" i. oor r . ~l , P ~ dlClicn 0( f[ "llJIICn l~l j ,,,, I'" l hwa ys becOmc1 ;n<......'ingly dillicuh with in _ c re", 11l~ ";IC or a molt",.l•. F o r Ihi•. ,c!crc nre '~lta I re p;l rtile; hy fa, l ile lar@es'ayaik hk prlmod collection ;" Ihe ,Il a; iabl~, tr}' I;Olldo t;.. ~ . he n*r. ..... . peClm or , imiiar mok.ct ,iu . R<mcmbor thaI abuod om:c . .... ..... . can >ary by more (hon an 0""'" of ""'J:nit uJc bo(ween

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."ignrncn". Follow tli" "Sta ndard In..... fII''' 'a'''''' rIDe" dm e" in all""'pling I" \lm c(m", (0 lIn ,n o,om, 5.14 a nd S,1),

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fimi"" ;" ,,• •,fllle IlnlClU, al info n n m inn in t he "..>tInal rna.. r.poctrum elln he .,..rtJy oIJ~1 b)' l ~la l rna,,·, pcclml techn;ques, _ " llho l' ih" ...,mrle " de-'ICIlplion ,,' l"'-"" i, t>.:) M d t he scop< of Ihi, b<w ,~ . ~(I~ . hould h... .... a bIo,;e " m ; "" , il ~' \Oll il thell c.lpa bilitic, .

I,ow...,,,,,,!:.>' dUfF"" ~ja:,u... Lo"" 'll;I l l>< """"-n 0' the bomb.'rd in~ CI"" ITOn> (o.g., lO \5 i V) ",~J also "'''..r tho . ""'''1'<' It>ul ,,,,1 1M mmi",umj ;nw rnal O1l orgy allh., molocul", ion• . Such low-ener, y M - - tons ,,"-n ai, ,, b< rroouced h)' f>~ l ~ ionil" uo n. cn.. ~ CJlCh.1 " "",. 0 , p/lo I01Oll;''''li, m (Section 7.4), Fo r ", w , la' o <'I " " d d" iOll it is ""'1Il:tIIn<:>. ••• d ul l< . ..hmina lo higher-.n.r~y r..",,1'''"' 1111' $ " "e l<'COnd a l Y pr" d l>d io n, 1M' ~ ~ IOlICh 1<" ",pre,en tal; '" of Ih.. <>, i,li.... 1 ' ''....1 ,..., Ho"'e,.,, Io",er .lectron ene rgle, i"" ",a.. t il< re1at; ~a ;dlundllllC\' oi " rim a ry

rea l mJl ~ emc n l

, caeli" ", (1;eet ioll 7,2], F u r\h<;<. I.. ", <:ring d .. e~lI<>O

.....'ltrd <:C' n .... lite ub.",lure ab l1 nd :l nce ,~ 1,1' i<,n, ; . JtllOtlgh tb< "'&>Ii", ~" u n · ,I;,nc. "r (he m<>lecular ion incre" ",". it n" . e"hel~ IS noo,.. d lfficul' I" .1<,.." 31 lC""f f eleeUOll .~c r£ ic , (unles. it h. , hull o bfo; ~ ml I>f fragment illl" frnm a hi~her-ln ol e""lar.wcitht impurit)'~ Lo",~,int' (he molecu" ·, eneliY !s,,"h "'with ' urc'T, ,, no: e, pansio n. Amin...- t 'I'l l) I\di.n: ;
<_",... .

r.E' "'"I,,·.I"'.f'«k1 Jr- N O • ·Iiotu. T he mo,t ",,,,,,n on method of p l'odncm~ e "' able i"n ~""' ta in inl': lbe .am ple m"k'Cule i. ta react it with ~n ioni>'C 1<> p"JJ ~"" M il' ions from coml" ' und, Ilot 1ieldilla; ... ,. (Mc Lalinty l ~ n,,~ ( hemic. ] i" niz"tion (el ; ,ee M unson ~lld t-ilecu.... l hal do . 00

DolLyield ....>lc<"u!;O. i" n, by FI caD proo ~ ce CI i""" jLK1 icative "f the moltelll.r CI ronJ iti"m. r JOLlu." ~ b undanl therm a l d cetrons, gi v;n~ high ly em. """'Lclccuoo capT" . e l", negat ;"e ion formatw u from electroMga tive moJecllles ( ~i l'Un' 1.2. 1'1........"\ ;,;..;,,, l iJlll, l iJll3t>: lIo" io 1994, 19~9; Hite. 1988), R•••ntly a !ride vari"t~ or po ....rfol mcrh""" ,'" 11>0 i"" ;...-. llo,, or l~rll" m" lcc.lc, (c. eTI " r mt'd11 > ro- have been dcvclol"'~ : n>oo t y..ld st,ch [P molrc nlar ~ /!'.ct:l;,m to .2~ "'O~L

c.-.........

n-. ,..", ("I lhe ' ''''I:em lIilS R is introd uced tnte the iou SOU!QI1 ( _ 0.5 Lun-. _70 Pal al a u """",n' r..l;,,n in I;o,~e e.-<~ (_ 10": l i to that oI tb• ... mplc, .and is ion ~ by .""'ltOO ( _ SOO \') h"",h;" . J mcD I '" d ' >I:, rK; ,Ji""M ariC (HUDI [ 915~ Thc R' ion, 1O'l' Iny fo, med can . eact f'ln hcl ",'lth ,-,tilt . R hlOle· cu les to form reaCli... ,,,n >p<'CM." lh. , 1I,,:n aU3d , he ,.,m r le """ cl:\llc M.

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.\m " n~ ,h;, wi"" va.-ict) or p......it>!c 'OD'U I"''' re:>ctJooo. the mo,1 com11l00 a re: rroh' nau<>n (I!q ualit,n. 6.3 . Dd 6. 4 ~ ..hir h i. ra m nxl f", .."'pic mollX'ul"" 01proton i.:ulo.. l>UclI a. aft an"" amI cha, ll" eXd llln ~e 16,6). which il fa ~O<M for rea genlS of high ionizalion """'ID' • •U(·h ", hd ium Th e ;nleTna l e""' gy , ,( th.o , ,,,,,lung ;OQ,nx1 \I """""" depend. on the reagtflt choocn arid tilt ion ,. "",,"" lCftIl"'nermic Of, + reacl;"n. an d minor I'm (he N H ~ ' 'cae-1;"o. Such uoimol.l:".1.", Iragm e"lan"ns <>be)' tilt mcoha ni,,,,, outlined;n Chart." 4 and R; til. major m.iT I J1 l' rod",-'t ion;" formed by CH"CO OH 10", consi,te"t with Field', Rule, PA(CH ,COOH) _ ~ . 2 cV, I'A«" "H ,. ) _ _ K7 e V. The m i2 IS4 product ;n Ih" "IH .,/C I ' 1'O.:l rum corre, po LK1, to CH ,COOH loss from (M +- NH , l" , Thul C l lpcctra Cil D pro"ide " ' Ul: tuTal a, well a' mok cular weight inl",m;« ;oo. Sim;!ar Cl ' ......1. 11. <::la

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6.2 lanl ntlon ol lallle molecule .

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w lli" enl \'. 1"" prc''' Uf<: lOI> M >a l'''' ;' '.... m ,,'" i,m ..",,,..,. T I>'" "". ,'erel)' limi" tl>c awli,:ati" n of m,,~ ' P<'C! ro me1 TJ lO ,mponMI ';Ilm!,l", . ~ch ~ > ",,,lo g;c,,1 m""rnm " I",,1lk>, 'oo u" na l pol~' me r s. and pelra leu' n ~ d lLt$. I nl ~ 1>­ , i"e ~m re;e arcll I'r"'8te>.< ha> ",." Ill..... in hight, u..,;rul mc," ... l.. Tloc m."" widdy ".. ed brielly IIOU: m.l" y ucenl refe~ncn 1'>«liO!l 6.8) ~in e, t"n, ",'" del~ i l, F~" 'I-"',,m h"m6"nJm<wl r f '-t H) , Inl!'V
...

..,.a...

for m ()I " " ~I: or wd ~ h" "p 10 .. ~ U kD .• j\l.-'lUlams rt ..J 1'ilI7: To...,... l'l flll). <\ . oJlllion of the ,~m pl~ ill ~ I" w-' ,,1 ~1;l i t), ,,' ul, i, ~"",h .. ~ly""rol is bombardN with f. , l, h. :I>')' ;Itoml (e . ~ .. X ~ : ions I uc!\ R' C. - ~i .c .i mil", rL" ul..\ in the ioll '>d is ~~ ry con o~n i~t\t fnr ~Pf''''rria l" ,~", pk... b"t ma lr", read,oos r md U<;<; b:l ~' ~r"" n" ions >II neal'1 y e"~ry rna" oa l"•. 1'1.o 1~'" Jt$" rplio~ ( r D ) ":" " ni ~ ,,,,,

wtJ I~.~, Jr""p';,,~ II.D). TI>c"" 1"11""" ionization

an; p"r l ' ~u l all)' 1";labl. for th. tim.-of- nignt i"'lr" mrnl.... b ;c ~ ,,",

aJdll i<.>ll~1 aJ " "1Il4~" " r unlimilem ;' ;'lg lIj(n"i n ~ " ".'cn I ~~ ~, K ",~, '" al. 1999; Hill.llka mp eI ai , 1991). PD. pio nocnxl by ~1 ~ cl~ rl~ n e 1 l 9 7 6 ~ fLr<1 , "owed ~!l" t m ~" ' pcelf:! could I:>e ohtaill.d rou li"" l, r, ,,,,, L,' lI" m" k ",,"' ,. Fi"ioll of " 'cf produce, two 10000M "Y pmn frag""ll1at i<.>ll, rO" i,,,:Hion of m" lec"ic, 'IS large a, 50 kDa ..i,h ''''''"'' " ",,,,unn8 c, m " "r ± 0.1'\: 11<,,'. boo. ll reported. P,o l- rin" Jas< r dewrplion ILU 1eapa nilili"", iP,,,thum,,, <,I aJ. 1978) haw hw n g n;~ I I)' C'I,.", l.;,11K ~ n" :lnd Hillenka mp 1988) b }' dissol ving Lhe , ,,mpk in a ""Ld mal' ;, Iha t i. a higt.lJ enlei.n l :It>..-.Hboor ~f the la, ~r radia tiM . ", .., \ n IOnIZe m<>lecnl.. ,.. LlrF,e .., kl)a (Hill cnhml' '" ai, 1~ 1 ), Tho at>.. n c~ of m.... " . d lect, aDd rna.. me".." ,in g errors o( ± O.O!~,~ -0. I ~,; ma'c UJ " pan icuI.t' ly [lfilnu";ng method I",. pTl.Hcin ",i. 1O
1M

3\_,

Lkn"",,..... imU _ _ ( f'. sIJ. !"i.,....,l. d b)' Dote (Dole <J al. 1 ~ 71 ~ Ii" ~. S J " $oluut>n or . Iu; ....mr lc " ' l'Tl'Y"'-1 ~1 al mosph .ric prcm ,,,, thr ough a ." ," "' al· IOlOa rd lhe Ji fJ",,,n ~i a U~' pllrnpc:d . nlta""" to the kilo. oI. poI~ "tia . diffe= rna"" 'pcctm meter 4,>milh et al. 1m ). TI>c =u lli"t d"' r l c ~ , :1'" ck " rr". l:n i. call!' cM rgN;:U the ...J.""' .~~ I'l>J~":"- ,*,--t, ost" h. r.~ulli~ u prod ucei "H"t~r and , ,,,,,II, ,, droplet" no bl I'" macromolecul. ;. ~' l"'II",1 H",,~u"l":d" with ch rg"" (h nn e' ",- l'IllIII Thu. a prolCln n b«Ir J protOn ro)r ~ , .,. ) 5- 17 amino acid>, yield i"!,, peak> ... ",.I.. !lI.l---20 ~ ' ~.,, 10 1 ~ U)" pN lerni tFent "I

......, _. "'''''.'.'.' al. I'I
~ i mild'I} .

,

."

P<, I)'llLICle<>tid.. Can yield

n.~"li,,, io n.

of .uch mi. val..... by

a propo,tionat e llaTl' b
fo r 'n/: mc.'u,u",. nl mak.i ESllffi<'o.1bl. 10 mO'>t I l'''''' of ........ ' 1""..1rolt\eters. I' ~ I rna" ~~ctra hi ' -" bt(n meo. , u,w for .mol
(IeR) mn~ IfleCfro"",1 '~ \~l;"n l.l). [;Sol ,pectJ'3 of myotlobm

(1 7 kD aj , h"",

'Ii ~U ~ _ ) ~'I ..i'lr PO" "~

. ,Id <:0.001 D4 m~""""'-4.urinJl' . rror.;

(lk a d "I, I9'<J)

P'F",Ir-" ' . U...-Iul l!I"crurll in!o, mar;o ll "ooU I ,~ .... pl• • miu " . ,.,. "r hil h m.,. J. cub r ".\~ h l. ,..,; h .. !;>;o<.' c. i. , r L. nl .!"-'cimen.. ( O.flL high poIym., ... aD"C1I. "" Iheir 1"'. ..... 1d"",m,· po, ition plOd llCU (Mttae" Ar ~f " I. 1,,!\Il, 1 ~1lU: St.-h uhe n 19'16: BaUislJ. ' " eh A' <. pid 1(. healln ~ af • wi", to iI' C U rl< ' en' f" U I" ' C l . ...T• •"" .k , a nd .>l h.,. ~.>1l ·he.lti u~ methN l h" "e " I", hccn " ...'<1. Of raft" "lar j,.,erelt i~ ~Il au ,o mal-N ' r 'l'' ''' f.or "mt;n u· OU' pa ft id c beam sa mple iatod ""'...... ,.h C uri.,.",rin' r , rol)" ;l in tbe M S , 'octlUln eh llef. Tho. . y........ ~ n disUn3u,s.h d, ll"uem ~ t " LOS of bact. ri;<, rCl")(ting ", It<..cry 15 . (Snyd er and Hard' lI IWll)

...1""",,"-""""1 or lhe mas; of an ion .. i11l , ..tf",;"nl .<>c"r",,} p",,;de. an a llcq ui, 'ocaI identIfic.olo on .~ i1. c1cmen.al i. nd ....'."ric) compol;tion, Th i ~ technique,. of..... referred 10 "" Mhigl> l'C'>Oi " IJ""- mass .peeIJOmet!)', , ince dnuhlc10000001lIg IFi gure 6.21 OJ FTilC R (Sct,"'\ io" 1.3) in,lrm" Clll< a", L\IUa U}' used. H........' u . if inl,..-k. ;n" rna_.,. .cquirillg h;~h t.",lution JI . ab..nt. 'U~1c;"~ ll y ",-"u", lc ma... m."snremenl. 1_ 20 ppml can be aehio:; ,'c"d r", I",. ,.", . " ions "'lib singl. loc:usinl or Quadrupok in,tCY, F;KlUC

"'J""""t",

,.

l

\

h

"

~

-, ,,. ~.

... 1

~ •• •

- .,

•• •

~ •

•

••

_ ~ O _ •

,

•

••• •

a . a • •

w. _ • •

_ ~ ~ . '

• • • •• • •• " __

0

_

0

"

Ii

"l o • • , . _ 0 • • a . _ • • o _ "_ • • 0 " . _ w w O .W _ U _WR" . a . ' • • • • " 0 . _ ' o a _ • •

':" 8 e e • • • • • • • • • • • • ~. u 1 C':: U UI :I =:I J I . n J II~ • • In i ~~ : :

,

01.1 • • • • • I " \ ~'\ :

,.-

.'gu,. '-I, {' ltJ()ro lh.> " , h

(:. 3 """":I Ih.

,,..__

M '0ll"n . 1""", .00 nOO

n~el

--

<>1.,....,,,< ;0'" of m/: ; 10 <""taining ea
ll1 ." 1_

b~~ ", S't ...

Ml

''')'!I''8 . ,.......

ffi. '6 (If . ,-ariely of posr.ibll io:>n. of m Gl
d i<, iG~lIi,hin~ tho:;", '"~lIi t'<"1

, .• hndem rna... g ~ (MSI MS)

"Ooubl' (c.(lna""'· locbru'l ' '''l. re _ i' LlI in ",veral .peClr"""""" met hod'" In

r",

mOl.. "I'''' '''''''''''ry thef~ ale an;,.I,'l!" u. MS,i\1S techn;~""" ~~"'fill ~ t ho:; maS! .pectru, n or ~ pcal in a rna.. Ip O ~t rum , S"" il """" ndary IlmfJ>..."'.... l.ar io n 11"''''''' '» 'h"u kl be tilt ,arne a, til""" rfl>Jueing DOnnal m_ ' reel/a, MS/M S h, 1"'0 m8jo,>r app/1 em iom (McLafferty 198); Ru""h ct al. 1 ')ll 8 ~ o..c applic-.,i"n ,"'" the first '1'<,.:1"'......". (M S-I) ~. ~ ""I'~rat i l\~ device fm m,"u' O'; soli iG D i Z ~ l j (m pm d ucn \t" . "" a , jrnilliT m"lt:c ula r l pe~i ~. fu r c",",11 oompenent, All"r MS·I '"'!'3-ralion, ~ln i . ~dded to MH ' 10 y;clJ J........ cialio n l',oo ucL io,," thaI ,,"" lhen ..., ... 'aled ill ),is- lI ; thi, rna"• .ptaru m " Ih"n u,cd for ltftJC{un1:5-1, fm gm"nlc'ti t>r ~<Jd ;njl: • .,erg)', ",,,l tne I',,>duct iollS ",pa rated ,n MS ·lt to provide n" arly 0011>1'1110 KG""""C info rnl" tion I M ~ I ..alJc.- , y el ,J. 1970; Wipl" . 1 ,,/. 1913; Iliem~M "nd Marlin 1987; T"nlCT I'l H9). lbc I~ ml<m ,h'u~l ... lo<:".in~ m"... ' peetrn inet" l IMe La ffert}, 1'l8O;> 1 1~"U pro....n J'I'o, ticularly "Jln a1:>k f<>t th ~ "'ith F T/K R pt<>mi'ill g [o r Ia"i"r pept i<\c' Llie u cl ai, 1993t The m,,,1 ",-jddy llsed in,l,um e" l for ..
m""

f

""to'

-1

.,---...

n.

'

,

..

,,'ICd . Hj~b~ne'n l~ .~ .• 10 h Vl ( :A C~I1'C' di"ociat ioll (CAD) up to ~ 2.5 ~ D a Riemann aTI ,1 M ~ n; n 19Sn bul of multiply cba ,ged ESI 'VlI\ ~' Jar~c a, /Xi kDu (loa er ",. 19911. t he """.n"" n. rJ · Loni" ilion (En mal. spectla. m""'uring MS-ll m ~ .... ' r-." u" Jt<:, ~. ·. f. " gm ~nl iom ", chalFLCle lilt' thrir struclUre , (Sh"UnOll lAd Mc L:o(k, ly l w.;.~ F OI eX;ln1v1o, ill LM rna" ' I"' clrum o r , he h yp<)l h< l i " ~ 1 m ~l ... u... A, 8 , C. !he ,,1 i" ", ~"rrespon d m g in rna" to AB' and ,, 1;(;' co u ld indicate "'I~er of the mo tt.:ul"" /I, II e R A or A .. Ii R C ·,· A. 1!00l,
pu;;e1''''

\rum uf the Aile· fragJn<'n! ion ,"",uld Ix: P"S'iWe. b" m ng ,. arra ngemenl", lho , Irud ure A B--C - B- A. In 11M; m ~ .. , pc<;'opropyk;" · hutylaminc (Fig"", 9H I ~·de.l~a*"e'S $"'" the "mminc~ \ ' on, ;01 ... ', !ltJ ~nlDl'O'llions yield " ,htr a1'>en b.ll} H,"" <\'Cr, Ib" ~ b"" 'V"l io " " f "',i. _\ ~ in toc MS-If .peo:tru Ul n ; il, ' I":<:l....m , ho..I"- . h",. nt!~ 11 4 • "'i t 4~ .

r",

b.n

,

O
,. (Cfi, I, CfiN C >< , C , ~ ,

!~

- C~

- C, Ho

,>

,

I"

(6,' )

~ ""

"

GH,-i fiC ,Hr CH,Cfi;r

t ,. ,

'",

~~ ",t

- C~

'-"

- C~H , o

u<,a<1,X' ~ ''''' ",', ee

I"~

CH,=t fll' z 44

11"

•

, ,-~

., ~

""',86

'",

I"~

nu i5ll

"''' "" ICfi, I,C HN=CH,

, Cfi, CH= N><

"

,

i

(h _~ )

H

H 1 = CH

'", "' ~

,

l/"~' IQ .. n ~ .I .

Tty l'non"""n 4 .1~ al!am, u >m~ lhe me,astab le ion (m Ol dat a. I, '" l h~ 'taelll1M m, ... m,.m' - m, ',"'' ''1' When run undet the "" me c,pcti""'nla l ~~ m ol i li m l'" lhe nor mal £ 1mass speclrum " r & p&rli. u] at mo leelLle. "Leh os loillene. i' inde pelKlent at the sample', source, alld can thul serve a, a u..rul " fJ n~c ,p ri n f' ror iolcn lir,t alion, III lhe "'Ill< W&y, lhe hir h-oncrl'Y C,\ O , pce' TUn\ (Mt L&llerl)' e' oj. 1973••bl of a particular ion i. \'inuall)' ilKlepelld

cc!t llm (Mcl.afferty Ie' at. 19~Oa: We'demiNis ,md M ~I ."lTc rl y I~ K 7; Holm., 19S9; "1cLalTefl y I '>90), Such dissociat ion of the Unkng.. . ~

' .a

'"'

". ec " .,'" •• ., n'

0.' n'

"" •""

•" •"n " ••"

•"

",,.. '00

....

,

U

"" "..""

., "r.t " "

,...... • ". .. U

'00 - ,

I,

!"

•

.

"j, , ~

•

" •

• •

'" '"

n

•

'"

,n

..,

., ....;<;.,.t......,••

corre;;pondinll n<"lr~ l. call make po"; h l ~ l ~ " q """tilati~{ = 3':',. in Zh n ~ n a l. I ~ g , I ~ ha n<: l tri:.a h.>n " I i,m. !hol iso",<'rll" e~ ..jly,
I",lrumcot '~" l e m , con' b,nmg II ~ ~. ~ hrcml ,ll oll"lph and rna" ' p«!lOlntltC (GCiM S. M c L~ IT"ny 1957>, G " hlke I')S9, Mch ddcll 1973; Gdh a m ~' uJ 1\lM, K3T. ",' and Cl~ me n t I ~ HH ; Md ..,lJn t, aoo Micll""wK;z 1<;'ol<>lI t",1n.ud\.. r l~n l e, traets, pollut , nl~ i" d.....ria l PT''''"''"'. and sam r b lor fo"'. ...'" .t l«l~. Wilb an on-I;"" "" n,!,u"l. useful "f'n-" lccuk s .. lal~e J \ _ 1.000 da llon, . Ot ltef '-"' Y pr omisin g co mb; ~ ~ ti ' >fl tech lliqlle< """ , ...... id S ' lelcctian with ,upon 'll ,"",1 0..00. c hH>m " lo~mphy (S'niln "' al. 1 \I ~5; Choil t , anti Pink, IOD 19901 a nd "" p ~ l.1 ry - w"e cl.,ca" r nnr c, i, (Kuh r 1990). \IS- M S was de"" ibed d""c

"w..

l.ef>""" """

'.6 The _

......"...

Of!"n Ih. ,,,:k" l;"'n or a 11 ru",1i,,,,, L1 ~ I' O U p to a large m" I""'uk ""'b as an a lb l" i,1 ~h~n~e' tbe 'P"d m m•.,.el y h~ ;n,r.~,ing the rna"" " f ine .~f", ;"'n lr~~m.m, ",'ni" n mn l" ill Ihi' fun"1,ona l gt<'up. !>u t without greally changing Lite ",Louv.: ablludallc", olllle,", i"n. ~",m.pl~. An ohviou, e~~ml' l" i, i' olo,,,,, m t>Slilul; '>n: deuterium labelin~ of a ",'ml"",nd iJlCf"'~ the mall of ea"h io n bl' (>fit fOI t ac b deuterium a ln m tllcorpo ralN. but u..,h 'l'\' .'ffcct, CD ion I'elat" ,o . hund. nee. al. jten."all ~' ,m~ l l. R"plac""",enl of a hyd,,,lt"" hy a ''''>Llp of low lPO"",,,,,, (,w:h a. m "'b )"~ "'t tho, yl. or chl,,.-i"" l . , a ll unrea,I ' " ",,,,ilion (for ",,,"' pic, . ring. especiall) ~" a'olll "tic ring) often gj .~.. inn abundaIlCCS 'imila' tn Ino", " f the oril" nal l peclTu" " I I, jng thi , to diloow r the nature and J'O"in on 0( " , ub' lituenl ~dJcd I" ~ ruolerole h ~. Ix: "~ l"rmod the ""hift = h ni<j llC~ by

r."

lIicm ~nn l . \l(>2~ ", ho, d<mom lr~t.J ii, 8"'at uLi~ly \ he ind ol. alka loll!l. Th e.., ,!Obit r;,,~ Sln lClUl'", ccutllU fU G~tional Jro~P' lhil ' lronyly inn~ t1>c , minimi,; ng lho clr<:<;l " n the 'IpL;;lru m "rm"Ioc'Ular .ub<.l ilu. Lin,,- TI.. rn~\h <>d; , I~" USdlJ r~r n.., i«ule. conta ining I<' s·..,nuwnal gr<m ps, ..ocII as t~lpeU
to nknown 63 . The spt<:lrum of Ihil unkuow n illdole alkalOId Imldd le) i ! computed to tho sped,.. <>l t "'C' l no wn ,lru ~t uT"C •. Wh..1 r.....,Li.ma l ~ ",ul'> d,,,,, the

A, . ft;, .

I

-

,..,

,..

'..

Ii

,or ...

2Z>

-Woe

, ,'> ""'e,J""~""~I ,.., "'I"" ,., , ",,. , ,.. ~

iJ" j :

, ," i!>

'00 {

C

_

-

- ...

...

·.,.....,..... , 1' ""'~~l

-

,. ,., J,.,

.3

•. • alP. Il, . CH,. Y. 0

_ _

l"t... ,.,. ,. . " i,. ,. 1,. ," " '. " I I ' , . ~, 1 1,. " ,,. ,.., - •.'" "'~'=~~=-".,'~_...:,,-...:,,,h,..,\~":~~"~'

unkno wn ..~.n ,~ i n~

W h ~"

a . e l"'y m_

probobly I""",ed , .., ' he "",I<:cuI" ,

.keI Cl on ~

(" hcm ;"'~, o.m,"",",.., or ~ " """,.u nd If> ~ n aJ'l'f''I'''''''' d t ri\c. l1~ CoI n >(>fOt" 11m... lmpT","e the r~ lllDS ma'l5-spc<'l . al mg 1he COlli" pound", V"I")T I"",'u' e or by ml1all' " ' Ih the de't lopme" t of IOntul ion mel bod, fo r .lOo, ·olatile oom p.>unoh (Secli"" ... .2~ Inlr OO ....1 i" " or a 1.."",jo". 1 ~p ...1ucl1 ...-tIl stro ,, ~ly dum lbe rra!UDenlat ,O" dor e. ample, ami_ Cl h" ylcrJe ketall ..dl , uborm" I,Ol' (Anok,," l'lgg~ T hIS co uld be uK>.!. for u . mple. 10 .:. (r~l"'""'I.I""" i" """ nr 3 ""'rold olOlccuJc " bool wbich . he or~"al lD8" spedrun, ~vt hllit ,nfcu', MI;"'n

n.e

{Sa.1~ m 'oI "'~

a.

.,rue,,,... Ic.,u,,"" 'II'-'"

Deri. a li"u ion ca n be: ....". a d.... ",i... 1 ~ I kenle. ,,·it h ,"" mau spc<:tmrn of t he IUb.fqUCltl product t1scd l: jl IS only 1M m. ss. (nol the ...... 'i . c ab undance) o f the p",J IIct (ormed ..·;, h lhe 1.,11"'" " urn"", ..1 de ul," n unl "lolllS tha I neN ' to '" Gt-r.e" N . Sud, e.chall~ lI\.in8 ("I ioni.<:l' ~.n CIIn he ",,"le"""l y ",.n ,uo "·nl fo, n = r"e, ... Iu, H,O.. l>,O "r NH,iN D. ". the IQ1,izin~ ""'f"nl ~"'" Ilium ... «I. 1972: l la lTl" , ,, l'l ~ l. Pr. 1:t9- I], I

Beckey 1977; Bud de 19 N ; B " rH ,,~ .n\ e a nd ('u,tag",,11 . ?R}; lIu...t. eI aI ' 'lKK; C<",.. I?B. 1 ~1K De<Jra e¥e 1 ~!l6; facdlen i I ~U; Gu kfa 1'l 1\6; H.rris.on 19'1 2: Jen"-,, 1 ~ 7 ; K"ra;ck I~K.'i; 1...1 I ~ K K ; I ,,\>m;,n lWO; M,,
7 Theory of Unimolecular Ion Decompositions

To u""lc" l. noJ lhoJ ou ~h.l} lh~ oAl' abiht 'Q . ~nd « peciaUy lh~ hmiu ti.:m" of ma" ' pec lam il"" ....il h the ba,i. Iheonlio:.>J . ' pc' l, 01 \mimo lecuLo. I, ,,, """omj>Qloition•. J, ' ~n <.l '. 2 are ,' rr"'l"i"tc ror inIl OO llCtOl)' "" ulUI d..,i~nc<J 10 In cll rundamrn,;>1 inler p"' li,'" , kilO< rhe no mc nd;ot" n: . 00 abb,e"'" l;"n' ~d Oplod t' ..T< rollo", thoR <,of d.. GIANT mbk>c t Lia$ // " I. 1988).. ",Ii " .. iuu <>
*"rion.

Ionization o{ 1M " " " 1'10' m ule"" l.. ",ith 7tk: V elect",,,, pm<.l",-u IllQl"""Ia.

ion, ",h"lie ;,,1. ,l1li1me rgy valuu '.E) ro " " . b10ad range (010 ;.. 2 (l <: ·,, ~ " ••r_ ag inF " r..-.. eV U e V _ 23 kea li mo l _ % 5 U /m"I). In til< appcr ""n o! t.he W"llfh.rJ ig (1% 2, IQM ) di "gra m (Fi,iur. 7.11. (hi, d'<.Iri bu'ion Do J""""lbod by l" "h~b il ilY funell"" r lE). Th. 'M" ~ or ener~ie6 il dramalJC;j1t~ rl L"'.LaIly foll1ld. w oo n den~ - f'l'''''' reacoou 'J'''' initiaU) r",fMd M+- iOIl> I1Inse from cokl III ''t r_ Onl y ~ ~;_ I«lJlaI" reac';", .. ", 'e ",,">ltd. for th. gasoo u. it>t.. r" ,,"w b~ CI ,.....tl ~'R <"'""'t<>I:l " ~I. 1952), W;,MU. ~,, 1li ,.j 0llJl , it il rh. """'~)' " . iginally depo l,lt d lD the ion r" m, lh~ io niLIIlimt pro ",,", {plus III. "ffiaIl .m,,"n l mp"•• 0" ;ooll1 eriu , -flit i""hahili l~ '" .... y .ucfI c!lo n i, .X j>' ~ a' lh. rate cun. ' '''' l k. ",hich ol)"km , ij-' mut>! ch~ n\IC ...,th the pm;yr""" Kill'. I nt . m ~ l en erjl:y, L. Hy pol hd ica l keEl fyDctjuuo. lh Q'A'i~ s the <'h an~e 01 Io-'fl l wilh F. or" al", gi.-tn In h gure 7.1 (I o""tt ""to. w!lir;;h 1",",1'" that io... vi

,I><

".

"

-.........__._._,._-----

, ,

,aM , PIE)

,

,~

_lEI

,,

..I. __ •• •

'. ,~

...... n . The W"',l\;lfu,

dug_ I:

,01...<.,,,10,1' '" 1' ( ~1 ~nrl .'.1:' I,,, ,m;",,>IOCll'"

......" ' mp."'Ii'... < ~ A BC n" . s.r Icol ~ ..- ddiniliom

110.

end

I W. ~ rfWlj g

1%2,

;"n

1 ~ "6. )

"',,'.'-1 ; ~ te rn al-< l'Ie r:y ~ol ues 10 ,11 not loa. " apl'm:i.~"le de.:omp
in lilt ' l""'tnJ.m . A

,>I _ 10" • ' ,,,, 'Of len) L(l ~k ~ 6 on the en......, (H gnre 7.1. l ~ w er hair) f<: ""n i",,,,,, r"a~'!ion ," te, producing m.asur"bl. frag"",nl lon, ca n "" much te....~r in \ , ~ ppcd jon , ources, I h. ""tu" l iou "bundallc, ,, a,c Jcl L,minoo! hy hoth the 1'(1;) an d Ih" LIE) J< l.oli"", hlp.. Th~ rclal iye pr oponion of M- ' jon, lhat remo.ill undi!.5OCia,1'ld i. dc!«mined by th . lowe" encen teq ~irW for lOll 'ourtt di,~ "-;~t;,,n aM 110. ,.131i.. propo rtion of M+' ions for"' c
a;; M '

nl k: "" ....... 01

~",a l"' i, ""~"'''Y fo, ;0" -'10\1["" ckornP'J"irion t1tW I"," _ 10-'

wilh I ~ . h" k.-.l ar~~, .>f Ihe Plf.) eun e rop'" "'''l' nll l'''' . d .lln-e prODorl"""" lormed. JI It..· ion izi,,!.......~"m < "" ' ~)' l' lo...n ...... rh;' wrll ",.:. <>f ~ + ' ;01\\ lormro .....Ih hlghel mor~~c. II Ll.1\' Iha ll it .. ~n rednc. the numhc' ••( Iho,e form,,, willi ~>l•• r (no,. lht ~ 1I ...rt "'....., '< Pl f.) c ul Ve l_pre ..,,1 ("" inilLal ~ bun<J a l ",", <>f "' 1) a ,.u ."-B· , Th_ ioruo l d v..ith ",ff"'\cnl ' nlenwf ' '''' ' 11)' "ill Je,;" n, f'OU fm th. r: tho: .hu,,,b n= uf Ih~ r~, "lting p'od"~i 'm ", (and of Iht .. ndic. socratc rt AI j + ' and ."- B"J "ill (\c pc",j ill luru on 1M P(li ,1 " nd q F.\ ''''',l'<01I' ,., A D 'an ~ A ~ - _

,.../d".....

The hYl"<" M ' l( al J>, Icm "f Fi~ ure 7. •, in .. hi,·h [.,,"B~ ] > [ M 'l ' ). illu>tr~ lt' 4,,,,11.... '",po.>fl onl ",peet .,[ " ~;m"I<.,-,,b, rm i, r~ i •...J II>o pti. nUt.: ~ h. yield of Iht dno l'l'd prrulLJel ll' ,,"ugh '"killen. WfIlro l.n In Fi ~lJ.r " 1.1 II.. rc . c l; l'~ ~BCI)+ ' ~ AD- ' t1a , tho mOIf f.. ",~hk "~ll h nl py. bul ."U ( U · _ xe - hJ llllIO mon: f~ ">T'n hl • • "'ro py. I'he lra"",iou ""'"' .I'll ",I'" io b ll'lJ.'" 7,2 roo' d .nc " "",iot>< ,.';""-.1 i,,, lh.. bcl, ~ .i<>r, 10 Ih. "' ~ ru n~". ml:..1 I'trlni n ~ AD ' I""••",,,, bond' "rt r"rmed. oIf. n oerilical ene'lYfor ,\ll + form1' ''''' i. h;~b.r. "'00;>,: Ih;. '"'1ui,.. B C d .av age. H o ~'er, . he . I.. requ i ,"mc ~t< r,..,. AD " 1"'0' 41'" '' at . much mu t . " riel than t"~ ror '\!J - [u,m, li" ,,; i" lhe I .' mm " l, ~ oft~ n II IC<1 (" . , uch lroll,il ion "'" ,""- Ih, ,,,, a re, j'<5P"Cti . d~. ~li&hC .n,I ·~K"<" ""i' ~tro camp...." FOI h,p.-r-",,",gy ~ lIcn ' i""... Iht IJ- C bo nd dlS"",,""'I..,u CaIl Inke pia•• ""1" '1"", ,,, sulficient "ner~y "=",ullo",. . ill II,i, hon d, Hu"'. ""•. (01 A1) " r"'rna lion, , "" energy r< q ui ' ~metl lll m" , l be "'''I al the , aIIte lim. Ih. l A ~ nd n ott.

'T"

' --

-1)"·

\e= -e'

"'---0. '

•

=<0

..

1 / ......... ..-.. .. _

_ .h _ _

~_

•

wi' hm """"' 01: di. tanu:. whi""""".... of AOCU ' '1......, othctriDIl eo lh.olpy a nd cRlro p' - elk"", in ,..,,,r ,,,1 1c...J I" ~ ...t>. .o n. lial DU"'bc.- " f com"... ;", pri",~ r ~' r"""" i, .... n "",nas the ........."...." >eCOOdary ~nd f" n lt« .....ctio""' rh". t he rna", speeuu m of 8 Ll qo;t ~a D ha~ hnnd~ ot pca ~ .. lh<: """,peti, ,,,, ""lure of too..: , cact loJ'" n ",ra n Ih. l

mol""" ,

."ut"'''"",..

rclo". e ly ..nail cha" gco in mo h "lo.' ,,11 ;n lo r", oJill ,\,n"-':1 in po,;a~ """",lam"",. I'm Ih i, <e>.on , in intOTp ret:' D: 811 unb lOw n "J"X'l",m it i. horIpf", (0

stud y Ihe .pttcra (I( cI
~

<X:'fI' lJ<:lund...

1.3 Ou.as i....q whbr"""-., TIle 1am ou, qWl';""G U\~ brlum I b«Il'}' ((.'I T~ ,,.,, i,,,,lI, r.o"" \Il:I\«l t»' Ro~L Walle""''; ,,, W. lu ll aft;g, .. ud E~'nn~ ( 19n~ .,,,,. ide. a .' " y. ielll <1""" -;1'1;"" " t m a",,-;;poc!rul hc h \<;.", in al'pl"o lim atN}' tW ' · '. ,n' ualll };.I ~, t he .' ~l\td mol""" l.r ion with out cha Ll~e i" bo nd I.." ..., h (a ffa,,~k -Con dLltl l' ''><:<:>' 1 h· """pt fur th" ",,,,110Mmul<,t:ub , l ", m i ~ ,m , 1x:1",... n .11 tt.< f'O'I" N~ ffl
of lhi' ioll. a rc , " ffi<1<: nlly rapl d IM I a · qua ". hililic", " f Ihe ,'"""u, l" "" ih1c ,1"e,..m l"",;li",,, of ~" ion ~d (o "l~ 0 " it> >.InK'ILl,e and inlernal energy, a nd nO{ on the m ~l " od uioIXt fOI lh.llllllni ioll iu don, " r on the ,Iru~lu~ " r lbo precuL"lK'r for, 01' fOl mat ion n"",ha lli"" <Jr. \ be i" " ~lHk f ~ u i lL~ Joo" mp",il i"n. Th~, " n i"n ', d"""m!"",it inn d.."..n<11 only Ofl hs iLl I" "".! t:I>Cr~l' an d ii' qEI fUn"li~n< , Wl>cn wo 111 0'1''' m""l1an" !1C4lll 1I1c me lecul., LOn wilh a 1'>ealizoJ char8'=' an d r:l,<\i cal ~; I o , it i\ not n ec~ " . r l thol th" i o n ilat i~ n a "l~ any "" n" , o, an d cc1ro n " l l.h..1 , ilo; , hi, i, jll' l " 01 M" "' pt to depid Ih" ground ~kt:lrQni" ' I" t~ b'C been [" uoJ IQ Ihe Q LT r he, e " non_c r g nd i ~" (\;" lXiatioll5 80,.." ally i"y uhe 'mall "'oJe"ule' (lewer, m"" o widell' ",parat<:d ' Iatc, ), o,"it"d "l"" I' on;" , I"t o, lhal arc , imilarly "i",lal"U," and ""r)' [a'i d""omposilio", (", Hr " s~ 'I he large;1 i"mc ' y,tem for which n() n . c rg odi ~ (\i" "";atio,, hal bee" .uabl i. hed i' cn ,q -o 'Jl)~Il, --+ [ClJ, q -O') r;Il , J" ~ [( M {; H" n :l(M CH , )' ] (Tureeek an d McL affert y 1984; T urecok ~t ul, 1990), The Iherll">eht:mical a ppea ra ncc cncr~y, ,~I f; ,{,\O " ), i, lh~ m i ni m ~m cnorllJ n""",,"r}' to pro<1 lICOAD' [mm the w:rollnd-, talo IlOUlr~1 moleculo, The ~litj<::ll ener!D', I:'.IAO' J, i' the minimum inlOnml onerw:y oj' M ' uq~ i rod fo.- lllo det:umpu,i liu" l" yidd AD - , ""d lhu, A E,(AD ' ) _ I E(Ml + E. (AO ' 1, (The' " and olhcr rdali"n,hip, t" f>,,; di,"u,,,,d ta l'" '"" , h"wn in fi~~r" 7,3.1 Molecu· I", io'" ~ont,il1ing ilHornal o" rrgy "' L" ,,' nnut uewm"" .., , ej aN le;,. of t h~ amount of lintc allowed rur dccom i>Q.ili QIl , Howeyor, Ih. pr ot>abilit)' th£t M -, io", or im.mal e uef~ Y > t.', will p roo uce AU - in a LCiml , " u",", uOf"'nu, un tm:

--_._-

"".

....

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.-

t '.... ,.

1__ •••• _.

_ ~_ ~

,

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0

:}

I

If lltD!

' f ' A llo- }

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I

•i •, ,• •

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e -;;-

A8 "

' CO

A",olA S' l oA" ,.-'CCI '

I

,...,.. U . l1lcrmod":lIIucool ,: IU:r lt ,....,.... . """ 1ft the m. .. "f"d n .... C~'T.

"If"........1:<........ "'"

...-J

d..~ ............

I. ", c"""otanl. l: In[M '-:J..l M · ) _ 1,). ,,·C""'.tl dcl'iM C,l"D- · l(h~ ...-. 7.1 , • • I "" In, ,,",""1~ 01 p:ra>no. iom . ~ h.o..., l'A ""' 141 ""-too,,,Jil, ,,(........... ,1.0: M...."' " ...... '\1' ....\ n- . _iol. , l, . F.,l AIt ' , ;,. lbc 0 ' ctlC1ll, ~NclI>C>Il5 ~ lO.>l """",nt. '" Air ad AD ' •TIl.....'" prodlll.l' " I>' 01.... 10" ... I"" 100< f(JU/ CC ~~j , .. iI.Il etlCflY'MalI a\>o.Yn: l it< cQDillll !tlUft>O( """' ..., 01"

l"",.na: """'!Y-11>.

"",....co

[ ~dl....",odI.lr.ic:ol

. alIOt by

tlw _ . J

.1'PkI"""'"

it)' 10 l>o: b;5JloCt IlI.o" F.. _ f;' ~"h .. 1 ............ ttw "'k "~lC , hiff", aJd.o«p Itt.. to .. finl < 0111 e~ . It .... q be u ,,,'" ". leV jl if"" ;.. I Q ~ !, R u.uo~ ."d Duo h . Im l ~_ Lbal lblt _"u",,Jc or 1M 1",_.. "'if! Ollot , LIu1I I'" DIU' of 1(0""'" ..ppoa"' ft<>.: ..,h . , ... ., - i.n FilOU1C 7. 1. iILO adJrlJ........ ~ ;u.:"e beiOf. 1M 'OOG1 per, " . ~ . hilt: ' 101", 'F~I\l.cilN l " l~

""'' 'fl. •

i""rerr"", , h" lY\C;l' uro:! "r pc~ rII n,... ."'.,,. "' ~ " nb ,c1c,c,,,c to £ , (A8 -\ \ 1",( MO' '0 '" ,,'I~""' '''''"' IlY "' '' 0Uf~,",1, I" ' mol "" 1""0.>.1 I", l .., 10" ~- ' fur M -· ... A1\ ' ...·'11rlOC<'mP""'" in",,,,,,d '" pr<>d uc,/, AO- , l.incc .t lu. tbi. "'....1I<.> n i, much O b r~r_ r ile 'n l.... nal enc"J " I '-" ' l!l1»1 k £ .l AS ) 3S sh"",,, ill fi",~ , . 7 J III >'.ld <'qual . ate> of fo rma lion fo, AR- ~ "d A I) ' _

"1""'.'

;111 (In oprctrMe<1~IUt>k~ Slale .. a ! .... ronodf"an'ioca ~y unslable 'late that ha, nol )~ , di"-Ocia,ed f..., k" "'11c r-,."",m.. i " <, m ll ~ .I , in MS a "md .-ta b!" iun"i, Un<: ,h, \ 4_ , di -.;i~~, bul ...how dio.wo., .Iwn .. J.:L)-OO 1o, \;'in<:ti, rea, uns.] n", dllCnm/'O';ti" I" of nlcu , u hlc ~ "" in a r.d,I-I", d, ill , , ~i un n" '<,eli" n, " r ' a l<:-«onsl" " ' \'.l ,,~ jU$I t>fto... Ih. mm"" "m ' '''luim.t 101 ) i.ldi"~ M I "I"'ct' 8 tbu. "'JII''' ''''! a inu-,ouree dr>coml"'SlI\c>n HIC l e ll aDd nar ro" ranl;~ ,,1 If val.w.. ..1 0 ' 10" mnl ~ - ' jmu.:h ~, ....., •• ••"'" iUll-I ,,,1' i" ' lr um enl ' l, In Fi ~Il ro 1.1. An " ", n, in Iht M I 'f"'d",m of M O', (I",i l;"" led .. m· (M O' - AD-·J. thu' rr. l. " IN hy Ih" ar<M"f lhl: CC"'C'l" mrling ""'1'<" '" "i nd" ,,' in 110" 1'(t) ""r....... T~l "'-"'lp lc ~ "'"elions, which ca\\'. a larger k'""ti< '~ l f,. "" II tnu, le lld to Il''''' mOle .~" "d~nL rn e L.\ . I ~hl . illn <Jewnl\lO>ilion " In the "une "'" JUter d te ll............bk lull> mOIM- ' ... AB- ) ," u, ( Mri," lrum M ' of ene' g;'" cnrre 1 beI"'""" 10" "nIi u,( hj~Ir -t:n.r~ y di""e;"li"n pmdllct , "n J the .. riobil;ly 01 " "• • ba nda n"" . Wilh prceur"" r int"rnaj...,nergy di
,...;oct"''''

f".

en-

'AD
of

"IE) f uncti o n ~

\ 1.,., illCIlk•.h I(), llpp<m.imllling P(EI of a molecular i"n ;n>ol,·" me""" eme nl " . ' L>loc"u1;n r nod",:ing M - from \1, t" ",h i"h must '" added lhe "" trnal e"" ' IlY of M bet..« ioni:.<..aljun , Ikea usc i (,"; /,~ ( i ()n invol, '", ,, verli""l tuUlOJhUIl. 1M f...~ ""= ""'}' [" produce M ' < "ncr~)' of a " ",,1eI;ula j' o facto' l (01 lbe . Im.. con .oIul"d ..ill. lhl: in lc ,~~1 "nl:rllYof tho nouttal m"Itt,,1eI~.q" a l 2'lR" K, 0 07 eV rOf C, H , O an
._._ .

~ -

,

l

f,• - Ll " ~

• t-- "'-

j ~

-

, •• ... ,

-, ,

"

, --

............

,

..,

...

~

......... "

1 F",",. •.• P. ""''''''''' ron .!""" ,,,m

'* N, nor, v.r''''1

' _~1 ",ol,), """'~l>U"du'jj

'""'"",ic.',-i "fali0".1 """ illY Icvol . of r-" .od N, ' -, .. od "",Jc",,'. , urb,"'b 1~':l. ., i ,h permi""ionl

at.

"r ~ , (0 .." ,

1 ~1l. 'I11e phOlocled ron ,peclrum lTu me l tt at. 197U, Uho,h 1 9H ~ , MOIri'on 19% , Song \ 'J'-) which 'cp,,"c,,', 'uc h lr>t n,id ,,,, p",,,,, hilj,b fnr P""t, .. ioni, ., ion , pro, 'ido, a usef,,] appraxim. tioll of P(El frolD eloctr o.tl ionizarion IMoi'cl, er ai, 1912J. Pcnnin.ll ionization, lr. ,,,ferr ;nll . ncllO' no m tI' e 19 H·rY 2"S He a,o m" i' 1ll0ro fa ""ra l~ o I", lh~ " u,o, ",,,Iccul. , ",nj,•.I, '. Fuji... ",. ,I u/ 19M). "', a ,impl' ,umpl, I Fig",o 1.4 ), t he p hol"" lc ~t loll sp¢ ct , ~m of " , 11 , lIo"11 with a ,."lIeal e" ergy scnle (a, in F igur, '- ~J oOl'rela"d with ,h~ e ""r~} d,IT~I'. en"", he'w""n tho gTO'Jn ~ elo"tr onic " " ,. of no~ tra l .... , and Iho thl... 10lOi elt N, ~, ,I,clronic llal ,pacin-,,\ i, 0 ,212 c\', ~ , m all <1«',"a," f",rn ,h. 0.2'l1 "V "I the gr ound N. ,t alc OOt ba nds, ' 0 tha l lh. 2 pl7, ,t alt is nearly nonbond,nll_f or tilt n~xl band, eleWo n 10" fr~m ' h" 'lronll' t><Jndmll 2Plf, k . ol, 'lK: . p;t.l.1nll i> m ""h low. r (0 ,229 eV, ,h"win~ jh" .xpt:. ,t:d Ix"".! w~a'
n,

a,

P ( El

,,

,,, ,,, ,, ' ,_I, ,, , f

, ,,,

,

,

,,,

,

,

, ,

,,

,, ,' ..._,, ' .- __,_..• ·---+----- e'

-~~_~

.

~

'0

,

a

,

rc

'.

. . . . . 1.f, A f'f'ro1.,",JI~ I'l f. I ~ "" ~ . t. )

..

"

1." ",,1__ In, I"" ' .... 10" "" C, tl , Ctl , C H,

C,H,' ..... C.R.CH• .... p-NH. C". H.CH,CH ,CoM : ~ "' H,f.:, lI.U 1, - + (; , 11,_ CH, . , and kI"l for c.lI,OC, Il, - _ { :. Il , O Il " , ,"m. llt>.l \10: " "" llY "".1< i> m.xhlicd £rom t~.' of •.''!t'"'' "I ,,, . ""'" \"" d hl of OMldin. th, p-NH, , ,,b'1;I>1onl

'" i" ni/.aL;on. -r h. man}' v j hra li n n~ll"'a~, ar< also consi".nt with tho high bo ndin ~ char",,!«. Wilh th. lll<JIl'-inlcn.c """,,00 pc ~k r~ ", L1lin g [mm il> more f~ ' '' r­ ahl " ,'"r lie,,1 l'am i 1~11l. L" ", "r\1", H' )Inin a ll)' a nliho nJ ing 2.u. electron , ho,", a ,l i ~ h t l y iocr.a,.d (0.297 ~V) yibrational , pacing, consistent wilh bond mm~th· ewnl wil h ionization ~l hi~ her e llcr~i c,_ Th e 2~. ;md I. ckc(r"nio "rbilalo ' "'1uite .1 ~ an, l 4 10 "V, "" jICdi,'d y. f" r d ~ cl"," removaL A larger number of m ~kcul a r bond, im;",a,", Ill" dcmily ,,-. k,, ( r ~ n wni: (T. bl" I'd l, .m d tho"", 01 honwlogou' ,e n.; ""n bo l'daled "",pin""ll)' (H olme , and Lo " in.o, ENI), I'o r " ",10 1"'l:"r rnolcl'uk. , Ihei, inili"1 inlern"1 ener~y rnu,1 bo "ddcd 1<, lh"1 .., ,,!ling fro m ioni.:olion (hot band , of lower Jl' <e",11 onl y lrom .ibralional excita tion in Ihe electron.ic , tale tr om whicl:t ionization oo C Ul~ ) , Lo",erinj; Ihe "m ple lemp"," 1'"'' her" , . io ui," Ii<'11 "''' lh '" ifl'''''''' [1.1' '] ""d alTo", prnd_ ' '';1 " bund. """, (Maccoll 1 9~ 6 ; Bowen and Ma ccoll 1989; Braue" "nd von. Huna u 19'101. '1ho moSI dramatic offecl' ha, 'e heen achieved with 3upermnic n l'~,,, i " n " r lho ,a mp", beam (," ", If. Y1991), finding M - ' I", ak, with El Irom a laro:e pr oportion of molecul", that do nol , how Iho" in their nOml"1 m,,,, SPCClra, T he Initiall' (t;) 1" 1\";01\ rot ~ producl ion A + fOfmed from ....1 ~ · (,"" Figure 7,61.,.ill b< delerm in.d by': (1) 1'(1':) of \.f ' : (l) k(l':) for Iho To"cli01l lorm;n ~ A ' fro m '\II ~' : (J) kW) for ot her re:>ction, CClmpetitive wiIh A + forma,ion (M " --+ H' , M - ' • C ~ ~ and (41partili ouing or Iho e, ,,,,,, onol iIY in :-1 +' botween the.\ - ion ;",d o-calkJaI\"" , [ m O), [Of t he furlher d.romposit ion of a pU1i"ular (ra~menl ion 10 tho ' "'" elf til< molecul.r iu n tru m "' hlChit i. funncd, In j!;C1IcnJ, for a h<>rn ol"g" u, ,;erie, 0l"moleculal' lun>, _ linea r tol_tiun i, rO~ll d [or log([ m+] i[An +H '"l'; u' th. r<:oipl'O col or lhe number of ¥ib... ti<>n«l de~",,,,, of (reW"'" in til< m<.>lt>."\llar ;00 yicldin ~ "R ' . M""o pr.f;'" ....,.h\ld. ~ r e a ".i la ~ 10 Ol" d;' lhe diswcia tioll 01 ioJlS for"",d olmO<.W1I of inlorn al ..... ~y. Charge , xchlljl.c c ~ n be . pcc;flC, e.g, "' Ith I ~~.A r) - 15.15'11.1 ..t 0.10 . )( , ,r l ~-< M i - 10 0 c V. ne ulr..li... li"n " r Ar ~ (gn>nnd

_"""lIi,

".

, I

,, ,, ,,, , I...·I.....IA ' I

,,, ,,, ,, ,,

,, I

ta

,,

,,, ,,, , ,,,

_ .'j

,",

I--" j~:M- _O-, ,,

,•

J-

"/

_

•

.. " . C ' ~ ........... w' _ ".

,, E.,,, , I' 0 :I 6 --- -/C- -." I,

_ ,,"

,,, ,, [OI "'h ,' ,, ,,"

,,

,

of "'" ., ~_ _•

.,

,,, , ,,

, ,

,

r_,

.... ." , ,

'

,

,,

.. .

_ . ' ~ N'

'-

,

, E. "

PIEI...

..

"

HEl. .

,,

" R_ r/

"

"

9' _

E+

Io IEIr

e s

Ion Inte,n.1

En"~y

_

,.... 1.1, R"" ,;"""h ip.-.I 1'1 ~.) a nd kit) for ITw],"ul.r and prOe, A, ' , nd~ ' (MeAd" "
N' .

.l~ 1.e)

by M , hould yield M ' with 5 _7 ~ ,\i of'Alta lll{"," .1 e.tle,s)'. /1'" loc\octm n· phol... ; ~n; '''T im' c"in"iJ c"Tlc" iPEPICO) . pe Cll'O' oop}' iO\lize. 1>1 w,th a. kno"...

eM , gy pllotOIT, rnoa,urinll the , />Cr ll)' ,i lho c~"iltOO pI\<)(oekctroo, and lhe r,, · , "h i n~ prod u. l i"",, in ~oincid o r= (j)~nna c h e r 1 9 8 4~

,.

,.~_

_ ,.. t(E l _

0; ...........

.U

=......,:

1"-

'I

~

-,

~

,

..

"-~-

"

. -..... ,

•

,"'

, _. n

n., ~

"nd rClU!<' ,or cakol .,i,.,,, rm 2·hcxanon, and

2-un & ," n~ ". :

(>t ...... ' ''''I
In< PIt l" I nd Y(Jc " " ""'~ ' i,j "" I
7.$ C.IcuIHon 01 k( E) function.

Soo", of lr... """"""ibk

""""l':J'

,tales "r an i<m can cm,u'l"md '" ae,inl.l; lh e minimu m CllcrllY "I wh i W L , fur I t.: mlfllm um CDef ~y . caction. 1b: rale ooD!>laDl fm a part icular "~"lj o n "'ill be a fO" O(LOI' <>f lb" "'''-~g~''''''le 1"'1'nlal i"n of ih aUlin lcd ...>nlp}; ' ",T~ l i." " , IhI: p up ul~ lj un "r . 11 otloet ~"~reY ing ion. I h.. IS do.-. .... ibod b ~ \11.: Ih "'. h m
...'"'1'.....,.""I"'Hc " '

l ~ n) :

uu

"" he , e h il Pla n,k'! conemm, Z u 11" Pl' ttiti" n hlllW on I" , Ih~ adiah.. rie de g= ,'I I, c,, ,lom. I feier , 10 the lLeli, . lc-J "" ", pic•• • ref.." 10 III" . CI;"" molco:ule (""hich II",,, i! Ml ionie 'poN:i ~!), T'I(F .• F..I i. 11K' " " mlvr"f ... '...., ;n ' '''= L"",,'l'~ ran~o E E•• and I'(f:j il Iho " en" t)· or ' 1"10'<, ntu l !l'I,>,1o,jo", In lhe ' C I1 , at~ w mple, one: del ..... <>1 ("",Jom h ~, be"" I". "..ronn'e RR I( M rOf'" olthe IlIMr)' ;< fl rdtf '~ btQ"Soe If UU . "n " ' 1 ,,-,"m,,..' ''· 1iOll of , Ill [,,,. H " " ""' , ""''''' cl ma s.<-5p«u'" reaeli"lI> "I L" .... 10 u'" til< ' W", im" '., f
f",


(1.2) ,",'!lw .: , . .. the freq u U U~ rCJem~lll,,1 inc~a ", in f ,,"'ill inc'e,,'. p I rroflo, l;onole l}' much mOle lh. .. ,... The . ale ,,( m.." on"" or k wilh E , ho uld decrea, e .. E E. bee""".. Iorge<. "Pr' Odehi,,!, " ennn ~1 fr.-q" t n, y f Al "ll I;'m 1.1 flnd",t. ["ti ber that a change in m uctu re can ;affect rbe klE ! f"nch on ~y tffecl' 1m ( I) F" (1) p1ir', an ,1 (:1) ;:1,...,.'. ( I) F., . If a , tr ucm ", l "hang,-incr,,,,, . lh e crilical energy , Ih. ex"""" """,~~ , L ... I.,. of lh. a"I;~ated com plex m....t d~"r.a,~. >0 that H' e numbe, '" . t. k... rnu n,l n.er",-. ,.n r., ~nd F: , h""IJ . I, u Jcorca"". Thu ," ", jll e~b ibil . l ~,..w n lue. ,;nC~ Ih~ f"r nh,1bilily nf :lCCum ulatif\l: tb" , nerg)' E,;n IOC rca<,1io n ~"QOIdi"' I" "'ill ~ dfCr.a.
n..

12'

I

k~. - ~ r "' IE.) '

(73)

'-"

,-.._. ' -- '"

_... ......._.

will ~t", t>< "",ucod by ~n 1n.r';d . ~ in f., b<,", UW " f (he j llc r"~.~ in ,,·(t' . ~ NNe th.ll ~ n increa.. in ~ . "" II inc",a, e bulh 1::, and the ~ in" ti o , hift. f:. _ 1-:•• ";n ce the ""'f<' "f 1(1':) ",'i\l d""". d' . ' II I P',/p·. A modific;,lion of Inc m" lw ... l~r ' t , u~1 ut" ..-h.,h . dd. or ""t>In"" I, 't~I",. or chang<:' Ihe energy ,--,,)0(1 .,( IU t.5. WIll ChAng<'" p t: p ' . ~",l w;ll lhu, ai,,, change lh_ li E) functioll, n. while oth" p"rJmcl~., a," ""n , lan L. Ih, II ... ml",r " f " ,b, U lo WlI <JeJU.... of/Toed " ", fn) ill the Toacl,m l l" n i, ln Clea,""" I' " IL) ,,"'iIl lncru ,;:. This "'; 1' I" ....,.. 1""•• a tld will thu, u,ually iucro" "., l h ~ li/Wu, IM t. ",hodl It I'" amo" nl of . xcc" inlem.:J one[~y ""ce' >illy l ~ rta<;h I. _ lO". A m.lj{'1 r",I(If llu. " e' <:J· ",i"e, p i/I" i, lh~ nalure ("" otsr k ,cls and "'"" d,",UII...,j (" I ", o~~ i,~, II is aleo p.....,.;" .. 1""1 Iho num l>or of ",rire mlernal r"l ,"i"",,1 o;<: ....' m pk ~ n if t ho.: num ber ..r i"lo" ..1 f(lfQlional Slala h.ve inc, ,,. ><>J al Lh<: ~ .pe n>e or.·ibra uo" a1 .. '''r'~ M 3\10ll of I ~ GU"'hn<'3 1l1, sin. o tho dtn,i ly of r(\ld ti~ n, l ,T" • • " ",uch lorI"" lila" that of vib,.li" a.l 1 ,mle" Thi , )ll~di c" th31 r~3C1i01lI with li{:hl eomplo n will "'-'"C ~ ",non fDl>t:tlOn includes the 'rmmef-TY f30tM. wni
i,,,,

"*'"

nO".1

I", C'''' 1 ~ n ol 10

COI'""l"'"

h.

A ,,,h"anli ol ,,f k,nk lhermochemi",,1 ofut~ beth.-• •(l'-'i (Ln~ of Fi ~uln 1.1 7,J . '"'" thennoclttroi...,] rol~llOl1­ , hi!" for , nc"" r<",-";"" , ~r " . h",., n in Fi~~ n: 1 ..1 ..... 'l' ..dues for , "" 4BCO -

~D "

A8CD

-

All '

•

· CD

-"I) ' .

+ lI-----C

vr,4) i} ,5l

'" corrosponding "ucl;on< of 2-h.xnnone'. Let il.JliAUCU) signify th e h.aI of formmion of IIBCD from the constituent eloment' , and D(B-C) be tho di,,,,,,;~Ii"n "ncrgv of Ihe R-C hondo .~Hf(AR I I + ARy ( -CD) i, Lhe ihe,modwm,cuJ ,hre.'hold for Equation 7.4. At'{AB') i, the rl,ermochemical appearance enorgy of AR+. " .. that .11'{AB )

JEI,\R('[)) _ E.{ABCD'

.,\B I. The adi-

vale
"r E.(re,,) are more

commOn for rearr"llj!,emont reactions, If L,,(TOV! i, negligibk, 1'.. for roaclion 7.4 i, <:qual [Q Ihc oorrd-di"oc';atiQn energy of the iOlla.nd j, predicted directly (rig"« 7.3) fwm r:quutiuu, 7.6-7,8,

17.6\ •

"Hr!AB·j + IEIAB_I + AH!I·Crlj -

AH,IAOCD) -

IE(ABCD)

(77)

N"lc Ihat F'I uali"" 7.8 u'os !:>"",l_di""..-iatio" c""orgic, "f "eut,al ,pccic, frahlc A.J), w which Ihe organic chemist's inluilion and knowledge of mechaniSlic

p,inciple, should be dir<elly appJicabk. For two competing rcacliun, of the ,arne molccular ion (and thu, the ""lILe .I:(M) \'alue,\ I;q uali"" 78 predict' thai ,V:" i, determined ill' AI/-; 01the Te,poeli.-e mdie" I, (Steven,on', Ruld a"d "'J) "f the ,~,poeti"c b"nd,. Further. a structural chang~ llsllaUy affects I HAD· ) much more thun D(AB COlor IE(ABCDI. which is wh}' product ion stobility i, u'Llally thc mo,t influential factor det£rmi"ing product ion ahundano.; ISceli"n 8.2) Potentinl-.nergy diagram, (FigUT.' 7.8 7.101 call provide a mor~ graphic Wlly l() pre'ent the lhernlochemicul rl_energ}' poil1l on the ,urfac•• which often correspond, to the tr"nn em Iho righl_hand ,ide "I tho diagran" whieh eorw,p,)nd, to , quHibrium configuratiom of tho pfodllctS AD + CD, ,eparaled w a diSiance al which their mutual illt; negligible. The onerg}' ,0,,1e i, eh",,,,, t" r"ncel the ,clalive lbeTJ!",ehcmical
,. """"_ '''''00''.."

..,. """..,..

•

"",,000• e

ME ~- A B · · 'cD

ABeD"

e

AS C;;.O' - ,,--

A B~D

,

AB' .

'co

AS"

co'

Aa:.t O

.

Coo r d i n a t e

,.

.1'''"1:1' "'"" kon l'f"".....'
F. ... 1.. I........ "..... e",,," d....... rn h • ,;",pl, (.al.." """, aOO ,bl WJtb ."""" ","~i,·.,iv n "",r_J,

. Il: m"oI ly ,m k..",.", .",1arc

dr." " . rbitrarlly on ly 10 i"dl<>lle Ihat the mOUOIl . Io>ng Ihe <earnon """rom" le i. continuo" . , Tt.,; """pi< .oJ"'..·.!!" ,,,"c,j,m In Figure 7 . ~ (a:. i, charo.cterized b)' ~ ,omin uoo ily IIIc..... ,; n ~ potenl;" ~"n ... gy <:\''''e " hie" rcae he, ic. ma , imum in the I'mo""" "'tioc>n, The t'an,ib"n o>" l be thcmlOchemiea1 threshold. Thu' the dccompo , ltion exhi bit• • >ro""" ..c1i" " lMJn ""'''!~', wilh D(AB ----CD" ) lor the Il-( : t>mtd grealer , ltan lhe II>c, m llC hermc. 1 ,·" It", " nd
, I Th ••"

"" a

,

.

AS -CD

..

".'m.loo,'" I.n Do""mp"n,. ..

/;I, ••,0

~:;-':~'t Energy

.

=

b

,

A

+"

, ,, ACBO··

.

0

.

: ,,/ .

.

AS-CD

~

.

8~·-':t

•

•

AC····"BD -AC+.

,. ABeD

so

.,= .. •

Coordinotels) .''''''' 7.' •. 1"',.""al.c",cl'g\-
ili~h"

or .bllowcr ,imilm,ty [or

n"lv in the [ooa,;on of the , I. clron, and thus ~orr"spond to two different elee''''Oli, ,tatos QI the '''!,<''}'ICOl ii\B I- cot', 111 7.~1") the chargo is loc.,jized largely in the AB pan of the A[lCU·- jon "Old rem,;n, lhere as the fragmen\; ,.pamte (charge I.lennon), For example, ,,-d.a,'ogo in C,H, CH,OH- produc", m~i"I), CH,OH·, If(CH,OH') _ 7.~ "V_ ",j,1l mud, Ie" (16:.;) C,H,', 11;((',1 r,' I _ 8 I "V, Thu, ,he gr,'und electron ic stat, of M+- ~orr"lat~s with 1he p,C'
,."'..'"_... . . '.".."...... .-- ......... """.

'"

~

sl nnn, lill fir' t l 1C;I, d . tate of th. producll, ",he,..,.< the product . 1:'''''0<1 . Ia le, -CH ,OH (C H, :I,CH' . "or,..,l~t., ",Ilh .... <,,~, lJ:d "" Ih. enef~Y ~ap l i' ' n..l . \', I"" '''''Tl!rii",Uy r.,...",d p rud"d. pro:d.....UlI.lt. n Iorr,""" fI oI'. 1'171]

.toIl",.,

(Ste<em.,.,'••

"R. nd",,,·' rr"",."xr--./I. l lT« u lead ing 10 closely li m ~a J 'peena f," iorooc" 4. ~1 ".., .lw boo ,·i>" .al,m ";Ib " ""I'~ ",,1_= W'K"" -: Wi_Th..,

Ix "Ii ,,"

elfe, l, "an r.: ... '" ' plc• . c" lIlllini" Il ..........·ul ~ """I ",jn,ma an d u I" ...1i" n , tal .. ("'oil J $ ;on·ne .lral oolTlf'k~e.~ alld IUcl ;"n$,""1 .re cit"'" fF ' I"• •1I","u) ~'f Of ' · IHI. AIK:V' - .. 1.,Mll\".' -_ 0 .\'· + 1I-"('., '1"0 I"'" "'" clk ", " ,.."di" 41.",, " , , ,,,,b a ,'8... "'" ,uul hd imonslOnal. ";m:e Ihey .vnl~w. I~ O 1e~'h l d the oollds k m, I:>f(\Len ~ ~J into a ",,,n n,...., -.... "dina",· ",hiLiI ""'" ,lcpi< b d in....,,1 ... m' Q "' n~ tho ",a.lJou r "t h liM ocr<". rMI\'ly a< I graphlCl l mea ," of ~ "~y'nll ttl< ' In oelu, . <. 11 ;,.,. mor;zaLion of an io n io; r a lr-d ."' lIn inU1 ~ IWill"' m. 1\1 17 ~ the lendrnq fM a ' '' ' '' ''''hl" fl:"",,,,!!,:m.:nl i. Jcp.:nd<"r un lh. Ilei ~ l'l .>f ,I>e bArrier sep ~At l n ~ 1M ;..,mrcic p=u,
1m, nunimum""""a """""'" I", d"':""'I"",;I;,," In

.' C·..

p,n r,,,,. 4-poco "

alld AC RO ' -""" ",tereon ..n ....ro,... ~tion t-arrie r d"", n O\ n<:"c'' ''Krily Jc~d III , tTnelu",1 "",m ~n i ly. F'" c, fnm " ~ "on·,Ii,lo"ic i""Jlcr, "' hid, mLlSl inmlvc ;t m" lltpk.lCp J'I" hway 0' an JI1te,medi~te ion·n'l11r~l comr ie"

"""",,n.

r.,.,.",

Figure 7.lOlbl ,how, a "arrangement in which the isomeric ions aro ,eparaled b}' a higher en"'-gy barrier, whoso hcight detcrmines the tc"-,,!ion "f ACBD~ that "all <.,"ape revO,.", i,,,meri:,ati,," and dttOml~"e directly to Ae ~ RD, To produ", .'Ie [rom ABCD' imtcad o[ ACBD' r"4uire, ero,,ing thi, higher barner through a tlghl actIVated c"mplex, '" thal the 1>0=" win form AC- at dit1el'elll rale;, Other ABCD+ db,odatiom ;u"h as AB+ formation "an now be importanl; Iho more eompetilivc these arc wilh the is,,meri,.~li()n_ Lhc more diITCTen[ the rna" 'p"clra of lhe i",me" will bo

1.1 Examples

The applicability of l'q uation 7.1, and especially lhe usefulness of lhe c"nccpl of the "IQ">en.,," or "IL~hln.,," of the aclivatcd cvm pk" arc illu'tralcd by a fcw murkl c"kulai;"n, Ihal h", bt;en carried oul fur largor mokeulcs 1E4U"lioTl< 7.~ to 7.11). 'I he be,1 agreem,nt btlween ltle experlmenlal data and ttle cakulateJ k(LI fum:liuu, (Fi~u,.e 751 wa, obtained by "ssu",in~ thallhe ""li.ated ~~HTlpk, und,r~,-"" an iTlc",a", 01 on<, ur lwo rree mloc; "Vcr the iOTl ror F<ja~­ lion 7.~. a reli"", ion or on" fl'ee rowr in Lqllat;on 7.10, and an mcre"," of three Ie. four II.. rotors in Equalion 7.11. In Equalion 7.~ lh. imporlanc. of pnxluclion '1a1"lily I'c~ Chaplcr 4:' ,ugge'l> lhalth, aeli,'aled ,-"",[,1", rC'~lILhb the PWd\lCB mOl'e than the precursor. III such a mod_I the central ( C l>oud will b<: suh>tantially d",ociated, lbus lowering thc balTier to rotalion aboUI litis Imlld. and iner,a,i,,!\ the nUllll"'r uf rrce rolor, ill the acli"aled comple., (E, _1.3,

E, _I.B e','l

17.91

p-H,NC,H6' IE, - 0.7

E. _ I.~.','I

17.10) 17.11)

<0 >-C"~,",---@ .

«.!)--- CH,O

GH'--@

~

C,H/

t.

C,H7

(7.12)

(,luile n d;lIc"nl
... .._....

lJJ

"~0~~,", (0) ~

'" ( )="o'",-(r5) F 13)

tr on denlity in the N - C bond of the nlC'locnl ~r ion; how.ver, in the act;\'ated Iho p arl i ~l ror malion "f Iho " " " nanee ' ta hilizod p_amin"h<1l7yl i"" . 110" ld . 1'0
19 Th" "titio"1 ono r~ fOT f 'I"Mion 7.1 1 i, e"en higheT Ihan lhal for EqLllltion /. 9 ,,"oau," ef tho lowored "a lL,o el lC', and Ihore is an evon ~ ... ter inc.."," ill the \'alue of 11", oo", bined kinetie and competitive shifts. The significant ,h lm,t.n oo nf thi, r ro ~ l1 ct ion in the 70 c \' ' )J<-cITUm indic ate> lha l kiD lar llq llali on /. 11 mUll ri", ml1 eh mo re rapidl y than th"! for ['luatioo 710. T ho tr all, ilion-l tat e for Equa tion 7,11 mu,t involve an even greater ;"CrM." in free tol,,'" Ih.< n for F.4 " .< ti" n / .9. ha,ed " n lho r~" l l hal the panial charg. on th• • mino gro up and t h ~ adja""J11 ",omar ie r in ~ must now deaea.," in Ih. Immi· tion state, lo werinl: the doul>l e-bo nd character ol the adjacen t bo nd, . Th e aJlotMli, " 'orttl"l ion "f C, H, ' from an e,d«d eiect ronic , tat. would con'titute an ulIl1iuaJ ~, ce p llo n to the qu",i-eql1 ilibriu m 1h<0C}',

,"~,",---<>;,---@ ~ rl:oN~M.'O(-....-(r5)

-

M, fIe""',' ; C,H , (7,14)

So ... mako l""'llbk no", ,,,,'>ct Lon, of h i ~ he r- ra t e co"'ta nt, ~ , e r on appr eci~ bJe 'lU Ll!" ,, ( I' ''.<:u'''' ..... ", ,"Ierna l ....-LC'q\...... n ,LO>- U\C dr•.malic dilf. reJI<"" b.:<....""n ",~ 'f«tU of d<:>decane and l-aminoooo=ne (F;~l"'" U and 1 (6) .< '" d ue pOm" ,ly t
n.

•

cun'., >0 (h~ 1 "high~l-.Mrg)' r"clion mUlt have 3 1,,(1;ei.," I) 1~1 ~"jVillN ,omrle. in " , dc' 10 t:oc """,po:tirive, SUU
",n

III".' ' 1"'''1." m, pan "'"l..rl) in (h~ ub"nd..ncn of lhe molecular and mt{J" ollle iom . Addmoo of a ",· ..mino IIN"P tu 1 . 2 -d I Ph\n ~1 ellu"w 1","'C1i lh. crillClil cllC r~y for 1J<'uzyhc clea'a~. by only II 2 cV, " ui l" .. ,,", Iho inn;"'"'i,," ene' n to)' I,r CV. lhi , rrn>J """ II du ul>l lhM "I lhe moleculal-ion abund ance. A!iding a r- 01110 group 10 l,1·d i p h c n~ I "' h fi nC m;,kc no uppn:l;iobw chani e in either t"," 0 : • •1". or Ih' mokc uk or tho Ai·. al"e " f (he f,oTl / )'1 io" ( 10..1 ± 0.: , V'I H""'"eV<'f, ' boo nut c> g, oup g",alJy m"n; ..",,_ th" \IN'ulution of the PIE) curve <Jf "' . "'ou nd IV.5 I V, Plolumobh tll,..>u\lh i""i,..l;un .. l [he ni lm b""' lUp. no, ""11m, ;" ~ ",, ",~I.(, , ~I ;"eTC""" in Ihe ion . hlLnd. nce .,,,,ng from til< m.U...hie
decolllf'l""1 ~ >0.

"" -er. IIlN , 1'n4; h ur. U 1 ~ ~6; G hOih 19 ~): Holme' 1986; Lov,cn 1978; I ; "~ ..'. l H" I"'..... 19f,4; M~ rk 1 ') ~ \ M"rri,,'n I n />; Robi"'on and Holbrul,k 1'172;

T u rn ~ ,

19 7{\.

8 Detailed Mechanisms of Jon Fragmentation

"''''t

lnlcTfl<0tin g ~ "' ~ ~ ~ OOI p1 "A m<"Jl<euk "",'II a> d i",. ni"" WI' ''''' 8.11 s""~1d m;)}; e oil!, m~th~11 nlmgf l-l" "" ,-c" ~ ".". "l.. ne<" to ;/< ;nf,..~...,..l ~nd " ...1"" , m~tnc' ;" "'.. "", n,,, doul* " ..M rould pmt"''''dly ch3ft['t lilt dwo ml:, 1' Q•

•.",

'''''0:1'.,.

"r

.. 1 Un n.olecul _ ion decomposit ions

dnd reemph ocize th" "",i h ,'" ion , cac-tion, im pon alll {.:or ded \ lCUl~ . ,,,,,,Ion:. Ih e m~ "" ' l"" lrUIIl ,h"w, ':O/f/pI lhe m iginal mo!collle, and lhus provid. di.."t e, ido n"" of molenl l~r ' lrUcI"''' , Ex"mpk , "n' givcn in F'IL,"li" m K I " ml k 2 (ror 2. llo , ~ """,,- ' "''' ~l"" F, ~ u ", "nd Semi"n 7.3), Valu e, in . V o"el a rT""" " -p"''''''l the " . " , all cndother mi" enthalpy chang• .I"''" ,j" i"j ,id I'n ,, :IlI",.• : th. dc ~ >n ""I ' on ,mot>,) (IF) of Ill" """"'llOnding neutr al. h 'on if ,,,me nult C'l' IS con,,..tilJ,.e with primary di, ,,,,,,ialion , " ' tru ~ u r"l1 ~ inJ ;""'l j\", '00 cnn be lormoo by d is'o<;L. tiO\l of the i,omer (btu.. i 10). Such a ~ 'p«: i flC re " rr~ " g~lI ", n l" C"" i"" ., I,'. dir. "t i,om. ri7.l1 lio n t o a di~,1flk , adi<:al iun fa To

. ~ i "",

7.,

'1"'";,,.

,~

!:

I

• • i

-~

~

•,

l

• • ~. •

i

; ••

, ! 1

, I

., o

, ...... !

• ,,

,

,

0',

..,

,

f i

,

.

\

o

I

(

•

if

• , I

••

' 1I

't,¥; •

,

s

,

,

" " ~~ I

•

+ •D

~

. 8' . 'co

~

. ' ,11'

. a , . (JJ'~

t , o'

A6C'

"" , B' , C'

~.L. I I

.D ". ec MH

~

81';"

radIcal a nd charge , ilC'<. 11>1..1,," , ... . ,1. 19841, 0.11" CH,C H" CH,CH, q -O- HIt' H3 llvnl ~-heunOllC " 1 f.'11L~ li o n R.2: lhe v e.ev b.1ITi., i, ~IJC In " In ", ,,., lI~ l; ,· a tio .. e.... ~ y 01 U . ~ oV): lhi' ion i' M t nl ,t;Jut>k b y (lie"et ionin lJo n of ~ . 1~l>Ic .;<>m p<, u n,J. However, h}'dro~ n ", i ~ ''' l i n n ' a n al'" 100(1 10 an i"lll<. vf another mol, cu'_ ( o, ~. (\H , ~ ' ; Eq""i c'" ~ II. 'On Lhat l1,i. ""4u4 ,,~.m.m incrca'c. lh' u"u rM;n1r of id.l1u r; Cnll ~n: tho lIm;ertaml~ ...·ill ~.U4lh Ill: g"oater for a 10 "'0' i$OO' t r;' al;Ml I'an i" [F i, a,..." i.I 0(a) .. 7. IUtbj), IN" undorg" inr •...,h " a, odo rn ~ " JrrangM>d " li,m 11.7 .~. r", f . 1I,CIl -· CH, ,." U.7 ~V IN <', H. COCH ,+ t so \II.Lll sev.....al i" 'm•...-iY...,i",, ' \"1" tn, j,omo, ;c oquih"",' ;"nl Ca n "" compel.i,i•• "'i lll Jb""""u"n. In r''''''','' " li,," di"-, ,,ci ~ [i,,,... tl>c runlw, •• ~c l ; on. or an cr:' I"" dun iOll , ud, n' C. II , - ... C, H, ' ([ q IMli
J;"w...'I' be\',... n i"

'_ n

I F,!Ull l i' '''

8,2) ",'itl

~ ~H,(IE ,

5,mO)

lt nd !o"''''d

.u; ...,c ,

•

- o~

C) o~,

.u., ,

IIlOnI

;wme llzation: the

+ ~~(l\O"4.1

" ,,,,. • - /II "

88(75)

() -"

•

"

,~,

c.s

"

CoH' 11

1ol~ ; )

.

",

- 0'

,35%) (45'll.l

91148 1)

9,3\lI. ~) Q~

.u,

""ollfldary

"

,~ ~

Cot<, ' II I ,M)

•

., 0

) "'\00%1

• 9,9(g.71

(~, I

)

.,

__

~".," -' '' - ''--

co • •C>I, (5%)

t.t

"

" -,-'

- 1.1

C,t;,,' ( I""'i + 0 =11, !1J(801 - 0'

." ,

'. ,II 0.6

"

r f.!

1 l.:l 1 9 , ~J

l¥"'. ' I~O"I • 8 ~ IQ 11

-"

."" rs

•

"-"

G,I\,- , l O%) 1 ·H

i .&,8 11

aa tlG)

" , <>duCi• .,.-i lllhu, h ~ •. < k " ' lnLc!uc,,1 ill\epll~' , .ta d , nn. " f:II,jicana: (>1' "'TUC~ l u,~l ~"isn "'<: " l " 'ill be much mol'~ 'J'<'C~~I'tI14
""ric,'

84>;( /«/0", ~/fecr;~!: ;o~ 1fh" I4/JQ""... r " h" ah....dM . III a m. " spectrum. u fra¥fficn l 1<1n m " ,1 be pr od L«bl ooonpelirwcly from (,"C M " ' ' '''' pn:eu,"",", .nd IllU'! b. rolati.'oly " a blo 1<> further fral:m':DI~l i ....., '1tic rn"'l com peliti"e frag_ m, n luli~n putll ",~~ , of n",h:cuLo. lun al ~ Ill_ 01 til<' lowell !'In-energy ~h"ng •. • noj Ih,,' 01 1'" m"" fa,,,,,,," I,, change. In <111 1>.11'\' .n ll ,-nlCOI'Y, Th. ""lh"lp) r""lt>' .. r~n.."" lI,"d'Il !he Sl ro1l11 lOndol"')' re, form the ..nIt -1m"" l"">d'~H. t:>{>o:,';~lI , d", "'''''1....1..... ionic proo uct. Quahfyinl: thi i, the 10 " " r the 1ell }'l Sf" " P " f''''"rr<1 ~ntl lll < If«·I;'..... on prod""l ro! m ~ l iull-

It."

"OJ

"'"l,

""",~/ili,, ~ ""'Cll O~ ' (l'igule 8 2), the relati ve 'l,milily of ",,>d..el. i. ,>I' J'J irna!) ;rn!"Jlta noe ill illl;lImll ni their [nrmal io n. ,.. .....,11 a < rtdllCing . he hm f>c. diw>ci _tion 01 tll" r>TI ~I ~" L i" o. h lt ,imr 1e "', I>d--<:I"" 'Q~ . re""lion! lhe "'.w~ activat ion e""tn i! UI" dll)' . "' . 11. ... ' .....1 lh< drivi nll Im~ i, lh< enthalpy change of the !.~ c ti"" . 1't: llll iYe I... llIe !·31uc.; Inr mher meh com peting I"" ""''' Y' · The Tclati,-"en lhalpy ,,!uI,, ~e i< dc..nDirocd b~ .he heal> 01fonnullOn. • Qd th u. the stabi!i' ie, of the IT!,,llinli i" Di< ~n" ""u" " I I'...~11>C1 !"ii•. A, ,!",,,'n in F il'.u re 7,J ""d Fqu atio n$ 7.6 1 X. Illil l<eq uhoalenll 0 . he d,,, ociatiQ11 energy

...

_-

\1). I . Ne .\ ..1) m lhe hond(,j d ca ,'cd in ihc ncu,,·~t "'''' ''I'''pan or lhe Jea<1~"'

prod'."

pI..l Ih. i,' n,zaIKln e""r~y (ILj "f , hi, reaCli ~ll'l th n '" i" n;A:d. Ih. f. el , .... . 1f " h.K:' J"I",ml m ud l more ~n ' IruetlJ.f~ th... U >Il l..., d,' iT able >\. .1) i., lbe ' . ' l M' why pr odu ct- ion ' labi lilY i , "r key j'''I'''fl lllOe ror del~ i mnll: frag".. nIM,,,,, !", lh" uy, . No' o, h0,,"O .- ' . th r ti,;, ~ Pr'''-'' 1<' , t.; ' ''''' f''l tJ.'>" ndanl prod " cts ", FE ' ion. "'h.,,,. C(>fl'C'mlX' r!an! prim. r)' p',"; lIo1 i" n ' e,m:m· bel' to che.:k dbun,lonu: " f ii, "",,,plc,,,. "t. , y prod"e t ion: '. :r (CO ·I _ m/; IAOCD ') - ",,'~ . A U · ) , h.: oomp
I""

,..;"" "Milily. lllu , ,,,,!inS thi, rr; m,ot)' ,;ti lcrio n, the I E(RI ....1...,.101 H', CH , ·, C, H,' , ;,,~ C , H,'. al'd rcrl · C. II , IT~ bl . S... . p;rn a raIl4'" " I I> '" ~ y, ,,' h n." I' ""'. ..ilh i",,;o " H, " . h"" , pa nni" g a rmlg. or S,li c\-·• ...btfc;l> Ihe tJH, , a i,,,,,,, 01 the co,r"S.,oDd lOg n" " I, al , a,\i"a 1, , I", ,,· d """I'<' ,,.. ,,"l y 1,7 . V Thi, lll(\oh-la r~er d fOOI oJ , tlllCtu' C (>n II' ~nd ,),11, " al" . , of iom Ihan on t h,,!~ ..., nell'" \, ""li n . ,. " he >=fI rnr " I....' I" M h"" ahllr l <>1 Table A.J, For the iOni.:At",n ~J1<'tS;', nat. tM! the ""W>luli" " " f a hck " ". " "" in l" "1' alkyl radi,.._

'."1;"

cal can fT ~ ble 8,II ;'lC[!'d'" IC"H.,C H , - .... C H.,O ,

~ ,I

...

~, 6

"Tt:""" I('H,( H, · ... HOCH, '. 11.1 , · 7,6 . \11 the IE , ~\u~ r_ ' ,f. ~flC~ ~ ", ~"np '6 r6d IC6i"

• "

"II,. '"

io<>C,H,

,..l--C,H.'

o.

., ;1.7

.' ,

'" '" •• HVCH.

CH,

"

'-' l" ' I O.311 6l

. Vj a, .....011 ~ , d"" CH, O' j;

I ,w~k:l

61'

A lk y l

, od ~, ."

..,

....1011' )

r.H,v

C H,V "

IEf" ' !

M '-,(A 'I

,.

u

.."

.e.e

,>

t ••

-... ",

S-_ _ ,•......,. ...

r

M ~ ~£}

' ,J ' I, ' I 0.1 (HI

.

". " "" "

..,.

• I "".,.., , , _, . ,_

.. ... ... ..

, .

"",1;0""'.

and 11< Iri pl~t ~ - l ,1 e V I"" "a ble ,h' D C H , O H I ~ ""'1ill"'" heteroal om ~d,Ni"" ~1k'\:I ' lh. !le"nal mNe th "" til< w'...... pondwf jon' dJI} Ph -) - ,l.Ii,l l'hO ' ) ",',1 ~ . V, hul M ! / Ph . I - M t;4rhO · , = ! .) c\i , reo ncctj n ~ betto, ' tat-ili, ,,\i(l11 hl monM. lenl ox}'" ,n of lhe .. npooin>J n, ~t r\lCI U [al tffect. on II' .al""" ~'" to,.. " II , . ~ . e, peeled from ,he prihCll'l<'\ oj " h ~ . '<;,>I _o' ",n lC $"'ur..-l h,:n,, 1 ,~,lic.,.l, YC. ll . CIl ,. ... jtb HammoU.. . II,o"'n ,,' .'ah"" tal.... ..... I.,a' l ll~ ~, 1'_ )11. and Tur,,'ck (' j al. t'Nlil' l; II", ' ub>llt nIJ"" of p-NO , by f""'\ H, dt<: ' e,..h~ S m" l<:cub YColl.C Il , C H, (\ H , .. ' .....th' ro. of ,hi5, ~....., ( ""' 013'C' WIth ,, ' .'alue, (Scc ~ "n 7.7: ftl> IT
f",

"\I'

t."".

uf flU! ~~ .. .14.•" ",.,., . Thi, , ule c' the maj or n ee""otl In , ~c impo rt. nee of 1 .''''' .,,,t>i lily_ tt,.. u," ubslituted a l~ }' l i:lOG!" "onded , ,, the ... mc. Ol ~ '1 .. i¥ ~I.n l. cJ roon "100* ), tho pmd ucl_i" n ~ ~ u oda ~ r rodu ced by lheir l<J;"", ...·ill f ~ n~ ~ 1 I h~ "'~ of th, alkyl group, NOl~ l h ~. ( f.l" ~ ­ li<>n 8.1) C, H, n .)( :H, · yickl, 2:-, C . H.CO~ " •. 100\ ', CH,CO ' . C\'tn ' ....."i!h " ",on.,I;"" " r lh e latter roqui lo, {1 4 c V m"te ClK'~ch ", fwm ICH, J,U - ' ot "h(,OH ~ , u"",Uy otdJt"dI". ~"',"" . ,,f ~lk)'1 qro" ~" larqcr ,h"n 'Kd ~l'l. Al~ )', ..... atld .lli: yI q an i.,. , at> d'" mild>luI in, j)M¥ide 'M exc'pt ion T he~ , how ~ hj~ t>c, pref'....ooe f.' r H - 1. - I h ~n m,>,< 1 "" ",,po und, do, wito [1M - H))" > r M +-I; for elampJc. f"" M",Cl ICS · , [ (11.1 _ H) '] - _SO~; ~ nd [(M - M ~)" J .., l ~~:':' Iou< H m.. """" '" nlmos l C.,lu,ively from the melhyl alOUp. ,\ 1><1, ~II. ~ I loM<'. from <>I,,,,,n _' nm. ,I" no t alwa y:; obey thi, flll<:

p'''''....

Im/"'''''''''

( P fdTc' ~" , n ~ ..s_ l \l ~) ~

:r-"b(lOlUlultm,<: prod ut.l

..

,

ion, (pill' an~ of (h.:if rutl"'" ""'o ffi l'O'ition \iT<'duct<) is mu . U~' in'....·",,: l~ 1"0' porhnna l to thell m.~ ,I",. of d h)'1or l nr ~ .. j.1.dl~ ub ~ I ho .x-d'"dYdj:l ~( I J tV (to eliminale lie':''''...." <1.'00111_1\"", ' ) \'>1'0dlKU p<-~ , b~' 12') , I I! . nnd 101 with re l a, i~e abu oo~ n ... "r n ~,; , ~ ~ ~. ;, nL1d 11M"'.;.. ,~ j ... jy; prcdicl"l! "h u nd~nce, arc lOl: l,N _ 1~~'; " nd I I ~;' 10 1 _ k~ ;" (AI ~I<" lro n "m:rgio, nU l tOOr a l'('C3no.n020 II", ,-l.okl. Ihi, d~ nol hold: c.•.. I"" t"" " r C. H.. from C.H.n.)("II, . '. I!qualion ~. 2, ' '''l UI''"' mor e . ".. ~ Ihan l h~ 10•• of C H, l " Ili. rna., b: on<>lhor mo.nifc, hll' Oll of tl>< " ~ ~ """,""" r. f.«J om" ~U ...l, m ", lljch l ilt Ab.. n,h ",,< " r lh" ,am. m ~ t n l!~ h ~ inn produl1 from hom ~IO(:oll' rrccu""""" " f()" " d l~ b. inw rod y rnl~k:J to the nu m m ,,' vibu li<.>a41 iklU "'- 01 ,,.edom of tho d cm mp (), in g loa (M, .o.d"" .., ~i 1974, !ku, I ~. ,l~l i , [i cal dl't ribUl Koo [ ~1~ )1 ~ ro u l'

J..nu"J"'''';''.''

(I ii ' S,.',n.,,,,, ',, H~ I~, 10 ~ ", p",) ion, ele. ". Kt Of a lew,lSOu·s Rule and lIS modlfied f"n " \I ~, ~ " ",, { A ....Le.- I !IW, H~ rr i """ d al 1971; Tu rcf:ol ~nd Hanus 1984, IMle ,'''' , i " ni'l~ ti<>n .........~,y . a lues ~.erll char:c , elf nllM "'- eh" rgC' m i~' " I ~.n in de<." ml'O"i l 'on~ D"" ,,@' lh....; ~li on lh. 'f l' af~l i ".i ITagmcnl' "", m l""~ r..., I"" .1l ~",", wilh Ibe ..,,,,,or ~n8 ;ooi" d. If i" M I ' " ,"' 1J~"d is clc:I.td "''l Uat LOn> ~ . J 8,4), l\' " illcipiom radical , peei« , h" chs,~ •• "h.r.~> ...i, h two OOnd . ('~~,~ , c"mpCl iri~ ~ i ~

dl~,.g.d

I""

0"·'

"""'1'<"" (",

,

e)~ ,c..l-l,

8 ,h V

' 6.'"

e.,tt,'ct<,p: I1! 8 h V

69

ev

<- G,H,' COC"......

,,-

a.e

.-" 1-

-

c.....•

'"

--'--

C,H, ~.

'"

JO~~

,W.

G1

-

OC". ,,,, { ~.3 1

•

x - c . l1
lJJ vV

--'--

• --'-

(;11,.="0(; 11, 10J"';'

CH,;CO' , ~

,,~

,ll 4f

~

n,ol~c> com""," Of t ho: ' ..... n proou cu fh.!I.. ~"",n' "fl"......1 ionil~l.cn ont'l:)' (I F.. T.hle

cte... od Il:qu;m oo 8,5) 1"' '' in" 'J' ienl j" dir~' ,h~' lI# ,,~rnlX'[i,ioll,

"

.,- _. _.... .....

'"

~ . .. .... '

-'!'- ~

:

~" ~:tH

..

0

-

~

-

"'

,, ;,O., . V

"'

"'0.'

A 100"':'

" ~ .,

'.

0

-

"'

e "'e,

(8.3)

~H

=

A ;' is b \'ored to ' CIUlU II>< "h~r~c and h' b<;c" "," lile innic Imwl..ct rf'l' Jlt>lt cntro tlie dfe<:Is are d ist:~>,""l C ,,,. F'~ lL '" 7.9 and orbital .' ymm<:try ror E4" .... i" n .~ 6 hd""'l "l olt 1"'11 ~~' ~ll ,., n· \ Kule Dredid s cor rect I) ' thot I f>~ ' l .,. ( PhO l ;n 1M rna", «'O'C\ru m of t' hO Pl\, IE{P hO ' ) _ R ~ cV and I F~ I"~ ) _ ~_3 eV. •' e" thoat h I'll ' .. ,n,,,,...I. bIc prod oc! ion: .i1l/ WhO ' l ls 2.~ ~ \' lim-er in."<Jna" "" ,,"l>;li...... ) tha n ~",l t'h ' ) i'-tt ab<>vc.l Th u. 10 Il>~ Sl~\'en ."" '. R ulo yo u d o not n...d I(> t \'31u.llC p , odl1Cl Leal > of la tlnal;" " , ,i nc " Ih o"" 0;,0 ",,1 nul for co m plemonlMj' h' n."' loIclitl al 1"'1<1""1'1. i \icrif~ Ihi; )'<>ur""lf UllMg [qua. ILun, 7.6- 7.8 [,,, ,1", .." mpJ"m,;.. ' ~d U\.1·~ , ~ " ntiloce mi, kollljJlIl!~ , a" d . ddib" nal r,,~lud f",m"'i " n hy " "'f'I'no.' ptllh w uld ha,.., th< " p",,,,;lc CIl'CI, ,\ppJ r~ nl ..a mple> ioclu.",. J iooc (ell) and m.t h~l .ll ._ y d o p l o ~ n" f..\ lCI') It m no.:cl ''''I'h. h~ k:"" ~dd",1~ (F ii ur e ~ .J J, T tIl: 3hu nd1nee. of the an:m, . tic (Ar l . ,KI C,H, fr"gmenu l<'nd to lhe ...me 'ulue. lJe'Ju ' . the" e"'rOS I)f" ~j i "g U' v. ILLo, m"t<;h '''0' . d o.cly. A plol . of Inl[ C. H. · I'TAr 'J) v. "us I E of the IUb. llt u'od Id Hana , t 9 ~4 1 . r., ~m pk . in,lioalc (hM r hi, mcth.:>d $..... """'" .., I I: , at""",..'it h i n + O,O~ eY, Slmil. rly, the rclro· U,c!>· Md or a~,li on " ' 4- .m~L..}clv"" ,~nc an d ",1>,10,1 die,," dim. " fOIlm Ibe ro", ['lcm,,"'. ' )' ,1""'0 ion, 1313Dd Ibl ll:quah "'l M./» ~f n""rl~ "'l ".1 ., h",><:1. 11,""', ~ l Ih""'-'l b) i"'>lvpt<; lalxhnt:;, llu. JK'inN. If) Q .1' ,,_

"'w,.'"

f"" "

si"""

$1'''''

....,_........

J.

..

.,

1 ~.6 1

Ib i

.">1; /lK'\;h..ni• .n of lhe ,,,acrioll in""l vlng Inn ' )''''m" lri" o l"'n- rin ~ illlemtedia'C tP~ ....ii

a"d T u~k 1 ~ ~4; Gro;;newl>l d and Grn l< 19M ]. (btl l h ~ n:ad ~ 'n JIfOU'Ul,\ 1 in . ,~ ",. ,,,lOO mode under N bilnl·.y",meln-' ronm>l, ~ "" m d.:>J I.t! O il lh~ ' i,,}'lcyd oh,,' cnc "'"l oe"l.... i" n "';1..1, "I thO' ~~""rc li" fragment (b,I IT~ •..:.-t ~ nd l " n,,~ 101M. "inuo the ' Hlg doubk b<'nol i , \10" j"ni,n\ion , jte(IE ~ ~ ,9 eY. (,,,,,pared vil h '1.6 .V lor the

,., __ lUI "",' ," mil"'" n C. II•• 'J I ", b(>Q..,JeJ<

'"

'" \'in~'l I!OIlP~ ' udl w fle lali.>r, ..."uIJ r~4 uirc prd" entia l romt:lu "" ,,( I l>~ Coo c"ned n.1n,. llid ...Aldcr J
R." Jnm ..... lUi/tiPn rear.....'~__" . l. n 1'\..,Dmme iml""Unl rtccaul inn for thi>. ....., 01 I E va ll'"' i, l hal II>< prOO llCl io o ""'~ ~<1u~lI) ""I't_""nl " mo ro-, ta ble iwlncf m tlle rorre'l"'nd ing . u h.in Jctmc ill the oniln41 mc>l <cu ~ (Rowe" nod Wdh.am, 19110; Sd,,,,"tI IQR I; '\fortO ll 1nl: I Q~ ~, Bowen 19911. T hi. 1< L...pc<.....u.y tJlK lo r Jo.. ..,nerg}' '" ,1",. ( m C ta I T ~ b lt lO"l l< l" i"n ' ;",1" ,,,<1 ,lipo ic ' Oltt$. C....~ ling a !""tcnli"l " . 11. WI"" "", hig\1 ..........Ti' IU ljWt nrl ra pidly ."",~po,: Ill<: \' fu, thn:Ihokl -.... ' gy rrngmenlO "" n be· tr apped 10m, m"ulh lo r j 'OlllCI' i.< ~\ ;" lI h. ' ''-'-'Of . .. hie}, ",~ n Ihl'n )'\eld A mono-' table ;""j~ (MINt'" 11<." " ,,1) p,, ><.lt w l(. :I, Fur U A~ ..'il }, ':'( ~~ V io nizatio n Ihe ;. H:/l-.:ka ' a," .....rro Qt<m.nt uf "-hcxanal ( Eqg~li"" RS I ei,'c, m" iniy C,lJ. O - ' (I~'A + ].(:.H •• ,n a c co r d a n~e wilh It... ... ...... ILIC H, -C HO H I _ 9.: . V an d. 1F.(I- l>ulco..:) - 9,6 ,.\, Ho w",'or, 11 Ie'" fl«t ro n eDefI'.i<,< It", C. H, I ' ion pre.~ , m ; I\;t ...... Will> ' ub; \an liul h}d l o~en tlehang<: loci..." "" 11><; t: , lJ. U ~ nd C. H, fra8me n.. (I( la beled M ~ ' (Liedl ke " nd nj9 l The<>reuca l """-... Iali,,'" lBulI <:houx "ai, I9g7i indl<'ll le IE..... I;,,,, ~. , ) Iha l In" ~HIr"s"n excha"F Ink.., ~l~.~ in ~" inn_mo looll!c <<" npJ
""""
I .

~.

I '

tu ~jj l' ion;""d 2·b Ll'CM (IE _, 9.1 cV) " od n.u l'a l " ""' ald,,h)'lmnl;on. ' ;nCl ic . " .d i.,. (\l,'t'hetd "I. I 9~ 2) . T he ,am" IOJi dominates the 7U·c\' m". l ~ t ", m. a., e. ptct<:d from IE ,7 9.1 eV fo' CH-, -C(O H), ,,><1 '1.6 uV C, H ,C H---('H , .•\1 1.-" ,i'" hfelime" ho ,",'c,'c' . lh. p,imary pl c.thlds, l>o "n ~ in ~ n i" n _m nk<:uIc co." plc... undergo rCJnaJl~cmell t alld eharal; ml ~ration to }'>tld 1M l· bul. ... io n el1t." ,'i<;h..,,,"/ I?fIII.;.an a~o be import ;w1 in 7v-" V d eC\TQn ;" ninlw ,,- 'peef h~ 1 Vr",,,p b~ ~·d'"""6'C ~ " I'" ...h= ,I>e C 'l"""".. trd "xireo~ io u. $1Il~ ' hil i> a h1,tt- <JI~,gy Slraiued -flng rr" ....uk a nd Mel ~JTer')' Im l, In
r.. ,

."""ies

-'"

n"' "

j~

"',. V, 2 . ,",,' 'I )' l\ ~ l r a hy d rdu ,. 1I.

which produ« , a " . f}' 'tab le C.H , t r io n h~ 4 ,rcct ~· ,; l e u ' '' ie 'B uucholl\ Of "I.. I~~~ J . The nanallylic los< 01 ~-.lk yl radic. l, h om un ''' l LlrM l~J ~lJ.:hrJo" l ot"".., a"d ~,t.rs proce~d. ,.j" a , . H ""'-fTlngc.......l. ""-,'I,,Vou, t(, pllolond (lOQua!ion ~.\I ~ "R a n d om N41l'lln ll\=lll<,.-n I, " a'c lh. b.,i . feuo n wh y Ii>< ,pect, a o f Rl,l ny i'ulll (!::qu ati on S,II, , ueh .. I· ....1:w,ulen<. a re ";milar. Tbo aeti"aliou e~l g v lor ;K>I'ltl;(Iulio"- of I.C. H ; ' is 1.0 . ...-. ,"'..,.. 1.Ii eryy
.,- _

".

--

.. ....

•

'J'<..~ r.1 ~ •• mo rt effeCli ve in d ilI'''''' lih\ in~ Ihc"" ;"",rner. (Scc:oon n ~~ .... ~ lilt

isomm'3,ion an d

d; ~~ (lCIati o n

bmrkrs

0( 1 " " ll ~ 1 ! .c~H.

,,'" nn rly "'1',,,1

IFcllJl ~I aI. 1'.l8'.Jl

T" .Ir:WcI a ,.,.... l" m Of hklden , ~ art3 n ~cm cn t, remo,,' bcr tha llh will hIo\-e m1Jdl high<1" cnfJ"!'Y ' C<,uld be much m" •• C'' '''l ...... ili. c . 1 h,... <'JoelTOn cncrg ;", or in m., l « a"'" ion <1i"" ":'",'",,, ,\ 1"",~t "C1 ion ", h l'U .b u"da",,< m"rCa'C' ~llo" eM','-or prolonged ructlon tome «>uld 1I be formed by l'"nr r~"~",,, "nl . e' e" ir " lllcohni' licall)" l'h \ll,hle . "" I,I..-d. ~~ I... T ~ " a J ,,, n \>I.- drdwn to :occnunt f<>r ;1, forllLa t i" " . t :hU'I(t c(>mp<'/I/i"" I~ Ce- J~c",nJ'<'.mfOln: f'uhl'~ II~ . Ah "",,~h Ste vens o n "

Rw. j , . 1", a p r lica f>lc ,,, FE ' io ", . Qf "J diu",,-,I pn:d;':t i". ' all", i, a propo '-li by fleWl ( l ~nl , nn'p1ifiod by /kno.'e n .., " I ( I 'P SI TI.;. r.,i nl, om lite ..""~'1!" "td"omhili' y ~I' ji)m JI" y "• ~ t1~ I",,' I'' '>too ,.g i>W ~. (PAl in
.,,,,,,1,,

"r

<'I ;',n(. I~ l ' p~ rt ""'li " lly to

io ml tho;: l<:ower P I\ IlCUUD!.) Corui.Jer ~ l'>ll h" til"", "f PI\(Y) on lh. one-bond cloh allo 01' ..., EE ' 100. ,''V _II ' . Y, l O 10..., lb. m~ loc u l c Y Iformation of th e ... di<:. t, A + Y is not fa.".."./. '>cctio m- 4 4, 4,7, 8.8~ Aro,l.Jj"lll " Field (1972), the te Mi. ncy r", Ill" co......."" "'. eti<>o. A- + Y _ A '" ."o uld depend on lire amnily ,,{ Y foJ Ih" A· IOn Ll!>e cnti<:.al .... f~r 'h... u~ t I", negligihk: (ho re""r si bill1y (t: H., ),t:HO~ H, .. ((,Il "loCH ' + H~O II.. bft n dem"m lr, leoj, Tcrluuw ct ~I, 19$61. 'r lre ..clali ", a m nii)' "r a Y moi«ull' "". " J"'l1icul art "hNJ l~ rel~h"l I" CH : ~mni [ y "Alae '!: H'"urnan 19 8 8 ~ ,u thllh. ten "'-"'-'Y rm diffeT..,1 AY· ions \1> I"", til<; Slim. A' ion .!l()uld he ~prf<>l'ma!riy in !h<' "" ""'I: on;I..., '" PAlY, of too "'''JT''''''l''' nd in~ Y mO~lll.s tlJ~lt '\ ,3). Th o lea.i n~ a M ine. ," fhe 1
....

_-...

'"

l'l" i",.. I", ,,,,,tJ h. U . II. i , '''m hl !",--.Ji", ,hc I" "" " f H(l I I'A _ 5 8 ~"-"",m;o " "" ""al, d ohl"'.....lh "" 10 b< m"m ~rtal e1 ' han , "" I""" " f " ;01'" lI"A _ 7.2 oV) f,,,m ' ho <..." o' p...... h..1; r' '' .on ~ . o d ;tJuld 1'< I~ rv< ' Ih;>n 1"" I",,,, ,,' NH, .,,-\ _ '1.0 < "~I r" ~11 .h" u"n.,..~"'Ji,,~ I'''''''''. ,.... ~", i,oo. •• iI. Quon l italivd ) , , It... i' < ~ ..r,,"<ecl<1o/y1;c hon " J .. """j~.i(>n cne. gi"" f hhlc " .3, TIl(' ,:"",""",p<)n.lin~ y~""" .1. HU · · K. LO. V, H ,0' ok . l. t> . ...; and H , N ' ok . 2.9 . V. F",... all yl jon> 11>0 I"", or C, H. (1' 4 - 7.110":1 i. fu. ",cd II"" of hi~ "'" ;o.~ ,"'" l " 4 I M oeH - eH z I - 1 8 . vJ " " I JlC«l$3'!; "","e. e,. r..... Me.<.- 111(' 1001. (>/ (.·H. (1'4 - 5.7 oVl i. fdn"r.d 1 or 1M uJl£.... um.cd lil'- i ons. R- OC= U · . K - l~ U ' , K - US::":'U ' . ""d k -O' ---'-C H" or ~".I imem al ene' lti~ ' he Ios;es (>/ CO, IPA _ 1.':" . " LCO (1) 2l SO , (I> I>L . "d {}--{"H , (1."L TC'flCdiYl;t)., . ..., ,,hl .IM" &"'-n:>t'" ",i, I> m· ,,,,,Iarly, m [.qua " "". 8 IUand II. 12 , ...... , h,,"1d .end to he more los ' of Immaldehydr lhaD (>/ ~ce1~k1myd • . 'ho hiibrr

,,""",.cd.

""'."'''gem'''',

pro'''''

"0'0I ."" .

,H !)

(@ .1l1 "",Ion a lii",,;.,. of t"""" I1nsaruratrd n...l ra k ro D mak.. '-">ItIptUti. c , 1>0 "-> '
t CO rca rr""gonent nld u~'1 -io.. pll,,",,,,,,, r '" ~"'p,un: til<: 1""'''''' d..pn ' '''=''1 ..." it> PA v~l 11e. ...ilh F",,,al i,,,, R,1J fav""",, " . " , 8.11, RearTa n;......nt io ~"nlre'itivc ""Ih indnctl "" dra.a~ ( l' q uaUtln1 ~. 1Il and ~ 1::1 " " I ' ''e PrOOYCI a h""d. ....... a re a!k<:' 10 ;Is ..lmn<1anu: " f HO C HCH , ( [his ...it 4-' i" n .. ...-It C.H , O ' • C. . H , OC' yield. ",,': ~ , 00 O ~ StlclI l':l + ",ar ra np:menl .~ ,-" I"""

,,,act,,,,,,,

'i""'" ,1'>,

"

".

- _. .... .. .......... -.. ...,

•

"

..,

(~ .1 4)

C, ,,,' • O·-'"I;H.,

dlte.tly u",ful fur PfM i<"tillll relmi•• " \-",udall"'" of prod uct' that at 11lgh"r cllcr¥ic. ""'p<"""nl (he "" mp"liti" n "f i ' nd , H reaction>, The MI >pcclrllm of C,H ,O-- 'l'H. - , bow, no C, H , ' , blll HU CH,.' represent. a major peak (W;tb"uL 1'''loP;" l ~he lin ~ the prc><1 ~ " " ~ n:: tho ,amo as th", " or Equalion S.II; Dowen 1978, 199JA' K ing' lon n " I. 198J: 7oJl;n~ .. an d SeibJ 1985). Even in 7Q-eV s!X'cT.T n, 11M/ever, lh. pmtnl1 _oound com pl'l reactinn can .,C1t,O · - (: Ii C I J" leadinl tn 1 4~,~ IIO ' =C1I C!I , a< well as :"2~'; DO ' - CIl CII , . Equa tion 8,B "" n form onl j' the laner. whereas both will h<: r"rrr",J (F'l uali" n U 4) hI' Cn ,cH,O ' - ··CHC H , ;± CD , - C H, 0' O=C IICTl, or CTl, DCO , O += C rrCII , <=, CIIO = CO, "[[-"'0= C HC H , ... etc, ? rololl·lmund "ompk ,c; play a role in Ihe dcc"mp",il.;"n "f pml.nm,I"d pI",,,)'! ' . I>II I"" yl . ' her (Fq ll . lion ~. I5) r" rmcd b}'exother mic (m'than,) Cl. T h'

d· / . J....,'--"'-

IH 1'i)

'"' "l H i" n. "'~ L~" " "" b;: !"oJ d ul. I ~ ~ J l. <earn,,&,", to a I'rot" n- b"",Kl UJ ..,lit .. Ie
tl>c pro t" " atl.odx4 IQ pbm " l l l' " '" g,5 eVi " r butadiene (pA ~ ~,4 . V~ At [" ",,,r lOl" ta ' lattle i" " ' i lhe IKU<'''''U:: (",. Ih" .. u,,,, tx" ie pl",,,,.[ l" tela in ti,e pl'Q(on l>t,."mes even mo.., l" O' '''''n.:eJ (M tl' <~ n l ., " I. I ~~ 'i l

"""'l'''''

Q ua e rompetition betweeo I"'" mc.>kc. b r" , I"~ ' ''''100 ron· to iu.«l ,n a I'''"o~ho'und com plex ean be u..oo lQ de\' 'nei 'U '" ,..;1...... m
collisio""Uy ," 'i vatM dJ" ",,;ation or (I>;; ,;o." plc. , " ",hm ~fTi n i li •• hB>e bo.n found \0 = <00 ,...'ilh i<m i,~ IK>n C'IlC,gi"" .. ilhm a ",, o K " cl ~I\d ll" rll" e!lYIl 1\l7\1~ '/ h" . Ihore i!; ~ qu"liu,'i .," in " ...", "'lalio""llip bet",..,,, S"'"""",m'. ' '''' Il''\eo ''i,,~ O.E " dec(>Mp,,,,tionl ~nd lllu.l:: ror ".t.d""n mp"';\io n, (1'''ble ,\,3~ w>t h , lr ocluI'e gen' l', lly . 1fe oo.n be nriJJe.rdittl «>r Tcac· liO!" Iha t f<>rm i><mlcn c ion ; or ""I1I f1, I, . Llr for tbo ........;,: ~,-,", ~ ll i .' . n "s is ~ ".,, ~d by b~01i c .. no t lhormodl.m;;try, A, 1"",. I••:":yu~",,, . all'ill.lU.; ro,' larger "".i,.... /C H • • C,H,' I can loUo..' tho ~"'l<' N :>0 0 ) l'~tll", Ihan 'hI ler prown "m"ilie' (r-; ;> s ;. O ~ as ' ''''''d lor rnO't'holi~. , thtomof ploolit>e. nnd 1,4 ' l h io , ~D(" IUl1 rin,ty atld C~ m l',ma 1984).

:",', ,,,,nl-pro.m,,,

[l"<,pn,, tIr. ~nua~y high.r impo rt" n"" "f rr,>du.~· ion ,ta~i h"" li o n a; a ...;1Cfion-d ri"mr f",c" . • m"r.·,l~b k n"'00 by nt~ lra l ~\ w.1I '" lho COnll• • I 'tI~ i,m 'labHiation; <1H, ({"H, - I :HO H - ',I - <1H riC H , CH O - 'j _ ll,H . II WI." . th. po",ihle ;0,," M •• ""all y the sa m. , t"h; Ii ,y. II><: dr~"l " cJe.rn; Ih. ~~ l
\ ~, l M

ntn"'S.,,~ It, .1 i flcr"n ti ~lc lit.," pwd "" u. hvwc".. A "",,,, -; m ro rt a~ L anal" lIUll> ,,,,,,,, i< t ~e ! OF,- ion< a l In ,,'; 1j(), 144, 15\1. , . , . :nu 11\ the m" $ Ir ""lr a "f ll><: n...!I .~ 1 ~ l "n

.~OCH,

.ICI1i'.

1~_1 7)

., .. __.........-.-

.1\"

of 7-. ~ - _ '1-, . J7· ll y d , ~ x y "' t u d e c a n o ic "eid (I>u t u ,,,,,,,,," ol,ng flI'a ~ , a ", 0,,1 lmP<'II""'t 6- ..nd l"w e, Ilydn> 1 l -(:.H ,~ •• n.u, -2.4 . V lor C. H,CHO _

r"t

S"RJ I~"'I"..., Tt.<: k<' ~II-1>d 4.7 eV, i , aon oll~ th. hillh. >.l l ll< ' ''' n (hhlc '\ '~ ~n Ihe ma" 'pe< ~. no /" L i"" f:n"'$Y of ,t.< rn<>k 5 eV lli9 f",r tha " IF.(' F, ·). "..l ia g UW" C - - t ·· ) l><."lIal1:>l~ .m~ll . I" ",mira" , lhi, dirr"TlOnc"" i. ~ . 1 . \ ' ( ",,,i: allO" ..I _ 4 tl of r: F. " similar .,a mple ,~Cel , ., ,...h j;h IF ICO .- 1 H .V , t! Ie" t n ~n I EICCI,F -l. ~ .() ,,\' , I n" . h" ""."",,,. m (Lq Wl Linn ~. I *~ He'" '''' yl''' ~ olld d i " oci~t i(", a t a n U,· , "~ o n lhe o::ati" n

,.It,,,,,,,

-~ 1tIC '

"

,/"

_..

",

R'.O".. ~

I\'(O ' '''~

=

, -~

• ,.

..• .,

I~- I ~ )

~

nll" I; I)' of Ihe lea ,j,,!\ ~",up (";d,, .'·" fWd), .. ,h ic~ on ~ha'gt mieratioll lorml Lhe

,..,,,,•• 1 1',,,.,1 ,,,,1. How ever. hom ol ~ l ic bend d e.a\'38" Inrm , I"' '' ood- eleetfoll 1" 00' '''' '' and 30 ," "" II;' 'elJu,"", m",t. ~lO" enerin lUI'. 'I'M hQmul) li<: 00n ~ ~i "oc i al io n ener ~,.. 0( \' Il l>on&

U OI.,., 'Ad"'.

.,....djt." - -

,

' ff

1 ~191

in pto>'o ~~ted alcohol" "kkh~ .Jo; ~.1I'n,;.. ." 1" ' " chlor iUc..., . lId ' ~'Il n id>:s (re' "," ,e,o nd , Iep. I:! G u ~ti "n l' 1910=....-.1 100 40 w 4,J -eV ,'a ll,•• nr C;- H ;,,,n,l, (fin-t " ''P) ill ' ....... lral a ll.lb<S A.h T hi! impl~, thaI h~·d roi.n­ tra m rcr rcar raOl"'m"nl. ffUm "" .... m . " m.. III O . Cl. '" CN t o )' ieW do. ,j""""iI: radical ion ' N ¥ " H e", ofu.-n exolhermio. onerV llcally fH" r; n ~ t"" ", p",h..a )•. Further. , e,n l lhe KY" H wnd tho' l e .,~ \ In \ "H 1<-.., The C'J\c-rgic, r"r hctcm lytie "~,. lLolI of these bond . follo,,' the rul~ kn" ..n Im m "'ionic chcm i .' r ~ ; ",ilh C- Y \>unt! , lhe Im alOman~ ~lIin i l, . Field" Rule) ill lhe hcto m,, 'om-comainin~ ~roul>; C- OH , ' ., C Ol l k· < C NIl , ' (M" lI un, 1 9~2; Rein.., Han i.. " , l "' l\4~

n.b.,

,,,,,,Ie

8.3 &"'.Ie facto,s

Alt h«"l>;li'...... uf proooc" Md inlcrmediatC$ ." ," ~ ..., imro" "nt fa. mr< ;n ~erm; nill" ion . bundancc, . _'1" 1,, a h,,, affect lbe I"" l nen '~t; un k;'ICll<:5. Sle reocbe m "t ,~· ..,n ,omel;me. be dl'd ,oor< rn ,~ e n n ' l ~ n l rn, a gi. m rnx' " \..'" I l~ ua li on 7.1\ "e!,",nds 0<. Ih. number " f , t.. ,", 4\,all.hl. in til<: u a "",IJon eo m jl le ~; lhis i. detcmumd b ~ hnlh Ih. uorgy bamer fE. . E., I ,," '. ,I>.: d.:","I) ,i ' 1"1... The lIt,tc, (crm rclllXlj Ihe numhe , nr way' i ~ .. hich , be l1'3n" lroo c'-'mplea can be fomKld on' lw " "y l" Ihe prod"".. , ~n d i, lf14lW 1" Ihe 5'eric ""l u' I'C me,,'" 01 the d,,,,ooau "" oc "I,,,,,,,,~ 1Ill", ition ..a..... in ..·hid> 11", " uml,., of .. t ~in " hk . talc, (e<pa:iaUy 'hou d... ' 0 inlornal ''' l ~ li on , l d ,ff"", ~ tll" f.om that in the fe. Cla nl ioo. It,. ." " I, u,l. ill bond",.l i~l' ('.If"",mut jon, (re"' m ni.ln llfl tl~ ....In<"'" 1hc llllern.1 1'Of,lIlnn, lUll" he rfCrU''' IO " Ilnw for t ~o nnkrc,J ' r"",i liutl ",mple>.. t or . xa m pk in lbe ~ . !I"'{i ­ c"''''a ,;oo reu" ul1 grment ( Equations 4.33. 8. 2 ~ , "c 7'" H will be wi,hin ~ lX'nd ill1 "«'nn"" LlI the rOld icnl , i1< in only ~ "",. lJ proro . tion of ,~c tot, 1 I"",;hl. r.nnlorm.. I ; ,, ~, ' 0" ,,,, ,I,,,,u1..r ion. Att~inlll~ It><: " . n, " ion
f",'"",

"" ",po,

"r

'ili,."""

·'_....._-_. -._altoolljlh p" ",l llc1 'l ~il ; li( ic'" , ~ n " I ( 1 f" ,'or 1h ~ r"!rouged l , H.V _. ' 0.... b~ 0.6 c ..... lhe ......., ... an: oom inA'rd by , he C , H ,o ' iNIS (11)(1".,;) flthe. h~n
"'''''·'0In.

If lheI e ~ .c n" ni"...,l ,lifr~r .n ," ' in th e 'lshiht!" of the com"" li,,!> p,, >d"<:l' md intcrmedla1e<. M';II IIw: ac tivat ion barriers. the rill~ , ;,'" "I tho r... rran~,monl Can he "" (I<" l" n, r ' \'e' Mot! ,i . -tl,,""nhcrc.! lramition l t~t~' Ql e l!~"cr. ll y f"",,,"hk·. [or h~·d r~II ·' l'3..u" .u ctions (:>.1cAdoo ' I 01. Iq~4) , wherra' those ",ilh (..,UI .m el thlfC·momhettd ,in~. ", e '"m. (Sect ion 4,'.i. reochon , 4.37 QM 4 .40 ~ the e"," lelll ,",Ii" , of the helero..l" m affect< , he pld t ncd rin~ size !.\. F,limin,,,ion (fiv< -melll""ro:.l lin~ 1 pl'Odom iM l<:'S for llCl and HRT chm''''' · li.)n< I,om ~J k yl ~ hl ori dc , end broll,;de, (F.'lu."l;" n 4 .40 ~ ~ ,..l "'~~ ' ~1- ~nd 60"'~ 1,4·rlimi"" lj",., " I H ., ~ !, ,' ~",r v,d Irom thi" I,. M:tinly L«l imi fl ~ ,i Q1l of " " ter i. found fro m M O' or , hon·ehain alcohol' (Equat!"" 4.J R. BIId. ik ic.. ic.< t l Ill. 1967; ~,e , II" . , he fin" l prod ucl I'rom n-h" l>n" I' ;. "",' hyky..-J(>pr<' \>I;;r k... lrum , hoP F.f. ' ion n-C , H ,, - CH OH + IO f1T~ fT"'" (n-C, n II ), C II O II ,K u.. cr 3nd 'Ocll>! 1~7 6~ fJllcrc>l ingly. 1M - H , 0 1" r...,m "-C"H ,, OH --; \ I,,"ntd ...;' h 1~·~ 1.4- "",1 63 ~';, 1,5-elimins tlon: h"",e,·e.". m"c h of Ihi> ~r pca '" t" "" d ,,,, to I" Mhe' kosb of ( ·, H. lrom lile 1.4_prodnct. "' (M C, 1f,DOt oMM U ~ ' :47 for 4-<1 , . 5.-d , iBuko. i' L ~ " d RruI,i. ic",;a I ~~ JI . $,mil.,l y. the ellSpl""""...." f'eIlCIio., n 44Z "I II - K Hz', Y r ompo" nd, yield, eyeli<: (M - R I' inn< ;n 1"1>"", I"" /i'....membc1v<J-rins ' PC'''''' pr. dominal e fo r Y _ C I. Or, J nd ~ I I . ,>nd \ke ,'x-mcrnbcfcd 101 Y _ :"'H, . T he " ",rer. c"'-< "" -" " , .nl. l1l her. d lran,ilioll ' lalc . 1,,, ~ f'I'Iic.-< h ' ,I><; cl1 m i n~ t lo n of wrmaklehyJc ft" ", 2· p1>cnylclh" nol, whiCh forms II><; .......l.ll bk: n. ~ ~ V ) m.;' h)·lcoecyc!ahexadiene \<>n (1 ·:qua liOll ~ . 2(l, Burl"u ~ l d1. f'.ll\1l

r'v'H, _

/ /

C() ~

~:D !.~ I~. 4'

,,'"

-,""

~ C", •

-

"

"X ) (8,201

lie

0

" '"

.,c

'" R ~ ute (b~ ~lOing c"" "'<m:.,I~ bl " loluOM j",~ " n 4 41, ' ''at invoh . hytirogo" tr and.. b:I"'.. n ""'d1 b.mnJ jn mp' on an .."""" ie rin ll- n",,, r"Hrran)l.~mcn ll. "~ Jf<'aIl~ LocH_ il ~lc~l hy IlL. rigid pIa,,", a n ~me>ll of lh. ;nl orac tin, ~l'I'u", Ib" l impost' n qdic lr~ o .;liVll in I"" !l.>od, a ll~ ( 1II:d to and in the awma llC,(n ~_ I his IS w ry ,,,of,,1 r"t the loc alj~n of "" Iu>- ... l» lit" onIS, as the Iarg. .. ,p~ti a l K PI ",.,on I:let","eMIn, ra_ " nd pu....... itu. lc..:l Y'l " pl wa ke, una lo~ou, intem" 'io,,. "" ",h.. . ~" kcr nr n<me, i, '.nl. ~ lc rio: dL.1; ,'tln all o ~ r i ," from non-bolldin, , In ;" 1..., train rd,d . ..him promote. tl1< -di · , ~rl· bul~·I bc
"r..

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is

1-.,) ,,"• •" " ".. . if16~

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btr ",.,rJis ' , rr...,wJ;" . Qui '" dt1l:erent .lnw cIT",, " " 1',:1 ~l" III f, all LlJent ation. pmooo
. '

ol io' .... , ......,""

199JJj In (he\e di...,...,~ 'i ~n" tl'" pliula r)' i" " ~ n ~ ll\..." ral rr:.V"onh do n<'l inunodi'lely. hul ", m ~ i n ongaged ;u, COn1pJe4 hold .. tgelh< . b}' all.o c· I;," ;o" ..li1'o'" " r ;" n.; .... u ~ ,hpol. forcc s. SllWe lb. ;on-,Ilpolr i" ~' ~ "lj ",.. • r~ much Ie" d;r":l j(lnil.l ' ha n cov alt1JI oo"d " lll" j"" a" ~ "~ "l .... eoun lf " C"ll ro tal . ",lal,l'e I<> ..,..,h "lIlL"T, and cv cn t \t ~Jj y react al , ileo; m""" ... .... "'~ h' " ;" the ",i ~; na l strucr ure. Anal"......1 Iv (h. 10" or Cll ,O f", m I'hClI , C Il , 0 jJ , ' IUl uat ;on K 18\ I'hOCH , RH _. Jose> e li , - 1(; I",w " w , here the """" ",..tile I ~ H" _ O.~ .Vj PhOH ' ,. r,.. ""',1 , h' {t\'lIh on i on ·ltlol~o ul< Ull" n ,,< d ;~ le ( I<1 . " I"~ I~ R2: H"m i, h ,, 1>(1 H"'m•• 199.1).. 0 "", <~ the roo", dmm~lic .,ample. of , ,,,,h WtHHnscmm" " lhc l111cr""tion of te" ",l" lV" u,.. l,,,,... c~l in II>e .1- " nd the lI- or Xl-poo' lIo", of Iht ' lel'o ld , kd eWh iLt< ngt'<,jallr 19l14 , l " ~ll ~ oll ~w;nil the ~'- Hi/l -d<-a " al!>" ""'ua ,,~,,,n "" )1 (>f lho 3· ~.'l~mj do ~roup IEqu al;"" ~,2 1 ). the mokCLlIo o( N.m~l hyf.1a:tamid~ ,~p~m l.

"",Is

-r

I I •

I

(~.1 1 )

w

J

,.i J "':>-\i '0. , H, C

fr'" lOCI

CM I ",roam, lit 1"" "" Ill;I) of tho ion and mo,.,. Hcm .. lhc "'~ roj d , o: e ~ t on to f",n, . 'I~b i "z( d h ~ d . ~", )- I-" , m l ""m1'k' with the 2!l-am;" u "",up. T h~, r"e" wall)' d;•.....,j. l'.. hf ,...lca"" g~ 10 form the Inn "I ",:c !O3. ~"t" Ih~l "the, r a 1h"'"J ' to bli n~ me r......liu.....t Il!OU!", 1"8eltd (he r1!UiJ ,r.ckt nn DI' tD cl< h C ...· '·..1..1 c..:--<::

'" oon< CH O grCl UI' in the prnw""tcd ",-...~.ld""l'd. of l:on 11.12 Gall "'·~ I • • c "' ~, lho aromntic n nK tv reach ~ ...n",'~ ( .~d " I"... ,\.,j"" itu=.., t>lC) m el ho ~ yl , fO'l1 l l; n ~ in d i",,,,a t;oD 01 mtthyl r.' rmat. l Filfl.'o and G rulLmachel 19 ~ 6)_

,-cHO 'inli w olk

",, -- e,ti,

1~ _ 22 )

+ tlGO<::>CH;,

h",,,i Ji. ........!iNm. Ck.. v~ ge , or a l i ll ~ ~ b~ ml;n ~n UL - - ;01l ,~n be I'" ;M1 < ,, ~ I ~im n_ '" " · ,,,b' I. I. a. o:>tItroI dC II'>U I Ij, ~ Ot ~ .. m pl.. (M H)' "'M formridfldlt&d h~ d ro~ell """" ("~,, the 11'3n<;- , " nuIJ led i""mer a are m<>re ~" .. nd. m lhim ' ",,"0 fro m the cl$';S<>m~r I> "n d J.l . n ui I Q~ .1 \. In R.23ta~ Ilw n"n - I)"ndm~ ".o, bita! a l Simp '~

,w," o-d ifferenliafjll~ if

ff''''''''''

(~ O' Y¥<' II

.tom [un. li" m a . a oontro l ~l0\«1 ", ~c h i~ ..e mn ;,," ,n, ",..., top ill tho "....,;IJtJn . (~ I~ (MC",oc lcctT<>n ic ....,mroL Tu r~cek and Hun u! 19S6. T u ~l 199 1..). The ~i$'~ n nulu tcd , ~elel on coi l< ~ 1(hI mu, l ulld cr ~o 0 ( " " (Ya.. ~ enl 10 att ain a fa ,m~h l ~ ....,lIforml<: bond. ( ~.~ r1<'l h.l urn 1982~ FOf eumpk . 10.. of ,hlm i"" f' '' m 110.: ch...."'tlOflro . ""' ~ o M ;"" me fl l ~ j to (0.11 in b ju. ' '''l\ 8.2" ;, ",,,. lplh" elJ rl u/, 1 9 8 ~ 1

·._.... __. _._o~o

IK 24)

,. ......,..""._111•.

UIC - ' T bt . 1.t. ~ ""h . m ""' l , c<j u;,mK:nl' ,,[ Lh~ I, ,,-" .il;,," ,laic for hydl 0lt"" ,~r< ."I";"","1 ""n h,: m~,'" "oun: n W"lU u, with un, a luratiun, a, well ~ , .,"lh tM r."rlGtoon< of cycltc '1JuCl u",. - I ~. ",,,-, ranllomcnt nf ~ ~'- H to on un" I "fa l~U . ll" " iO ~rim. eum""'. Th . , Lel" ' I.'..».! .~ cl'"- were u",J t" . how lhnt lh~ i -h" d, ,,,,,,, , d"", ""..l "" "" I ~ ... " ...... I ~ c~rbon )'l ~ro"p. and 1h" , Ih" nynm B"" ', "=,.i b ;l; l~' <:.an ~ affected b) \"" m3li. c m " r.gura1ion at the 1, p, o n atomi {Dicr... , ; "-no! ·h . b. 1%6; KiA",.I"'" .I ..J. 19( 4). F" , . "',\lple, 01 t h~ st"eoi, omor i<:: l d u"..... i_I .Ad lbl in Fq .....i.m 8.25. <Jniy tll< ",J~ i>.u mcT ~n d c,g "" , the lan M m ;- ·ll//l'...:ll--a,-. Il" r~-a rTa ~1 tll;"l ~ ~ ... nse 1.' the cydo~ntad ~n ol ;0<1 . 1 mit ~2 [ H ~I"""h. h
. ".. oifiD ,,--\ ..

,.,"

,.

,"

' ." -tt

"

••

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.

,~

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•

o

._.- ....... ID«h..DJ:<Jn rr.. , "':-d.... ~I. I ')')(),,-~ thi; would ,el. "" od_ lI yillOjl:< n If~" MaamCntl lD "" Iur utcd O lt" io n. U ll 31", n hlbtt "Vrrir.",,~ l ,*n"",,-t..'mi "~l . lTcct. Her. lile t"'''d-mak ing :;top . 100 depend> """ ily on Ill< >paiial pro.,,,,ity or tile . c~plor ~ roll f' "" d Ihe h}.Jw l'P' ....>10 t>el!ljl tr4 n>rerred. In the molecuhu inn of tr ~ ~I.4-I<'f'I-t>uly ~rlo "'"""c l. lh< I, t li" , y hr
." - H,Ol'.

1 ~ . 2~)

rile Ctl crgy needed IN th. choir-fo-"""l < unl"orm~li' >1l ..1e. citati on {...0.5 •V) i'\ compo, abk 10 Ibe "-jl,,al ."". .., for Ih. 10;, or waler IG=n rr "I. I Q7~). /';"1. tha t til< !erti • • y.H" n" l .. ,~ ilo,t>le fo, direct [ransle. "ia a . i._ mcmbtred t r~ n oi. tion , Ia,e in t lot .-rH . otmr; lh ls I><.>m<: , climina l. ' wate , to a nm.;h )e. K I e ~ te n, a di ff. ,,,,,I.noch.lrnt m The """"""hili,y I", I. a......, " ' , h lelal hydrogen alOm" can he ' ... ·$u d f....... precil:ion molecula , moJo:!. cr lfl<Jl~"ul ~, KT~l'h "", program•. TI, e n abililY '" Ihe inw mel~b1 ": ' 0 ,~i . pre"""", can »f <:>.t 1M ' '-4''. '')I''",. nl path...ay compete, "' ;r!l %-cleU I (t<' of th. hierinA l'ill(o ~

.i.

''''So ...

'"",Ie

I::t;" ,.,..r"'''It~_n''. Stericdfm-. a... f'l" "'~.l.o r'~ 'l",nl'- in the di>sociations of 1:1::" 10111 p,-oJ>lCN b y chemical ionilali.on '" mulrifunctlo nal ooffil' " uIKI, . Th i. ",lte llOlty I'CfUII, I,,,,,, l...n ~ . I.fi l i, .....1efk e" , (i) I tll.btlilal,on of M H' by inl, a-

molu" J;,r prolan elldation. ~nd (ii) nelg llborln g g rc>~ p pa rticipa tion in the d>mlll;llioo of , mall mol<'C ~Je , . For e. a,nple, prot on ~ to d. d.- 1,4-cydol1e.aned.iol jll.17. a) sill' "'' m LLch It:s. Ira~)I)en lal;O " b ~ \0\' of

,. tha n d"", ,he (Imt"" ..ll~d """,·isomer ( ~ 27lY. Wmkl.. a nd M. L"trorl)' 1974~ Fo llowing proro nalio... l~ ' ca n ~»lIInO a boat-lih ,",,,,r"''''' 'i,,n in " ,hid. the I'",t"" (" rm• • h ~d"'ro..... hr;J1'C \Io.1 """,n I~ " lw" 0_1''-'"'' . tom ,. ,II", "ahi~zing I II~ ion Ill' (t2 ~y (Gutn'l[ ~ ill l'iHI :>;" l ~d] stllbillln ,,( ...;Ll~r. ,\ mino-, 1''''~ 1''' m 1l2lt{el (H.>Ur ik; I>"nd.- in (d) lh lonen and T a. k".... l'lg ~ call ,,00 'l.l ~ il;'" din~ d. lhydrc>g. n or

w~,"r

I g . 2~1

M. j or stereochemical df"eu oro 015.0 " u5.rill~ Y""I' pant · eipa li" " iTl eli" "e ial,,,n . or MH ' [!Om eyehe ell",,, and ~... lcP; (Il~...po ndc'" fl ai, WI ~\ In prot" " Mcd L~l-d lO c<:toX)'C)'cl<>ltcun

c "tid 1<" '<'0 tin"" 3. l oton" cd an 311d DCIfhlk>ring-sro up pa"""l"'li"" a .c oftcn 'ylle,gill ite ,",'ith Illo fo".... illCl •• l-in. t~ st ~ bili! y or ti!·isome.. 900 I~ Jalt or pm mol mj

i..,,,,,,,

di"",,,,iali.,n, ,,(" ...... ~,mc"'[)iffo",,,l ("' ; ""'"1" ' ''''' polh....,,), (0)11,,,,.;,,; CI (;....00"'...) m a~ . it r<'",il>k In dlU;ngut... rtgio- a nd. ' I• ..,.,;"".... ric o:yclC'l('mltllnnt phtl Mad d",," {Fqua. li<m R.ll'll HCdd-t<","""d ....' 11>0... (al . rnt/l>l un.Ie.,-!!', r.."ik el"aV" 8" ,,( the cy d " .

m

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blHflnono " h8 Ii> gl V< l' !'{IlO natod "ycl" r<"tenone. Th~ l~_lp<'C;Ii\; t>.- h~. ior; 1hc , ,,dn·i, ,,mcc (CI rorm , a '"IY >W ble MH + ioo ( I ~J "U~ 10 1"<>WtI ~bdalion between I'" " ' ~ S"TI turlCliolllo. The MH ~ from the cxo-i""""", (11.., peak nl Ihr S~1n ( [ u mo nt it ..1. 1<)1').

., ...

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_-_. ......_--

FlimiM I,,,'" tor ., m ull m"Io:~"k", ,... n I-c ' l~<"""pcci r", =<."'" in MH - fru m polylunctionaJ cOm!Xl undl : ror . xampl. , MII + from (l"nne Th)tatcd ri l>ol,,· r~nQi ~ , limin;ol<. m~ th """l mo l\: teiWily l!>;rU 'd "' ''''' 1f:<j u. I'" '' RJ I , Mc........touITcr lU,d BIlI "" - 19l191_

(8.31)

.Ch il'3.lily ....... n " l1 tn:n .h",..,. '" .n""l Ihe 1""" . 11••" "r "" >1om -hound . om of o ptic.dl}- ' >ume no; """k>culos Ih lt$ a nd \~' ri lOh , 19n ; W i n ~1< , ,, al l "~ li Suming d tJ. I'llt(,. :"l il
pl. ~.,

Ita", d,lt m", ,, in ;n'. ' r ,"ting rna"

Tlltrlltl>(.'M"lk .... 'iank ~Jfrrt•. Th,,~ a 'pc<.1n. j . j ~ 10 ..ha l u tenl tho pt...cn ee

(>f all imllNtlnl )1<'ak \, due to oleric r...., <>1•. M a " ~ ' U rI an ~., n . ' l\ reacti(l Ll ' ao tln ou,h path.. ay<; llw: lll..ora bJlily of "'. .." ot


f,wo",l>Ic cru:rgd ie

;«.1''''''''


cnmf'l'liti' 'CIlCM of the , alc-dnn••• i, , l ~ . ffo.t nf "Tu. tu!. on " (Al. lhe r ""JEY deJ>O'lliM funchnn, HigM T_mnkmhr.",cighl 2." 1>. " ,,,,•• mow an u",,,ual C, H, O ' 1m,.', WJ ~~k_ which "pp" ",n poat i, ~-. ,>I ! ~"l of lhi: ha", pea k in 2_ undoc3 n<>n., i! i. '" 1'~: in l -bo u ,lOJlC. '11lc 1'111 runcl i"n, of I-'i gur e 7 -; off" an expb nation: then: i. " ..,,""'~ ' " lb. 1'11;) 1" , 1-h,,'O non., indicoting tnat rda li\'cly b. m()IOC\lI~r ion. are ,,,tmed with ;nl..n,,1. "" , gic, in , he mn2e 1 to 2 eV, To reiter.le. for eithe, "'lc' l"c l~l iLln or pred ict im, of mm, spectra. it i, im p<JItunt lo ' lu.-.Jy lhe . pecHa <>I cl".. ly . eh te
•.• Ae...tion initiation.1 , .dlc.1 0' chaf1l" sll"e L M: III th!l mech aUl, lic appro ach for" more-complex m"l ccHIc m nl,un;ng """ . cral ...,." blo , it.. I'or the Ic>cali zed charge and l,npair<'d e\e.ot rotl r.qu"es ",cigh lillf " f IlLc rd "li "0 im!X'rlance of e ~ch ,i t., Funll~ r , at ench ,ite rae impe .-

..._... _. ._..-. -

'"

t.o." "" of the' ta dieol amd 'h arl o, relative tn eac h OlMr, i $ reacno n I ~i l , .t " ", on "", ....., he p ,.iII caS"" of dcoomp<>\1tiMI r lly II, ,,-e111,>1 illlti.alinil lite, How.:' '', impor tant fn~""'"t~ 'lOfIO ""n u, ~, po.>1" ,;....-.1 l h~t the ' "31"' '' high.!}' ,t" bili"",,," (Tom er , r "I. I~~ ~ : CO",,,, l'IU i.

," o;n

R~latj "~ implJrl ancc of po>.ilok ..,~. , r OI a moJecule """ amlni r.On l n l~ la~ li!lll functlo n" l grou p>. lbe li" l \I,,,.~ ) ">niu,i"" ono' BY (IE) Ll, ua lly " ,,"e. p.:lnds I" the value d\~fl.e1eri>l. ic c t Ih. fun" ' ''''''''1 g, ,,up ~f tM low"'t I E voluc, Th" " illu
",,,,,,,,CI+,

C I<, S C H , CH . C ~ ,

fbl · ·g eVI

:OI "oV

CH, 8CH, CH, CHINH , ICOOH 1' 1 nov

CH, SoCH,C1I, ClI , 10' •.2 oV

r.H,s "'" I,CI ',co '1" l,i COOH 1; I .ltV

nol ~~~i~bly J, ,,,i.~ti,," wa h

;nfl uonc' the am ine IF nh", in , lycinc l$Yc, "nd J unk 1 %7~ 7U_,V electro n, can oceur at an y runc< i"n~l l!">~p, bul 11lc chari " ~ ~ n th<:~ be c>eh a u~cJ by I hf"" II:h ~p.><'e '" thr<>ugh-oo n<1 . ekctro n t,an, l" c (CIU. 1 ,md VI ,II. r I q~~ ) ...,fficicnll y fao-I to> p~ fl~ ~melll ~W_>n , The mu,t ~bul1d.ult I011i uf \11<:0< p.;>l}fu ortwnal moll \.i lt '" I," '.. e~l ioniz. tlon cn"r~y; the f,;"" pt.1h If' llte ~roclla . r" H, N- CH , ' far (h) and 'el. c.: H.,S (:H, ' for k ) and iIi amI (,'H ,!><'-(:H, - Jm ill:' and (8)· F or th" I ~t",r " .. u Ihi' I, tr ue 'ic' ri'" Ihe CKd tha I Iht apptaraoce ",,,,rgi,, at" -2.~ eV hlithu t n.. n i hKt fm lhei r (M _ COO H) ' "",,1.. " f>P'I rcMl1)' becau>e ,o>oondary d..."mj)O!oiuo," of

tho hi~hc:r"""""g:> C H, YU I,CH,CH

NH, ' yield,

~ddit .:", oJ

CH •r - (:H, '

",,"'N~ Jkfl1 ••, .'h.!:.....';t~ ;,.ili~';'m . The in itial cbarge 'lite ;n t/l~ ",,""'uJar ion 11M, ;" ll"ocral, th o "'0,1 fa--orabk m "lI vnmro l f" r .-abdiza.tion lor t ~ I"" ili, o . t.o.b>ltz'l"on ;." r,., plOOt'" ch,,' go. Olto n thi, i, ai, ,, In.: . ilO vi upll",,,m ion, f:>.. nr ing reaction' in which t!>e J"."' ti,~ ~h ~ , I!"-' W>L1I n"r move, For O F. ' Ir>l" , uch cha L'go -'~tont iDn =<.1'0'" in,~ yt ,o,tum"" or the ,~d,c'll 'iiI, ITahle 4 I. ~"OT ;"\1 ~ .5) . T hu, .ad, " ",,,UVII> lcfl~n Jl y mo, < o ~m m o n than ch",~" .CllO m (5.ect ion S,21, OIlthu ug h d ,"'.,ile rcaclJoos arc often t",'o", d ;n M +' ~om:>.lnlll~ "nl~' cl""1ro.... ~I"e , u\'lJlit llcn" M "lbo, intipiom ion' '" high . , ~hi hl )" . a,li .. · ""ne ~I "' ~~ nlct h3ni.;.rn 01 ha malytic cl.m·age [F"ig. " re 7.9lbl) I. d'..... ,...) fu, (C H,), C HCH , O H " '(CH ,j,C H' + CH , O Il in S«\IOn 7,e"

,ha,...-

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Thi<",,"n,,1 ";.,,, Il ~' Q weans te> for"" Uln.. dtr~ l ion 01p"",ibl. oJ..om,,,, . ;. lion 1',.. hYt'~~" ami th.i••el lliting proou~ . l.. hil" .... . ,,<1 . te. ic requircmenll 1 1K: Innit, of it, , ;,,,plify ma ;... wmptiml" howe"or. Ihoul<1 h<: rccognu oJ in ma...·' p"ctr a; inter pre," I;' ,n, S<>metifllCll. espc;:ially lOr m.,ltip k -bood cl . a,'~ ~ .... en bcl ra oJ" al or cha rll"-1Oite illll "'l;'m PrIx[""", the: same pt<>dIJct. ; tf'.e cyd l< ion ,1"""'''I''" it;''", 01 Eq.., l;<m 4,>11[ an al, o be wn U. n l~"I "" l l "' '' s.nJ a. a cha rge_' ;te ....ao ion. Tk """" ~ n \ ", 1 peak at m./z 56 ;n [I ", 1p.....I' '' "' of 2--mr lhyl_

o ~-. C --'-- C

~ ._-_

l" ; ~ rid;~ e

........... .,......

-

'"

c" uld 3M'll: (lhld l; ~icwi<:l U oj 196r. p, J161[rom a rel,<>- Dicl, -~ Id«

dec~ rnP'Jli I L~" 01 Ill<' ~·' lunJC pr<>dI>CI ""n 1 .Io~uu lio " ~ .34). l hoest pr od uc" c" u ~1 bl.., l>.: r,,''''eol by inili a! , -<:lea ,a~c in lhe ,in1\. followed by 10' '''' ofi..\ ti.

IR34) .." "'56

~nO.J C H, ·.

I.. OOnll'M I. t h~ ",tTO_ nKl' _Akkt F''1woli"" 4,31 "" rine.. a, ;",'oh'ing lndlcal-' ire mmution. ~. 'C IL ",ilh "" unp~ired ele'lro", 1''''''''' 1. c' on-decLNn jon, can llndcrgn renCll0m lhou ~h r t(1 h< ch," . " <eri, lie " f a raJical , ite, e"en at , ilo, remote from the ,hJl~e IU,"(1S' 1~SS I. Not. thaI \;milur r. ael;o,," o<:c ur in or!l~TlLc chemi't')'; i'. H,'~.cl"x ""~ ".Qlu,,~o m ."I' or "oQlral mol«uk, luh place in bo,h do'ed. ' hell (lelrO~1I0 re" eti(lll) ami " reno' hell (N()fri, h II pro<:o" j , y' ten" . while the,e und ~ ·H decomp"\ll\,," ~ OCCur lherma lly in c,l er... ,,,,,lha le,, , ,,Ifo,;do:;, and ~I Ll j,~ r t"J \~'. f o' lbe EE ~ ion5 or Eq u~ti {)o ~ . J 5 (Kraft and Spilcllcf 19lJl ~

f

I

IX )5)

~.~ hydro ,..~ is traosfemd ~peclrlCid l, t h W"~~ ~ .. , ",",,-· m l>.:« It ~ ")· H teur" niffl1ont to "" " nw\".aled v w p willi p-deau ge" d "",I) . imiL" 1.< 1Or: ' ["". li"lI> 4.n , 4.3$, and 4.36/= >h<> I::q....llQn ~ !n~ Met.· SU M [ [. LOM C!in ~ho "o>d<:r lf ~ !I.,. r"" rTllnl'",,,:nt ",il ll 1Ii{!1I Iq:i<. .,..eificily, ~QI;O,.d Ul lto ZoUin r0 po ,n' om, r ' , he ioci· ,k". e .. ill. l E' I "'..ell I.:......,. tllUl t!\at .,ith U le' ""' •. '110<- r- 1I:,I1dea 'J~" ~.ran ,c ,. t if> t ho; ('I .~ttll ..r ""utumr ed m""""' les . 1;0 olten .00.. """ olerp.o n ",. rt." lI"menl>. or ' he EE' l'f ol",,~ tc
11<'''''''''''',

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I D ...,mc .. ~ phalJ ~ ..nd aromatic eti l~r . ~ ...I I'lK:nylalk•.ll ••• , be P"'ltioo rl i , l ri h ~_ toon .... ,"" lr an, b ccd h~d l'Q ....n il. qUllC~ ,nih r to the "'If' e>.po.>n
H" .... ". r, 'omt oI . h"", ",""I;,m, in ",>l~e ~I=";ve ",a rra" actn<:nl"


lhro ug h i"n·m"k:L~ or pr':>I~n-t>rj dg.d rom,,'"'.,.... , ,,,,h tht lhe ~tOO u<:h altO 'tr uc t ura U~' rdai<'d '" i• .""oric intcnncdia lt< ral h'f lila " In the ol'l"nal L1j+ ion (" ud~, ~I .. ,. 1'fT/: \'.... i" .1 ~1. 1<)$7; Terl ..... ," . 1 " I. 1986; H. " " ,," 1':187); the role .>f lhe n ri ~ i n al churg<) sil. ~ "oJ immediately t v;<.lcDt ...-ilhoul d. ' ~ ikd ~1", ...Iod&e of 1~ , """li,, n ,,,,,cha QI ~ Readi" "' " <" ,,Ill \';, ua!i.ted "" l>e1l1 8 initiated .II d .a llc. Ii'e, can al, o !<>lr rla'" in FE + io ns in .. hi,h hill e oJ' I ~ C ,'har~ laiC Ilndo.&btodly con lribme. t ~ ' he " c,i,a li" " en" ay of ' he I [ n ~ " ""' '' L T oo Io<s 01 lin r",,,, C H,CH - { "H , Cll , Cl ha' al" "'''l been 1I ,~n a < ~ n ex. ml'k: IE'lU:)'ion 4.( 5) H,...",."" "re mote -site fragnlrollali<>n' - ,,( EI; + ions, . l <,VCI" '"ei ~ od and dc",h)p«I l>y (1" ,", ~ n J '"u· ...ork"" ( I"<>met .r 41 19R5; G"",< 1 9 ~n "'m actuall y br mor, ~ ~ ~n ta geo u . thlln (...·i, cha r ~c- ,il ~ f .a~t i o ns for o.."d , .oci, . ~ ' !IUCt ure. All..., ,,, i",~ t ,thcr Ul! + . .... !Of' • " , ,,ally , equi re 1m C"""'ID' lor j"".

meri""t;on o1lhc ,,,,, .. n1 dOlL b\!. bond th. n rnt ,Ii"",,,,ittli.m. m;UIII. " b ~ 1M ,1",,1,1. h.....J. B" ,1~ l>il Uin ~ 1M c h ar ~ e al ~ f~n1 J'f0yi
In S<>.:lk:Jll 4.4, Ulllmoloncular ion ,""",c"li" no "wo d.ssili. d b~' t ho ~ u m bn" of bond' bwk , " I,..t"'~n the "'PaTlIti"", 1M dod noulral pnRloct, HOfe ~ WID lW \;. in mohO <.. ,01 11", des ij(Jlal;ons ..~. , ~n d " i" ;l>dudc all Il l"'" "f ' ~ "" l i o ", forffiula lnl a. 'n...... in' initi" t;" ,, " l n raJj~1 1 Of "',,"'''' sill:. n.'SJ)' i,,~ i" ilial ion ~ I ..,....oj" io" l , . o1 ienl ro r chm , e .,t,, " All bill ,hi; r,,,,l lb= """'lion' lIm ..l>c lorm otion of . ne'" ho.... J In. ....r1'al bv~d) fOI ....~b bond 1. iml"", ;ng Ihe energetic fa"or;,tIo hly of lhl: ",", (ion. Th " IIl
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n 1"" 1,.......,.,....",o rllY '.tr uol ur< has a very""" Cll! ('.B l 1J<~ ,o.l (2.02 A W " ' P3red ..i ll, 1.54 A in ,~" " L"""' U Ie~ Four <>Ibor >I , u,,",,'C! wllh """'1-. ...... ",ilhin 0- 3 i Ii ooo\' e thi, un ~ ha ve s.l1'o.l C t ~ l -tU J ,,. Ctll Ct } ) " ,u ' Cn ) C(4) bo nd. ( Bo\lI1\~ (1 aI 19~3:L On J",,,,,,i,II," " of ""'" a "'ta~e!led C C " · b,,nd, "'''' " f (.... at"",. wi ll bea r th< ~" "rgo, and I'" olher will \hc T~dical ';U l Fqu~l i"n R__~ ~ The product prdcrr-., c~ ",ill rdled I he h" ,,4 l'(lioriu lioll i A H - ' U ) u An ' CD I in Ihe molt-cula r

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"" prooU<;,-i<:m " b umlallOCll. l\it""'lJ<''''es. R- NO , . • h~", en han<:e<>rt am 'pe<:ual l""'b , R ~R 'Y .... It- - R'Y , in t:< , mpc l ; t i ,,~ ",ith tile "' jl ~JV1 (.'H ,t:H, CH , t ' , yi<>egati w [ul>Cti<>nalilic", "" n ~1 1W appaccn rJy lead tv . i~la h(.m ' \If Ih<; "lu" 0( [I", lKrt,c., t all ) l" ['uk (Section 8 , 2 ~ small Rll ;'l n u(".idcs and cyallJd• • "nn ' II" .... lm"S,," lly lHr~" lIycl r<>~"n' "I"m 1", <1." (I''I" .I""n ~,40) ICMlioO' I<J lh<; produo[ ion e~ ~ o l od on a lherm odynamlC basi. , Uo minanl ~ a'" ," Ihe .peetnl

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IIH _O ~ "V

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(H.401

of lar ~ r ~ I k y l chlorid e_ and bromi des represent ilalo11mm ions prod "ced by lh. displacemenl rearmngemenl 4.42, lhi' oould ai'" aW"unl f", II", prumi.

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"r

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callI' preferable. excepl thaI the los' of the largest alk,'l group i' favored (Seclion 8.2j, l\Nc tha( an abundant pcal:. from lhe 10" of H. (~" ,mall"'t .:Ikyl group. lhu, indlca(", Ihal no other ~-deay"ge i, possible. (or indicates the presen"" of _. F or -eN. S""lion 8,6), lInkn S, 0, ", R· > 1..-1 Br > H j, ~cncraHy the im'orS<' of tho II:! value' of tho COTrc'p'",d'Tlg radicak for eUJlIpIc {Tallie A.JI, H J C\J-CH,', 6. I "V: HS-CH,', 7.~; J 1o-ell,', 7.6: C,u,-Cll,', 7 r. CIi,=Cll-CH,', 8,1; Cl-CH, ,8.6; H CH,. 9,~ 0V, Item berg and Spitellcr (l 97(J) h',," mca'u"d the compelilive cITcel "f sueh Iulldional gmup' on pmdud_ion allundances Imm a.dea\'a.~. in the ,ame molecule, For the compound, C,H,CH(OCH\)(~H'jCH,CH,CH,­ CY--·-C,H" tllo abund'noc of the C,H,C=Y~ ian "lati'" 10 (hal of (he C,H,CH=OCH,+ ion in the sam' specll'um yield, lhe following values for .-m10u, ::OCY groups: ~-=CH .C!, :>CHRr. :~CH·-"l. CH--SH, 5: ;;'C=O. 50; >CH SCH" 100; ::OCH OCH,I OO; :>C(-·OCH,CH,O ) (elhylene kelal), 500; ::OCH-NH" 1,000; and >CH-NWH,j" 2,{)(Xl Unknown 8,4 is complicated, because it de>e' not coot";n" molecular ion, 11

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0 111.' " nd II. q = O W "' " lem b r ;om , tbe ~- and i - e! . ~ ' ~ ~e prod u"",, " ""1""1" f"" , "" """Il!", ~ ~ ull;"n ~ 2 ' howed Ihm Sleven" ",', ltalt- " >r' M y pndi<.1,,1 1m ....C. H .-COC H , ~ · thaI [e. H, IJ « [- COCII,): th... "' In"" ~. It - y ' , llCnerall}' produce i",,,,,, la nl R ~ ions ooIy for ...,,, n,,, '" 1..1.11. gro"pi bee. u," ('If compelj li. " ,,,dk l ].";,e .... U lo~ For lalul" t"d ",yget! fun"li"nJlifln . /0 "nd "",le,. . ag"" di""",iat. d"ierent 00,,<1.. ...ilh R' - CH, - Y ~ ' ("""inll R 'ClI , • ;md CH , - Y ". ,e' pte' iv.I )', F n, R- 0 H ~ ' , II' i' ,ml""rta nt onI}' ror ..." d "' . __ lind J.,I..aJb no!s, al{h ou ~ h lbe (M _ H , O ) ~ ' pea k o[te Jlllfo vioJ., lbe "" me il,ije!Ur1! informati" n, Tn. L n d ~ !iv" rtf"'l ClI n CoOn"" Ji.......ialioo uJ".. mut< pol.r,~at>le M M 'ha l i' fort!><-.,. a.... )' ( F~ ""ufl" ~,24 ~ for la l,~,C C H , O H ( ~ 4 "atJall 8 .4 ~J, the energy of lb. oil gcn - " hil"l '" ..n ly O..~ .V llOOV. th at of tbe hl~heSt """co pied r, ..or hi, aJ 0( the

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.1k, I l"0l'p [I F. _ 'J.'J t V: It -' 10.2 eV for (CH , I.Cj. T hc "'oil 'n , l""enliKl '''lh~ fo. I"" ",,,,,p1.m'".lI;lr) o,\eeomr<', ilio" , [Fig" , e 7,91bl l .,~ Ihe,d o,", ~ '1' d<>K 10 ... "1> <>lh. ,_ .1 lo.; "'·il1~ lor effieienl , urfac. b oppin~ h . glve p. o!l yield lillie R · . bur D I(:H , = C HCH , O Ph) = 2.2 .v, and C, I1, ~ ;.. fhe ...... rt~k in 110 "P'.~nl m .

.-k
RF. ' .i"l(k ·bo'" u.J.<.1;~ TIlt m",n re" crio" dcu ing o!lC bOlld in .11 E1:- ;" n lnv" Iv<;, , he I..... or . ....11 sta hle mol«"ule~ (Mcl afT. rt}· 198Ob. H. r< " 1 911 J ~ Oy I-Ield', lI. uk Ix. llo" R.l) Ih" ,", "r the la"' . !! prol"" affinity (pAI e c..",,,.f ... Ie• • ,nll I'r>u p< 10 fo.m t~e ",m< rmU1k.1 i"n. T h'" ~Olllllwn rta<. lir>m 0( R OC- O ' , 11 .. --0 'H (from CI prolonOlrd cI1 l<'t""l k. n.. ~ Ret)" . It- ---OS-::O - , 1t -·nl , CJl , ~ , R O ' H " It -O ~ =CH , . R - S- H,., and R -----<:_ ~ , H in . ol. e 1" , .." " r CO , (PA _ 5_7 . \'~ HO ( ~ A e\ 1. HR. (5.9/, HI

". (6,5} co (6,n

so, (606), C,H. 17,O,

H,O

( 7,2 ~

C H, O

(7_ 4~

H, S (H ) a n ~

uc re

17k ,. Note that tl>.: I" " u' "r prn pcM lPA _ ' .ft eV) from R C II ,CII ICH , I' . of """ h. 001 (7 .9 t V) from p' O!l"ln" •• rl mOThll . ' hcr., "f . tx:l onc (R . ~ . Vj (m", R- O · - ClCH, I, . an d " I' amm Mi. ( ~ , 9 t V] from prOtoo. IN amines are r", Ie" pw nn unocJ, in .cl; ord.n~ wIth rho hi, 11H proton n m lll lic ~ Qu;ol,(ymj; tl1"o predic Tion'_ we M I. t n" l ,h• • I'll ion. "" n i" ,mc, i", tn r,,' m m"'.,....tah.. mucture" and EL - ..,.t;nn , ; n v o l" i n~ rh. d,SloOciano n o f t ..." bond", di"'lI!>..ro heln ...., can be highly com pel]ti,-• . In Ilenrrill. ttlne 5in ~.· bvn<J U : ' oJ«:umPO tV, whe..", the i-d . "' -"go C. H, CO ' _C.H. ' + 00 ....·"d. ~2 <·\' n.erounteTpn n c1eavag. , of "" , ~1 elnu, Cqu.ali" l1 11.46 aftd Fi.' lT~ )9 req ,nfr ~ 1,\' ~ll<1 ~ 2 ~V, =pectiv<:I~' , Fa r Eq,••u.ianz ~ .2 ..n" ~.46 I I>, "lk~ 1 ;<>n. ..re (am•• d

"I«.

c.n,co

c.,H.,o' ----:-(;t\ I

!.»oj

,!-rr-c>\

~.

(8.46)

In"' )

l->' l>o'h the ,fira:t 01' " .Ii, ,, "'....'i"'. ~OO II>:: lW()..'IC ~ ~ath"'a\,, A lth o u~h Ihe Ia"", u. . ....rgr".nUy 1= favor able I b~' o. ). o. ~ , Ill ,ho,n i, . n_ _I"1' "" " nl"r . pen. in EQuauon 8.46 'h. ,,.o-, tep ]XI\ h , hould a1." bt im1"". tant, teeau•• a . """ anli" l r""",i,.,,. <>f \11<: C. H j , 0 ' ~ CH , ion. art !",mod "'"h ' \lffitaenth hIgh In'ernn l e....' g' '''' h)' M,,;ns 7(h V ekclmn... F urlhe r, 1'1',' i"n, h... ,c • hi ~ hcr I,nd,n~ 1<> lu ,.a ngr tMn do 0 u - : ions: m: - di"Mci a' icn in
'i"...

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i

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11•••( 'on' .1

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chali e rel( lltiOn, R· ;. Y '. T he hj ~ h di,ooc.ialion energ;' " nen rouud roc t loc: hOln ol}lic d ea>"'!e ",1. di""u,,;o,:l in Section S.l; lhe c<>lliwtl a ll ~ ;u..,>at<:d ..Ii"",,"" cialton ~I'c ~lra er C, H,O' " CH, al>n abunJ ano.::. Ho""" er~ Ml J ll lonilJtion (flU ll)i V11 11 ~S of ladle.l, . '" b<:l"", \lot..., ,~- tlu: ""rTCor"r1J~ even-electron n(ull al . pe-. ici. .\rum, l,. m,l;lnen l, (h "t,,~ .n , NO" C:1'.") . ,,, ,1", mo' l uClable c.. t<> t he ~e ",n · el.ctron lulo," Thu " In lh" m.." ' l"',<1U "t 1,3- .nd 1.4••hnilrobeoze"". tlte C.H~ il",~ llf ~ , 1). 1un~ C. H, ' I"," of li N,O,l r rodlJ a r: <>f """Tly U{ua' ~ bund . ncu (onl)' NO' j>, • mo.>re...lr" n
,,,ption,

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. • •• •

••

""

••

"'" '" c...... "•'" """ '" ••'" ,. " •

n

'" "

m

51, C, >I, O , t

,~

"" ,a

.. . ~

n

"" •• ss

,;

ea

.," '" ~

..

~

••• • ,

"" "" "

""

"

"

, "

'",ro

.,---_ ....... ,

.....

S~ lll l' k pressure Itud,tS Ihow lhol !h ~ 'fIr';!I'I ~h"l\dan o:: §,wn m Un.......... 8.6 il no l dw; h' i,m. ",,,!"" ,,I" ,.. ,...~ io n>.. f .. et moss ",,,... 'e<j lli,,, the c.:,H..N a nd C, II ,O u6iC/lIl'eDIS I.........' Of ' "",I f .F ' ;,,'" "'. , he" pn .... 1em in C ukn O\li Dij.7.

,,,.,,,,,,,ts

.••', ...

Un".nw. U ~,

••" ••

.".

sc

,

.

•

,,, "" ."" •" "" •• "" "

M

.• " ,," .•

,. " "" "

.. .'.. ••..•• .." •• . .. '

. .,

". ,,, , •'"• ", ••

...

• •", •• •• ." n

zt

,.

"

"

"

f

•, • • «•

,•

,. , ' . l+.J. " I _. . • o. 01'" ".. '. o. "• , ~ o «

,,'

/",: , /

'---'

••

•

~

--"-

~}o

(Y~

;Y ,

<: >

'"

T

,

l -" - D'·(S 4~) 0

/ .....x~

0

-/"v..........

\ 8,50)

... D.._

_

n•

_.

(~( ~Y" ..

~

..

'

E

18.511

•

18.51)

,

,• r:

•

_ '!.. ~

) •

•

CJ

,) ;/-'j

•

QO _ c~

(K.S3)

,

--"!..

")

(T

--'-

("'

C__/'~; ) •

~

.} , (R.<41

C Ie3 " a~~

of al I~an I.... ring """ds in a CJldk ion is e ecessary re f" ' m product IOn. by lll!o' fr ~ g "", n l ~ li ..n (do ubi. -rill>l d. ~,' ~g . u.ualiy demand> an addl tiono.l ""' fT ~n>", m.,n l .lc p in lh,""_rocm hcrcd rin g comp"und.. "'"" R' mdh ylu. i' R"". Lq... u on a.a, <0 Ih<se a", not discussed he..,), Two-bond cleavage of an Or! ~""'''U'''''' l"Rd, lu ~n O E- pnxlucl ion; cbmi,"" "f a thin! b,," d i, "'-""......' 1· 10 Pf.. an; t ile , illt\ .. <~ il.IId .. h
r.,.,""...t.

d....,...J. Example, ..eIe ~i" en in Section 4.8 in ..'hiel! the deav,~ nI two 0000 1 in "" OF · ' oy. li" ion led to lLhundlLnl p,,>dw::tJ;, n.... inool"ed io"i ,,,t;",, in the , ing, . " eh .. of the ,,-eJect,on, in cyd ohe.,,,,. (I" I,,,,li,,,, 4.10). n.el
n.

C~ , '

•;t<,

..<ell

~­

".,C-O..,

""C.II- GIl,_.• (('

·C><

',>mcCI' ,

IC ~, ' . ' ·OH M. fe ll, l,

...".

' o . ~·

': ' _01'

i" ·r;

,,.".'.9, G.

mI. lCl.

« ,..... ~ __

0< ,

..."

1M

H" C---<:J -

""' ,C-<) ' ~

•

....,c """,,'-(11,0' -01.

--_

m'? :>ll. U .

~ , C - ,," -

MoCH- NM. ' CH, _ CH""' , '

....,C- W>l-<,

<0

110.! ,

"CH,W H__-<.><.

C ~· ~ fII\'"

110,01

-CH,C... C.......O' ~

· Cl1. ~ · " -eo.oe ,

10·11 I· ·II

(; tl.. t:'U r

,.,/Z oo .... _ ~

- " H,

...c ~ c'-o<,

v ec

ca,

MOCH--C-OO... •

' .7

M ~,C

'""

Q-C _ O' -'

C "0 '

C_-

CH,-QtCH - CH, ' ~, 1 CH, _ """"" Do' C H , - ~ ~ -o · · ~'''':;-.:HCI I- C> I'' .,'_-,,,-_:c,--=:::::::::=,-

,'... "

-0;><'<;><, " .. " " , ".H I

C · ~O· '

,'$~ ...

'O-<,C",Q'_ "-'"

" " ", bO, 10.

CH,-<: -<:tl. '

...

'7.11 "

CH, ~ -

.."" {....

C

~"

-",'-'

~-

•

O - e-~ ' _>r. ~ C =ff,< · ·

- c:He _ CH ~ .- '

..-.

__.:::,-.:::,,-,.::::::-,,-::,-__ ~,

;.

CHCH- C- "" ' "

d

4,8), T no '1'aC(;\ln is usually a I W"-'~l' (no n-c unccrtcd! ('1<"""" ill which the r,rW<>oJ liltl4k d ri' ..... h, , " ••,...hil. ll~' of the " f'<"I1' '''' i ;" ' erm . dialio (these "Ui '[(l"ic~ I.dical i" l\11 al~ al"" formed in tbe fu !>olJ 1.J be eu, il}' recogniu d. l lo~'e1" lhar ~t>undancc, <.'~" I>e .lmrpl~· red uo:d by IXImpy ,. ...kn" ' II",... I"a~. l' isu,( 4.6)h ~ " . ", . i"h' I h ~ sa nle i....mcrio: , tr ",cl" re as ionized qd <>h",tane, WhOI' ''' m~,h yk:ydop<"II18n~ " yielrl' "",h m"Lh yl, yd op"opa" . ' · and f: H / -- H - CH C H , ' l F~n ~ , ' f ol 19l1'll. "'M I e ,'al~1 of 9.9-IO .j , v rUT tl""", C, lI ' 0"' iom c" n he 1"." ..",1hI' all yl , ul:>stilulion to ~. ~ . V; p/Iffi)'l lUbstitorinn of C, H, + ~i w.. l1>CII = CH . " , ! F, - ~ .4 ,V, "cCll unti,,~ {or til. bi>.c P':"'l m It" Hta ,.,; "(J<'«rum 01 j)M " I'lq d n h<.ane, An u n <,n urak~1 ";, " ",,, n , hc r ~d riLlg provide, a ;peci.Ll . ilua no n m. " o,

i.'

e

.....,.....

'"" "'n

,1>.,

h

..... _

.._

...

1'0..,;1>1e a <:o"""rt..... as wd as a ,,~pw ""' , di ,wd ~ l ion o( l"' o filii ~ o n<J~. 'I'~" <e1ro _IMts_AldeT "",roun now ~r <>ducn ll:Qunl io n il.~5 J A , e..,,,,,, ,":. sld,il"" d d ie,,,,- - in 1,lace of [he olorm-f ~ ,,,, , ;,,. llAIl., ~ ' '' ''' ''' lll no 1 ~. In"

,.r

1''''''''''' ..,

," 0

--'--

()

.Y

c ,,".

<,

",

C?r

III531

,J

I ~ H> ' corr.~po.>n tli~ n ,u lr~l

by .. I

~;

. v, Th.

--'-

(J" -

,pec,licity of the

, ix- llli:lIlbered -lih~

..ur

!o m. ..-hat ;llilueuceu b)' Ih. I.!llkr...~· uf hyd""",rb< ,n, In u ~~, " tnd"m n> . ".Tl ~."",n l'; Ihc <.:. H. ' . bundance f, om cyd ohexene ,. ~~ 25",,; from m~th ;·J[n.cydopt ntane and s: ~:-; from melhyk yd opcnt.""" t\.I1:yl 'u ""tilY';O" ....n nlake dLene ' - roundt;on eyen more rum l'diti ,c. l",.'cr;ng iI, IE " '""" 10 .. S cV. H"",c w' . ii, i,om,.,.;" ' I'" if,d ly can be di.>. ppointm.:; ,1>< th= m<; thylcy,loh, xcnol, mcthylenecyc!ohexane. ami cydoheprene i'.I ve C ol L. -. aoo C , H, . ' iOM of rcl~ti\'Cly eqoal import an"", C" '''~ flfd !"elfC-Dicl,...A1J c, J coumpu.;ti,,,, J oc, <JCCor in ""c luhex. "" deri vau' -" l ~at ....af ' oMtil" ent, in the allylie positions; in , uch compound , the eneJ'J!IS "f ol"'n-linll inlcnllc dialc, arc higher tha" lha l " f lhe Ira",ili,,,, , lot<; f"r ,"" ..,,,,,,,,ted pn",""" which ('ICCtl CS near Ihe therm ccllttnic:1i threihold and I l a~ l a <, 1~1l<>~ The erit kal ellcet of , ub' titucnt, on thc , 1• ..,0....."';,11)' the , ettc- O iek-Ald., react io n \\la, discu,,,,-...! in 8<>.--(;0 " ~_ ~ IT u,,,,do 300 I bIJU ~ 1?il4, M ~",l cl " , u m 1~ ~_1) _ I k l erl>;l10m . uMtna hon for {Lquation, 8 _~ J -~ _ ~ 7 . ~ _"'~ -~ _ 5 21 or On ( hqu •• lion I\.j J ~_~) ~ ri-n ~_rH, can ~ ave " neg;llive .. well .. " positive dI."t on D E' - prooU
n"'......

""'
or

'"

• , "" .., . ......_

ill Mc , C - CH ,

... of ... " , _ , , _

(!lcu lr .1 I E " 9.2 " ~'l YO",U, 'l.1 c,C - O'

(9_~

,," J ~"J

'Cl! MeCllM.Cll , · (9.1 . V) ""0 ' ,CH MoO +=C1 I Me 110,0 " VI, Thu, '\lb. lLtuti" M ~n U' YI\Cll fur ~ ri ng - C H, -, n.:" uld Ill " '.r tho pr~duct ahunda"",c\ vf t:~ lLlLl i l "" 8.48 and 8.50. 3- M.t h yjw ,. ~hydjoru mn )'i; -( ' H,··-fY - C H., . m.';: 44, b" t IIU :-; C.H, ' formed by CH}.l In". For it<

"x_membered _ring analog. m,ahydto p}'ron_ th e ' P"Clr ulli ,l,a
,

[~> . .

O=CH,

mlz 56, 55%. ~

",'z 30,5%

(8,56)

li a,,-evle with the charge ,ite than i, ox}'gen. ~ lI d In ail llleh ions rhe unp_i",,\ d cctmn i, , tahili,-,,,l h)' aU,-]ic [""ma nce. 'C R. Y- - CR', . ,C R, Y ' C R' ,-: Ihi, accounts for ,he bas e peak in tho m." ' p"c1 r" m "f J'ymllidme (D uffield el al. ]%51 and important OE ' ions in tile ,peetra of ;N hom(~()g< _ P",!,mli"n ~_ n _ How•• • r. I"",u," the " eutt']

(- c R, - ). rmmeJ a i,,, from the ring atom, mu,t h ,'e n > 2, thi, ion ""ntaining

-

o

,

:;""

~" -,., .

... . 1'.

o

Ft . ~ ,: m·z

~ .C+l, _

IS,571 (3, 101l"l'.

"' .H:..rz 57, tlC'IO>

... ""'.n, ..

A

'"

.

oo.

0: •

•

,.

•

""

lh."" rin~ ~ h .. '\lI . hould oo! be for med read, I~' from a four-membcn:d ri n'll U -OIe",ibl}" lOt-med by I,..., nr ("I I,G I,ell, "'lIien i, Ie", stable than the oIcfill ll'Ol ;n F'I"'.. ..." , II.S5. Sub"i!u t;"" <1 unoa'ura red fU Ml;h,." ,. ~ TC "f neaTly cqual cl!c, I;v<:llCIS: ' 10,CC H " M~ ,C---{·HOH . and Me, C= ClINIJ , h"v, IE ",IL, c. " r *.2, ~, .., ."d -:cS d '...nd '\l e, r: - C-O and Me, C-C l'H haw YaIL"" O)f 1l 4 a n.1 _ ~ tV " <>rmahon 01 .h. "" i~ " . /"'m lho , uh, liluLcc! C)'dobura,,,,, , h"" Jd he b~Mnl. sin« oIe/in;. T>eUlr al. at" til. oc-p rc ducrs: C , H. O· . nd C , H•.-O' -a re by fir the m" " ~ h ~ n (t. nI ;"n , in Ihe :; pe<.'I1 ~ of hy ~ roA~' - ~ nd n",lh... yc~do bu l. n c. fC o ~lj Hly, Cycl" hul" nnft c, . h"" K ,i ", ila' b<:h• •ior, Eq.... hOD 8~, Otlloe! I"b· , I;"u,i nn can cause oh",~ e mi~' ~l\ o o . 3.3·,hmc1l1ylc}"t'lob""'n",,,,- ), . 101. 100:'/,

••

• R _ H ' mlz . 2, ' iIiI'I'o R _CH,

mlz 10,

I~

,~

..........,-' -_.. . . .._"" ,

'M

,.

'001

I 00 I

,,

..

-.

r_ u .

• •

•

I

h ,-'

00

•

"

I

i

..

"(5

00

j "

,-

I

M;»> l poeirp m ~I 3.3.5 t rimclhyk ydohe" n<J<\o.

,m

!•

... ! '" ..

;r

r I , , I

•

. ~ -" ,

.

•

T I

•

•

.'...

.

~

,"

"'~ I. ' \f... ' lJCI'l, pPl 0' ~~ h l· )cyd" 1ltnl jllim "'.

C~H. ' (l ~ _ '1.2 ,.",. " od 5,}~ "'i~ 42 (9.6 . \i). Elll"r~in~ lh" r inll• ..., Ih;lt an

dOl."'"

d .,(,,, .. "". pro.to -d 'mm tho ring . , ~ ncul, ,,I. m~I;~.. ...JJ i,i"nal w lllpd lUW rc;oo.1 n. """l'i t>lc It><' small miz 41 in Figl1 rf 8. 5 " nd .,;! 11 IC H, - ( H!' He , H, ' ) in fj ~U I' 8.6 pro'·ide exam ple, oj \h,.. I n t ile ' peCl . um of di..."'Jn .... n" ~ «y.;I" h.: .. nc. c,"" n the highly stab le ;an 0 I,=( ll " l("ll , '. .. (" nn,'" i" '''''1 15% nbu ndoncc I:alt hou ~h tll;, i, tbe se<:<>OO Ja '~ Il"a l ~ Wo h h<1cr""lc m "~ h\l "" , ,,n Lho I"", "r " ,in~k: rillS",..lion "'0 occur onl, by dc ~"~gc <>f ill ~dja '~ n l fll'l8 bonds. T il< mast oom m"" n,,,ml' lc j. Iho ... mo;. l im<,<;-jmp"'l ' l\\ t" ' 1 or <MOOn mo noxicl< from o:,d o al'annn ... I.:.qU31i' >!l I!. ~~ I r ;~ tL ro S _5 ~ Howe_'c" the 1M - (":0)' ~n ~ (M - CNCII, i- -JlC'lks ar. ~n order 01 m"inilud, b . impo,I" " ' rn tht ' ~C "
'" (8,591

ment" m"k in~ lh. r.",lting Jarge OU " ion;; usefully char~clcri,tic of ,ub>tiluted eyclG h..enel, The h~· dr o xyc~·d o h. x.n. mass spectra show ba,., ]lCah con,i,tent with the ~, cle"v"~e< of Equ,holl 8 .5~: with ,-illyl", and oI1ylic hydm~y
(8.00)

:'>Jo to. ho"", .."r, lhat ring un" tllrati on and f\ll1ctio" ali7mio" ""n lead , 1' 0 10 rinll , tabilizaho n, In tho rna,s speclrum of l _ mc t hy l _3 _ hy d wx~ " ydo hc xc ne tbe h~"" I'" al i' C.,H , ~ , the stabk belll.nj utn ion, a nd C,H, + i' of 20)< nbnndaoc. ; lhe b tl"r [ M - 21)" , hardl y . "I"Sic, 1 I>CLlt , . , I",," [&ctio" 1.,\ ), emn;'pn",t< tn ("I - H , O - H,) , ~ Cyclic EE + iou, obo

llncler~o r in~

clem-age in a sim ilar manner (Eq"ation, k ,~ I , K.~ 2~ EE ' pmdu~l i,m, att rormc-d withoat ch~rg" migr a,i"". "litre_ c}":Johexane - 10'"' NO, 10 yield 'he EE + cycJohelyl- jon, C, R,,' OO~,~ ' \>"n dan"e; the C. H, iou, of 100','; abundanoe presumabll an" b}' fLlnller 'O~I of C, H , " n " l o ~o ". to E'l ""tion 8,"~ to ~ickj ;oni. ed CH, ~CHCl--l ,CH, ' (IT' _ 8.\1 t ~-) or of it~ ~ y~li , ed ilome r (1,5 tV), Similarly. l _nit; ocycloh" . ne y"Jd, [00'; ', C. H , an d SO'~,~ C ,H , ', "'iI h the latte; initial i, omer II C -CCH , CH , + of "" "" ., IF _ ~.I) . Y. Itetere atom 1' lo" !- T ho n:lru-Dic!>-Akl"r (RDA) li<;.. "~" 01 11li, hl!:hl}' 'I~ b k ~ldi, ion )'i<; [d, a [0.... "bundan<;(; 0( C H, = C H'- Y+=<;H , (fn/: TO ~ OOlhj ,tClll ",'itll iI' fcla ti,'"l)' poo r r">eM IlC. 'I " billzation, 1n the ,pec-

• I 0""'''•• M~' ."'.m. 01 100 .,..m_"'''"'

'"

CNl~", H

'

r;j("' --'-I ~,

--"-

<,

m'r98,

~H,

,/CH,

C", • ?

10~%

(8,61)

fTI' 70, 12"{.

trum of the oxygen analog 2-methylwrahydropyran, {he (M - CI [,J+ base peak on RIM decoml'",it;on }'iotd' an . ' -en les' abundant 14>;,) CH, - CHO' =CH. Ion. comi'tent Wilh (he dCClroncgati\'c alom
e'

_R'·

•

GlR ---

o

•

(8.62)

TN'" hrmds c/_a.ed. Th e rna" 'p.ctm "I func(;onalized cyclic (;, five_ memhored rin~1 compound, commonly show a ring-deavage decomposition pathway Ica.<.ling [0 a hclcmatom_,tahilized Eli' ion which i, quite """rul lor structural char~dorization (Figure, 8.5 and 8_6, Equation, 8.63 and R_64lRadical-Slle· iniliat.d ring op.ning 'eparates the radical and charge site' to form

" , 1

... • H,

m'z84,1000/.

(8.631

m'z83.100'l> (~_64)

a oJi,wnic fadieul ion similar to tho first steps in Equarions 8.57 and 8,58. Tbe ,"cond (16 f"r RNA,: MoH""a and Lo"g"vi~lIe 199m gi,e analo_ gously C,H,N', C,H,O-. and C.H,O-. respectiwly. as their base po"". and [hc 'l"-'Clra of umub,tilulcJ cycloalkannnc, with fivc lhruugh l,;n_m~=b"rc 90~'; abundan",,_ This palhway pref.rone, i, consi,t.m with the resonance slabilization (clIar~e ,ite removed from o~Yl,, rH readi"n is charaClcrislic for particular compound classes ",ch", 'lcwid, and oillcr funchon~li,cd bi- and polycyclic compnlln,b (Secti"" ~.6), il musl be u'Od wnh c~ulion in intcrpTctOlion, beca"", olher deoomposi-

"

.

& !

"

.CrJ,CH,R

II,

(1 & <,

CI-l,R

11

11

,

o

6

fr'("'C"'~ ~"" ~

II

\"f ~

,

c

~I

~I

"

~

"

18.65)

'"

• I """ " ..... , .,_

_ . . . .... .., . ..""......,

two, can c"m!,,<'t.c "';11> il< lh" :l 'ca fl an~omcn l" ,.'ie-IM :lnd Ga umann I ~ ~J, Au"''''' ... ~I. 197 5 ~ In Eq ualMm ~_65 lh • •c....,nd "~ d ,, '8,~ , ,e " fl ~ Llg . n_ t le~ d, 10 mO rln. li nn nr [he ~nd compc k" "1(" a -d eavab'" 1,,,, "r ~l k~1 (E<j uatl<'n ~.bl ). !;lnlctU1~ 1 [•.,"'", lhl j",-~""", too la hllity nf ! ~e h}'drof"n l ~k 'n s pa rt in tltu = M>d rearranj>emml fa,-.J;l~ l" II", 1 "~Ct iol1. Thh ' """m ili,-ily "f the ~ . rC4Clton 'OW" rd n il! ";"'" and it, [li lt" """,iti. ily ' ... (he . patial ".i ",,"~a.l e b
""g.

<"

"

"~,:o

ooJt. ~

'"'•

•.....'-&1,')

(8 661 dl"'~cd h<1 ~romo m func tio" . 1 ;roup. n:tlu cillll ihe ' teric tequ irrment> or tlo" hyIt, of tb ~ ~ , rH ; cffeoc: ti,... FOJ nie,,,",ne (Filluro S, I h~d pipIIi , ~4 Il<:ak

(j) - -. "

"

"

€

\ K ···1

--'

,

('" m-~ 6 e

,

'"

--,",

I~ ~i)

from Itt< >ubU;tUloo 1.2-«; rho I I ab! lr." h" n "f F<jua lio. n S,(,1 cou ld "",~t fro m lh. aromatic ring l<> ~;.el d a bicydi . i",n

"r

... 0"""""'0'" of .... l~ _

.

"

",

Exampl... In Figurc 8,1 the addition of" double bond apP" "red '0 chan!," 'he 'pedrum dramatically. [-,'" 'he (JI..'+ ha;e peak; in bo'h spectra are 'hose expected (Equa,ion" 8,48. 8,50) from a cydohexalle,/-cne ring sub,tlwtcd by an ammo group, a powerful initi"lor "r radical-,ile me"h""i"", 1J::'!uat;on, 8.68 a"d 8.69).

,

~-

~

CH,N~

--

".:z 96 •

r~

CH'N~ m', 125

m/2fH

OH

.. 18,69)

When the pe'ticide DOE. CI2C-C()J-C6H~O), i, irradiated in '\lr, a compnL1Tld i, f"'mod wh"", m"" spo<:lrum i, ,h"wll a, Unknown 8.8.

.,_....

"" U. . ..._

• ••

,. " ,.,. "' .. '" .. Wz

".

,oo

b l

0>

0' eo

-ee

.,. -.. ,., • ,. .' .""

.. oo

,'".. " ,. '" "" "' '" " '0

"'

1"

• "

t-- ,i•

". . - ,.._

"

.

0>

,.

."

"'

'. ,11-.,. , ok '0 o

.,..I, ~ '" i ""

••

ea

'"

,oo -

I•

.,

m,',

"" '"'

"

CO

. . . . .. ' . . .m . .... ' ,..,

I ,

'"

•

'0

0

'0

..,, "" ~ " " " " ,,,, ,, ,,,," , .. ............ . .. . ... " ' -" ;" h

, .,

-

'" 1" ~

Il'''.

'0

-

L " \;110""" ~." .. 1M 1p«IUlm from. 1<""" ,,( ,.,hn~ powder found ," lhc or . , usp"1CIJ .m~~aJ .lcTI l with lhat which ;'ou .,uWd.... f""" :Jl·11l~lho-'l'c..bon) I-3P.""'1
p.-, '

WIt '"' ' K1"f'

..,

L}

I"

••

~, >c . """&,......-,-,~ ... •

•.

- -

,... ... "', I "knuwn S,9

,

•

....

_....

~

-

...,...

'"

'. "u

t} .,

~ .

......

~

"

. ,,

\ ""

""

*

'1 • A

~

" D ,,'"

'/

y ' ~

, ( U {ll

"), • "---..

(8.1 11

,/--,

<,

~ P-.b~

, w

.(8 .12)

" ',1; ,'. - ,..

,"" -r" II -......v".. . .

•

A'

TM ' l lf>.' b, ~i "m "r cydi~ iun diu oa a llon, lind hI d' OjIeu « n n~ I l gc m en l' ,h t..... l ey . imijari!;c.. p"' fli<;~l~rly ill lh e formuio n " r ; , ,, ,,,, n ~n l oJJ-dectron iOM ;c 1:1:' ion l .... ' h , ~ cka ' O;l1\' 01 1"·" 1><.",01,. an d the r",m o,;"'n
' hno"'......

.flO""

'" O lLe (If the ,,"-ft.e- l oot op;C_Lltly I ~ I"". " I el h ykll< ,,"" " >n ni, od bu tflno i<- acid IH "I'~ "nd ~I.c ", a r l 1952; Eq....I;\Ion 4 .3J ~ H yd < ul:c ~ ,carn0l\<"

r,, 't

Illelll' ha>" close ,,~wlnchemic~l ~ nal ogic>; fIl.ra lleh bet",,,,,,, the NQr ri,h 1"yl'" II realT" ngem elll (If kctn n.:: . ~"d \ooit Uln.. . pootnL Md e",,_ (19.16. 1959\ d=ti~d lll. bwad int"pr"t 'I,~

.lln-

;U,

utillly 01, uch mecnani' ms lor a "" de variJ rr ~ ntfl M nt \, b ke cyclic "'(l m~n «,r 4'ocll 'f'CdT~1 in lcfpr< l~ l i utl. ~lw,q. chock , et"",,,or •.,..( 1'" of d o...ly

e'

rela ted "' '''(l UlU.

T_ 1><M;h d "41'<J.

Th~

~fl(' ~ ."4J " r"'~tn

Ill<: nuJi",1 ..."d

Iir"

,te ~

vi a" O l " rea rra n gflll en , IF.'lU~lio u. ~.70 ~ha, ~ S11~ . 0 t",n 'M y can ... ,1 illu"!",,,·

-

18.741


Ii\;< ' he FLN ' lep in

IIn~ <:ka~3Jl<'<

(Eq " ahOfl'l 8 4 ~

~ ..\O_ R5 J -~.54)

1 )ff~ tt ' I\ il t he

en t w pi c unr~ .", ~ b il; l~ of . ea flon ~f\1 e l1 \ l , lh e, e J i,<wnic , lNIk ai ;OL" ylIJ . KJn" with dlll r~ a nd Ilnl"'ircd d cctr on at 1l 0nad i;lOXfl' aJld adj="1 . it respeo;:ti. 'cly (Radom r ' 01, 1984), "" n M fcm ~, lo . hl ~' more ~tablc than 'heir pl '" A. di..""""d in So"' io n ~.2 I:Eq uatio n ~ 19l tlJcir »t" hifi.. tie' can be ..." 1<'<1 from 1M in n ~n,l n.; !orrin!",," ,., " I. For lbe hy d 'o ~ 11 T ~ " rr" " gomcnl tlI .n uw .... uralcd fu n<-1 \(>n a h l)' 01 Eq u at io n K70, l he duvall" Or a ll al iphlic e- ·H "' ....1 in Ih< hyu ""c. rbon ,IUlin remo te (,,,m , he d,argc ; j l ~ le qu;r.. - 4.3 eV IMeM Llltn ~nd Golden 1 9 ~ 2) . I " ..,'c. e[. ,hi, i; mol" th~ll balto Dl'«l tol lo"",n~ ~n O -H h' l1l d in Ihe iOtlil>t\l l "'","" ln 'I I wen ~ • • 'h~ rjIC .ra biliz
' 'l
1..";",,

1m "

,I.

i a "" r~ fU. ' hI:'«: 1)'["'" 0110111. T he pmdl>ct ot b<j.... I)'-'t1 $..70 ;. !,~ e r«nn ~n " c · , " bJ liZll'II ur><1 a n un,atur a ted o",," ul Y'(; H -r-cu, wit h ch...rgc ~ lw ' i Ol' ; chn,~e mit rati
' .K _ . " ",,_._

_

•

'"

by S l c.crISmI ~ il. ule. The [10 ,'~ I""" or th e CM_I",ndiDi. " ,·utml, " '"" ~ ,,,, .t rhAli ~I>o>c of the . -d e" r rodllClS; e.a.. in E qu ~t ~ , ~ (h. (' , Il , n X ' H, J>fo dum CH , - ("(CII ,J OH -' and CU,CO ' h"ve 110 _ ~6 and 7.D cV. re· . pn..'1 ' '''ly. How"" . Chew Me more thon " fllIt'1 Dy , !Ie m Ul;h-Io"" , t" llll h.-,~ d­ ,li"""""all"'" energy it! "" """ I C. IJ, L·OCH, of 1.3 .\; '0 pnc'
'"Ill'

i,'"

, h...-se ' CleMi" " ,, [avond . de-n lo a . ~ (u ra t .<1 fun<:ri<>tUlhl)' IL:ll u ~hcm ~ ,n) "'m . \" , (" ,," a m" "'·' l.l b[. d iit ~n ", <.d;c.~1 inn; tbr \>ond -di.."",i~\~·~ c n<'[;)" wr t ~ " ~ve,>c [..,I;1;" n ,,( " " "kohol. DI.RIH10 · , H) - 4." ~V. is ~cn", [[y [3'-10"' llulu F-f't .. 5.~ c\' . t hal lur . h'"'~''' but Ie" 'han th'lI fo< ~n ~";d. DI J(IUU j{.· O ' Howc,,,r. wtthool the "" ~ llL ' al i ,, n I" ,toe Y grc up bl:aritlg tl« ''''''~~ S. d hydoot""" , ub,.quem cLoYM~'" "I thai C ·v ' n b" "J i' layo1't'd. Thi< IMds 10 YH,- /~"", ~e Tc[cnri('ln,l ,>r 'I("A".' (.harge m;r 'a unn) p"odu~t'; til . I"ur , 8'" al' o r..""ed in cyclic compound di ' ''' i" t;., n' (1 abtr lOt HV fl" rJ UL1< ,,'ef> U HC!. U ,O. CH ,O H, n" d H jS ha' bigh ;M iI. tiDli 1I2.i. 12.6, 1O.'I. lIIId \lB . r"l"" 1i ..,[: ~ ... (hat fiva· 0' , ; , ...,,, rnl:'<'•• J -, ing fonlll l"," " Ill>:: ·(e H , ). , ch ., ~ c -m ig to l ' '' n ,,"'d uel l" - ~ or 4) i!; fJ'()~ if fin ~ d " , ~' e ~~ . .. tbe eM,..'r<>lldi.. jI. ,.... ..., .I<. l lE _ 9.'1 C\" T he: mo,.., ' l>ectru", .,r " ulanol _.•hn.. ~ ""Iui'file" l " hLln ,Janoet of II>c % .c1.~ VOl'< \If,",,''''1 CH j ~ O ·II . ne w ~ f~ l I E .. 1.6 c \'. an d 1M - H, O ' - ; <>lktli n ~ Ihe 2.J-<e\' dllkrm.. ,n I" IF;, ,,", 1,3) i' l!W WIIe""1« in nUll'.,.1 ooDd -
.,"'.1';. ..

ft"'.e"

". trum', b~"" r><".u,,, us [orlh", melh yl I,,", yi;c d Ihc high h'lcwlYli'-'"I'on<.1 di, . ocial ioll .n.rgy (2.9 . V, n 1.0 . V for JI ,O - -Ill « loti... 10 that 101' the ~ m,,~~ lIy j'~"' o, ~ b lc x - , k ~ va ~ e rea, lion; I l(·C H , N H ., ) = 6.1 cV " •. 1I'I ' CH , OH I - ~. ~ C V (W"s<.IcHLi"li , . J " I. InSI

bot.",""

..

n, ~,, ~,,' i " ~ ""(llIIf~ I>U'~',', T he llnp "i, e ~ electron nf the OF' pm,l"cl inn prnd " ced by ,urr ~nge m e n l can also induce a fnrlh" rearrangement. For example, thi' i' p,,,, iblo in the onoli, DE" ions produced fro m alkanones

Ir ,!,,",; ,,"

R . 7~) .

<;,,"11 """ ",ce Ll t ;,e" , e" m ,%'CmcTI I, e,m "I,,, "ecur ror

,-

II f 8. 7 ~1

'" " ~~
EE' io n, (Eq uation 4.4<) ), ' uch os those fro m , arbonalo,

r.. H ,()(X) f)(' , H .,

«: , II ,0 1]1'0"

.... r., H , OC \O H 1,

("~!.,

.... HO eJO H" ' ) ~n
JU O). r+ t.

f".,

P"....... i~' ...""1 rt'''"''~I1''''''''''' N, ~ c I n. t t he [1C< Lcnd ... 10 lh" form, tlou ",I 8n O E+' ion b~' de . v . ~ ~ f two bo nd' in . ~ OF. 1'1W'U""'" ,., ~ ~ i re< I h ~ t I hc two l>ond. "" 1><,,.,..... I nc !""<enli.11 pe' ~ ot count a, • bond tlc"''''d. .....-t- a. , H ~.ll" ,.'1.'" by ",-dca ,'a~ k"", "f R· from R---CH,CH ,eH (110.) 1(+ I<>mt,nt (;1l , --C Il C n ---CnCX---O +1I (l:qlt.1ti"" g, ~j or lhe

.. " "

"

., .""

195

1h1'elhn ld fMT\1a l;nn r1f , he more-sta ble RCH -- :;H " i""'''''' fro'" IC CH ,:>I~ ' [Eq uQ1io n t hr'l o~h Q "d j, p1 acement ,u ct j",," (s.,;, j" " 8.11). Suclt a

s.n ,

-

.<

(K 71)

"~Tun~em en l

Iho, efk<., . an i...,"'en...' i" n..r ....... o f ' he prod uct'>. i' ''' ~' mg ns bld bjli l}' bur ~ompromlllnll Lt. dl>u"'~,iz;LllOD of ' h. "' iiJnal m<>l""","', , t, ,,,,lun:; .~ Ien .h. ,,,,,,,er;,;1.(""'" of Ihi. l) P: ~ .. d i"'........:J uuder " Ran.:k>m RunnlJ~."'. u,,·

nl Ih..., oj or thil s.-1l" 'L

Tkrrr MNd_ ' d~lI ..d. , \> "t.,.:n N jor , ~, l ; , c.....pvund dto:"mp:':l;,i" no, lt~d 1 l>­ ~." f.ar'fa, ~. , ,,",, ' . ..., .~ • •, .. ,hi' d b-"Un (Equ.- ll"'" ~, 71-8 , 1); EE ' prW'M. ".nn,-d d,,-. 0"'l'" "f '''''' bonJ foll" ..·.J l>}' 'C
It,

cw.-

>.i<: «aulp!<> i" .... "" ..... r " .. .,1l.O'ueu' vi ''''0 l), d l O\llOI> aWJn. "' ~kLo.llerly + 1." Eq" . tio n 4.4611(> I"" Mm , 1'1".......,..., 1'h;" i. uod'" l r", Ch,I lQClenZlflll f" DC{i"" " IoI;"" <-.>nlAiui" $ , "".., "r "'Ore h,..reroa ,o ms. ' lO ch a' e"1O' " ~~'O bonu "", 41l1id"", ...u.....,.. p bo,pl'"ll al''' ~ nd pllo" ' ~ a' co; Ill<: I'l'I3 U lpe~ r", m of is<J.C,H ,OCO C , H , . h" .... ~~.; 1M - (\ H.l" and IS% 1M - C,HoI" ' (0..0 i""-<::, lI oU I,Oil 105M ( , 11,. 1<> y,e)d ,~~c~ H /"O H, ' , ",.:, ~ 1~ R .~rr~n~in! l ...., H "w,,,,, uf K'OCOK · · .. r......,,-.l bc1;.. ~ ... 01Ill• •"" on J n, e 11 ~ M i z a l k> 1l of loc l>rt.... ~d H ( J - C K _O ' H o+ H O ' ~ CP; _ OH , The he r OI O ~ I Ml\ . nu y he ..t.... ratro Ianh:<' ""n il H ,u , u nil",,,,,m ;n , ycli, en"'pound< lI: qUJ tio". 8 6J- R114) yiclok r~ ....... Jl C<..... l~hit;"'J RH ('= CII ( R'- \ - ;0 \11. lhe ,~ can also ","ul1 frOll' ... . nan~rm<'nl "I I""" H alom.\., b LJ I l"""" ,"" l"""fc"",, d ill d,IIrT...I di,ect i",," 1<> lhe orpo!oi lr rrnduclO . T h", !Il<: cnu n ter pArt p r odu ct io n o from IlC H, CH,CR <:JIn he farm
,1'»""".,,,

Y".

=",

..

,

• ' _

_

on ....... ,. . . ....," "

<1e,! i t Ll ~ n " no lMe ca, .~ .. , I~ , '" the funC1 ionali (~' [th o ,'. H ,'ca,nn~.nl ind.. ~\~, 111<= in mes-P""l,i<.>1l j Th ". In >,,Ih m, u b, \,lu'M n lC(h~l ~'hr",a(c " th. l ar ~. OIl: ~ 7 pea l rt q"uOl: 3 1.\) r,mn .1-11 or .-H ll~ n>fcr ,n I' quatiol1 ~ . 7~ (ni" h.NIl",.....
'''i"",

y

,<

•

'--

"I

"" .~

"

•

.,. ~ ,

00

(8.791

~ _N, In [ '1,,_hOll S,Y the ~rodu~ il ell, C HCH -" C H<:X- O+ H. an U ' ;011 "" Ih . ....l11i"nn l ,", ,,nance Ila t>lli,.;1tilm An unu. u.,l ", ample !.,i pk.H ","frangeme nt i, iJln",,, '" F' I""';'''' 8.&0

"f.

(Ahh" n <1 "I, 1979).

"

.,

HJ.b.'Ji ~n I" biliry . Tho firM 1M en. 'l!~ " f , h ~ m te rmedi ate ~ ,,(\ lllllllCOC<" <; "'"'''" ng..''''. ''l. Radi<; oJ-likc M;'dr" l\fll t",mok... Im m ' ~l~ra l~d "al b~n " tes '" r........... "" '". "al " ,," Ofe usud ~' e. ... tho"";., ' n." 'erthd c,,, It":,,, c~il.l both "'oer&.\' cnn"l"aint' dllc I" n",,, ,c~li~, ble ~mneIilali on ba, rie ll a ~d n ",'c ","', !Taint> duo 10 Io'i uf In.''' rQ(or> ;o .he Ira",i ti" n , t" le. Th.... e<:>nolf 4,n" . ... ,el'.u d if the C -H b ~ nd b",,' en ; n", ~lI l has a 10.... dim,,-i ;diou e"el ~l , ...h , ~ h , ~ n al, o It"d h.' hi~ h l ~ , ~r", rea,m nll.m enn , r or "" amp'" (Ta ble .. .1~ D,PhCH, - H:I " U. S e V Ie« lhl!n O(R - H); thi, p''''' 1OWO 11>< ,ttlLen'lnUl' ,i ~n ; r,""n t h)'J[ ~~cn Irllmlen '" ,.. , o.'-, ub' tilulod . w n",' c" 1'..I.......lIect" Equ a. tion 4.4 1" . lId ."'" .N, ~ad I() r~n .-mn~cmclll> (ht0 0f h 11!m ition ""te, ,)(

'"

II

unu'1 that ate

"''''Y .. ,",(ul fo r identifying iu b
ho ",,,,,.,.-, tha t lICul ra l-p rod uet >la bila y "'III ai>o facdll"'C H lJ ..... &:" U! IC (}--- HI is <1.2 eV h'1'/lw..- tba n n , R -H ~ ~'" the hy,l<" .,I_H C" " .1", "",rraa"" ... Iee[;,....y th m,,~ " oo;j, a lal'i.. -rID~ tnu";tlOn . Iate Uiqua"o"" ll. 11. ~ .~2' t>ox;o"... •1l , "" high lc. Fo r ,h i-< = ,c!i<m h},l ro\1m <\cti.'a tinn i, .Ill"" cau ","" 1>1' jl.roo !'" l oeh a , letn. a m,!IO, .1 1Ier. and Iri" le{h jh l\'lm y, '" wol' a , h\- d u .;n hc"""h ing and ,,".. ' ..... '<>0

",>Ita"t

lung _nUll" m ;b""alio n< of a ct ; ,<. t"d h)'d"og. " ,1 0 m , can .Ill", ",",ur in com·

(!e
".

• I ...." . . Moo"an," .., o! "'" .,.....".,,""

a/-RCHO

,

·... ...._,-----...

".

"

'0

-

0

• "•

r "0

"

~

II,

11 "" 00

" ~

~

-

r.a

"rF

,~

~ 0"

(~.&4)

na l ~r.

III th< orj~jn al H , + ion: such d~comp""ition, mo", low In Ihe absence ()f ad i,'ating r~n et i o n a l group' in EE ion" pr ~t() n -nc h ange reactioIlS can procwd in iOll-mokcnlc c"mplcxe, (Equation< 8.1 4, g . g~: T.d o ~w
"' ii o, pc "ilici l~' .

CH,

>"'\ -, H

.1

CH,

H,

i C,H 7' ~ CH,OH ,~

I

11

"

! C ~'\.. ce,!

s«,

II····

"

ce

1",

\ e,

II

~ ce,

d" be,

--

•

"

"

'\",

C,Ho

~

CH,oH, ~.

e

ce,-If

h &"

be, (8.8' )

'""

• I

D" ...., .......

"'.m. or ''''' f"""",_""

are determined by lhe relalive prolon affinities of the donor ,nd acc
,,

CH 0

~OCH"

/ CH,o

~ H

CH't:,

'iQCH,

~.

CH,OH CH,OH

~---,

~~OCH,

70%

CH,OH +

1,10

"V"

"

,"'

..

Sit, ,e""pli,'ity. A, di,cu"ed in S<:diUll K2, hydrogell lran,fer 10 a radial >ile al a hdcrm,lom or mulliplc bond [orm, " now bond. m"king the ;ite c",,::din"llonally 10>, un,~(uraled, The strength of lhi, new bond I{ Y I H i, thu, a m.a;" ..e of lhe ,ile recepli I'!ty. Thi, fa"Or> " tramle, lhat incr.a.,", lho "oordinaliun n<Jmber al ele"lronegalive "10m,; lhc homc'lylic bond di""ci"tiun energie, of Table .'\.,3 ,how RC~N+ Il > RIo" It> R(iJO)C-O- u, R{ROIC-O~

H

;>

RiH)O+

H

;>

R,C-O+

H

RO-

H

RH,N' -H > R,O'-H > R,HN' -H > R(HJ~'-H, ~.~ eV --+ ,J.~ c\'. Thll3 transfer> to all of the", ,ites musl be considered [or mo,t 'lerically allowed H at'HTl<, ,ill"O D(al'yl_H) - 4,0 _ 4.3 o\'. Ions po:.Js,es\ing enough energy to decomp",e Can al&~ undergo re,'ersible hydrog<Jl migralions Ix:lw""n two or mo,,' l'<"chan~ bel""ee" 1100 hydroA)'l group and tbe hydl'Oc:ll'bon moiety be[O[. lo,ing W"leI (Ward and William, 196~: Turecek el ai, 1981; Bulovil> and Budlikicwin 1~~JI, Under fayorable ,leric """dilion, Ihe high hydrogen .Jli"ily o[ uAygen-"omaininl\ J'WlClional group' c"n induce unu,u"l byrJrogcn-lmmli:r coaelium, Fur eumplc. ()-hydrogen lmnslel' is opemlive in the dimination of i,obulene [rom ex,"",,,-!b~lyla(lamanl,mnnc, which prou:cd, through a ""e,,-rnemberl""u!<:', rigid geometry Tho enJo·i,,,,nec I,,,,,, only c.. n o'

(M - C,H,!," 100%

(S,871 Hydrogon-lransl"T mechanism, can be more complicated in mUfli[unClional M -, io", in which the ch"r~e and radical re,idc at the fundinnalil)' of Ihc Inwe" i""i/alioTl o"crn; b~,n"r"l1y Ini, will niJl be Ihe ,ite of higheSI D[RY' tll val~e. The competition foc h~drogcn lhcn depend, on the rdalive pro Ion affinilies of the J'lInctional ~roups (Equation 8.88'1, Table .'1..3 slw""" that, [01' common fLJHeli",,"1 group" Ibn,,' "r nilmg"" ,nn\Lld n"w be Ino 01'''1 1'I'<>'1>1i,,, ;il"', followed by sBUm- and ox}'g,n-contaioing one," addilion of all amino niHogen ~l any of ,""eral t"""io'" ill >!-C..H,()H ' ' n",,,ly .li111I11"I., ils lal'l;e(M H ,ot' ('""ducl. In Equalio" K~I the ground.'lale molecular iLl" ,hLluld oLlnlfl"\ lhe chact'c in lOC "",mali" ring: IF.fa.1kyllx:menc,),, IF(moth~'1 este"}. H,'wev"r. lb, ch~rged al<)rnale can [unc1iM a, " 'I'Mg add (L.ewi; I ~Mb). indu"ing p"OlOn

..' \

.. ... ,

l~

CU I 1,

( U ~)

t.-lJ tr~ ,, >Je J

frem

"';m;""'i Hyd~

'h~

bcIuy Jic J>
r ",~lh~ ....l.

~",u p. ..hkh i n i ll ~ te,

the

n. lra...ltr rMction, ~~n C ",~, ,...~.." ~, O E <-- i<>Q~ f(>I""'d by ""-i",,iz~lj"n. " hich fonn~i1}' ~ o nol contam cwrdl""li.... ~ll) u" ~tu ra'N [.~ IF i~ u~ 808), tile tern" .., 1 ..o pr<>pyt g.oup. or 2.m" thyln" nam, and I, J-dim et h ~' l - oc t,m " ., ~ ci<:ao1y indic/lIN Ii,· the importanl (M - C , n .l<-'"n,; the 3-m.th yl ~ lV wp of Ih" l. tlC! CO"'I'",md giye, the le 5 ~ lmpwl;ml [M - C , 1-1 ,, )" . T hi> h ~d",t''''' lI~n.rttl''-';>;'' \...0 rorm" Hy ""h .. ~ l<.>.l p.lJh ;" ",ado po.sibl" on 311 lO1I · m~ k ~'U k m mpJex Wllh iUl el"",t!"aIM ~ nI ", 1 C- C

'" bond IWendcl bool: ... "/ . I~. roaoptor

""rl

1 ' ~ U l h ~l

W
,e nto>-. ' coo rd;" alw nl l r«l !ur.t;on from T heor etical calculatillJJ$ for CH , ~. !rom

~~

-J," H'0> 1 WiC , 1889) acetone" sh o w t ho.( in k,w -<:ne'I!Y. Silllple· cl<..1' -d l:" rkcom po , itin n,,-

I.~ c

""(i,,,,

" nd r." Ii,-. I rr ~~1f"",l> Uo " <>l. """""'ariJr Uy . "' ~, In lh. direction of the or;~in,l /J'· bo nd, bUI ra lhHity for h ~ d lQ ~ Oll tr" n, kr (Heimich " , <J1. ( ') p,g ~ !It""H.. ;/I«u hi 01': , - ,.....""'Ii~ m. ~ t> . ,ura lllcln....o ....,. e dio;ru"ed in Section L"" ~

"';&"11;'" '' ;"'li.ted at

radi~,j

Ilere c>d ., n, ;olll effect.
M ~ Jl )

~_ , ;

site, (,. dleal·like

f<.Il f<~n""",cn"'l

"'......

6-;> ~ ,. :l-_ mh.:" ,d lram iliUll .lale" but 4-mon,bcrcd 0.... 8'" renerall, en..fuvor. d (Wf i' kt and Schwan, In3). The ].,n"",bered lr1l Dloi!ion <:"w ... ""c da.1.ttu, musT be Ill_ " in ~ n anlihonding ",bital in 111 . t,~n,; ,'"n " .1~ I hIS b.uTicr ""n he l" ",.",d ii l l\c~ i. a n electron"'; lndmw ing 1'.""''' d ,,>t hI Ihe mip~ti"" s.il. 10 dinllni. h lh. ~1a:1 t()~ d~'n>ily i~

the tr an, ition . laI c ( M "" ,J, ~ , <Xl)1 in lon -mul,,"uic ",,,,,plcxc, ,Section 8.1~ th. .. "lien """, II in nonspecir" ht .... <'lI\'n c "'....ngc between th.· oountCTp. Tt~ ' "~ .mok,,,~le .:omple.. .. ....e h. l", L"S 0l!lc, It) ion -d 'p<>!e or ion-mduad dil"'k' IOI ~ .. h"'h ~ '" ,..",1• • II..... " Jl,ular d~m­ i<;~l bv ~ "';, a l high imcr1l.'lJ CllCf ~"'" ' h" a p,"y d l" OOllIO, <,l,mini,hi~~ lh. i,· ~ompcllti "¢l"''' in fut (!lu'¢v
1'''''''''-

"'''''ple.... .

L n,~ r ""'1...../, rf/m... " •• how.. in Figure 7.7 lor alkllIlun••. bighe r homologl , ho w a h~bcr .eb..,." a bond. na' of J~ .. ""e' g) M [fTO III T.<1""i"" \he 1'1 £ 1 "hokn "..d lb lle, t (H <."Un ( _; ,hi< can II( viewed as a · <,l ..."""" l re....8n!:" ' '''''' . ' " 7O-cV ' f'"OU:I 01 large nlO.Jeoulu, l l>c <J"ubk'-b}"dcogUl .c-

~n ~ "I"""''Il ' ILq" . " <>" 4 411) e"n ~i "e ' ;S".n.:..n, j)U~1 for compound, "," h no, c.,.. ""'ere"" om 011 the c l ~a\'l'R' j (CHI,P ()1I ' ""'i, ~~), .. id,Y\("'h ~·I ",!C.. (II> R C H,U,X><:!l ,.' --> R· t C, " ,O, ' , "'.'J. 7~t Tho ehm,nah"n l of .... a..... m d.h. yk:n<: from IJrllt:r ~I kan itl; . ..n ~;,., n "" '" "hunda 'lt PCOO;l(1 ion< nm in the 'pc,I'" 1" ,, 0< hornolop (hd"" 1le,~nall, [qll . ti..... 11'10 . \1 ,*,ol'>on er ai, I ~70J In t" ~ ''''''''l '~ "r primM)' " nline, tbe C ., Ho'" ~ abund.tl~ inc'"" ' " ' from

1,,,,,,,,

"r

.... IX r,'r "'" ~ I" ",i" e ' 0 30.\ for d<J..- '*eImn c~," cl' , e, (Bowen """ :l.1""""U 1 'l1l ~~ Thi , '"p5Cud<>-1dCm' ng,;" Ill""I . c:< a mult i;tep " )"<1,,'1"'" . " d ,hleial ,u,"3n g~mC'" ~.d tHn ~e 11:: ~".tion 8,91; " "mmen,," " "I. 19R.1 ),

~ .... - H

..,",

"

.''''-,

•

-"r.s

-,"

,

t.e

~,

r r"/""-.---.r. / '

.

'

r. ~,C ~ ==U-I, If... U

EE ' U>N " um"'l.t""'JU'. "'" mO'lt 1"",lily r""mal EE" lOll> a,. gcncno lly for t h~lr furt her demmI" "" li, ,,... ;I .",i.ly c>f retho ", or Jug.h Ild,ility. "-Jfan g~"""'tl ,~tl be rom..,ti!;• • { M" L. rrcrt~' 1 !il!lJb~ Kt a C1l00> 8.92 1<.> K95 are

TIt".

1 .10 " ......... ~_

1

..

,

...

com m.... I~ "",,", ,"od ut 1M u..... l u' ~lUd . it. of lO r, ' lollS. ," uh a. th" .. foImcd by :Kl.~""g~: . n .nml'lt of 8.94 (Lqllal;M " .....) \Ii~l di l~"'''''', if the un",,,,," ti..,, j. in Ill<:- rir>~ or the ' c. tr; mgcm""t If. n~uon ,ute. the 'i ng n.. .:red . 0 lh l lh. do" ~1e bond ~w,,~' f. " m I'" H"c'CCrlor " to (8.\02 _lid 8.9:1). Will! onl, .. " nile bon d ~t thi, .il. (.~ ,94 .nd ~'~' ), cle. \'. ~" ..r I h j , bond il rr quired (1',...... hl~ j" , .. ' lOOn wilh H rea lT~nll"m.",tl, ~lld a ~.n.'Y co! tr"", it io ll _ $I: ~l>O ring 1< o"" ervud In ,ome fa . .. , ~ hl " "a'e, lhe,e 1'[:;- k'll ' ''''Ha [] geIllO: DlO clo"" l ~ ,~"",,, bl " lheir 0 1:+' oo"" '~" I"" '"'''' , pei X, ,,,,,, ,,N .ed· rin ~ lr"",i lion M.lt<: (bq ".'I <>Q 8.9 2) j, ( " ..nd for prNo" o'" ,1 cl "~ 1 ao:elo1l, [E qnJ tio n ll. 91a); 8 9 ~ ( h- .r), Po, he, k In C , H o 10" invol .ins the tan. b " r ¥-H, - :!lJ.\ il-H, and _ 50':;: r- H . Thtoze i. per'''....' ''' ...idence lh:o l l ~j. " 00' ,"'I " , ull Ir~m II "'1"~ ..,h1jng in lht (', II. ~"'''D IHim l ~ lhe II-tr.mk ' ....'l:u mpan ~'inll C,H. I",•. For , .." h ''''ltlMlKemenls ;n OF: """ that invl>I;'e • ", ' ur_t<;l!'.,ing "a lUi'; ~ n ..a' e, lh.; a " .l o~ o lllo C , Il . lu;, I,,,,,, Of "' 1""1')1 phon)1 ",her ", ,,b 'tIla/ lOI1! ,how, ~ , ;... il". H-. "'e di,tri b,," oo , B'

.,.JI ""''''.

'lZ\1'

_)if.,.

•

R"--C, H. + fl V=CttlCH,I,I'1' (~ .'M)

(1'195\

,""

,. ,

• I .., ,,,,., ....._ _ .. .... r.

.,

•

.,

,,'

18.% )

dl":' C.H. I,,,,, flOm CH,CH jCH, CII , OC.ll,-· ""mp.o"'d 10 1..... fm m CH ,CH , C ll ,CH , O ' " CH , (F'IuKli ull R.94; B~k ie", lCZ ~ I uf. 1 % 1 ~ eve n the f lo" d.>pIP,"",,
-," A l t llou~h .1buDd~DI pfl KI""'h ~,.o formeud to a fo" r-mcm hcroj-till , lnl..medla tc. tho"e ~ r . .. nf~ '·"JKhIc: rrum orbil. I_l y"" "" lr)' <:on,idem" on. f ~ .. h"" k and Bullill 1'174; Wllb"m, J977l am] "~ IL I" ",ff(! "';111 io voh('ll">t"n' rJ lon- molccuk cumr lo,co I Il~m ",n 1 ~~7J, T he ~."Cfll for E<juation ~.~4 vWt ~ .'1~ ror "",i"". i• .,•• rul fO f d.du<:jo~ , (ruc! p", II" gI" . 4,4 .,. Unh ",, " 4.7; tJ,, ~ 'lQWlIS 4.20 and 6.2; Buw,," 11 ' n k«pi u ~ _ ilh lhil profe" nc., fOf roct iUldb l~ ;, m d<:, \ b ..... tioo 11 94 ~ bul th" l CH , C f) , CH_ ·\Ur,. (EQUal' OIl 8.92) "n<1 ( :[) JO ('H , 1- NH ,' " "okr,"c"! ~Ofl\l'~le IliD ><.n mbhng no,he I"", IIIe\hyl.."" Fo r (" ~'Il"""I",1 ' nn" four i'''mom; C,H ,O ' i"... _bow Ia.." e k"", >hould tlt due to F.~ ,,~t i o n< ~ . ~ 4 .nd 8.» ~. m ~ I; ""IJ; f", (CM,j,e =O H ' aa/ " I'I'rn pria le ,\ ruc tu~ un cl« ~m ~ ~~ Ihto llgh 8.92 pi", "- num. ~ r of "lhe" . l'" r e<> rad lO'iol loileJ Iffi lllonlly ,," cu," ito Eli· i<>nl prodnced by CI ( M . L ~ lTc r\ y 1%IlI>. Ha.rilo n I ~M 3j, ome that "",h w.el"'''' h~ ,e II() Analollle:; in the c!le",;,-

f'I'Ck""'"''

)') .1,.

"'''eT

.,1.

tr y nl d""""I· , hoil ",,,inn, in , ,,Iulinn. Th;, H ' 'm mf~T <:an ,,,..., Irllm , L:kLd = rrJng..m..,m ()r lnto..-action, in ion-molfl'" r. pn:u:daJ by hydr' . ",,, ,,,, """.. th.. bast< hyd,myl uou p (Bo\\ en an d Willii'Oll 1~flI) a. ,,~ .... ~I " ' ' ~ \Io'"lk."" 7 f'f " I 1 9R~,,-h} AlterM tllely. f/'lTl," ng a" ;" n-m/'ll«u le CciaIjun. H P: Y· _ II H· - Y. "'lea.... QI... wo' dina tion ,1Wnt. ", k,eh MW C.l" 4i'l
.,,"ttt:<

.1<"".

~.

in_",,'••

." • "

(S.9~ 1

CH,.=

•

Ctl ==CH.• • HP

In "" ,j ' ~m, fm m hi f~ ~ " I;" tl ~ 1 ~u ", pou , ..b " ilh l",""j~ible " elic oon. (,o) i"l<. I",,' on lI an,lor "" n """~Lr lx lw",'n ro.;CplU' ~ lO ur'. directed b~' Ih.i , r.lill;". Jl'I0lon ~ffi nl1 i<;, I~. poinlcd mLI [0' 01.:+' ions, Equarjon 8,88. th. , i,o '" highc"H l O (RY ' H) ,'a)"", will nol be fa,-oledj, For exampl e. in " icrn ul ~m ; "Ml co hoh 1M . mino a",,1 hydlO, yl ~ ro up, " ", in;li.l1)' protonaled jn ,j mila,- proporti on. by """11>;l1l' (:I , rapid proton transfer can take pi""" Im m R--{) H,' lu II.. JIlO'C ba, i<; R'- NH, gro up to produce a mMe·,table CE o ioo (l<Jn~c . ; .ll" '" " I, 1919) Hm.,,,,,,. " ilh ,uilable steric constraint'. di,,,,,,,i. ti<.>,,,, 110m III. KO H, ' IlI nOlJon"I]!}' ca n he "", ",voll F] n~lly . hydroll. n rearrangement can occur in an EE' ion to a ,itc th~ 1 h ,

" ..........

~_

. . ..... ...'"........

""" her a charJ!<' IWr a multiple 00",1 (E'I"" l.io'.. 4.45, ~ ,99, ~nJ ~ . I r», ..... SlIr ........pf" " f in lhi' . ""Iion ao d <_Ie""i"" C'~"' p1., by z.,ho n:z ~y 1 9 ~K 19K91 HY d imina tion in 4 4~ amI K% p",d uctJ a doable bond in <~"'Ju~~ll on ...\th 0lM' '" lhe r<"""""r ioo; produ ct 'IIabd ny a Pi'<~" 10 be lbe rna", dr;"in~ I,,,"," i", A9 1, to al ka ,... "'lrni"ouo rlS from pro ' II"''' I..... l . lur..'1 lHalrison 19A l)

"""log"".

r8, 99)

- 6'

"

IA 100)

R~"oIt>tn """"~t"" (~ 1100 ~i<>n> ~.2, lI,(O~ A I&d of I'U< l.iYC .." n" ", ill all i"o r~ul11 III hi ~h , rill,al C'IC,,~jfi (0' tbe dis><x....I.i"". ' ha l u.., tol e pI..oox. and m,,'" ""m""ti li ~e r~le. Ior I.... l"'m\lk plior . Itd ooooo""... n. ""'' ' d gt"",n il , POlenhftl-eMrS)' 'U le in" ' ''OCI"",. which "," ""r" r~ rc • • al'unes. ;no;lu dinp thn'e .u ~ Oli t U l "d wilh h"l"g" n, "y' M, .nd nilro y o " l"' , n o.; ,!"-'C L. ,,m "r (CH , 1 ,r~ H , how, a C, H, ' ion, and th. 1of O '::I, FG-':'-' ,F' sh"",. :I CO, " ion; 1m . ""ak , "" more ahundant, I",,,,",'or, in Ihe >pec t,. of n-<:,. H,. o.n<1 t't1, Ct1FI , ,.."pccl;-.ly, C ha ;" hra",hi ng and un,at malinn rlca-oaoc."eh ....."T4ml>li ng le"d" ", i", I>u' ,I" nO! noc."arily . liminat. them; ' >e"pcn",-"" ( F'i~_ ",. 3.1) yiold, Cl ll,' and C,l l , ' peab lInd pcrfllloml>cnr.cnc )'id d' C F, ' , H1J " ,&"" '<"TAm hti n ~ i, "ven mo.. common, Th. ""0 poals in the . peClc. of m..1 hylc)'cIoh<13n< and Miu.,.,. aT< (M CH,I ' and (\-1 H)' , ro, pecti,'dy. u' cx\>Cctel ' ao.1 i"" Irom the alkyl pon ion of Ih. ion. For EE' ;0"" ra pid .xd, ~n !", 1eado"t' to H -r~nU:m, ,ml)' if ''''' pm,'m al1i nilie' of Ihe l.a"ing

. ro up ~nd thRl of tile olofLni<' . oume' p;lft do nOl diffe, by mOle th~n 0.5 eV (H.t"""n 1 9~ 7) """"" Iu"n lly, ",l"n,i,,, ~ yJ",gcn ",,,han~,, ;" ,>Il ,",,",,,d in pm_ lun" ted eth.mol PAle , H.. H, O) _ 7,0, 1,1, and protonated melhyl i",propyl et ~ or, PAIC, H" <,H,O H) _ 1.H, 7.~ cV (Eq uation H.H ~ ~ hut nnn< in pmtonatod dielh}'l OIM' (£quati"t' 8.97; PAle ,H . , EIOH) _ 7.0. 8,2 e \'~ or p,o l an<1 pr",l<>nalte llndergo i,omerizalion 10 a mi,lure of intorcon_ ,e,tiAA ItrUCW"", ",atin 10- 0 " wh",e.. isomeriza tion 0 1 the Jlolldecompo,in~ ions is incomplete in 10-'; ":<Xlnd, Thu" ",di<:"I·,ite H. mig", ti"m '.pflC" r to he facile ill II"''' Il",a\~r~ lod OE" 10 nl. Similarly, 0<:-' ion. from l1 ll< ,,'e m,i, 27 ate due to the 1= nfe t h ~ len ~ li m ,;,. ) and of methyl (2 ~~ ~) : a lthongh the r'>rmcr to Il><:trno<:" cmk.oll}' tavore<1, lhe pathw ay, yielding th~ latte< are OOnl plu ( I" I" o, ion 8 101; M'<,A rloo ~' lil. 197~ ). A f" vnmhk: i><md c k:"" ~b'C i, ,",'"il· al'>lc rilC The inle""edioto from t l>< 1.5-lJ , hUI "",t Iho I,.f-I L ,ran, fer; by 1,1-11 , hill the l. n er yield. the I!oble one- I,I-·ed ion.. ~ 1 .2-mi ~ratioI' of t l>< protonatod "llbo x~l ~,oop " n,1 (u"~cr 1-2. a",1 IA..H mi~"di",,,, clT,:rti "d~' ..,,,-mn~c ....rhl" pmit;", .. 2- .r.d "- a nd. [0 a 1"' 0<1" euen t. C -l lhrou ~h C -4 h). alw ,,;nmbJin<: I ~~ h.,I"'8"n, in Ihe C i t, --<:(0 11)," product ( McAd<>o et ,..'. I" ~ ~~ Seh,.,·", 1 98 ~ ~ ~'icld Lnl:: m(lfl: ' l. bk pa ll!,,<'t ions Iha t a re of\eu uxM fOI de ..., Eq ..al;o n KlS. 11.....ow . , , he .",li",,1 ,; ,e ...-cah:ft,p.:tlli\", . kelctal [""rra ap:ment prod ucing 3 It ~ ble U ~ io l ion {Eq" ",l' ''' 8,102, " uti "--..- ~ ", I Su",,; l'l IU, Wellkt an d Sdl1';arz l ~i>~ A " mda r r<:.1rntft""""nl in io~i.r<'
"_,,,Ie

,,, yield. 42':~ I:M - (;, H. )' at 70 ~ \' . bul This il ll1 . b o.K pc . k <>1 ' he "f"'Clru m at 11.V (M:~ccoll and M ' \l1e" I ~~~).

,

.

'

.. ~~

+.

/

-

'/

C>i.- { • ••

CoH<

-'" u

~

"'Y"''' . A!

H, C ~~

y-

_ _

GH,

J

+ ..

. .""

(" 101)

...."'. "' . .. ~~ ,

,-"

an

~.,,,."'-

· .

H,C/------' 0

•

--

y-rH

U <:]

- , •. l:Jl • •

•

~'"

j

•

, r- , r-, ..;

r(

e

CH,=CH,

.•

\~

•

..

"..

,c'

(K Unk""". S. , .

',;,:,

'"' es ea au "sa ",""

W.

"" ""' 0 " eo"

"" "'0eo "ea , " •••eo "•• roc se " ." ." ""

mi.

,." '0 ,."" .,••

7.0

.... .. ... " .

" '0< "".' '" "n m ." ." m ."" m " '31

13"

'0

00

.

m

ON

... . ..

ii.'

"

'" ioe

'00

'0 •• """

,,,

'" " "aa ". 11" a s

i.a eO

;0

." . se

Int.

101)

I~!

D.'

"

'00-

,

• ;

I•

,"

"

. ". . '" ~

I

" w

..,.", f '~' -- '" ,, I 00

'00

,, '"

,. , ,

...

on

« «

,l" 'w

_ .."n 8.\ 1

..," ...."., " ".. ." •.,., ."

-_ ...

.,

'" ~

"~L

co

,."

.. ....

"

ee

se

.

•" <:," .0>' "••

"

;

I

"

"

",.

"

.

'00

""

r. ,~" o., , '

•

!'

.. ..

~

,..,

''' I

»"

• " ." "

.... ".... '" "'''''. ..,

"

,«" , ," ..,

', , 0

Un"now" ' .11

.,

~

In: .

., ,"

.. .

•" "<" " " " "»"'

.

.,• ""

..,...

""" ,." ," "

" " H

ss

"" "

.,

'o'

• " " " " '" "

H

"" " " "

«

•

..... 0;

",

M

'.

..

oo

"

",

.

•

..

-.. -

... ..

'" '" '00" ". ,,, n ro '" ,,, 0<

~

""1

i1 oj

'o'

I I,.. , T ~ ..

" 0

"

"

'.

'0

'0

1

tl'.,,

~,'",al

c.nm pk-. " ct<· ltivcn . ;"I ~' In whic h thc "'N" p,,,, n .. of a Hrenn angemenl ...A. 1Ilq:dy due tn pro duct IUtbihty, S;""" ' '''' •• " reh fur the 1" "''''' loCne' llY p:>l.h lal c. mnr<' time fm ":"",, n~"" l' th;,,, fnr l1mpl. bond c1u '> , GS. ..... ...· crf. d' me abo cril k;U, U '" """.." Iry oxum ple, ill Se..1 ,QP 8 3. In \ ln1 """"n K) 'h e Flo, ' , ,,,,-rra,,,,,menl ,-=.H." ,!\' O - .... C. H.N · ""OlIId hnc ~ n "n lm po n anl indKal<.r "f hJ
8.11 0tMt '_ '""'i!emenls

u..pta""",cnt·

iJ ,"--\

,. •

.s.:

0 " • U .'. 0

, ",

"~j

( ~ .I n ~ 1

•

-"-.«,

U

•

i, ~ . I t» )

("-10 5,

Fb ", ina\ ~", :

..,

U

'I')

>- - ,

>~

"

•

•

'\: j

•

•

"/'-.

...

;

/S,Iil6j

8o.;au, • • uch a ...i& ra ",. <>f in tern al eI", r~, •• I:. 15 e \' ) is. dep""" C(l ln mo!ecu, 1, ,,,, t" n nc'l ded ,,,, in~ ,t ruc lurc "t "u k""., .. 'l'tt'nl only if lho '(lCclra lor "'_I~ ,,:...ted <:
·,....

_-_.... ..... .. ,' ""',

•hesol' a ~ " "P' in "nnil"n, fC..." .." l"" ...." l>w ~. ~, 2, ~.lU), ;>n<1 .0 a~ "sdul ' Iru"t" ",l1y Onll' for " ion ~rie.~ tl'PC inJ,,,,,,,, ,i,,n. ~ Il' cu 'nple, a lkyl i,.... ~fl " '''" h ' 8n ~ u ""fu l for ded\iC,ng lIa _.

"roc.",.

be.n ,,1~s.i r..<1 il<:re a, "di, pbremll (- <1" r lac",,,e," , ,r ~ or the c\<:ava jlle o f ."-0 bon "jeel an iTlIC' tr. grnen. f"elimrnati<>ft, , , '''\.

i,,,

n,ne

fJi~_8I'''''''''''''J. reactions ...rc I... ·orabl<: . ... '1;1'1..1111', , incc a new .....nd IS fo rme-I. ,, li41 >Ie rie 8 d~ anlf Ih. atom. is m Ol><>-

\ alent, a major ...
h yd rn~ n

r•• rnUlj!eme nl.>.

D i'rlOLeeme nl .. action> io '''hing h)-.lrogen mig,.';"" c•.n h.: im,," fl4" . Ie"",. r, ~ ' ''' li " n ~ .n~ b " l amo nalhe mo. l \It , ~n n g example, of r d r""eli,," • • re . h",,"

ill" Ol" ing Ihe mono\ 'm O lL cl,~,~·,, " d, ~" i l\e and b, omi ne ("""Iio" . ~ ~ 2 . nd R.i 03. y . Cl Bfl to )"lCld lhe Ita b," 7<'l<1 . yelit: halu n i" " , WlL F.." Y = l,.' Ihc C.!l / '1 l""'\ l"'!z 911 is the boO... ,"'01 fM R _ C,II, tbro~Jlh C . H " IFI~U I·. J .H 1 an d 1M ""'molog u,,, C, H ,, (1 . ro ok il " ' ",,Ily S 10 !/J'\ . , OL bunciant. F fL' Iti.", m4ju. p" ab ~ t·i ~u.-e 3.24 and I lnk D"'. " R ,l ~ Equation ~,1O:1 reo,em!llts lh. H ·""'" a ngc" "'" L in pr ima, )' cblo""",)hn,.. t hr" Ll~h • r." C~ rllembeJ ed- ril1' U . ""'h.... "al. (Section ~ . I IIl. Inc ..... l )· Tl dem'in ~ the ",,,,, I ;,. "',,'" ,I.. " uIl'. O\ b)' lbe formmioJl of tl~ R n +R ' b ~nd nnd l ~ c ' La h'/uy of the <.-yd ic .-t,l""" "",n inn (Van cl< 5.allik and M e La llerl)' 1 'J1~ I , a ,oln h ra nching or " t,," sllbst,n,ti.-. n ~ , o " i a<1 1 ~' ..... clu~c, II", dj,pla",, "'~". ,.,."e, j"" .• irn;l~ r In Ih< eOecl <>" Ht.'l l~, (rom c hln rnalkanes, r he re:u;unn can be ~ 1 "", 1 hy , ,, bs lil l,"nl' which >tahi" ", , 1M: R· p""l uc~; the " ""'. 'fJe""~ n( rnc, h~ 1 ",-amin",l" " ,,," "" . h" ...· ";g," r"'''''t 1.\1 - 'CIl ,OOOC"H , l" ",'~h. Tho 'l""'lru'" I'>f , nd tc~ M n u ri l ~ . (F i ~ u, e .1 .2';1, , h" ..,. an in' POl1~ ". ;Gn ... ie, Re,"eli" " S. IOJ "a ll Ol.OCUWlt 10. tho ..n e'! ,'" , imllm ...1 I,f " 1.': J!, 'l6. 110, 114 ....'z II U , ~ _ b~ wit h the Ia r~ e r ing ..'" n,f!o;;Li"l'- lhe .." de C ' ( . hond angle f", ('. (" :-N, The tcndcnq rur ~ Cll" n 8.101 t" pTI><:cod t htou~h u l;w ' """n ~I"" (Y - Cl, Rr, Sil l " ,. .i....~ , n ber~ (}' _ N il , ) ring ", di""Ll, ,,,J, ;a Secl km ~ .~ a t h ree- m.mhcred · r;n~ i "Ic' '''''d,~.~ C be iml'Or la nt. , " ..... n in It.< f.m nnt i'l Ll 01' " yolK; C , 11. SU- tJ"TOIOI..' cl"l ' h iit~n" ) [tom R C H.(:H ,:;H (" on de Gr...... i. '''\~ M d .alrorly I \l nl 4
I, I N 7lI, 1980) ha \'. pointed o,n that tlli, re.lCIl"" do "" l~ r~ t~ l kl> bsh tll1 iun at ""lural cd cadx'll l U (~ · . adt cal oh, mil'l')', and invok-e<> in" " '" ~ r conr.gurat ion ~t the c........n au "dr.d, Solution-<; ....'1'll>.tl')' ...... ..... ...""h ," " "e i ~ hb "r i n~ ~r(,)up !"'-fl;ora tion~ or - andJimC ~ a, -p ) ........ di. pl """"' ~n l " sij' h 5lu eo, peci!ie f'~F m.,;ntd · Ii"", are treated in So.olion ~ , l . 4 t", in d ...... p" rallel lo , ,,lutio n ehem.... ,.. lltt oIi' rl accm~"' l 1".. of Dr· lroPl 2 · phcnylethylbroPlld~ ("nn , tho olhyJ.:ncl>t:l>l.J!lII_ ium CPhcnonium'"j l ~ u"l i",n 8,107; K" ppel and M ct.ffm j ' 19'i6~ f ...... tion X.1 0X(Loo. ""n t'l W. 1\177) w;o, , h ",. ~ 10 involve o;yc hl ~ ti ~ n t" oilro""" flOl (I~ ~ll""; note lhal a . illl lic ho,>rod IS d,av. d, The prolimilYof IWO 3rom;tlil: n nll' 1<e.IJ> \ <1 ~ lad .... di,pJ3ccm.;m dccomp0, illo m luch ~ $ lh , """ in IOq uation ~, 1M c;..-bukrL G , u!Zmacher I ~80) . G ",on

~ n m " I)-nc

i""

In a d" .oni, I'lldi<:al iun, di,p! ocem,, "' cu, ...."<".11 rrom an ~t o m othor th"n IIu: " "" .' llb:h ..J Il, the migr~ti l1g grnup r OT n ~ m pk. lIe" l\< d ~ I , (19"74) h o.· ~ , hewn that the ]" " " f C, H,. aJl ~ CH, C -V [,e m ethyl -'-phe~ )'lpr"rWNl1 e im'olvc, (e4uI!\i"1l 8,11 0 1 ' di,p1uuncnl .1 ... lyg: Jl thol mo,'e , ~ o " hl<>- hrof,,1 ch. Taelcr In an ndJ ~cell t (. 0 bond I" cI:t,placc l h~ ~I ~ yl ~ ro u p oolhat o' ~',e n Noce lhal ih" ,it:• •.• !lt' R'- OCOII ' _ 1\' + · OC O II i , l( , u.JI ~· unfa. ...m le t:1 "OCOC, Jl , l rro'~ r , H, OC'OC, H, >. is -< I',\~ Sinlllarl)·. in rq"" litlll ~. I I I . n o ,i ~i ll d )' , 'myl", ""11<:1 i\ ck. ,~ (] (Toji"," "' ul. 1')$71 f.' ~ "l,.,... il....ru.pI.o """' e lll I'N <.li" ", tak e place ;D F.F ' i. .... lf.qwlI;on 8.1051.

'"

. , -

-

-

..... .. ........

"# , -

I~. I

WJ

", . OCQ .

(S.lI l)

,uc'h as L2A-IC H_.U I, C, H, I,CH· _ (CH , OI, C,II ,e ll, • b¥ 6·1Il"" bc rrcrl 'Y1ic ,,~rbull {C",. ulu"1 " I. I ~I ), U, u~ ll,Y lM EE ' prccu"or i , bifunctional, " , that the . it. of the c h ~ri' moy e. ( Ly u~ Liun ~ .J 12, Seilcr and H~"o I'l6K,I . The ,h~.~c\eli.li.111ShO w, mal;ma in thll sen.., at mi' i l , 129. I~S ~nd 24 1, Th e met hyl a lka~o ~[c ' IF i~ ~ T" .1 . I ~ ) . h."" m~. i m" " I ~' / l ~ 7, l . ~. l 'l'l, 2\5 . !.Jven "hid do n ~ di 'l'l ~, ~m"" l. ""n ,..,..IlL III Ill. loss of wa'er C I· pro lonated o' ime" H , O is di,pIKc",o i",mcrs were found h> u",k:r~ " ,hi. type " f """'1i,,"

r,om

,.G) V'N

(~ ,

-, . .•

0 )"

'y~ ,

.s.:

0

•

o. ,

(~

11 2)

'" I

-f,

~

",

.:c• •,

f i

!

]

e

,

,

•

a

-"'

i

-s

e

E

>-.: ,;~

, !

•

,

-

•

•

,

a

• ,, ,

• _.....•_... ,

,,

••

j

«;

(8.1 I.1)

U"k"ow", 8.13. F ormul~(c a di,plu"fficnl rearraogement which will rationalize an abundanl iun in

lh~

rna" 'pectrurn of {J imlOn., l: nknmm 4.13. {For th.

am"", '"0 Equalion 9.29,j

E/iminat;an " aclimt. with gm"l' migration". Th.

gon~ml

mochani,tic

f"rmlll~_

(ion AHCD+ {OE+- or EC-j -+ AD+ + BC (equation 8.106) would include hydrogen ,..arrangement' for compound, with A ~ H. Three classes of non-H elimination ccacti"m will he di",u."cd here: ""me Iype'

or,~

gro up' exhihit a

high tendency for migralion, ,mall stable neutrals a" common!}' eliminated a, Be. and the new ,\D+ ion can show a substantial in~rcar;e in ,tability ovcr the ,.\,BCD+ precursorR"~rrang"mcnl of u"ygcn function"lil;., is relatively common (Le'-,cD "oJ Schwan; 19~.1l with mctho,yl migration probably beim; the be,l du~umenled nUII-H rcarl'arll.\c"'e"l. Tlli, ha, bt:t:n ruuml in a ",ide "atiety ur pulymcthoxy compound;, ;och a, d"rival",ed "Ild olhcr aliqcli" compound, IlJuiliibewicL d al. 1% 7: Winkler and UI'litzmacher InOI. In eycJoalkanes with lhree ur more molhuxygroups, Equaliou 8.114 ~i,'e, rise to a major po"" in Ihe 'peetrum. Trim elhyl,ilyl g;ruup mig;ratioru; arc common, allhough the,e u,ually ''''''UT thmugh five- l" eighl-member-ring lran,ition "ate, (Iltooh 1979~ the lene, can migrate, ,uch as: CHOH Ihroul\h the eyclopropa.o.e iUlormodiale in E4uation ~.1l6 (McAdou .1 "I. 1ngJ.

"'gil"

CH,O)

1-'/--;

. (CH,I.-,-6 H"":"';:CH,),

(H.114)

,

C H=OCH,

CH,o-~cH=6cH, m'z75

EE· ion. <;;
•

, ~ ch ~ roUJI n "V~liom

in f 'l"a l ifml 8.117 - ~_ 1 20 (8. I IR-

w.w <'I " ,

,,·j,h

" \; on ;n ~ti oo,

a, . !town

lY'll;',l

"" (~

, t~. I171

r

rC><·I, ~o .

6S ( Cft, h

(S I U)

F./h .u_rl"8 . ' SY",. Cl'm mo " ly 1.....' from M ' I.hrmlgh hyd rogIe molem l<" ,uen '" Co, N" CO,. nnd SO , I. IE _ 14.0, 15.6, 1.1.8, . nll 12." respc<:ll, ely) can alio be highl~' fH or. ble OJl a n energetic ba , i,. R""KU,," ,IH.= gr<1Llp' CKnlH,1 he IOClltc~1 on the tc-rmini " r a molecuk Iholr fkl n'e" rr~n geme nll ",. mu , t occur f,om " cycli<: lI\()iety (e,i" Eq ua lion 8,59), In spec l.."l il1lerp retfll1on. however, their 10<, i, 1101 cletil1 illvc for , ring 1,>c "l on; > I",,~ il ca o ">rnc,lrnes ,>ccur by ellmlnalloo from acyclic po, lll m", despile tho hillh enlN py rc ~ u i rc lIl<-"Il l ' . Thi , elimination i. ul,u ob",.Y<:J for HY mole cule, an d f", , ma ll r:wlc~ 1 'l"'cO::." , uch a, l-ICO' , 'CF, S, " nJ ~'
ra 121) SHeh dim;n"!;" ,,, a rc rd " i,-ol}' m mmOll In e" m pound , with ,"'" "mm ~,ie ri ngs \Wl:r.olek '" " ,- 1%81. A var iet }'of l'-u "benznnillde, ....ere fouoo (Broxton ~I. ~I, 1971) to ellmln"te CO " nd Ihen H . n", Initl. 1 C}'e1 i"'lion belwe. n the "",m.,i< , Io!,/, l " t. 1\, . (St·e.Ii"" 8.11 Th ... 'lO d ; m;n ~l i "n "" n h.: c n h :rn~,--..I ,, ~' an mlh"..iluatoo fund,,,,,"1 ! ""' r (Yi~on 19_1. IW2~ l.O
.ri""

•... ao,..-al '0""0<00

'\

d

(8.112)

1

oP

•

H '~M' ,llk"n ~I' eiim,na" their 2,J-c «ho"", ., (" H. (12'l Wllion ~ .9 m a, ~ "'.. i... l..,,},r cyallid< IBw ~. lma ", 01
i8, 124) T h~ . ",. 11 , la bl. molecule, '" .. ~ic. l. ", ;",;" alo:ol ,or" not noceuali!y prcteOI ... OOjJJ1U ~ blod ... in the or igma l <tru ctUTel. TaM< 8.4 .,;"", lu r '~c r • •s mpln of . hmindlion l\:" rr~ "W'",.n,",

'-c .''''"-", 1978; \.klalTt11J l lj ~ : Howe ~ r al 1981: Zw,,,,,,,lman . , .. I. lI a rr;",n 1983; k ;"'~'I"" .1 ai, 1983; Zol1in~'1 and Scib1 198'i; Tl\f~e~

l ?~ J ,

1 9~' ;

222

" _

Ib mrr>tnom 198M, Tellouv. 1989.

\1" ,~d (l(l

1988; Heinri "h

~ n
_ ... ..... _ .._ _ S<'!1 .... ~t>: 19119: B""iol'$ . 00

"ou',.' """IM'od

"re

CH,.

o

J •.

00

" CHO ·

.,

$ , • SH, SHt

"e....

RSR, RSAf, ••

RSS Il;

C, HoC'ICH,I= N- OH

o

ooI!_ CjH ,.

00,

'." - -'- " 'lew . '

<"""""'''''

""

" "".11

~

IiCO,"

se

cr•

"

C.",

C" '-

CH,CH.S '

ASO, P'. , "'S(),OII;

9 M ass Spectra of Common Compound Classes

N" .. "'" ... ~Il au ..." ,.. to apply the prin,il'b .,,, rurll' d ,O\'e to rloe inlel P'~I~ lio.>n of COIDmOD Type' 0( (lTg~nic "" "'I"'utld, . 11 II im po rt ant rOT YO" to ~ a ' D ;Ul ~I'p'c'\;i;" ; ",, " r th< reliability_and l" ,~ ot r,h ~ t.il ; ll, -_.. f lhe ~ a,io llS lyro-" "f m'S$-II"'''lml information in I'f(l" iding c,idt""" ('tJ1I~nunl YaJi(l~' ..ro<1 ulal ! e ~t ~rel. Nul, ,h i lhere i" all ,xponcllti.:J1' nCle"... in the " um"". or I".... il>l" " "8'''''",I\;On palhway, witb an illC"""" in I"" numhe. of ''''''l ion", ili ~l i n g sites: this CaD t>e ,een by ""mpa, inj!. !he IIrh3l 01 t ~lel l .. , '~ l~ " l of either kctonci < ';""'l"chc',, ,iv< volume of Dudz' b . ", ioz. DJ«"... i. • ...J Willia m. (1% 1) W. f« \lJl1lntnd tl ,II a ba, i. rd , ,,,",,c ; the (X)rnfl'Ound d aloS,flC.ol ' lions in lhis ehaplCf a•• p;,"""",d " fk r it. '.. wealt h of ,pe.;ifio IDaI. ruI1 i, I\> he I"".nd j Q the , ......., . 1;,0<1 rc"' rc n Cl" ~ 01 S. ction 1,9, In d.."I; " l' with co mpo und. th at COD"" D more , n3n on" r.. ncTionol iUOnP. rt memb'" , hat rbe,c "" gnoal CliooaJ ~w u p to i n~ LlC "'-'C lh.: f' RI:mc:ma ti<>o of a mol. ...ula' ;~ ... Fnr c' am pl., in the , ' pec!fum of C,H, CH IOCH ,HC H, l..C:H, I"" ~ -d.~~~ g. po~k, C,H , CH - OC H \, i, mono tha n (.... high u a n) <>1h
",,,
k< .,

1I)'drocarbons, " nrnn"na lcly, ,,>hihil ~ , .. I>-'a"l;al '. ",1"" •.,. I" ..~ J.;r ~o:> Modm" rearra!ffl<'l'le!U' (Section 8,9 1 in ", bich Ihe "ydro~Il" lo)fII J'<'!';t;OIlfi, •• ,d. III a

b <er nlcn l., ,he ClUt.. ,n . kelnal a mm ~e menl ~ ~ scrambled T il;" .. tha m". ~ pro noolflced in .Ilanes. ill ',; II..:h lhe o·;""i"'l;'m f" llo:> ~d b) C-C boll<:! cle ~'" a<-,", IScctid UllUlUrauon : Ihc . dd;li"n "r .. pola r 1..,,<;tiD"''"' gn,,'p c~ " n~o, tho 'I'"'"ttUOll dra mal;,:all, ("" mparc ~ ig... .... J l a ,lfl J.16). Sillurllltd Illip"".i<: ~yJ,_",,""". , _~ •• h, ... n in ,he ..p.....1 fa '"
j"""

c"Hz.., R-,C• + ' Cl'"A"

Y (9.1)

C'>!ln" R, C ' CH, R'

~ 01 C~lI ,~ " al_atle' a rc r" , mod by direct ".dcava<-", ror" > 0.' m, but th" t ' ~ l S~ ~ ;o n; formed ;n thi, wa y for " S 0.5 It" In F ign ~ ?, I on ly the ,CH, J,(' ffCH., ~ . (mi" gg). (C H ,),C ' (m/= 57). and CH, ' p;;ak , can occur b)' dlle-:-l " .dt' I.'all", The " arrangement C,H, ". L' peah that a" larger tha n half ,t.,; m,, ",:o; ~l aT W e a r. olw io...I}' Ie" abundant Ihan tho,. of ,maUer maos, . uch .u C, . I, - and C., H, ·. Peak< , c, ,,llin« fw m , ec " n d a ry oloa ..,,£.. a,. !cfi n to", "r , Ignilicanl , pceili"il}'. ~, in F~ U' di " n ~ , 2

,,,,i,

(,~, m p;".

Fi, ,,r. k,kl.

-"-- 1'1 '.

-"

","- h 'en;ary I RR'WCH) ;m
m

' .1-

'·1 ,f •

I

T """'r'~'

,

ld .

~

•

. I-rr-

" ,'

,

•

•

•

~ ' , r" •• ••

imporMll ; ("',( ~ - R.l- and (M - RHI- ' by c ~~v ,, ~ c at the br ~nch«l carblm (Eq " ,,\i.m a, ll'l~ l-'Mel~ l'b\h",,, Wilho ul L"~OT R ",b' titulioo us......y , how lhi, (M _ C , H.:,' I"'" k to be n lmpe:'lUlnl a, IM - CH, I' (I·ig..re 8 8, lop' no CH. lo,", II _ e n , ); M d;n ~ , hi: l- meth)'l bI a ~ c h i.....·""""" jM _ C, H, j''', H" ",e. er, ionl eow " po nding 10 C.H, •., · "n d C. Il ,.· (;;0 o " Iso Ix; p'UJlloN b)' bIanohod oa, h<m dea~a llC'}1 ,sron,,",d ucls, T h~ . lhe lone ;mpoflanl (bo lh 4~{; l f"\;' mi. 238 and ! ~ ((',,11, " ,,00 C , .H.. ·1 ill an alb "" ' po.>.1 ' um ri le lhe M+' "b, o"",; in this ' pecl, um lh. (\ H ,,' an d C , H ,., t , pe ak. a", "o 1 impor l,m l. For R ,C H n<>1c that ,he numbor "I C,,,oon a l.om" ~.' in I....... ""a k .p~ir ion, mu" be an ood V"hl'; a C ,. H' J /C " H,, - ' pa ,r l~n value 01 " uld ind,cQ' e IC , H , I 4 (;. I h" , lruC!UI'.' R ,C H( ' H > and it , C(C H , )., ~' ;eld a s,ngle 1M ' R)' / (M _ R H I ~' pair. ' ;ll<.'C ( "1 - C.U . ,_· II n" t. i mp" 't a n ~ 1>0\00'0" " , R, Cn C I{, u ,ml' ''lIl1d. ll Sl ",lly p",du.:e lOea",mbk 'vi t · and ( M _ C H,)' I"a k" h t<:nJj ll ~ th is, tu,o iml'" rca nl 1M R)' il M - RII" 1M'" "an arise l'ro m R, R'CIl . R , R' ,C, R, II'C, R, B C IC H, )~C III~ " alld R .1 qC H , J~C R , (""'" im-p" rlan1 C,H , ••,· dno:! C,ll , : ' p<~k, u>ulJ al<.o . ri", fron, R' and (II: - 1-1)- ; see al:><" ,,) Wilh " and "' 'q"~mln g thc numh<: r " f c.1r bon a~ in R dlld R', tc" pocLi.-d)', the nnmhc, », in 1M l "~' 1M - R)' . .'(M RHr pa1I!> 01 R , R'C H .hould bo 1>1 .,. I . nd" + II' +- I,· "f R, R', C 5lw 'u iJ be ~ +-~' + I an d" + 2.'- +- I; of R,R'C . h" uld be In -j. 1 " nd I n ... "' + I; ot R ,H C'I CIl ,)~ C H R , , ~,, " k1 be 2" + I and ) ~ ... III F 2:· "" d of R ,C(("H, l"CR, Ih Quld Ix; ,In -j. ,

f".

f"""

""" n

".i ...

~ nd S ~, ... , 2. ,\ ~ ~i n, IIR'CHCH" RR'C(C II , l, . ~n d R, R-CC H , ,.-ill ..I", yo.:ld I.." "", j ,~ <>11!>1 - R' I__IM RHJ' peak. , h ~ t ",(1110.: ~ niza bl e il l"";' M ' ~ nd.'or 1M C H , l ' peak, can f>c hkn tlf~. UnkllOlOIl S.7"'.-. It, ~"I"". of 10 ~ nd 1.1; r", II, II'CH_lhdn + I pair would Ii, onl Y", - n, yiclJinp . _ 6; f" " n " + ~ . + 1 _ 10, ll' _ 3, indicating I( :';H .. l,<' HC, H,. Ihe reneel a"igom" nt (nol( rh.rt I i , no l iltll">Tla ll' l r Ot tbe RI R'Ie' snuel~",. 5<~ ,'iTI ~ 2" ! . ' .. I _ 10 KTI J • + 2,,' + I _ U y~ ld. ~ = ~ anJ ,,' - .'1, the "ruclu," (C,lI LL ), C(C , H , ), (now C " H,,,I ' i>olOld aka J'1.>J~ these t.... o peak pai" . but fortun a tely ,he '1'<'1.1 tuln ...., .., C . H , " as mo, e lmpo!l~n t Ihon C, H " - . .b 'en lhe II, II { : ~t',,<:l".-e ((\I I,hCf'~H" iC lO H,. ) i, eon,i, t ~nl wilh Ih. (\ 0 IlIho" , h no fiI ;. p<...., ible r", II , H C(C H, I~ CIIR, or " nJ C ol I"'a ~ R ,C(Cn , I~C R , . -\llOlhe' <>.a mrl < {n<) ",, " J show, n, ", lue, r>/ 7 " nd IS (C, H.," • 20/;;; (', H.. I • t 2~;; e " II," , 7':-;,; C j, H" " . 22~-;;l' c" H" . (, S~~ la nd ,he n.... t abund.tnl of C. H, . ' to C,. H" ' \ f>u l eLL a.,' i, ""Iy I~;;' r.r +~ . + I. 2" +"' . I. ,md 11 + N' I . " + I;' and R R 'CH(C H·, I~ CH II R ', ". of " + "' - l. 2~ -t It ' + '" f 2. ~TI!r uel,," , " lK'e l«ondary decompa<:e' ca n be correlated "",,1'1 ion the,mochenlimy.

C.""

('la'''''

"'0""

UnA ",,~~.., T.y the C, ~H ,.

I.

"""''''T ic I. 11knOwn< 5.4 10 5.6 ag,in,

c,

, ,, ,

{1

o •

•

,., s ,, ,•

~L

, •• • , I• , ,I

., •

,

,

• ,, j

•

~ :

•

",j:

a

,

,.. •

,

,,

rr

~_ II

r.

-......... """"'-,,-_.-

., .

,,"

V ,..." I"....' ''t tllip~tlt;c lIy Jr""..,.iHm,-. T he ad ditio" of a double bo nd to an alkane IDefOasn the " t>undaDOe of the C. H .,._, • ",ld C. H _,. + - ion """"" a~ . howo in tho , pcoll um I·dod""," " (I,'igu t\: _u ~ ' ''IC incr"". ing importa nce of Ih. C,H " . , • J lk~'l iO Il SHI. ' ar 10'. ... ' rna-=. Auodl of I,,"-. r mo1e<:\II,. . "' ell>hl. Cis and ITtBIS il;OTJJCTl; u.u alJ ~ h~ \ " very , i",i1 . r m..., ' I""'lra Alke". ;('Ill ' . ' hihi! all ~'Ii<: d ,''-',*", (61.....'10"" 4 I ~ a nd '.u~ bu t als o sbo...- a , Ir" ng l"ndorl "~ Il> ' ''C>nl. riU Illrough m' grnn" n of 11>0 double b<md. I hi, j,

t""

"r

.

CHR _

=

.

C~ H==C 1-lR

rs.» e'!'CC; all}' I' '''' (",

all ",.. "'·'th ..

1""',~ .m .. ll'C"'ar· ""'~llhl

~

0 often sh_

an d 'll'lligh' och. ;" a lke" ... B, ancl>td

specifIC al1l lic-clel1 oa¥" or ,""m oog. ment

""""nlpo"n" ,,, a. rc,"""kd h) C"l~';''' a;.b.:li"ll ..ud.... l "1af'l"es d at. 19~4~ ' he rna" ""'..... .. ,...l' . nn and ' ''I''" ia ll) roJ,.ene'>. len d 10 be indotpt"nd em Dr dDubl¢.bo,od po cnllo,n•..,.l 'n rn)·TQ;nc. ... .. h .-I1 lhe <"'uved

+

h..nd " douh l y al l f lic \"
(9.4'

' • .o0Y I

C,H,

Henne"" r" a nd So< conj ugated 1'o";ti" .., rt ~ · 10V1'«! by ~lly l ic clca" Ub'C iF'Iua!io .. 9..1). Lev,"n or a ), (T97~) rLl">n th al [.,It!.

.h<,,,

{M _ 57)

ionizatio n m ~.... poectM of alkene, ,110..- allyhc c l",,,- ,,~ c", whlch allo,,· " 11<:<1 ";· "" :a l l" c,,I;On or the d<>"hle hoo,nd . r Ofmalion " r im portant C, H , . ,. fnogrr'ltll l ions by C~ H , ~ d llniJI ~ li <.>n ""n ocell, try ~ >arl.! y of rnl<:ha n...... (!>lodlO,,- rr al. 1 9 ~J ~ Unbran ched al ~ ~n ~ s arc cha racl.,ized (h, L" C l S, UOknown 5.10) h;' a SlpI 'l;,;"nl C. Il,: ' O E ' Ion IU les wh",., I"'"-k >lll~n. i"c, ~TC rda li,,-ely j~dcfl"no!~l of douhk -hond po , iti,m; ,n if" or tllc d" uhl.; bond to inner pt";!.i01\i lA~bltizc M ' -. ill!el'llal hTa"d, lfl$. a t the """bl. bond jl p al ti ~ ul .f ( ~- eITecti"" 10. '~ d ud ng . p. c;llo di"".. Ci. !iOll b}- lhe l'hyd rogea re"'T. nl!Cnl ~ lIl rEq ni\li.... 9.6. R-- > H ), ,\, di"",,<ed

..

.-

"~

:D, "

.

•

,J

..

in Secl;"n S.2, an electron..u"u l"'3 all)'l iroup al R- .UlliliU! lh. charge; PA(C'H, C H C H" CH,C1I= CHCH.) '" n c \'. hul p.' r.CH, I:C CH, . (C H, j,C=CiKH , l = 8.5c,," . Th e C. H, , · - abll nd'l>CC'; ;n the ....... lrn "f l · aad 2-<1oo ooon. arc ",,,.dy ";"';13" CH e< , uMti tution . 4 C- I .. nol .IIOt:t i,- ~ , The +. 7-, 8-, 9-, a~ J 1l """, 'h,I·2-~ nd ."" n e , "I.., , h.... C, U",- - a hundanee. lhat ... rclali,d)' , imilar Ie> ,110oo:: or 1· and 2-doo.a_ e_pI tllal lbe 6-melhyl l lllll. a InOA: imponanl{I O':{1C, II IO .- peak, prCII..m ~ hl , l h~ Ch31'g. -m;grali" n ",d C , H ,,<; 4.ltK.'tl!yl !!i, -.. a baSf C , H. I p<:ak rrom aUylic (It'ia ''age~ In 5--methyl.2.unJe«'" (R' = L'11" hrancb;ng at th. """",.I "'.. no! d~~ ""d l the C, H i • • i. "1.,, In",. iml".... tant ( _ IO'\ ~ \>1> 1 ", il l! o lhtr C.H••' .., t< , ub"anl;all)' red ut:<:d_ H '~ \fl , J -m. thyi-2"und=1\t' (R' -= CH, I gi,e, "' lh. mOM "bundo. nt ion C,H , " - , cU t'e, p
pr,,""

,n

"

"'~_ .-.-e-

1(:. H"l,C-CH, (R" - C ,lJ u ) ,jmilarl~' }'\CJch " ~ i "'I",,'''ml (12"/.,) rrak tv,mP<' ooma \(I on.h;h an un...lu_ .~lcd >llail'lIt hyd'a<::aroon eha;" j, to introduce r..nooti" na l at the double bo nd(, ) thut CUll in Ji rr.". ;n ~ ill lh_ po,ition Oflh. tripok bu n,1 <"In Ix: d''' ingu......-d rrom lh tll m~ss opectra (\f ercer and H ~r"",n l Q ~b~ ( M ' ] inc... . <es a , the II1p1c bo.moJ """ ,:, in, kJc Iho hydroca rbon chain in keepin; ...·ifh the in<:n:asJng , ,,,bi ~ I ;"'" or ,h e a l ~Ylle OE-' ion, . Inter pretal\o u (l( the ~fIC'.1 r . j , d ,lI-'c ult 110...''''0. , ,ince . ommo n ulI,y l 10'" c''' ~ ,,' o """,n " II, ro..s '" mcl.~J I, dhy l, .,,<1 ( :.\H,' DCCUr in lhe ' p"ctn lm " r l,ll· n ollMl' ~nc 11I:"t>loir>• • ",1 1',,,lcT 1 9 R5 ~ leddm g apparent l}' to cydic FE ' l' '''d ....1 i,.... To ,";Icta lc. eo ml' af i,otl of 'pectra of aU a~.IL lb " ,,,-,,,,,,,, i:; nc<:c" aT)' for f e l ; ~ h le ;dent, fICa tion of alkene:; and al k ~lI""

1""

' ''''''1''

Unk,",,," \-"" ,ho~ld , 1m> be abl< tn dj'l,n~"" h ~'"-''''n'

m<' rc ,,,,,HI belwcC'n lI n_

U lnd S,lo.

"J..mx:",,,,,,,,

Sal......" " .ticJ~"k Althou~h til< mole cular ion. "I c~d ()llk . """ arc "", rc . bUlld-l lll Ih,m lh"", 01 tlleif acyclic C'()unlerran .. ,hJ ol lllrs" r . It an", (Lquatio n 9.1l ln ll>e spectr um <.11 u""'u:ykJdo· pent a"" ttoe C . H. ' an J C , H, ·· a re al"" the largest. but dc. n, ~ d"mj>l/l tt lhe C,H, , ' ""r ic... Cnlli , iolla l aCII~at ion , tudic> (In ' u"'Li, ..",d <)'tl..... lh n" t lklr· che" H ~1. 19771 amI Ion ph " ~ >rm initially J· alb no lO W;, Alkyl. ,ub,I;\uoed ~ }'d " rr " l' an ", ut,.urgo fa" and u .'t "'hIc ring.''fI''Tli n ~ (Zatkin and M,ka y" l~MJ; cyclopropane SlIuct,,,.. h" . c """" ~"n,i
"",,,,,,,,,00,

'"

' ,1 " ..,,,,,,,,",",

'00_

',f

".'

j

'00

Fiom.

I .Z,

Mas< spectrum of methykydoho,anc,

Skelelal ring decnmpo,itions must i,,,"olve c1ea,'age of at least two bouds. which ffi"y eontribule to the inewOled randomi,,,tion observed with lhe,c compound,. In the 'pecLrum of methylcydohc"nc (l'igute 9.2) IsOIOpic labeling shows tllal the prominent (M - CH,j- peak i, due to 10'" of thc methyl substitucnt, However. only hlf the eOITc'p'mding peak in methykycl()pcntane ati,e, in thi, manner (indicating a greater degree of endOC)'dlc cleavage In tbe CH,,)' ;,m which i, live-membered rlngj, and eyclohe,ane i!wlf ,how, a (M n'\', of the b~," peak. The (M - C,H 4 j " peak of mclhykydohexane run he rationalized on lhe basis of inltiallonizallon at tbe endocydic branched ,igma bond (Equation 9.7j, labeling indicate, Lhat (;O:;~ of Lhc peak arise, from the diminaLion of C, H. originaling in thi, po,ition.

,

~­

(9.7)

However. cmdlll spectral correl,,\ion ~an give valuahlc "'udaml information nn ,uch comp()und,; thc delailcd 'tudie< of Djeras;,i and his sludents (Tokes et "I. I 9(,~) on the ,leroid h),dmcar!>on skeleton provide, a classic case. For c,am· pIe. in the mass spectrnffi of 5-~-pregnanc (Figure 9.3~ Lhc (M - CH,l- arises from the 10"' ufthe angul~r melhyl !,'T'>Up' (mainly C191. Loss ofCoH, by the noqdic fragmenlation of the 17-20 bond is neg~glble heeau,e of fa"ored 1:;17 dem'age of the D ring produ~-;ng the ,tahle leniary carhenium iotL Radical,ite reaction< of lhi, ,pee;e< ean pmceed e;lher througb rociprocal hydrogen transfer (Equallon 9,SI and 14 15 ol.,'''"gc to yidd Lhe charactcri'tic OE-' miz 21S ion. or Ihmugh cleClmn donalion to lhe neighhorlng bond. resulting in Ihe miz 232 reak lhrousb 15-16 eleavage (Equation 9.91. A ,ubstmlial part of the

i - - ., ,-

,, ,

-

l"

••

,- , , ,• -" j ! •

,- -

.,

-~ ~

.

.

• , ,- - a ,-

,,

,-:

--

.,- -

-s

) \

\

\

\

(9,91

~, .

r, ~

",".<217

base l"'lk II [ 4~

ion

i.

",i l

2 L1 11 due 10 C L9 llIoth}'1 I"", [[om "I,it nl.

~ ' ; n:tll y .l hc

mi.

comr><>ocJ m" inl)' "r . jn~. /I amI II. b
m~ ha ni ' m

o por. ,i "¥ in coujulIClio ft ...'ltb • lri ~ h).lc·tt<".i, u), of AiD ring. ha s . Chaf'llCI~risl;~ tjf~t on Ilul pt'<>OOU~ i~ OIa" Spoctru ffi 01 t he 5-P-(~';'''''wmcr. Ill: ,'l 1 ~91I""': lSI] ;,. "" lC~ In..." . '''',~ i~ ,h., u r the 5-''''''m"" This "",,,,-1 "" r~I'lli .<:I ) inJ,:",:~J<"1 ,If Ihc ("[1 ' ukl i"",nl (S
r....

t""

t""

Ihe pI~ of ..... w i..,""'.... ,,, ,'c",N! ~c,d. in hir hl y rompkJI ....",1 .'1" 01'011 10 l be ~ me.i. oJ Ihi> J'C,,,,kUJIJ i , 1"''J''OSCd bcclIu se the b, 1e acid' of man" "" I, ~J C l'I:lI ';I ~;oJJy rel~ led 10 lhe p.1t · lieula. a~'; d , ;'1.,n,i,",d_ F,a8me lllalion. of lhe D-- rio!, l&jillll ion 98) and Ihe l,w< " r N- alic ,,, 17... """i',,loo .",mid.. bul do ... '1 d.~n d o n Ihe PI ~ and ""I.. ... of ' ''.....il_1S io rin gs ,'0 and H l/ ~ . c' .l ;' 1 97f1~ ,..", •• ample. ch""''''~ Jlc dcriva"ves '>bow 1l'I"ClIII....... 01C. H , , ' and C " H,,' from lhe molecular io n .~ ",d l "" rm'" O il ' f'~"'-"TI ' ;.","-

.-oJ I"

c""l~bfub

pel rol e~m mi~ lu"", ~ni ..... ,

".mOd

li _ J .Jicydk ' y4r",,,,,iIoHu.. F or n",oy lYpes oJ ~cl ""l . .....c'" ioni.... t rn. a , do a >an ef'!' of C , H, u l1lu« rin ll" + do uble bo ndsl lSOlUCrS and O1h... com",,""'" "il ~ a hi!!h dq;rn: vi u"""tu'1l. " d hyd r" ""r . bo,.. (C,o" ... 1"'0 rmg' - 0,1" .."", hOl,d,) con....inm" a ""-d" h"'..... lin!! a nd an eueriOl double bond eUti b" spc<TIa ....hleb a rc consis.l.nr -.mh iu,ri., 1 " ",n...r i",,';,m I" a cydoh<....c"11l." >1 ......1" ..... plu' 0'''''' . ClI ...-~ n!!'........I.... ~ ...... a' rncTb)'l n,igral'ou , Cydohc, ene d. "'..." ..... on Ihe orher ha nd. can uDderi<' q uil. 'P"cif,c fMIlmenLo'i" n....... ill""tnuOO by the "f'l'1..1 n<m of ~-y d"he.c"tIC il-\df Wi!!u,", 9 41 T he ba>c peak can be rationalized by a h}d rOfll"\ abstracllo o " '''''ha niwl tun.· lcr nIlll the unpaired el=on to an an~llC rndlCl.l ,,'" I f q.... rlOn 9. IQI fun_ cd bJ.' me th yl I"",. 'I'be- o.i""ir."",nt odd--ele"'ron ion of m.. .~ 'j.t. ..'hieh at..... through a rcl ro- [);eh-.'old. r f<'act'Otl (Eq uaUoni ~. ~ 1. 9. 111 is a con•• nico t ch".>cIcr'ff~ lhe cycl" ho:; ll<"TIC .truc'"",- T h" """',; ,,~ prod ....... a. d ;'_; and a. m,,,,,,,,,,,, fr"l' mctll, a nd can be h~ hly specif", of the double-boD
""''''0

r.4 ""....,.pc•••

,.e

'00.,

•

m'z67

(9. HI)

I · ). 19,11) I % ~ I , T ~ c cyd o nn c"" douWe bond can f>C a par t of an o <1no- hete l'O a ualo~' ~ K ~" ne an d He,,'c 1 9~ 2l. lu, t a. happen> in ", ,,,,y .iI'n~ -c l oa va g. ami h ldrog~ n · rean"n b'l--mcn l ~ . c· ~ ; "" .. 1M pnx illch com...." for the po, il;YC d 'larte- Ten " hyJ ",cannab ;nol prond;n~ 10Ihc " .nidd n'onoene lh ro ugh k", of C , H,; [.q N lion 9.12 i. OM pol 5,b l<; IOlli"'l.ab.ro.t ion o f tnc oloc\ ro n ,hilt.

""i

"'1 3 14

_CHa o

" ",·,<:;11

(9 .12)

,n\'o l>'«I. NOle Ih 3 t CH, 1051 f' ODI the O f" ",/0 24~ IO u aivo, 11lc M,", pnl k, o;oo . h l<;nl wi th lhe aromallo ~ t .. h ;I;7.. 1;(>lI aohioved in In i, fi E · proJ l>
"" N- D,ell-Al"" , rcac t;" n i. olio a CO!l'm o n dcoomp.:o. iu on mode or OVCfl· i,m" " , that a ."bofaut" l plm of the m/z 231 pea. may be ro, mod by C, H. In", from tho 1M C H , I- io n. ~)""'''' ~

..=

The spectra or ~ - a lld If·i....."". il )"11" ,,,,1'1 ' 4.12 ..rid 4.1 31illus....d> !t:llrlio"...

[I" ~...,

In k

ArM'4 ti<: ~.,'dr« Nao. tK... t 19'J'lJ/- n.. Sp«lra 01 ~"t11e l l!n ~ M" n ", ~~ naphtha lene (Unl ,,,,, S.II. i""",u' no!ine IUnk _'n ~ .l OI- Du"lbend ne (U,, · known 4.1 8~ he~ylbnlltnt (Fit-ar. 3 an '" ' ''1yl ho,,~n<; Il l"l oo u.n 5,7) cu ml'b. The " "" Hion Q\ a n aloma n.: n"d en. 10 Illl alka ne >uh<.la nti.ally infl u' il"'" the "f"'ctru m . M ..Ie.........·,,'" !'It'''' ~hu"""',,t (I S~;.). Arom,lli<;·rin~ <:I<•• J'f'-""">'M u.ually m.jllue relau vdr ..,gh cnc'lk... a...J a re accompanied h ~' • hi ~ h Jcv;rft or h ~'d r os: e n and tWU d::t1t UI >Cra mMing; thi, lead, w the dl.o f ac I.fl~ u C ~afflmat ic j" n ..." - (h hlo; A.i> ~ The ion, C. H n." --{:. H".•• (.. = 3 10 (.1 Offtn p rtd Olmnalt if t ring COnl ain. chodm· negali". ' ob'til ....nl' ; 11.., "", i"" ( '. H e ... --{'. H , :. t. m o ~ T y p~l of Ih. presencc of cl""tron-d onalill~ su b~ljl UtnU or htt tfocyct;., "''''' I'''un''<- .\ "'" Ihe ri>Ig po, h i"n " I alk)'1. uh, tiluti,,n 0' 0011) ha. lin lt .... on lhe ~('>l:rl ru ", (I". ex.omple. 0 - , ,n- .olld p-x}'le" e h .·c ....1 y , jmi. " rna.. ' p"d ra), A nOlh~, " h~ra,:t"';, li<: l1Un1'~ ~lIo U j ion >ell" of p/len~l "lane< am "" ••:".. in Fill",e 3.7 al ma"e~ corrt ' l'0 nJing '" C:. H,tC H , I.· emf; n , 91. IO~, 119,. _,): lh. ~hUll d1lJlc ~ , 01the individual ion. I re llluch nr",,, k n l o n tI•• " roolure of lhe nrnl eC ol~ tMl n Ih" "" ,>I the I"""'·m. ,, i".. ... ie<, 1I0...,,.,,r, ion•• lahi_ 11zed b) the aromal" '''Id eo. can ho rm""N lIy a .'a OO)'· of rratmtlllarion pa Lh"" Yl, ' 0 tllal the presence 01a la '~ e Pl: a ~ , me ll a, m i ; 9 1, , ;gnir."" onlyt lLd lhe molecule CO 'llam. " ne (" morc "r ",.'cra1p'",.ibl. m uemr al feato""'. The mo, t chamc terlstk ion of lhi. ",,;e, in Figar e :\.1 "" n '''t><md, In n ' pmre r>f II><: bcn,y l" bu nd " r Ihe la'lIe, t alkyl group; tha , I-phenl'lalhne<; ". hiM;t an abundant C, II, · iO'1 (L4uati,m 0.1.1 ). The rc,o"ance-, tabihzed beuz)1 ioll i< <1:"i~ lI:d n. til<; C. H,· prodl1ct, but in pa rlicular eK"', the simibrl y "abihNl-It~bIe c~'do~rt~l,ie" e m"l""a lae io", which by H loss forms the trop yliu," ion H i~II.... ner ~)' tolu",," ion , h.w " a hi ~h "r tcnJency to 10", H before . uch N>n"'T" " ti"" .o Imm hcn,~'1 'o" s, bur br Dzyl ions (Mi,- _ 9.:\ eV) of ' uffi ciently "'~h "'l~roal "'''1\)' can i" ,me, u.c (eriLieal energy 2 eV) ro tho more ; lable I r"p~li,om iollS I!lU, _ 9,0 eV~ Tho s fron, wloeno or cyclohel'\"tri"ne the C, H , ' jhold "" "'J':.e<. pu'. IWI'~' li um ion< " rc fOtaled. ch"nJl,ing to.o minimum of I : I LlIo pv)juml 'T benZ)'ll at 15 eV, bUI 2' I at 70 eV (McLalTony anJ Hockhall 1979; "" rli", ....m l .. "-'".......'c,1 bJ Geubh an d Meyerwn 196:\), Such rearran gemtnU ill poI}'alkylaromalics "" n a= ' a n' lor ,mne cun1petinK ~ le av a ge at lhe ring...lk, . bmul , ,,d . ". 10' lhe "",millenl (M - e ll p
n

sre

,.'"ll"

noenoe

"q......

,t '1'''

...

__....

'"

lal cd ~lul In., ",} r 119 ion ,Ic<:nm!,<,"o, I hrou~ h a. · pjleny l4lcd C)'d oprop"",," il lost in ro""in~ int erm Nli.11f; In I ~< ~_ "C. l~ "'"l~d an Klo~. 6j~" "r \he C . H, · .j

"c

"

.. V

~ (9 13)

(9,14l W""" \M ..:Ikyl , id, cha,u i, pro l' r1 'd ro~on reaTfallE;e.... m ""D prod""" Iho oharacteris!" 0 ,"' " ion IEq""I,oD 4.36. 9.(5). SubsM oen" in I"" "'l" "; lion tend to ,kcI>OC chis re<ma.ng<mcnl in r. vor of bcn7.J'1ic cleavage I E 'lu ~ ! i Qll 9. 1J). j,",. " lhal 5-, 6-, a n d 7· n,,,,,, h.-red -rinll l l'\ln ll· lion . late, Can be in..., h,-d (We\demJOli, er aJ. 19171

" (9.1S) Note !h t Lhc SdHI<' bond il rupture d in l-''1lal li<:>n 'U5 a ~ in , impk ht:n ~y li< (Eq Udho D 9.l 3~ ...h~h i, nol (",e fOf the .n;ok'lll"" reac ,ion, ol l'Olor uru"wr .,l<;d rum:1>o>n alilie, (E qllmions 4.33 . nd 4 .14 ~ Soomelimes the rat;" .of Ih..... ,,"m pct;n~ nali7l.~ l m lc<m. or the re~1.I ,..e ~"" rl!l" . tahiJiLa" OfI in their initi ating can....icallOnm, Th. re l a l iv~ a nunda""",, of lhe cones.pon d m ~ r, ;m anb'L'11Ienl ion. C. H, . - , i" the rna, . , ,,,,,cra of .. to!}l- and /,-wlyl- l-pwpKnc ~r e ~ .~ and o..~~ rtl, ,,,,,,,i,'d )'>tr>mpa, «! co the 8bn OO~ TI C C ' cl the ion rro m holll }'l;, d<"a"~t"> C , H" • ( Eq~ a! i om 9. t 6 ..,.j 9, 1 7 ~ . mb eleo!w n· donating 'ub>t' c.......,. ......" to ,he ~ lkyl- s u bst,tu,· n t ..,.. hanci njl: 1I-leu t angcrnc TI ( (Oeenl o",i.. 1 964.~ The R~n~TI g"rnefll j , unfn-o",ble ",hen .'; , hol ,he ~. or tbo o ,, ~ "·~ t ; on, ~ 'C ,,' mrlecel)' snb' titutO
... il"D

l~ o; pt ; ' "y

or. t~ric

of ~ n , ,,b,, il" Ie<,! ~ r" m~ li " (...th(>-c~ rl>()n i, d ue [" ""m hOM !i' tn Md eJeC!loJll;C facm" IK lICk 1989t

(''-11)

l'ol._,1-" I"~"yrli.' .._ I;" , ~>. The t>c h~' IN of ~ i !hct 4" 'malic hyd roca.rooo> can he ""- .1 ~. ~n C"T~ ('I<>loli"n 1M! ,Il' , Ikylbenzenel de'<:ri1x4 abo. ... The ......l ""ul~f ~n" " " uhly cha'~ inns a,~ 01 hi ~b< , nbu nda\l"•. Similar cha~"[ic alLyl >id«hai.. d,~vJ~ OX\;lJ r; ~",(>mpuli l i"n ' n LIl . u.....furatoJ ~ystem 15 ""b]"';1 ' 0 """,TC Io fd w f"" ~,....t .~tlet a l t<:ralU bhag

or

VnLw" n... Try Unln"",n,

4 , 1~

and

5. ~ ,,~a in.

f",

s.._ed Qliplwrir

.I~ olw/,. M a" , poclm haye he"" 8h'~n methanol (Un2.pwpa m,1(Figure 6.~ ), 3- methyl-3-hexanol (Fjiul~ 4.2), 4-(l<;r ~ ~ , ~ {tJ nLn.... n 4.19). l-d <>yli-t,,"' zyl ~ "'" llC l (Figure 4.5). AJdil'nn nf ~ h}'droxyl group to an alkane low. " the ioni7;ll;on cnec!,)' , but tbe molecular ion " t> u n d~ n cc dccr"~"c, I~nd "f" n i. nol oMer-a ble. U lU the ,... ,ar~m nr Fig~rc 9.5) M,pite thl, Slabilllation becam e of tlle illcreaoed u "" of de.;ompo . JUon through roaction, initiated at the ioni""l hyC1\atk>n an d. d.cllydratiot, of ' be ~" m plc . . .... e i~lI y in melal "}" tem•• CIIJl gi,'e .puriau. peaL> "",h ... (M - 21- ', t\1 - 18)- '. a nd (M - 20)·', alt hou gh tho.. c~n oJ.... It<;'''' IbrooJgh ~ DOVI'n 1.3~

""""oi,

,,••

"~ .. "'"

••, •.. • ,••

,. ~

•

• •

. h •Ii

, ..

•

•

, . '.

:'r

7 ~

,-

dcct.......im"""'_md .....,J fJ;ogm<.... I ~l u m; the I'R"""'<:<: ,ofthe a " l'I:>J" mJrns C Al> o r mcl~ 'table ion prod llC1 {Se<-1 'otl 6.41pro. ide<. a OOII....,it.. ' proof of ,he Iau~r_ 1\ . u......... 1i.l1 pca\ III ...... I ~ ....... b ilk D ";,, n iD~ bg;:;auso: H,O con ""';1, Ix J'I"><"1" hoc:o "", of ......... "l'ti< m in the- inlL"! ~Y 'l<: m '" .... a n ;"'1'''' ;11. Both ,be radtcal W and tbe cha rll" ";Ie m Ille bl d ro. yl voup a ~ ,nk rmM I' ale in [heir ClI ralHli1y lor """" i, m ini tiati on. w tha I mu , ......"<'l fa OlI",, ,h,,t. exhibit manl' " r IIIe IlP" H" rea~li""" n... linM in C hafllef'l " an d ~ I e" ;" ry alc<>hols roDtam the lar~ . and (II",.... ry aioollols the m1 ~ nesl. to ral a Mlnd.' 1I« or o ' tl,. ;n -eo nl.ail1mll ~ m . m <1" ,;. '1'C<:ITll . In all told the "1"'<'1'" or ' ....lh .." I.. • -clea,. ~ (IlqllallOfl " .171 i! , he mo., lIllCful cha raa ....... ic rea ct ion. In t he opec!rum of J.met hyl-l-hcptan<:>l. lI',;u. r 9.Sl lh.. p,,>d~ ,he ,m p<:'ftaOl ~ k . al

or

--,.

- ,, ~

c••

c.Hol~ ~ • ~.

,t" '"

~

H,

C,t1,.--.Kd

"", 1o,

-% .

~ ~.

- C.....

,.

"" -"...

..-f , _ H

-'"

C~

J:.d

mIz

I I~

CHp<=O.<

1 \l . I ~ 1

""...s

CtH.CK=OO

--

,. ~,""'" --,'" "". 31

• 1 M. . . . . ." ... of Co.,," on 0""," " " 0'. ....

mi. 73, !f)l. and II ~ r[qu,llion 9.18), whose a bundance reflect< the ,i ze o f tke ~lkyl ~"" p!j 10,;1. d i.p1 a ,, ~ n ...ltt

l'h",~ ~r~

Fo rmation of , u,," C. H,.., 0 I ion, thm ugh the eyd i"" tioll-

rearrangen.. ltl ([quation 8.1031 ' ho nld bt of little importan "".

several possIble paths for f" rt her de"ompo,itiol1 of thcoc F~: ' i.m,

(n.. onl)' , inlpk ~l<;a~a8" wl,i"h "" uld yield . n" lnOr t.:C ion. Equation 4.21>,

..c, onl)' H ' .l ~ "arran~.rnem of hydro~n to the carbon atom oft~ e oxonium do uble oond to elitninate C. H,. (Fu ll.ti on Y,9 S1 .;,n ~<-"' lUn l (oc the mi• .l l , 4S. ,,~

~ntl W pca" ; ~he m", ~ abund. nt ,>I tne", ;' Ih.llt I'f"" e"iII ~nn of T he ~lher lD.1;o[ d ecompOlmion flit lh\.. ~ p'...nhlc f", .k~ ,"',l m,""'--vlar """, le~(h to Ihc It"", ,or H , O ..nd .>ftH , O + C. II ..1 ( ~ n 4.-'l!. A, ..", bt ",en from lite ab~utla= 01 II... p, e a~o (m/, 31) and dis· " Iaccmcnl fEq uation 8.103) a .. lnlnur, T ht 1-.1 of the '!"letl urn c!"",ly ",,,,m· bleli. that oI l~c oorr~,pond alkol><. a ' c~n he """n b)' ""mp4rill~ Ihe ~po>Ctrs of I-hnatkcooo.>l ~ ...I J _"", ~ Jctt "" (lJ nl "" wn. ~. 9 ~nd ~ , 1 0J , T he promiocm c ,H,. ,~. C. II ",,' ,and C) l ' ._j, ion ,. rie, of l , ,,lk,,,,ol. (wnieb "" uld ari,c in p.l n di...-JI) from \t ' I C.IIl S;,'C c"idcncc tor h'~"eh i,,~ 01 Olhel structu ral roah' R.. ,0( ,IJC e. ' '''m , k .icto ,~ this ImgnJtnl J tion boh" " ior g.n.n~l} rol1o", ~ ~ha t ""tlined ro, Ih. co, rnpondiog hldroc" rbo n,.

t""'"

1fT""',,,".

",i""

t·~h m. ~,~

J' M , e,-Jew "g ain II}' Unknown' 4,19,

5.~ ,

5,9, 8,) . an
( 'ydiC Qlip~ati,' ;
.., ..""'''''..

,c '00

"

• "

®

" fig",. 0.1.

&

,J~

" ......

M ""poctrumof"_ rndhylcyclO" 00 100 Hcxanol. 120

•

7'i& ,:

--"--

~" I •

C,H,

ml! 57

,

~

~ ,

m;z 72

•

)" m'z 44

{9.191

--'--

~ II>'z

•

CJH,.

71

(9.20)

..

,

I I

Of _ ,

Co_""" C

..

.r, ,

lh;;; and the aualogou,ly r"",,oo 2."'''th lheunal ",oil al$.o. conl rihul c 1" ...... \0 ' nell as mi: 44 and 58, II, in th" m" " 'f'C'..1n o f = ydi<: "le...I." I.. I,,,,, Il 4 .) 1\) ('to,-ide, the ollt" major pIIt h way for M ' - d.lco m pos il lOR, Thi~ lllr,ely ;o\-oh"n Ihc hy dr ogen atom, att " "l>ed to .1. 4, and 5; Ir."''''' ,,( 4· H lI'q ual;.m K ~I\) in,'ol vo" ,-i. - I ~ ' ''''' ~ • . po;ted lro... f~l1 hcr dc<;"m"""i !i<m . of .uch triC)c1ic """~dT~ (;"" rMd~l" It.: ""/' M and ~ 0 (' + io n' would "1'''''''nt t lim inal>un of a brid j Ulj ~rO\l p Il the !liable C , II. or C ,H. lno le that die - ruk- 011"". of l h. br~..,'" alk "oJi"~ 1 d"", nO( OWly I" thc
""rboo.'

,I

~.

n.c Ol'Q,vum nf ,>-m
<e"e ral fra ~· " "' n II U",,S chl ra cl....ISlIC 0111>0 h)'d"'X)'1 gwu p on an "",mal ie r;n\l, T he .....ld· "I«...o n (M - CO," · pe ak, wh ich i, u, ually "cco~lpa ni"d hy 1M - C HOj- , i. npe<.;~l~ Il ...: ful in ,,,,,,,!!~ i.0 chlmeter istie OF" i o ~ at 1M .. lX) ' io lhi,
,.

W •• I . .' _.. • "0

i

" 1 .,

~

~

.

•

,~'

,I

;r • •

. •

I ."

. ..

'

M .....p"'VU... ¢I ... _ ~ y l pl>mol .

..

,

p"" k i n the corr<S!"Jrtdinl.l ""'a and pam i!i.omers a ~ onlr 3 al'kl 2';~; . ~' pe c­ ' i"" l, The lar~ , 1M - It ptnk arise> from the 10M , ,( tho: bel1zyli<: hy d T(I~ "n a l010

~ ~

1.9.H J A I~"h"I., <'Iintuilfin. "'..... r_lH1i<>tw1

1:''''',.... /l lipha dc hyd ra,}'] group' tend to "a'"

ad i"al e til. ~-hydto~ m, t<"o l tho: hyd ro') ! hy J f() ~ n alllm ~an Ihu. ~ et a. a re.ody donol for ,,, ''' lho-

-'"

'" dJect "", rr~I'''"_ Th~ b..., peak " f m<"thrl ",lic}i.lle i$ d ue ' " , ~ Ion of mel ... .." L ""II ' he ""rre"""" d '" 1 ~ l>o'ndll.nee. fo r , he ......" MOO /'oK ,h_n a re I">l.il>k fur 'he I""wl. net ion or l q wth, m. " .23 000 ., 24 C~ n ~ "" olillle these ('o)~ 13t ;"'" for t !nko"",.. '1.2?

_ _

u

. 0

..""

m"

" " " """ m m n. " " ,n

," '" ,"

n

•

....

~

~

..

'" '" '" ". '"

..

'"'

,.,., "" ,n '"

"

,ro

"" '"'" """ n, " m ""

"" "" "" ""

on

"

'. •.

'-

~"

'"' "n "" • ••• •• ", "" ., " " •" ,"". ,."" " • ," , " ,. " as

M M

~

" ".

'OO ~

••,

•• ".

j

••

,

,, ,,

"

"

"

,,

"I .

..jh~

"

J"

, , , ' , r -''" ' 00

"

,.

,.

'" '"

,m

,m

~

9.3 Aldehydes and keton es

AliphQtic IIld, hpJ, _. Illtd Ii f l oM .' . The m"" , »O. UII at !Qlln, ,]dehyde, 3-1>0010oon. , 3-methyl-2-!>u lano"". 4-melllyl-2-pcnlan()nC, ~.m "l h y l .2 .pc n l"n """, lind

2.3-hut'lllcdinnc bu,'. b. en ~i\'.n '" Un known' 1.9. 4,9,4.10, 4.16, 4.1 7, and ~,2; those of 2- and ~-d odecanone a,.. Figuro> .uc an d .1. I I, lh,"'" "r 2 .., [h y l h ~ . ~n ~l, 6-mcthyl-2-heptanone. and 6 -met h)'1·~ - b eplene · 2 ·o ne ore . hown ;n fi gu~ 9.R to 9.111

.oo


•

'"

,

~-

o

c .......l~ e,K, I

i• I ,

•

•

,.,

.

I I

.

\CH,j,CH<; H,CH..fH,ficH,

sc

00

.oo

'"

.. ..

.,

,~

(CH,),C"""""C"]

H'vCH,

,• •

•

A,Ma in" "f II "" tt><,n)'l ~rn"I' to an "Jh~~ I,,,. ,c.,,e t~" ;<m;7"-!io n ~n "'ln' ' allIlI" ",,1 .,. luei iTable A.1I of 9 .l 10 9 R eV a rc !>elm., dw ", of I"" « ' r1l:>po ooi nll ollpb;u" akoho li, Th. lnQ!e. u!ar ;<)11 of ''',<,,, lorO'''r kcto n"" wjth ... ,1nC ....'t"« " I d ' nin bt ." ,:" ing " .. "",II~' " f " " ",,,,'ablc ah<Jnd. ""'. M ,,\<:<:uliU llanl ially~

,u

s. ..... .. e. ..",.. e......o. CI. , ..,

• I ... ..

jon.; oI l.1 'llcr alip/lal ir ald.hy..... aro oflen , malt bul "lin "" iJ.:n lir...'y Ihe plOL-nao"rd ..r.u,1Cf,,,;'; IM H,Oj'" and 1M - (' , H . l' - fm ~ m. utl (Eqllfltion S'IOl- T he LaUef ' ''''. ' ,",Cyt! I>y I (I m~" un il. ...t~ "'1J'."'iaUy pro m i""nl in Ihe 12-<:V mas, 'pcc1ra of slr aildlH:hain alk" n al. l M acroJl a nd M ru<.e~ I Q86). The cfut.noo;lcn 5Ue po;~ h in Ihe """clra <>f calOO nyl compounds ploYide euu,pie; o r ......"y or ' he m~j", ' Yl"'> of I'ra l""... "'",ri,,n I"'lh",·.." d,-.:",~d ill Chup_ tc[';

4 and 8. The<;<' are u t,hu d ID Eq u all onl '.U S GOld ').26

,oJ

ralionali, . lh e

[''''malio.. o f It\<: <· """'.t<1 ~ .j' l ", !"'a l _ ,n 2'C lh ) 1 "" Ul~ 1 IFllla ,. ~ .~ J " lid (,. me thyl-2-heI'MlIO"'" ,f ifU'" 9.9~ The G-clefl••", . ......I'''n .. ~"n"r"lIy m uch b. importa.nl for aldeh)"OO than fo r let."'.. C HO ' 'm/: 2~) ptBk ;, pm",i. ne,,1 onl;< lor "".11<,. "I"" hyo I" b< ;,ppr«.. ble ollly ,.,toto t ile RCO ' iOll Whi<11 j, formN II ' ''Mlanl i>llly . ta !>ili,...,"". "" ro. a r"",atic ahkh) dL.... Alpha d." ..... i. mUd l morc pronunwr ,n a~phal" btOl'~ )'ieldln. I J"'il or aq lillin Ll)m 1m"": 11.1 an d 41 in h gu,c ~ ~ , a n ,1 ~ pa i, all yl iv j ; 85 an d 1 5~ Th e me r. ab undam ")II,,n, i" n II u. ""II) [,,11I••,<1 tly 1100 I or the L . ge, ally l 1!T""p. wt>< rc", the ,,'on lIl:>1md "m ;"~ yl '''0 IS usualll" 1'" more ~lable.

n..

v,

O,H,-

"(".' )1 ,j ,

C, H, " '" - •--'--

m'z l~ a

"'-(1. .. '

<;

m'z l OO

-

"

-

~ ","zn

C,f-IoIC,H"ICH' m'z99

'"

C,H o' m' z ~ 7

(9.25j

c~.co·

"'H3

,~ ,

II •

I

", o

A m'zS8

c,H'i '

,

rrlz70

•

"'0

A (9.26)

Ald. h}'d. , ilnd keton., . how the , h" ra,t. ri, \ic ion ",rie, t .~. :N, 4 .\ 57... d LL" 10 both C. H, .., CO ' and (: . H, .. , I ions. Allh ou gh lhes. ore besl di'lingnished b~ hith-l'. ,olulion dam, lhe ab. ence of a part i, ular C. H.,.,, ' ion ca n ,,,me· limel be dem OllS1t"tood by • tow U" 1- n' J.-l'" J i" 'lopi e.• hu ndance "a lu" \S':<.1i"n 2.1). t n il i ~ l rear'M~em.. ut of a y-hydrogen ,n om follo",ed by fi·dca" agc can gi I' " II" ~" <>I h,n Ii'll: 72 an d 1l ~1 in ~ 'i lU'" ~. 8 and m/ z 58 in F i ~ u r e 9,9) and ito compl. m. ntJl'Y alk..lIe ion. E.q u"liom 4.:13 a nd 4.34. 11>c n;la ti,'c a bundance, 01 th. 1.e c ;m: rdkclcd by , heir i" nizali" n polt1ttiol, (Ta ble .\.,1); .1><: "' ~et i"Tl i, m u, 1l b, 'p<:c; fk for aJdeh}'<:~a ll at will p...xtu,-" lne cc"manc. -' la hHilrd <.\ H, O I ;'-,n. C"m rati" m l>f.he r md uc\' " r lhe ~·d"a'..age and the {J·d...." g. cca<.1 i" n. In u, I""",'id"" ovid"""", of ,ubs!Ltue nt< at the ~-pos itioll('~ If " ketone collta;m ;-· h yd ro ~<'fI atoml lll both ch";lI" both b)ltT\lg<.-n ~l "m, can t-c rcarronged "' ; Ib h...., :.. .,t b olen" molc<: ub (""""=u[i,. re~rrongement..- Equ at;on ~ . 76 1 .

Dcct C' ;lm r te. at 711 c ~' Lhc 2·!leu n" .... io n I" .." pr<<1<,m ; nan~)' In.: C . ! m<:lb~I I" g". til.- .t~ble ~c)1 io n C.H,CO +, bo ",'..-. met a.table io n1 uDd. r!" ~ muU"t.p « aff " " llemCm b<-f"", r.nJing t he lo {-

""

• , M . ..

s,_

. .. Common Com,"",. CI.....

energy pathway for methyl loss which eventually produces protollaled penlenone (Equalion 9.27; Ho"chou.' et 01. I~g]). Th.lo," olthe C-1 methyl from mota'labl. 2-hexanone ions acrounb for < 3~-; orlh. (M-CH ,I" product>.

,

o

,

~, , , ,

CH,· +

-

'0

--

'0

,

," II , '

,.

n H~ I'

.

,~ '

-

•

~ _ CH,.

19.271

/JR.,aluraleli keto""."

I r (he ?_hyurogcn is vin yl;", (hi, can Jm
formation of ions from hydrogen l'earrangemem and >ubsequent jJ-clea\'age. Thus Ihc,,, OF' peak, ,"e of ,'cry low abundaJlce in 4-mothyl-6-hopten-3-one and 4-methyl-4-penten-2-one IEqualion 9.28). How,,''', in 6-methyl-5-hcpten2-on. (Figure 9.10). isomerization of the double bond to a more favotable posilion i, po"iblc (Equaliun ~_2g). and lhc C,H.;O" ,md C,H,' rearrangement ions a1" ob..rved in fai" abundance, although [C,",O-] i, Ie" lhan lhat in lhe salllrated derivative. Paralleling th. behavior of alkene> (Equation 9.5). doubl.bond i,omerizalion "pparently h,,, not occurred in "11 M' ; the mi. 69 ion. whlch would be the pmduel of allylie dea,'age, i, more abundant than lhe .,-cleavage miz 83 ion (Dia, eI aJ. 1972). The rearrangem.nt 10'" of the .i-alkyl <-'TOUp (E4ualinn H.9) i, ~haracl~ri,licor ~.fl_umaturaled aldehyde, and kclonc, (Sheikh et oJ. t972). Sometime, di,plaocmenl rc"el.ioilS (Section 8.11) "PPCar to be po"ibk at the ca"bonyl gl'Oup: 'uch a reaclion (Equallon 9.291 accounts fo" the ba", peak eorr.sponding 10 (M CH,)' in the spectrum of /I-jonone (Unknown 4.13).

.... ""'-' -

'"

."

.o, - ~- .A

-

•

"--0

11l.1N)

",

..

Alicyd ic k n OM•. T he rna.. 'peetmm of 3,3.S.11lP>C l h~I ')do ho; UIl Oll< (F i~\l l~ illu, l..-alL" major tildilianal rru rmcnlal ~>n I'"" h",,"\ , ~ '\lnd '
~.5)

ketone. (Equa tion ·UO~ ,md in So:;u i" .. N-" .

~

a rc similar 10 lh ~ dl""" ...~ 101 Clchc nlcohols

A"",,,,1k


o

I

;/

»< - co

-~ i -'- r - ~ ~ mlzl l ~

"

"",~6

-

I

.~

'"

O _C ~_

. ,

_ ' C>o ...

fuJI",..

'L' oknown ~ Hj;" 1"""""'1 ,xre ~"d p'Hhw~ l' ''' rot ~~~mrle, benz" ldchydo, sho w ch a rl <:( tr isl ~ (M - HI and (M - ('HO l" ions. I.. ... " f CO can = 1 IT a ble ~ ,4, o,[1Uo.-\.,lly if l be carbon yl ~w"p .. cndocl'ClLC. suc h as in ao tl" ,. ~ ~ ; n(l n " (fiqUll IJOO' 8.1 21), I,u" of "" "')'c lk CO i.
.true_

IMclalfeny" al. 1 ~ 7(l, V" kM"',," " . a ..... )' 01 """" "
a v. 4.10, 4.12. 4,13, 4.16, 4.17. 5.2, s a, e.s. 8.1. and !t IC. . ,. Eale ..

A""""n:,- mel' y l eHr rl, The d~,," c Mud;'s of S\cn h a ~. " .,?n l ami hi, c,,. ,.." r Ke]", in tho 1 ~~ un lht mass 'pretr" uf r:11 or 1M , 'alac ma SI .pectr~tT} r" , deducing the m \l~ IU'" of OORlple, n ~l ~r ~1 pmd LLc, m ~ ~ I" . Th ~ m ~". spectr um of melh;'1 . · " n
fi,.,

"r

'llI'fh ~ .h ~ ,~ d "" a ll oat~

~""" ~ '" "bs.:r"abl~

(110m

hu tlc rUu ~

M""".. lar i,m. " r apprN;i. bk

~h unod .

... ~hphalic I>'l' I>cr mo!cc ular we' ll"" ( > C~ ~ ,11 bo\l~h it

",'en f" r melhy! ...reI, of

big ".mG "'"ul",-w.j ~hl

",:i.l " [ 1>1'" ,, <>1'<,11:<1 fmn, Ihe seP., , " I" beh. " io' " r thew r.. ...-Tiun.alilie. , "ld , in Mdition. nt:\Oi ..... ctio ns apparcn lly d ue \" lhei, OOmhulcoJ d rcCl. Meth~1 eslCN \~ ~l do nal OOI'!a' n an add itiooal fua:;tionalilY ~ho .. (he e. p.x:tcd re..1;, _ of Ihe carb<>h yl gnlu p-- x-clr"~ 1< (Equation 9J lJ ~.Il<. 1!.., 1"" ."g~ ..i, I> ,..byd IOgCn fe~"'"~.nlffil t £.q.. ~li, ,,, 9.321. F0' m~lh yl ....~.h n~l ... ,uch a, F I;urc :1 .1:1, ~-cle."3l1C ; i""" ct..af~clemfic (M - J I)' a nd ~9 - i<m . who se ~ h u nd a n c ~ . kl..ul",.weigh t el len. Fur· tho, " ''''_ position of the a lkyl moiet)' pr<>
- -----

IC, >Hu') _

C-nHon " · , C, H, , .,·

~ =

(9 31)

ij .

·ui

•

F'

, ,

,

-!

,

,• ,•• ~

~

,i

•-.

• ,~ <-+ e

-. ,,,

,-

•

,t ;

>

.-

--; !

i ., • " , • , , •

r;;

••

r '' ~

--.

•

I

".

(93 21 ( ~,n "'aoch Ln8 (F igure 9, t I) p" >l t', 'ing unu"",,") hig h 3 b~ndan l ' M 6- Iv• • · ~ hJd l'<>l!en IE'l''''' ''''' ~ . 7~) f"t1 "",lXi hy 1.4- (or 1,5-}-hydrog. n slllft .,1<1 ~ k ~ ... ~'I; o f the bo",d "'LW""" til" p- and 1-alrbons. The fragment . ' 0l' ",,,, oting ,,lhcr p:.ok nta~ Lma in th. '''ie' '"P" I~teJ by fpu, <:l'ta;n " to m , I...."" 14l in F ig u re 3_1 3~ I ()I, 11 1, 24 1 and 311 in F;l.'urc 9 I I, "";n(orced Ill' I h~ cha in branclnnW Il,,,holl>l y '''' oil from displa cement , e~ . ti ~ ns lSc<1ion g,l l l (IT fu o...-tl . «:irrou l I,4-h)'dro¥eu migration, ,",'nion "OU";dC lhc 8"'ja<'ftI1 C- C fm d ca , age_ AnOlhet lLnusual w"ran~.mcn l yielding C.H,. _,CO+ ions iden lif'N by ~I~nh~~en alld hi' "''''''Nkc" in" llve-. the loss of !be " -, p., and Y..... . ' ... 'O' it ' ( \ H,- (MoUo,'n and Lon#" 'inlk l \l'llll Cnam clca ' ~l'" )'''lJin5 the J Jkyl ion <;all b<; ,igniri"anl al fully ~u bslnule.l ...roons; 1M """C!Tum "r . " C "H J,qC H , J, - CH ,O:XX:U , sho.., . <: " H., ' p',ak of ift'~ ~hu" J.."ce (mi. ) IS, 100'\ ; miz 74, 75~,;J i' .....' .......c 1~-nJc"TICJ rOT ~ do ubie hyd,ogen rearmn¥ernent in "",thyl ~... of l" n@e'nd cl<'avage can gi" a c~'njug~\<XI EE+ ion (Equations 9,~ ~. 8,79 1,

or

1><,,,,"

'£M,. "'n.

'"

• ., • •two

• •

,

'~EFt-

! •

1

•~

•

"

t~

• •

....

I, '0'. , ", , "" • " " ' M ,,"' 1.•2. M ... ' l"'
"oo""a.... cI 0.1:'•.

~I

.

~ "' J.,

Ir I"" . m: olTM alcoho/i(: .Ik~'l group K i, indi,,,teun 8.78) lhrn ,hmo"~ the /l·,ubstituent' by differ~1_ l n f llll", "".l l ll," Mi: j 'h nd 295 ious iudical~ R-COOCH,; mi=74 (aod 7 ~ 1 indi<.. ~ R' · CII, _ COOCH, >. oo mi' 101 then indicat", R"- CIICH, -

CH , -(:( IOCH, . b., ~ .q iii! :"", , """. T h ~ m,*,-'Ut" T ion peak of Re O OR' g~u ~ rall y bocom., lban blllyl (<1' 9 1 ""'laIc> Fi ~uT<; 3.14). Tho rt latiwly -.mall .. ben R' j,; 1.... ' PCCI" '1I\ of _ ·b.Il}1 ."""" ~ ("lUTe 9. 11) inc"Irat", lb. an .4. M) hydm [!l.. ...lom , is hi,JIJy ""'" acle",l;,, (E
'eT

"n"

'''''0

u

m'z 1l6

-,"

M I . "" ~~

-"-

)

•

"" A

l"'- z 6Ol

) »:

~, y

';;,...

•

~

f ·)l ...-,'; 1

(B t l

".

• 1M...

'po_

of

Commo, eo ...., .. C"....

For the formor reaction, aiken. iOIl formation prodominates for propyl and high", ester<, cnndure, an e..en_e1ectron ion or only mooerale ahund.nce. you ,hould k able 10 recognize it from its low rings-pills-doubl.-bonds ,'alue and beelus. it occurs in" rathe, unu,u"l ion ,ori.., 147. ~1, 75, _" I. Alpha deHage (Equalion 9.35) at the carbonyl group yield, the large m"", 43 ion, the altemati.elM - CHJ)~ pook at mi;: 101 is smalL This lattor poak ,,-{C=O)

CH,CO.,~

t«c=O)

~

?H,

-r

CH.-----C-OC H-C,H,

{O-CDC,H,I

---'-----

",/zI01

(Oc,H,) mI.73

o ct(C-O)

,,>'z116

".

CH,CO=HCH,

miz87

o ~(C-O) ~ ~

".

ICH,CO=CHC,H,j mizlOl

c,Hi miz57 (~,35)

actually ""n also he pnx!"ce<J by an a
•..

-

........ r"'''' "r I" " ak.~) hn] mniot}' a, an ald enyd" "",1,,<:,* ( rtti. meehani.... i. nol in the spectru m in Figur e 9.11.) Thi"""te~ R · ( ', H,S CO R, ... n g;"" a ",s n;r. "" nl tM - C , H. S)' ion (hble K.4~ If !>13 ;: and "'.~4 \>4n ,,",UT m nsccuti,c1}'; ~hc"" Ch ' '''"ICri. ~ic ion. ,.·iOa ppt'8Tal mil 60 a rid 61 jf the acid·s ~-c a l' bo n alo m i, not lubilltulod. n-H yl alld homoIot:ou. h ;~be r c a , b<,. }' l ~ t<:, cha raoteristically )"icld . 1<,,,, .I>u " j,m oo'"""'l"mding 10 ,he ~ tyl eSIOr (M,y, ,,on " , a), 1993l E'Ier> of du rro' li ic a.:il h melb)"1 mod ethyl) usnally i1ive >ny low molecular ion" t/>,:;c ""n "" . ....~ oyri "' d h, ~ h u nda n l douhlel' of (M _ OR)O ~nd ( '-4 - HO RI' ·, anJ f"'sment_ du e 10 , ub<"'l uent , Iimina lion of the o t~r . Jcohol molecu le tM _ OR H ORT . Dimcrhyl alh,," di o a ~.. . h.... Ch...-llClc<;. lic fNlgmcn" 1M _ C H, COOCl·J,.lo .nd COOCII , 0; t~ CII , =C(O IlJOCH " - ion i, ~bu DtO~nl

bl", c_fli";~g Mile_ ft,~c t M - J2)" ' ~n d (M - 16)" peak, (Eq\lall" n ~ ,~ 1 ). n ~ I...... "f RO H from M - ' app.t r . nt ~· is Iavc red " nil if tho radica l , it<: i< ; t ~ blli 2ied ; . h' , O E- ' i<>D <>fln>'Mn I...., CO tf"T ~ ..",ple. ort oo. ubI ( "H , Co. 11>< TC4uin."1'tIOnt of radlcal·sile sla l>ih· ,.,,{i,," ;, aIM, ""'I in U , and wme O E" jrnflment jo", ~f lIt f. " " '~'" Iha l cont . i" a Iabilt hydro""., 8,om, F'l w,tion ~ Xl. a, di, cu, ,,, d in S 8pp"'U ll)- mIgrates ,.adil)', for " , ample. ",.,hyl alkenoa.es usually sho w lhe >It,.'; 74 4fld ~ 7 i,m, chara d c ri, {lc of "" Ihyl al k3D<>a1n, ah hoogh in k", c-r ~ hu nd~ """ Alk.noate; gell'r. U)' gi,'. ",.ak ""'kt:..... r ~ m ..; , h. 'pe<:1ra con lain ab undU ll' C..H l . _10 fr~ b"n"nl ' " f lite all "'~ no I'yrr ch did. d.ri>ali\·n (Aoden on ~r " I. I ~Ul and ion <>ltenle re.>c" linn. IFerrer-Correia '" al. I ~7S ; lJ <JtlLi~ 19115; EiuIlo rn Iff trL 19115.>.b) ar" clkc1.i", ,,~y' to diff, umiat. ber...·c. n ~o ll bl e· bo nd 1" '''0"... (..,..;c w. and ern" 1987), .k~-Allenoat.. ,ho ..· t .... ' I'pia l ........ "r tl-- alkyl groop" similar to lhitt in cnnnc, (E<[ ual;" n ~ . 9) . U",..lllra. ed methyl a nd el h, l ""Icr", . hihit I"'ah rmtn the . llmlnatlon of CO , I1ld HCO, · (Tabk K)~ f.rn') a,-"C ~at"' and olh.. 'Insmurated " cetat., gi, '. ;01\> n ' n Olp.,ndinll ... ~ hc I"", n( ~e "n" . Polyacetoxy c"m p<> und, rlyl nu ; ra" on

"r

...,eel'. '"

'.,,'kJ;

J.""""

.~ ,umuri<' ~ .,t< r., . T n., cnmTl' uQ ~ , r.r rOJ , tion! , iled above are fou Dd for a mmat ", e,tero; (..e lhe maS' specm'm of beLt)·1 bc n ~ " a ," . lJnK"" ...·n 4.21. be_),l b"nzoate. ~' i >, u", ~. I ~; l'1"<1pyl p-hydrCllybem:N to, Figuro 10,1; phenybJanine met b~' l e'ter, UnKllo wn 8.2; and d ~ll l l' l r htha latc. Figu", .~ .4) . N ot ,urpri,ingly. cllarge , o,om ;"'n On \he .r~ k"n l"i n i nll fr,,~mellt i' slrongly favored. If the aromallc ,in~ com .inl alkyl grou!". \h~"" und ergo the typic al fragmen tat ions "f ,L.l. .......... d.,..,,,bood ~bo 'e . "O rtho drect' (Equation 4,41) ar~ u." 'ful in Il nfying ruch ring ;~""ri.m. " ' lc hy the "bility of the ~n"" . li c ring to ~ce bond·di'SOeialion " , ,,~ i ",, (Equatiom 4.41 and 8,811 m bib.. lhc i" n . nd . aJ ....1';lc,- ~nd provide an un saturaled sito fo r "'arra nge_ ....1Il, dlSplacemenl. aud . Lmination ' ... ti, 8,110, 8,122. lU l31 " . llII e. ~ m plc of Fq uauon 4.:16, CH , CO)- ' " a po,.k eh,.,,,,,. in the ' pectrum of tefi. lic of ar yl aceta' . ~"""l'~ IC.H. ( , " i , the """., M

'M _

po,, '

C~H,OCOC H, ~ The l p«hUnl o f diolhyl

ph ' haJa'" was given ... ~' ; gmc 5.4, In .ddilion to lite eA!'""l<und;onu: . at.i<. Jcpeodo, on lhe leulllh '" 1he al~yl cll. ta, 1lle ir f,,' m""o n is rafWnal!,U
-.,.,

0:: 1

'>.

\..

,{

(9.36)

1 . 5 _,

...

...- .

Acid' ,...,,,,,..11) "',"" ,,,. 11,,,1 ,,. m(>/«ula r ious whICh i n ,, ~a-e in ~ I ath'c abun. d..""" ...-111> ,ncrea.ing "" okc.-..l..r "'d gh, for .... lk~noio: acids above C, . ln poly_ ca mu. yh<: .....d. M O' i> ..·....k 0' I bsem, bul in 1!Ie.., II>< m" tc<;\l\ar ...oi;ht can onen bt ded....,d from 11>0: M H ' i.... fo rm «1 by In ion ·~,u~ reaction,

p«t,.

.4/ipMt~ m,..'c ' he . pe.:;tra "r d<>deean eic acid It'~ure J ill an d or'lCIadcca noic . ,-id jFi, uN 8 9) ...ith Th(Xll oft lle Ul<"thyl ester ( t'i"...,c 3,131 aod ....mde (rlJ ure H 9) The Ill1l$$ "r lhe p,...." in. nl ;-. h}dw llen· rurn"""mcnl f'<"..l . ( :RR-q O H), ' iodl"l' n , be ,:r-branehi"i (mi' 60 fo' R _ R' _ H: iff Section 9 01 ind ~ ChinR ,\ lid al<>-J.-pht1l} I ~ ropi "" ioc acid e~ n . t>ow, a hydrol yl , roup rnrr 'lftgnncnl in lhe oJecom posilion of lhe (M _ Br)~ ion p;. , . lId i"~ Ihf mrl ltoX)-l rea rra"te"""" of R""cli.... Il. ll 4. Fmm~l">n ,>f (M - H, O)O' in acid 'I"Xtr ~ ~pea ... ' 0 be impon ant h In mrt hyl cond llio m oolti..,.j c'lo",. Tho I"" ". en , i. otI en round to . 1It spect ra of diearl>I, af ;"" froID thermal drearbol )....lioo, Aliphahe dic.il,t><;Il ) tie acid' son\<'time< ' M "" o ~ar",, ""-;" ti e I"..,... of 3ft jH. o,J and 46 (C H, O, l.

w'

add." Arom atic acids gi,,,, opr.:tra oho...ing pmminl:Ill O H I,,.. followed by CO 10"' . A Iahilc h~'dro~en on an ortoo "" bsiit ut1lf CSUSC'> a dominant (M _ H, O r peak by the ' onho" olI
A",y drid. J, Thf rna" 'pectru m of succi" ie anhydride i~ s~"".-n in t illure IU 3. The anhydriM, of aliphatic a<-"id. ' ho w ooly a small or negligible mo",:,,"'r·;on peaL but again the useful MH+ ion ca n he f"nned at hlJlilef ""m..... pm"'.... rM ''] i' usually .ignificant;n un",t\lrat ed anhydride,. FQr miu
. ' _ _ .. c _ e...... ,. clo_

•~

,• •

!

•

~J ooJ

-.i ,,

~.

,.

... ".. ... "

j

,•, Q

u

•

~.

i I

i i i

•

I '

'00

- ....

,.

.. " .. ,...'"" .. .."

~,

•• "• '" • "

'.

". ' OO

n

M

" " " " "• " ••

•ec """

•

,

~

- ,t<

U,,"_

M

• " ""

""• rs

"

" "

-n

',.'"'". ".•• '" ",. '" ''". . ,oo

isc

' OO

,oo

'00.

" "

ee.

'.

' OO

,.

f

,,• •

1 •

.. . '

• • • •

-

•

•

•

•

J •

,"

..'"

' OO

.. ,.

1-4t'f.....,•• n.. rna" spectra or laet~ 1 I ~<>'" lC~ l un:o ""1M' similar to thOM: .1, , ' W I) pi .ptriallt . et hyl o r lar g..,) ,'ia ~ -cIe ~v ~ !.'C . Mllt, p;x lrom"\ri" ~T.. I;''';< of a nhydrides and Iilct"ncs i, m~de ", me""MI diffICUlt by lh el, e~tr.nI<J~' ,ma ll io nilll llOn ",.",,, ""di<>n' . WhIch de<;re.... l he
1.6 Ethers

A/ipIuItU' elkn, T ile lDll<' spectru m ,If dii. n hulyl et"'" is 5i\'~ll in Unkno wn 4. 11 and Ihose or i,,,pro pyl p<--nlyl eT her and be:ryl ether in ri ~UI"' Q 14 . nd 3.9.

•

i. j

,,,

.. •

,m

,.,.... ',14. Ms" spectrum
",.

,.

, ~I "i_ o "~ ~ n d~_ of

"'i' 1J !

r ho mole<;ular ion peal I, om ~n ~ 'ir/l alic . Ihe, teu ds '0 boa ",,"c .hu ndalll thau thaI from "llructlU~lly "'nil,a , alrohol or oom par"blc ma ln-m al..,ule fonn'llit'll "r lh. M II' pe~k caD be U'!ef..) lOT m"le..:u la"'.~ ij!.hl infor maiiOflTlw l.. gmo.... lali,>n <>/ el he", r..embl... th . t nf am;n= 001 wllh a . maller p, o pc n .il ~ (n, . ·de~_ate and a mu ch I ~T !I'" I cnd ~ncy for ch.ar1l"-";te . ka_ail". a' t l.fl<-"l«l fla m th. billhcr indutti . e IIo'illsdn wlf of elo<1",,,, hy a .ygen , T he imp<>JI.... I pp m" " dc a_ages of isol' l'Opyl pentyl cl het IUjen s,,; and F e",ela u l%.'i) arc J ue la l hcSl: two types or clca~ "t'" (.,;q ",, ' iOll 9.j 7 ~ F or th e com peling . -clo.n ail"'. tile [<)!o j nl nrclh~1 from lbe leMiouy Qolrb<m ,iclding ItOi' liS ;" almo" t " , fa-ora b'- u tho lQfS of the la' l\'T hutyl va .!]> from l be """ " ",Jile'Y carbon, s..cond Jly p' od\i<.1 it.n. in 1M ...me C. H ' . _IO · ian ""ric. (m.. '< J t, 45, S9•.. ,J "an be k,rm . d tly rea r m ngem cmt 10"" or " " " I. nll mC>loctJIr from tltnc

'"

• 1 M. . . " ......

..

~y

of """"""'" " _"" " ..... .

,I 0..

.( m,~

>...

i

1·

C,H,

~, o>'Z 71

(9.37)

31. In "Onlta,t to lhe spectra of amiD"" lhe mo,t nbundam jons. C, H,' Jnd C, H LI '. " ~ Dwduced by "h "r~._,i t,,_i niti at<xhc,,"tion,_ fX;ut"T ium.b hd in ~ indical ", lha.l ~ ; or til' ba," C ,H , - peak aris e, from furlh er de,,)v", ~ ",,,rra n~ ,, mc n ( to avoid th<: c nc r~c[i"ally unf a_ H>t"hk primary "nh",,_ lion ""<"lure (Sec!io", 8.2, 8.6, 8.10). I mp"'tt am ol,"i~hl · c hain elM" do , how abllndam C. H••- - ions; mechanism 4.38 can aeroum for abundant ions of this type ill pa rt icular c~'c" For c, ~mplc. ethyl hc'yl c[" cr and he, yl elM' (rig",.., ~.9) edtib;t prominent mi. 56 and 84 peak> in their ' I"'ctr. , (Char~e rete utiou in Eq uation 4,38 would ~i,'e C,Hl._10R " , "" hose " bundam;c , ho uld b< low b}' ~ na l" H t<> thai ordlC "" nC'Sr<mJ ing ~ I ka _ nol molecular jon.) Another
.....

A/iqrlk a_d _~ "" ' IWt1l,. tJ .,~ An i l l u, t r~ t i., " cump1c " r , u~b u lmp<J umh ! i, en by S-eibl (19 70, p, 126) is 2,6,6-trin~hyl-l-" iuyltetfJ h)'d rol'l'Tan (Fi~ure 9. ISl A r. tlOlla le Q{ lhe form .lIoll o f the pri oop:,l poa" ;, ~;" Cfl in ~ed in organ ic s)'JItlle"Sis to pro-

0,1 . " . ..

'"

(9 . 3~ )

tat ",h 1" c!) II.e hydrox}' gr oup; J < lu..!" It, the lcln'~ l dl<'pYf"nyl oxygen i, . n ,mp,," ' ant f'T<"-"'" in thoir fllll.S9 ' f'eetra, This gi'e< ri .e 10 a ~~I: at rn./~ 8, whicll « Itn do mi""l.. ll.e ' I"'ctrum (Equation ~3~~

-

o

~

('l.3!l)

\bcrOC)'clio po ly<'lhen I"crown elhe "'"l l nk M " . w1>c,,:,.. 1\1 - H J I a nd , ovm .t n" .rn.1 ""mpl< J'T<>Su"" . 1\1 H 0 ions art re~dily deu.cll Me. The main fragmenla lion p1th""'Y" " , eydic 1",I, Cln ~ l<."T\O glycol, 1E<J "",ion 9.401 iIl. ol, e ,e quential n pul' lOD of C , H. O uoi" M gd c.n ,0, - (m,'" 81) io..... Ind uctive , *.. ,a.~ in the latter give< ri ~ 1<> an inlr:Il'
- C,H. O,

"" yell.: un, atum tel! ethel'> M,e li kd~ inlermtn of Ihe lini\ ( Eq~al i o n 8,6(1: Mon .w' " " , 1981). The compotilion is conlrolkd by the k",i , a li,, ~ en e r~i e s of the one r,ag rnt llts lb ~ 1 dcl1em,Sl' }" <>l lhe RDA re~cl ion . Fnr alkll.y , ub..;we m, (Eq'~11l0 n 9,411 RDA i' cOlt,pcli,;"", .. """ 11>0 villyl other ions formed arc o'e1)' ..uhlc (.... So: ~ eV} For
pha'ic cf'Oxid<,

1.' -

0~ -

-. ~

0

I

_RCO ,

Q,

* (+

(~ A~k ~Iko l .

-

(94 1)

~oa

n.,; m~... 'pc
~ ~ ..-... ldix.

llC pu .h I", . ", - CH, )+, (M _ CII , _ COl· , (M C H, O )", ( M - OCH, )" and (M - CHOt (minor but impo rl ant in "'"n" d e
beh . im of mClho, ya ryl w ml"'un ds. Et h ~1 d hig"'" aryl <:Ih." l'ivc a highly cha racteri' tic OE · ' i<JCI II"'" Ih" d imm.. li"" of C.I I,., C . II, DC. I{ ",., _..... C" H"O H ' {Harn;, h and H" Ift>ei, 1991; look a",in at lhc 'p"CltUm of 1.ph"n" , y.2,ch lotoe lhane , Unu.own 5.1 4). 8<",,)1"Ihe.. , imilatly' gi.c a 0:' ... me Ci>rho.>n I"'",'ide" a powerful reae honiniliating si," . Tbe ", ilic,,1 e....-. gy r.". ~-.deavage, R-- ·CHIOR'), · .... R'O C H OR ' .... II·O-= C II - O R. iU llbot;lfltiotlly lowcr",l hy the re' ona nce m bilt""-lioll of lilt prod"'" ioo. Unf<)tlunalely, lhi' also cause, tbe molewlur iI.a I" r .i mplc .au:ll<J. a nd l elal' \0 be neglijl.ible, Some reac tio n' an; o ~ r-'~ " ·h,.It an:: due I" Iht secon d IUlKllO Daiity, ,ueh a, the elimination o f II ,CO from fOmIdkkbydc ac1..: ~ .41 H owe,er, in general lhe ion d.:c<....po... io' n p&t b w~ } , ,mlfutc't! abo ve for elhers are applicable, -lin interesting example i' Ihe ' lr i ~ in~ in n""nre " f l he et hylmc ktldl moi!; lY On .t< T(~ d rna" ' pcelra, a, ,ho" n in lilt .la"ic 1.-oft of Fcw. m ~ nd l)j eta Sli dOO l!>cir e,,·w m h o<. T he ' peelra 01 SH ln dro.'aD J-one aoo it. clhykM keta l ~re ' hown in Figure 9.16, Mocham, ml for \ 1><; ~ .rm ali"" oI lM Iwo major p"" k_ art i n'ell in FGuali" n ~.42; inlo""linp.ly, l1>c>e are dUeclly anaJ"gou, to l h~ lrugmcnt" li" n "r the oorres.p<>nd,nl j ·a minOlfero,d Call you "","ounl for lbe mi. 112 peak?

.

V"""''''''I 9.( A ""mpo"""

i; eJlbe,., 12· Of 17·."tu,tcroid ('"'C Equ atio" ne ( , 11,0, · pe"k in Ihe rna.. , p"'c lr utn ,If itl ethyleoo kelal i' lar ge:. Which oom pouod i. if ! ~ .4 2) .

'J< f -

,, , • - , -a , •, , •, ,, , , .,•,

• • • e

2 e

'i l

"

• ,•

•

,

• • ,

,

•

,•,

, ,.

.....-

i"---!

• • • I

,

-....,

•

~

, , ,, , , ,;1: ,

,

- -

~ ••'a••

• ,•i , •; - , •I ~

•

~

.. .......

."

• , ,,_ _ 9.T Th iol l

" c.non.o. e

_

and...-.

Tho mas< 'pcct r~ of (hi"l , and sul6des is,,mple ~ nd DJera"" 19M. 'a~ de Oru f ~J)d M cL~rrert y 1977: OJU n ~I. 1979) resembk lhoooc "r lhe cu,re' roDd10M~ 1", "' () 1 , and elhu " T he "f""''lrum of iso pro p)'1 rcn' yl sulfide (Figun: 9,I71 U n lie compar.d W lh.l' or ~ pr oPll p. nt)'!clllN lFl!Ul< ~, 14), FillUrC.1.21 and ; ,12 un: the ,peer", of dod",,~ n o l hi ol. and d llle> ylsulfJ dc, 800m. of lhe ",,""

•,

r

.

'~ll i li<;a1\l diff.,." """ ~ r .... fro m tho I" ", ioniLalioJ) ~""'"Tlli ~l of 'U m'f ~~,m· ""ullds, whi. " ~,~ ap protima ..,ly I eV ~l o ' Ih" "" of t ho corrc ,ponding o'x u"n compo\lnd . I hI' ma kes po ",,; bJ. t h ~ fa" " ; (>f moro 10",of"",,,,,rg)l molonl!;>T

i"n<, ,ul>sl~ull. lly ino,~a,iug

[ M ' J-

C1e~ " "b'"

. .. 1'" C '- S ,,-bond ca n OCCUT ,",'ith ch~ 1ge rclcnli"n ill lho ' !IUur"","'inin& ', ~ gmc n ( (Soct;" " 8.6 ) ~ n d product-ion it~"' Ii.t.aIJ OIl lhrough i,o.....-ri<~t ion to ~n RC"II=S H ' _" ""lure (Eq"ali".. X,77~ 10m ' ''oh a< lIS-, H , S·. H ,S I. anJ CH~ ' ""c ,," uffi<:i<'lll " ,,\>i lity 10 gi~ ~n ion ""' ie' \l' d ol r...r ch4 r~.krL,at ion; p,~" Ih.ll few OthCT lyl'O'" of rompoo~ J gi, e pe" k, ~t "';. n • .1 ~ , and ~5, TJrNoI•• F'IIPl• .1 ,2 1 i, tbe SpodlUm ,,f

~ ~ -1.-k.... ~ ge

yields tho l3.'F" C. H,.. , S- pe~k (ion ..."TiI.... 47, 61, 7S, " . ~ b" l ,*", age ~l olher . h in r"5il'''~ ' to )'i.1d thes<: i,..., i' m uch more prC" olc~ 1 l h~n io tho COITC' I"-,nd;ng alcohols, 11l 111 " i ~r,1 duUn n",rc"p'~m ( R9+ ] ~ rr5 °] Or l lOr ], indiw ' iull a r~ ,,,,,~ hle d ; ~ l n;a, linn I E qu ~ l; O ll lU 03 ) I",. \be rorm at;on ol C. H. !>II°, 1b. h)'droc.l I hon i" n ...ries 27, 41, 55, ... , an d 1'1, 29, 43, ' , .• ~<. d ... ra ,;t ~o. h·

...__ ... ..

" <.",...

.

t:8l1y larp:, ", j' h C." , • • " ;> + fv' ~ ;> 1 1M - 5H I+ ;. .ignifi~~nl in =<>ndary Ihid ", in ,o nl r~'l 10 tho lack of (M - OU )~ fTom alooJwl\ , In primar y thiol> the (M . (,ft)' 1'' '' ;, , upen.cJed bl (t.4 - SH , I · '. this , nOJ l he p'r u k nl peak. (M - S" , - C.u,. J" • "'he:<: ~ 2: 2 appea r irJ 11>< C. H,. + 11ll. . 2, 56, ... ) ion ""r~ ll::qua, io~ 4.38 ), Ar"mat ic \hloi' undergo lra j1TTl<:nlation, . imilar kI those . x!X'ted (Of ;>)0,:" ,,1, the main n orpti"n, ~ lnll t he a d ~ iti""" l (omw i" .. 01 (M - 5 .- ', 1M - SH" , an <J l\( - C , H, l" ' ...~ k..

r".

Su/JIJ~•. Altl" ugh th.; ma.. ,••"rtcum of C H, SC H , C H.C HO ltl>< *ooiOJDY. ""'l ly" od>>r rlQfll p.-,U01Oft.: WAllt r ' 972, p. 716) n hllm••ub:! tu li. 1 M · · l3 ~~·;) ~Dll .",l e po~ Eq""li" ni 4 .31 an~ 4 oW• • 00 " -dea~. 1l" r.,r n" C H ,50' ... lhe ~nd 1' 'l'''''1 p". k. SJml!. ,ly. JB lIdoJj lK>n to ....:Ie.o vagc J'l'odu<:l'O, C, H,SfI con,p"unoJs I~'pi call ) lor m C, II ,S ' and C , H , SH " p'''ik,. " . can be """n iu th, .poctr um "r isoprop, 1f" m .1 ' ulfode IFigure 9.17). (ClIks in the C." ,.' , S ' i"n oef j... ""n uow ... u..: from c1<11 "li e or lhe C - S ,,-bo~ J; lillS ....."'unh flO' II>< pt'c""n.. 01 C , H Lj 5' 1"1./' 1031 and, in N It. C,H , S ' 1m,:'! 75 ). "'o, tog"." 10 the b -H 1/11,:'= 6 1t ~c,mp,",;~inn of CH , C II-S - C , H " 1:>1 Equ.o ti"n 119l i> ;on ahern;Olive .",ode r" nn al;oo of lhe /IIi z 1~ ptak. In ro",ras.t 10 ' ''' ]>f0M l p<.:n ~l' 1 ",h"" 1h,. , uU" k '. m4» , peCINfn . howo oh r. act~fi. lic OE ' illn, at mi. 76. (C H, 1,C HS H " • • 00 01-1• 70. C..H '0 " (pi ... "",'z 41, C 'j Wf lbp"nJ illjl ru lhe romp.-:ri" 3 po-odu<:1S of ~4fthe rtltn , " .'ery ' ma li (po " ibiy o",m~ ' 0 the comJl"lllion of Eq u"liou 4.37), altho u~h lh. l;om poni01\ prod uI'l C, H , ' is ~llil . 11. ba'" reak P h~ n )1 ~I.y l iu ll"Jd.. ..!\derto n:.,.;lions l~ pi
I""',

,-dca.,.1'1

rot

,11.'

,i,...

HS,

Unh ",. n 9.S ;.. known 10 cont",n " h y d l ~ , yl groul' , Co uld ~ o u ha' " Jeduccd this ftel I'tom th<: mas. ,pc't'ttu m'! l ry Un.no.... w 4 .' . li S. a lh1 8.10 a ~ i ...

".

" _ _

,

_ _ 1.5

~

,.

.... " .."""

~

-- - ---- "" s.e

~

• ••"

•• u •"ee '" "•" "• • "" "rr

~

. ,. . '''... '....

~

'" "" ,. • '" " '" •" '" ' OO '" " '

tl

s

-- '... .,. .. • • • ',w

tl

~

"

'.

-.. t

.. .....-

" e.- ~

"" "

• "

'.

""

,w

~

'.

i• j

•

•

•

••

9,1 Ami.... i\ l i p~ . tic " m;ne. " . hi b,( "" ry [0",,' ionization ~r ~ ~ deipl!. this, tn" a mine gro up I'm . ideo . udl • JI', ,,,,,n ul O!.f al",.)" the b.", peal "",ult. from ., ..;:;lea- a ge (I ' " ""*,"",,,,," pi ", ol.f,ll-[O," ~ arr an.." "". nt , Eqll3.!ioll 4.44) !bat mo kwlar ion. are of 10 ... ," nq,1 il ibl<: ahll/l_ d. oce, F o rtu na t el~ , o wing ' 0 their hip, pmton o!tilllti<. ( h Me A,~j . mlnco can be sd«:<:i\'ely prolona tcJ at mod cnw,:ly hi~ h •.,mpl. pre . .. ,..... or ""Ih "IH . ' in ammonia C I to yield . 'or)' , table MH + thl rom_;"'- m<)I';u,larweight infonut;" n ( K <Xlu~h ,uKl [)CSt"bac 1'181; ""oMmore and Alau d din 1'186), S:l.l l' o f amine ba,.;" ....,0 not vap o rize III the rna" . poct ro meter: tI"", •••" lh. )' oft en de th e Ir.. am iD< nn d the ".iJ, Th<; p~sen.e of abu nd an t pe ah corre< pon . uch . . .n, sin "" t he.. ;0 '" a ", no t for med in abundance a. pr oduo t. uf elc c1.n m_;rnpa.I_;rK!uced rea"tiollL

,.octi""

i"",

Stndi., on indole , ~ k" loid d.ri"Hi ve' indi. ~le 'hl ~ualernary niuogen comp<>und' (K .. H) d<eomp<Jsc thw nally on heatinll in the rna", ,poctrometer by IwO prlDCipa l p;,th, lead;ulllO dilfenont leni ",y am ;n<' ( He.~ and Leminger 19M ~ F"r h, ,,mid. 0' iodide . all" d
r: -L.

~'

R

:)-R,

t)2, " ", "

~- ,

R,

• ','

(9.43)

i I' j,--N-.,

. "'

(9.44)

H,6-!K,

",I-I", i~

i I'

R,--N:

-L.

HC= H,

-

A/iplUlti" IUnilfe.•. The rna.. ' P'"ctro of I-om;uododecanc (Fillurc 3.16) und a numlter of C.H 11 :'i i'''meri. amine, (Ll nknow n, 4.4 10 4.8; Figures 4,3 and 4,4) hove hc<.--n given and realure, or their 'peelro discussed in Section 4.0, The mass ' fll"<-'\ ra of dieth ylprop ylamine, dihexylam;nc, triblltylamine, and cphedri"" were ~ h o ....n in Unkno''''' 0.2 and Fi~un.:s .l l 7, 3.18. and 4,5. The mass .pectra of 11'methy'I."'. i,,'pH)py-I.N.buI}'lamiue (Un known 4.20, see Chap ter II; Djera"i and Fensclau 1961) and ,",,(3-me thylblltyl)amine are given in Fillur., 9.18 amI 9.1 9. Alpha ""'..age i. a dominant reaction of amine. , generally PW
Sect,,,,,

R·

+

~ V

(9.45)

• , M... . ..... of C....... C_ _ C1o..-

""t<..,..'"'li' b ' ',~

,_. •

.

•

'

' lO

' ...

~ ..... . .11, M . .. 'P'<" u.n 01 "'· ....th.•1. ..-_rrop1~ "' ·l>ul ~I.",jn •. I"'claln , , OOnd.nee of tN ..i, ' 30 p< .~ i ~"... ..'nh """ ..wo¥ ... "'rIo p'rssu, .,)

,

~

,-

•, .,

j

• " • " " ....- ., ,. , "b .. . '1""" Jlnn of "

.

,

•

,.

W M' ,

,,,

'"

,Rd. Live . b un< "';' ' S3 "".k imu,."" " i lh incr
lc,,,,,

",if 44 ll""' ud,>-«-cl. avag•. Equ ation 8,91). and t o " ",tent ""i: ~ 8 and 72 ()' and 5-ck.1Vag.~ htco mc i"'-'Toa, ing ly important ("'.. . ~ 44 ~ 40'\ , in ,he "f"Xl rM'" of hc ' a d<>::ylam ine), ~'o r higher-molecula r-weight "mine . thl: hydro"., . l>t>TH H'" rc", k, ",I" , inc~a,e: in the spectrum of LC , H" C H(C H, ll , N H , the al~yJ ion re."lli u~ fro m a-cleavage (mi. ~5) ,how< 34~~ abu oo . na. bu.1 the lmmo nlllm ion from ~_dcavagc (m,/. 156) has au abllndallCl of only I ~-;;' " n ~m hcr ,,( ,oe c ndaI)' roarr ang. mcnl dcm mpo
I>a,.

OJ A"," ..

,.,,/:'-'\

ICrlV,Crl~-CH,-C,rl7 C~,

-" -'C,rI,

1>}':44

(9.401

m'z100

amine (note that the hydrogen is transferred from a tertiary carbon atom). I." bcling studic, (Djerassi and Feoselau 1965)iodic"te that 65/;; ofthe miz 72 in Figure 9.1R ari;e, through such a mechanism. Thc remaining FE' rearrant«:_ ment', Equatioos 8,92 and 8,9~, do not appear to be important in the al;phmic aminc
tn, i, that or N-eth}'lC}'c!openty!amin e. Figure 8.fj, Alph"-c!."vage in the i1kyl group lead, to the (M - CH,F peak 01 modcrale intensity, HowC\'cr. ~_ c!.,,,'"ge at the second a!)' ""rbon in the r;ng ,hould b, favo"d; this leads to an i,olated radical ,ilc wh",e IUTtheT rcaotion (Equation< ~.4~, Kfj.l) account>; ro, the miz 84 b"," p,ak, 110mologous e"en-,l'ctron ions at m,/. 70 and 56 can b, rormcd by a ,'"nely of pathw"y" as W"S discussed for aliphmic ,~cohol spectm. Thu', although the miz 50, 711. X4. and 9H ion 'eric, i, indicative of thi, geneml type of ,tructure, the individual p,aks, e.,pecially tho," of lower mass, "" less charaderi,ti" 01,pecific 'lTuclUTat fcaturc,. The ,matt m/o X5 pcak appears tn be I",m,-.,] mainly by C, H. loss from the eth}'l group (se, Equatio", 4.37 and 4..,9). III the 'pectrum of de.,_N -meth}'h_obscurin" a similar mechanism (Equation 9.49) c.ln expb ;n the loss of tbe -CH z -·--CH(CH,)" CH,- bridge plus a h}'drogen atom \n I"rm (hc(M 51)' ion. The (M C.H.r' i, of much lowcr abundance than th, (M - C.11 o tThe mass spectra of nicotine, indole alkatoid" and ,tryehnine are ,howo ill Figure 5,1. Unknown fj.3, ,md Figure 3.2X.l Other type.,. 01 reaction, that are p""ihle fot cyclic amine, are discnssed in Section 8,9, A fiv,-m,mbel'd r;ng containing nitrogen ejects two r;ng carbons and the;r ,ubstituent, "s an "lkene (Equ"tion 8,571. For larger ring compound"

t.

'"

• 1M... S _ of Commo, Co..

po,'" el.....

,

'~c:

-C,H.

,

CH'---l-"'/~'

HNV

~

CH,·

H!0

m

n1z70

;/

-,

't or

C,H5

-,'r.I

NH )

G

'~' I ,,-,:i/

"

II

t:

- C,H 6

CH,-LCH,NK

~

"

.,

r-c .

m'z56

W:V ",

•

-"!.-

• CH,=NH

-CH,"

.'2' I r'

GH,

"

-s-s-

('

.i~

m'z84

- C,J-I.

Q

~

-c~

r~,H·

•

d

-'-

)"',

t,j

-"!.-

C,K;'

"

m'zB5

m'z56

•

"'~o

t

-"!.-

0

,

•

CH,~H,

m'z30

(9.48)

C

./

""

-

C,H.

, (9.49)

'"

.....mid..

such a, 1.2-dimelh l'lpip<:rid inc ( t'igll~

~ .4 ~

Ill"

~J '1io n

i. of low impon a"""

(m/, 71. 1~~;J. Th e EE ' iOIl fonned by ~ ..d "" 11l" (";J Yll. 1 lXl:':;) ~~ uDderllOa relro·Di.I,·Ald.r reaclion t" l i ~ld ",II 7ll ill l r:~ ab und,\ n", ' Eq ual""" R.6 1~ Unkn"",n., . T" t l Oyr kllo wledl'" w,ll! t.:"llk nown.

1;,1;_4 8. 1;, 20.

S. II. e.z,

~ ,2.

8,3,8 ,9, and 8,10,

9.t ""'Ide s

rnc m ~ ",," .pc"II~1 bch~v ior 01 pl imal')' amide•.•uch a, d r>d. ca n Ollmi(\e (f>;~ urc 3. 19), ci" ""ly ,..,,,,,m l>lo;,:, thilt ,,{ the ~on l'p('fldJni 1 ,J,>Jc<:an" i. a";d and ils amide (Figure, 3,12 ~ n d l 19) i , '" "ll kin,ll hal lil1'" ~ <; ",rios rill: 59, 73, 87, . , . . ,~ Il rl f,...""" PIW ","", rl>o ion -.en .. 44, ( 5&~ 72, 86, .. . ; ,"'Ilh klngcr a liiyl .h~im nU l ima 8pt>ear a i i" ~.a b. " " 1'O>f'<moJinI/ IO '(~H,). - m,/: 72, 12S, 184, and !ol(l n l l ~(> f""-1 ed, t .... n in the ' p«tn III ' !Ie an'"'-'!!'.... ",,--i1 0... c'pe>i. U}', Iwo ltydro~n at""" (mf r bO in r ' I:]OI. 9.1U Eq..."on 4,46~ 1n

,.r

"T.

. I 1~ r l I

00

I I

"'t"O

' I

' 00

i '

"'"

00'

.

""

~C'" 'I'

'n'. . , -------

IlO

iL'

""

,

I

I'

n

..a

'H

n H

"'~

~·O

9't

'u,

""'

OO! L"

00 'lB

"t

00

- .. "

-----

"

~, ,.

"

n

.. ----

Ol "'"

.

I

-001

0'"

I',

"

6'0

flO (/OJ

to (tV

n..
... tt>

0',

"L

LO

01:

. -"

"" '"

z/w

n

09

n

'"

zjW

'"1

zfW

'luI

,~

n

~

'"

2'0

.'9 .-0 0-'

(I"

0' UC

~l

0' 9'

.'. "MO"'!Un J" ,",\lJ.U. U(lll~zm('l' P"Jnp.' All~"'~ '~l )0 ",n~""'I ""lS~ U1 u~ql '''lU'''~ 'pmu " UOTlU"l.' ,';l1uqJ 'OJ AOU'pU.) '~.L -Ir"w, ~"" ,linm" II "41 pUP, P.~'!I!qP.]" '\II"!lUp.l'yn, '! -_UI H N(J:)ll - 1'\1) 001 ~U1nn'~J oql JI "IUO SIn"", (Sl't JO 1'£'1' SUOlIP.nb:l) !ll1]p.1I0ll'Unj ~P!Ulg ~q] lUO'J A~,"~ UOIWJ\!!W "~J1"qo 4)!'" lU'W~j!U~.l.l~~J l1'30JP"H ""P'U'~ -1"""lA1V..,\')0 "'1:>00, '~1 11) '{R,d "1'U01,r.JV.4" hlOA "ilollw uo sum~~ ljlO<[ mO'J ~]qT"od :lJ~ 6C8 pu~ 9t.-t SUOlmub:I ~~n SIU'UI'~lISJJS'" "'!I~O"'U"" '~PfU-'~ AJ~f1,"1

)0

S~pTlU~I"J~

'ss~pql'''A~U ~'PllU~

p""

..... ,~ P"no.wo~ ""•• ""~ 10 "".d...." I •

.u

----

. " _......-.'

rn

more compl<~ ......lcrulc.. " ...' h u ne",id, or mercapturic «cid .. u'UOn) e . hibil ch""..lcrislic (hi _ CU,CONH lr ' pe~ks (Vcrrncu k n ,I ..,. l <ml ~ ~·R CO ­ SK U , ), 'pec! '~ e, hiM a!>u nda nl mit 87, 4~, an d 100 ion.. Pf_ m.h1y (, ,,,,, lhe m... h~n i;.m., nr Equall on. 8,70, 4,39, . nd ~. 78. l-1. ;ovago of l~ C N bon d to Iti .,c tile a1huuyl i.... (CH ,CO - in f lgUle! l20 an 9.20) is greatly redu ced '''C' lha l in cs.I.... (C H, CO ' is lh. 1>;0... l'C" k in ....·butyl ,,,cta~ Figure 9,12), The no rma lly unb oro•• bk C -N bnnd €ita,'age " ilh char~e retention on N, ,ueh .,;n lh. _..-md" 'Y am ide !Figure 9,2(1. " ,i: 72\. I' mcreased suh' tanlially in tlte ter tiary alolde ( Fill",e 3,20. mi' l 5til

The I«lOla ,i"n en<:tp.:.. ," aliphat;",nitrile. and OItroalbnes ure uou, ually ~ ; :h . an"- ,hi>. ii relkded inlhe nnusual degree to which Ih ~l!¢ "omI'OUoo, undergo ..Leltla l "'.>II" n,o"",ol on . k . lron i mp~et (Sectio n 8 6). T ho basic rules or roo d....mp.-.,;Ii"n iOPJ>COlr 10 ~ I." applicable 10 nilr ik. than 10 . IIY1I1hef oimpk """"",,und fInss. fo r the Ionization eoerl1io, ol YCH , • 'r _ eN hu the hit besl value of lhe .o mmon ru n" tio n~l it i", li, led in T:>hi<' A.3. eve n h l~ "" lhall lhal ' m Y = H 1,l\ccli" n ~ 2) Furlher, the principal nilroICn'COllla llllnl "'II ocrio<.,. ' ''und for nmi)", . C, H 2. _oN · ' and C" H,, _, N ' . .... ..., ba ric .. i. h l ~ rum moll lIydroc.l rbon sorie. C, H ,._, ' (21, (I . SS. ._.) and C) ' .. ,- 126. 40. ~, . " ~ M olccular_ion po:ah . .. weak Qr lM'glqrJbIo in ah plwl1Cnilrik •. ~llh~ ugh they are ",ually slr ong in aronlOll,( w mpu ulId<. "'",t" lIKtd }', aU phati( nitrile. hm'e a ' u b'taot;~l tendc nC) to. (" nn a n M H ' pu k by ioo-moleculo rea.tione. T l>c m ~" Sf'I'drum of dod~1 cy.nid~ i. givon in Fi~urc 125. I.. nv.ra ll appearall"" j . u.........l by ma "" ' ~ la l ,t ~nd a rd , ; il rc",m bico an ~ · a) k . "" Qr .:Ik.....pectrurn tFiK" rQ ,\.2 and ). ~, in h. lact 01 specillcity, bu t it II"" al>ul' w nl f'l':'h a, higlM'r .... ~ and ....i" or .illD lfi e ~o t peak> ",pa~ onl)' 0... mao. uni!. Th ~ 1Cl-l, i.C-'; · <eric, (41J), 54, 68, ~ 2, __ . , dominat.. It>< uppe r pollio-'Il vi lh. "!,",-1 run,, the hyd, ogen ' Nlalrangen", nt .. rio, oomi....l1 y ""Itt· 'f" ,nd;n~ 10 C. II , . _jN" (41, 55, 69, ~ 3, , .. ) i, uf ..,.,m!"l'"abk imponaoq lor ,, _ 3 to 6. Th. ~lrgest pc;!\;o in ll>c r" rmer " M are (CII, l, CN' aod \("H,laC N ' r""" lh. displac<meot reacrion Equ ati on 3.103. Cbain I>nonchinJl does incru ,,", the ab"nd,ln. os oh he appropri" te i ~n. in , r.i. ...."Ii.... bill .uch data mu.r he u",d wIth cautloo fOl , truelUr< ,lcl eTmin ~litln . T1>e C.H " , N' odly lhese ions ",e for med by h~dr o~cn .e"'T~"gcm"" . ..llh oIc1ln loti: RoJ ( 1 96~ ) hil' ,hown I", 4-mcl~ylrmt ~non"riJe that lhe abundam C, H. N " i,'n arise. from ~-h}'drogell migr" tion (0110 «1 t>y ]'-("l...... gc. ,\ furt!oeT u ual ""'tllre 01' 1"" spectra of ,~kyl cYiOni,j",; . lhat [(M - It] > [ M- l LouolJ ICN ' a n o to

, I .._

. .......

Co""".' c.... . ,.. c" ....

soa bil= !he <:hargt on nilrogen. I' m 1""1 " r n" ,-",... much more cl~ly in Ih. ... ",!,Itnt< (S",..uon 8 .6~ Only 1100 10.._mass in.... " 1'1; tormed ;0 abunda......... ",mini"",nt of Ih.. 'pocu a of alb "..,. lhe ('. H, . _. ' kill••oul d a, i... t hrotL~h I",. or C. H to,.' r"I." -.1 "t 1<", of H~ { EqU.lt.O ~
"yd"""" """

link"""'''l 5.1 2 ~ 0<1 8.6 ~ a ,",orlh Iryi.., '$l in. N;troa l. I ,.. "' h. ~ lot ' I ilium . tN II)' ,he rn. .... tl",cu~m o{ .. i' mprn",,,,. " :r-H fO'P"S"ion. IraCtUlr n liann.. nt; (he plneuoo iD the 1 be due to the molKnlar jon, N itro aromaoo
'n"""

1~"Cfl( ~=o "".6 ' ; 0.• "'.

"'i! 12, 0.4%

(9.30)

, , - _. \~lion

8,11) ;In" NO, ; w,ll1 ~
I'N21. Oxyge,,.,om I"", can also o-i,om e< }icl.l. (M -

~ "t;

ror n;un lo!um•• and nitroanilinc>l, tile

om' . b u\ th~ .... ~ n d r-i.o mc!~ lield (M

- 0 )" .

T h< followi,,, rn,,'" o.roear a 01 hlogona tN U>D1l",und, are IU,,>lnliw:: 11et,

CHIllr, 2,2,: 00. , a e. CO F" 2,S ; l.~-(-, ll ,O], H, e, HU " z 1.\: c , el F" 35 ; C ~ ,CN. s.u, I· bm m"hexane, ~ .l > l-(~hl"'''''''''lh y l}­ Unln"'.. a 2 1.C"-,F.

l. ~:

""rca"., ~.I ): aDT""lh a ne , ~ , 14 fi~ wres .lI D, 3.23, ,124, 9.21 , an d 9.n ,ho,,"' the mass ' pe<:l r~ ..f I, l- aDd l, 3-J;,,:hlorobulan<, l-ehlorododc':" 0". r.heomodod.,c.",,,_ k hlo,ooecan., an d J-b fOl~an<: . Mea,ur able m"r.:.:ula. iom ;In; "bl ain. hIe tnm> ~I k yl halide, (e. l DuoIldel) 01 mod<.Tald} luSh m oleculal " ,.., 1110 (>J with "'me 'hin hlandun~ M "

•

•••

••

•, '"

.., ~.

•

•

""

..•• . ,J, ~+ O/JO

' C l ' OO

' '''

fll"'. UI , \ 1... >1""1' "' " ,>I ; ·ohlo.-od<=ne. SruU (0, 1j and n, O .~-J ....... ""'bJ ion peak<ar< Pf">
"'i'

"

..

~

•

,."

.~•.!-r'-'"C~\. ~'n'l',..,,,~ ~'T' . J •

' ...... I n

p
fd ."

, '~ ' ~

,i

'

, ,, ~

deeant , sman (n. t X ) m <>l",,,I:.. ioa poOh a rc

"'i' no .r>
.

,

, I M...

"PO
i, "ften ncglib~blc ror pc,h"logcnatcd compound, unl"" they aro unsaturated, The presence and number of chlorine or bromine alom, in an inn j, u,ually rccogni'''bk lrnm it, charaoteristic <'isotopic dust,," (S.ctiou 2,2 and Table A.2). The halogens have a relati"ely smaU inOllence on ma,,-speclral reaction,_ Iodine is the mo,t influential because of the unusu"Uy low dissoc~ltiOD onergy or the carbon-iodine bond. Also affecting carbon.hal()gcn hond cleavage, hut in the opposite order IF "" Cl > Br > I), is th e inductive withdrawal of electro ns by the h"logen alom, However, lh. tendency for back-donation of electrons, which 'trengthen, thi, bond, shows the ,am. order (Uuorine great est), sub Cl > Dr > L For bromine and iodine thi, reaction is negligible for an but low-molecular-weight componnd" and for ~hlorine thi, "aeli"n i., of imp<>Ttan~e mainly for IC'Ttiary chl"ride,. Alpha_ cleavage does give unusually abundam (M - nt ions for lower-molecularweight fluorides. p"mJleliug the I:>eha"ior of alkyl cymlides (Sectiou g.6), The weak C.H,.X- ion 'erie' found fDr many alkyl halidc' i' '-luile chancteri'tic aud thus useful for general identillcmion, The second ,,,,,,ce of C. H ,.X· ions i, tbe di,placement re"ction (Section ~.I I: Equalion 4.42). TlIi, lead, to an unu,ual1~ abundant C 4H. C1 · or C 4H, Br· ion in the speetra of !I-alkyl chlorides or bromides eontaiuing more than Ii"e carbon alom' (Figure, 3.B and .1.24 and lJnk nown ~.I). The ahundance, of ,he,e ion' are greatl}' lowered by chain branching and are negligible for flnorides and iodides. I'he" are ,ull'lantial dilTerentt' in alkyl balide 'pectra in regard to tbe pro_ portions of (M - nXj" and (M - Xl" ions formed b}' C-X cleavage; the former is accompanied by seeondary ions ch'm'etcri,tic "f an olefin. while the (M ions characteristieolly decompose further by losses of C.lI ' .' A promineut DE·' ion from the loss "fHX i' observod for fluorides and primary (lower ror n_alk )'1) ,md secondary ~hlori,lc, (Figur", 3.23 and Y.1l ,. Bond-dissociatioll energie, (Table '>",3) account for snch behavior: lhe RF- - II anJ Rei H bonJ, (fiDE ~ 5,6 and 4,6 eV!) "re ,tronger than the C-H bonds 14,3 e'v") in alkanes. making the hydrogen transfer H-CRX·· .... ·CRX· H energelically fa"orable, The formation of 1M - nxj" can be 'lmn gly innuence,l by (he prese"ce of olher fnnctionalities that "nect the C- H DDE's 01' introduce labile hydrogen alom, (see Hydrogen labiHly-, Seclion 8.10). 1,2-Remraugement of fluorine has also been identified (Morton e, "" 1989, 19901. For tertiary and aetivated (for example, allylic) chloride' and for bromide' IFigure 9.22) and iodide" the formalion "f(M - X)' and In","cT C.H,•• ,' IOn< generally is dominant. Electron bombardment can abo produce R- ions of unu,u"lly low "ppear:mce energy by "ion pair"' processes: R X -, R· + X-.

xt

.. 00-_.. . .

'"

!\!thoug b C) I..._, - ,p n, .~ 01, ign ifical1 t a flundance for lo w·mo'"" ln ·....,. hl of thi, tyl"'. ' M y cvmmoaty Jme by 10'" ofHX from C. H,.X· I"n. ([qua· Ii"" 4.45l Perhalo",naled aomp<)und . , e.emble hydrocarbom in the., m ....' f'C'.1 'a l ""h••io•. Including a high tendcm;y fot "'''Tr8nll'''''''''t. T he sm.lkSl per h.<.loJ I ~ yl ions are usuaily the mo, t ' Ial>le; Ill, . Il.

~ ,.i<......

gi"" .aln able .ittail:< on the flaimea tatlon beha . i, ,.. tor Ol Mt d l \$C~ Ilf compound. ;",d appliaation, in partic ular ~," a rch a rcH . Sjna Ihe fhi'" «I ii'"'' of 1m. "' ~ , x tbe,. has been tt emendon, prollfeSS in the m..... ' JICI.' roD' c lJ1 ,of D" ..."lal ile compo und s (Section 6.2). "' !'f'li",, ~ (m, ,If l hese led utiqu., III idenlifi"'li<Jn. datcation . and ' l' oeture elUCIdation of compk~ com"""ne nti m~ 800 blolo¥). """ he r"..n d m m" n<>l!' . r h l of M Ot lil (198 1), MaNcal ( 198~l Fa<-d>eni .19115~ Burlingame aoo C. " . llnol! (l Y8Sl. (ia, kd l (1986), MoE..." , " nd Larsen l l99Ol, Sueltcr and Watwo ( 1990). and M ~ Cl o , k ey (1990\. F n glDeflf:lliun m",h" ni"", of , ped rlC cia,,", of compo llndl ure al"" ",o'k''''''''' ,n !he ~cn 01 5«ILOI" 1.9, ~ , 1 2 . and belnw; nnl}' lh" ", lin« the thi rd edmon oft"" hook will be 11' 0·<0 here , ~' or earlier work chacx Lhc r ,e. io", ednw "" '" I.... 1>0<»;, Sc<1i",,, 1.9 and 6.8, and thc com pilation, of DudlU:lt wlO 11'lll3 19\12), A number of

Co rtlfJou_d ClP .

Alka loid" Bud.zjl"' u 1 98 2. 1"8 ~ Ammonium 4IId im inium "" h'l: Vieth 19SJ. " n l; f,i , ~ n 8<" ...... edev 1991, ~ n tty add" Jen " l\ and Gro>. 1987; ( ·La: ) . 1939; I.d )ue.... H ~t e toc y<:l c " P,,' lct 19R5, I ridnld" PoJ'>O\' l nd Haooji=l 19S3. ls opr~n o id " (klfWot" " D I'I' xl u<:" ": [ 1ll1:1J duQ Ryhaao 198 4; Enzdl and. Wahll'' ' , g 19 R6. Lipid<: l ankcllllil t'f f;"I1.,< an d n u cl~o tid e" Lins chrld 1983:. Jl.ud, ixic wic, 1
.,M ...'........_C_

_

0Ii lt"~j yc osj d es: K o m o r; ~ ,

al. 1 9 ~ 5 com!", und " Iluw;k b "'i", I ~~J; M iller 1 9~ 1. P,:ptiii><>r",,,io: m<;>k<;ulu' 7;" kin and Mlk'y, 1984. S.cfO,d, a rid h"';o.I" ..hem...· .1;" n" ' (;'''' Lin and ~m ;lh 1984, Org" """",~jjic

" ppM<JII,_ B,,""...,..,....'" RurJ;n ~"me . "d ( .'\.~noJ; 1 9~5; Ga'ke11 1986; Odh'lll or aJ, 1984; r &<:<.' h.eni 1% 5; M ~ N 'iJ 19116; MOlTi, 19HI; Carr et aJ. 1991 . Smith 01

aI. 1992. C.... ,. m;n.n.'"

~ ,n
('osnlochemi~, ry'

a nd "pi le II,.,.

1 9 ~ ;::

Calm , N ai, 1989.

Dd . ee'er 199G.

<'

I"n, i" ",,,,cu1.lol Budllkic...ia 1'i8t>a; HJlco 1'185; K~r~",k ai, 1985; Clement ,nd l ....iM\di... j .... 1 9 ~ 1l. Enl )""'" M illtuj!..on 1986; Caproli 1987; M cn". k e ~ 1990 "' pl, ~ ",", y i...... 1982. F"',Of eo,np"" "' o' $: Sha'" a nd M""ho)J\' , I 'I!!.~ . • ,,.cnl'" Ylllen N Il7, 1991. Oeoc hcmi>try' Philp d u ~ I ~. G lycoooojup 'e<: DdI and Pallioo 191\6; " U" and POlor_K. l.li" ," 19 ~ 7 . Mcmbra M lipid" <.'o llcllo 1932. M ' l ~b< ~; "", : H• ..-n j n~ ~ f aI. 191<'1 Polym cr add;!""" [..an",,,, . aoo lIarris 1935. P, ~ym<: .-..: t.iiJ.,.-"'ald 19HZ, 'ichultcn and La ttimer 1'184; Snlilh n ~J . 1985, Pyrolytjc ""'d lOd" M o ~.daar n al 19M9; ""n. . oo AI"'" N lIl ; f1all;"lrcr; rl uJ. 1991.

X. " obK)!;",. to"ic m ml'(lund\.: R",bngamc f'I " L 193.l

10 Computer Identification of Unknown Mass Spectra

\>oth 1'" "/" "''<1 . nJ ~ inf" ..... tino "aincd in IJ1lnpret inll unk nown rn"'" '!"i'etr i . Thi. il eol""cially for KJ:!obllJ" ..n1..."" " ,, llw,. on which vel)' hllk other Iu·uct u•• 1 'nf",,,,. ti,,,, ill . ,'. ilable, ,~cll as spectra produced by " utom"ted ~ ••.•J"" m. ' o rnophilllSl. o;-, pectr"me{.r l) . ,,,m, tn IMc an"I}', ;, of complex " , ganic rn;u" res (e.i Kpo t hn ~ nl '" body nu;d" in"". ! drng metal>olltos, .lld pc l r olcu m ~ I n U"",aJ such , )'stems a,t ald. to the ;nf" prncr. "oo ", ill I-.: much .... ,~ ~i l ua~ 10 you J1 you ha,-." good \>• •;0 und er' l.nding of tbe imcrprdahon p' ''"'''' ~ri l><
C""'r~ln l
=

ph."""","" ,

avnilah lt Ill;,! it i, 'ol ' u" gly nnnnll><'flded lh81 3nl' unkno" D5peclr" m b<: ",am· incJ h) o",il an I lll<'riliun M ore y<>II rtm ' }our own ;n' e' p' "I.a'i,m etTorl1, ROOMI e' leusiH R ' iewJ 01 sud . ~..,rn r u lCr a lgo rit hln ' (Mcu flert y and Sta ulfe' 1Q3S; M,la"'en y n al. 19'i'cr, , hould be ' llldied for Ibe pnl>l;ipk.-. or .)"tcm, a .... f<>r , pec , r~ , uform ~l "' n on tit<; va';cly of a lgorit hln l lhftt ha ,-e hcelI pro poKcr~l ,,, b.o.. a!so been (\en,on. • Lr" ted 10 b< ' he mO'1 efficient , il Probabili l)' BallCd M" ......ing ",8"l ) (Pt'J'11a N ai, 1976; Mel ,atT., Iy .. nd Sta uffe' J ~ ~ 5; Loh and Md..aflert ) 19'91 ; :-1. Lt rk n y rI ~ I_ 19'1la,bl. T"" only lllle,p, ell'" a l ~o ti ' h lD wlticb i. t;eneJally n ailahl' (.me 01 the first u,"f"l "artI ficial ' n'cllig,....." " p"'IIram. , i!. Ihe "Self-n , irunl ln'orpre l;vc and Relrie ,-al Sy' tem" (STIRSj lKwo t n " I. 1973; Mun '" ~1. l ~ xl ; Hara ki d al. 1981: McLafl"f t)' Ind SW.ll"cl 1 9 ~ 5~ P H\t, or PBM and STIRS, ,n e a\'ailable now on ma' .... pccLr. """' er "'II'u.... OI ' yOlen" fro m mo,t manu. rac lu rcn, [,om lbe p~~s.ar~ lion (l 99 I ~ a~ d mr L"mpu lcr nelworking lystem"

.,..'il

..

,

10 .1 The 1llaU.1>.o. . 01 "le r• ...,. EI masa .pectta

The capabi lit;'. of a "'lrie>al algorithm depend dllrob . ... lbe q ual'ly aud ",,,,, p:rchen. " I rna.. "/'fi1Wll>tI,im wo rldwide. anI! there are no , igni"ca nl L~'I ""~ i<>ns of ooe plOpllc la ry 'P'-",i ra no l included III In;', da lab . "". u..c..u ,", rhew m=II .......enl. "" •• !lttn made using a wide " aricl) of instr ument, ,,00 e ~pcrimL"JlI.1 ", ", di lion ~ the abundance valuc ' can ,'u y by m o r ~ th n an nNn- or ..... ~n ;l udc. To aId "'-;th thi, pm bltnt, all availa ble 'Jl"lCll a "r lh. .. me oon ,pouod ale ' ncl",kJ ; ~ lhe data ba,e; thi, has bcc~ hmd 10 rfilooe Ihe mil'a! .. n mg ,,~ 42~~ (Mcl.N h flle-l llSio, en l...,. yicJdmg ~-~ lna ,chmtt relbhili t.y {",me compound "" " ol..f<'OiSOOlerl. 14% of ' he po"ib/e corr~t lIO>Wel1< w" ~ reca lled wit h lhe N [:" d. ,.. ba..e '..... us 36/~ ",ilh the Regisl ry, despne t be f.<;t that the tatk.. h . > 2., lioles u mny p<J""ihle wrong aoswer. iMcLuflcrty f' "I. IW I h~

""".u,

Sati,,[:>ctor y ntJO.d"nl of all " " k n """ n and a .clen"""e 'J'>«'t 'urn co ns Tit ut es the fin ll1 proof of moJecuLo. ........ (;l ~ (Section 5.5). Howeve r, eva ln.'ll ion of l!lc Ic loobl~ ly (It such a n ioc.. ' i[ou'i oo mUst also con sid er th e Jimi(ati" n. rna.. <poe• •romeuy, p"ak-abtln.e. ved oc t",'''''n , !'Cctta oJf ~Te"'O· ~nd geometric nd i' l""'~ hle 1><1.."", , pectta of o,her d O' ell wm ilar com pou '''''- Tl", """I ...,~ abl e ..wll eh i, obta ined by r"nnin~ the un knl>...n and rcoference lila .. spccIra undfl clo>eJ) ,......' ie,,1 experimental condition, Oil the same instru" ."nl H.....e"". llIe iJO"ible , tructures for the unknl>...n rnul' be roc" ,ad 1o a , ebli>ol) , m;oll num. ber I>f ~ ,'ai la b l e refe, ence comiJOurnk t.el<.>rc lhrir c" ",,,,,rioon i, feas ible

"r

i"""".-.. ..

o~pertment a lly ,

raMin"I>rp"ra ,os ' he unique fe8 1 ~ m
rnr d ocument retrie.,.1 from b tmu in [SoIIMl l 'o l...,. l hc \..1> princiro&l lyJ'"'$ of da la in Jow-resolution m ~ " "P"". t, ~: m. """" an d a bullda ........ Tho pfot" bility lh'l! ..ort icular abundaoces w,U """u, folio.., a IOIl-nu,mal di>lribulion, 1M probability of <><currollCC of moot m. .. ~ .. "". ...lso . a ries in a p<edicta ble ma n ne l , ... di",u.ood unde< roles ror

10.'

"' ~ ' . _ "

"""_ _ . _ .... .. _~

pca k · ill'r..m.,oce~ (Ch apl" h T loe la,!"" qlOl. cu!a, fmll"'<'" '' I. nd 10 ; "" the p"obability o( higher 01,': ' aru", deer. a•• • by • fa"I'" o( I...~ appro. i.... ' t1y n ory 13U rna", U W ~ Tni. .......i\lhti ng sy,tem i. u",d for indoxin~ ,t.: ~Imp<>nanl Pea k 1"d 01 0( I"" Registry 01 :\e ,..,v"" o ,,-, ar~ h in dlect ;s nOTci ..." h in rho unl nown tha i are " t'( in lhe ,deTe""" ' pec!,um, ";nco the se could be due to oll>.;T com ponent> eM e.'.a!u:>I<J n alisticall)' tt> find out lhe ,..1u a l lel'a\JIlity 01 til<' prodiclion<, "ased on the d'glee of rnatd. foulld helween the unknowns 'llld tho roferonco 'fIC~"a , T hu, a r. p" rtl.'d 9Il'/o.. Ji~bi lill value ind;C~' "' Ihal in ~O'>; of 'II<' Cl'a luation c ~ , . , in whictl P8M , clri e... d a refefUlCC ' I""·lru'" with Ihis df ll' ~" ,,( ; im ib rt t ~. Il>c u........ . .. . ~ "" e ct (thi. mo;• • u"" or , diab ,lit), abo a... ~ ''''' thMt a , pcct lunl of the Iln ~ no ..·n CODlPOUnJ. is flRSC nl in tilt.' ,.k...,,,.,. nit se1lrchcd). Itoiia bilily ~"''''" a ,e repCIrte.I"", 10 minimi,", suth m~""4 " "cie" >l>\I . 1", lh"'" of ...mpl. and rdo;'~"D"" imp ur ihc", Spood i"'T'''".",eut, ltlilitin ll .. fer.nce-fi le onkrwg _ n'la k~ it p'-'" ihk tu .,,,, ,cb Ih. 220.uuo ..re...,.."., in _ 3 . (Pa fj , ~ 1 9l' 1 ~ "'" enoullh to kccp Ifp with Ihe ch" "U, olll/' Oil each w"k _ .. " "y ex gmin",i<m It" ".. ;. '''I'' eler, ... rurlh. r Improvcmcot i"''Olp<''"le, "f",ward ,,-,",,:lllnll~ capa bilities, ~i .i n g . <Jdlt ion,,1 "" Ild,ing credil I"J In. a bseooe of nt>nnJII lchiuil b peciaU y ul. jlll fo' unltlO'Wn e'I" '""'I. each of tilt.' in;ti., Uy relli..,. d b,...t.m.lehiog rd\..,._ enco , pe<:tc.a ill ' U"" 1OO 110m tM "n'_n ~liu"' . rna tc h iu~ e. t;t. ~ " a l >1" ":(' '' ''' in I" , ,, ".,,;,,'1 Iho ulhet ",",_"..,tching spoctn (Sta " lkt ... gr, 19 ~ 5~ F"nllet . 8n ", ,' ad ma. S PBM" (I'.l-'IIM) h.a' beon d",o~'f'ed fm hlllh."" olu' ion >fIC'CI '" ' 0 ulilize the un" , ~....~ ..t;on dllluh ",. rem iclint I..... ma lch. , aCCOfding I" the . lemonl"l Ollmpo4ilio n {lj the ",reren« (Lob ~ nd MoL" f1eny I <1\1 1~ Glth {If th« c PI! \ f improv"",,-, nt, reduced the "''''''8 an,w." r' Iricvoo " y Iulf. I'a b~ 10,1 in",I,. t"" tbe P HM n~ulT. l<>r an unknown spectr um ' "!''P i''''' bl Dr. H"nClc""rg (1 980) as p.." or a rompo"'li" e ' tad}' or Pfop'..., d ide nt ifi ~ " . lio n ~ I S''' ll h , nl , !-D odoccne was lhe COTTeet ans"..." .nd .. UIi,,, lflCcIra of this compound in Iho ~.Ia """" ,.n e fo und by P8 M '"-' Ihe besl m" l<:he•. Spect ,a of I I a (!) " , her i, omer lC (', , H 2O compound, ..... abo In tl>< da taba' e; 01'lC of I""'" " ... . 10

gl".

W

"'Ii

"'1"'"

pc"" .

,e I

'"

""'-' _

C"H,.

,_ .

C,/<..

1-<j""""• • "

•...,",1.

CI. .. 1

Cl. .. .

"ro•

•

' ,,H,.

ec

" ••" •sa

c......0 e.,I<,.

W

M

eo

""

"• --_.

. ,"- . ,_

~

~

•ss

se

•

" " •"

""k,,,,· ~"

"".,.,,""

• •

•"

"

.'"

C,,..,.e),

C I1,.o, C

".••

e.....c'.

'" ,.

= ~

)t ~ ,

C" H "

' "H,. C ,,..,, C .Jl ~

o' ",yO1OIl • • ~ ",.

'.2-0'.

"''''''''''',)'< )'<' ' ',,,,,,,,,''''''.

1~"""""Y' '''''''",*,""..-2,

p.p ",-
"·d"',"

.....,.I
_...

2-'".'""...."'... l_.'ly"" '""''''''' 'u,"..'". ,o'.-n ~ " •• ,;...,.

II

C ..... .,t ,N,O

"'''''''''_ 0-._""" '''0 ""opo, " . _ .. ........-..."""""'O
C"""p,

= m

'"'-"

(: .,Il..

.ro

~

til" '''''' ,&CO"""""

""""'",at ....

•• ""

IV m,.'ch,,~ .. ,

C" H ~

u""""" •

--. -• _."

,-000« _

il-_~y l ' :>-""
_ ~ I" """"" _ ,-

c.....,c,.. .

~ {1

C ...., .

C,,H ,Cl ,

~

".

t"H"

• ., ....""" ooc......""....

C,,H..

0"".

2-d"".,.n. '_u"""'.,.

' ,,HoCl ,

dO

. 00

'·d""e, . n," 0'/0100 _

F",,"ol.

~

<.

, -do..""" .

c .....

."

-"' . = .""-" = •

un ' no... n

"

""

...

~~-

c. ......

,.... PBItI and EPB'" ~""Kt Clu.

Wo. ' poon

..... .. _

0;: ,,11..0,

C"H,,o, C..,.H " C. H , ~

c..., ~ C. ,>l,. ~ O

C. ... ,.t
m_

,do

l -heude<"..".,•

-,-

~_.

'-m..,h)'1pym,,,,, " oli ino

oct.ace. _7_10.... """" 0"""'' ''••

""t.- ." ,1T·d ;O 1\01' """ ". 1'" ""

. .-. - ... ".'.''' ''''"'""_" ...

_-

'" 'pc<._

11'1 "" .......rI, as r01 m" . l poorly M:l lctom~ l-dodecene lrum. Ob,j ou, ly "",t. I rc, uh, rOl a tme unk...." .. " 'ould lea\'c , ul.olllltial doubt. Khoul lhe identi/l..l Ilim\ (COOSi.rCllt ...ilh the 1>milarity ..flen fotlnd lor ,pcclra of iso,lK'Iic hydrocarbons, Sccliom although lh. oolo<:t,on .J II.. ",me co,np.. und for llie beat fl,,, matehes p!\1>'i<Jc, useful iUI:nI. .. li ~ 11 M . If . lnO cmcnl' lhe molo "",,,, .. 1M I I' BM doc' ""I ' <1 rit\' e a cn"oCl .n.",,« is th~l l h. corr e, pond, "! ~ sp'~ ~r u m i. "'lim I». ~ l" , or Ihal ltl ,I;m, .,.., ' "b<..;a ,,,. of diffcyna n "i. 1976; l.d :\.l cLifIerty 19\1t); Ih",. follow t he 'f"dCa1 ill'ClpTCla lion prilltlpk:>. al",&dy l>oook. Tbo," Ihal do not t.ill di. ....;l]y in lhe Cia .. IV CfI1u la aro oovered ,n ,]]u. tra tnl in T JI:>k 10.2 (Lon aod ~k l. a. lTcrty 199\). T lx""" repr-t'S<'1l1 lhe incOTrffi reference ' , el". ,·ed ~ l rhe I H% "",all lev. l in r.. nni n ~ P BM a,,,i 1'. f> BM on Ihe J~? random ly w-Iedcd "" knoWn! u, od l" trol PDM pcr rorm anoe. At Ihe > Y 4~;' reliability bel. tho numbor ofincor roct m ri<'·a.l.. 12 for PB M, ~;o. ....... red u ~ to 1 rOT l. P DM. Tho C' acl·mau d~1a arc d r""tlve ill d i. ,;ri minali ug agaiu'll "'te.e ....., ;;poclra It.. """'0l! el" "";' >lal oompo";:l' ''''.• ",-i1 a~ Ih. COlm· hos ' t><-"Cl'QnleU)', •. ~, 1M '''' la de o a d i< M yll'~rmlidiM ' P""" a aTe \"..""tj-e \<> ,he doubl. -b<' nd ('<)
cu.",

')·n

r-ra....

,hi.

(,r

t""

If PBM C<; an inlc' I'U t;vc algOlilhm ca n be u""d 1.<1 f,nd al I<" M p~rt\al ' lrn ctural i.. f"rm' IJOn, T hi, . h"u ld aid in rnlc'1"rota llot> of Ihe o:pccl, um and ;n ,1r....1 ur. 1 idCllt;f1 eal.ion of 11>< un ~n o wn . STI RS oomhOn"" fi kllowlodgc "I maS5-sponr" t f" lIm. m .tion m "" with ao em pirical >ta",h for CNfd"um" of '""len",,, ' l"'ctrn, T o 1lI,., ,,,, plioJl lhe fonner, 26 ""'Slot<

of mas. -, pcc t' al d;i, ~ ha'~ bttn ",,-lcd cd whi_h are indi "" ~,,, 0( p;tCticu.la. I ~!"" of ,truetu, al fea t" ' "" fur m" I. , Iow·m ~,. ;00' "" 0 be dlac&.to,. I" of . l.dmn·donal;u, I~S . ,...fl 1.hc ~mino SN u~ and aromatic rints, 01 $ 1M ilia. "" <1f n"ulr ~l, 1""1 from Ihe m. ~",,~lar ion can indica le d oclro"" , al'w f""olion. htl. f.." nd In a Ilisnificant p' Op<>r lion ill Ih..., "Om l"'Ulld• . ill p,"~ """ in the u n kUO_ ll 11 pt'abk. Ab-c-nor rg,m;'; eom po~ nd . ~o nla i ni n g the common _Iement ' . II, C, N. 0 , ~ ,S,. r. s. Cl, Dr, and,im I, ~nd no ot h~rs. 1'" u'"' the infor mallon pm~iJcd b} lhe STl Rl> iy.lc-m. "ne . xamines lhe compo~"d, or the hc. t-malcll!ut """"""" . pn 1l;1 Ic uud for each dal" ~la .. .....J idcmif... tMir cOmmon . IT!J<1 " ral fealUre<.. T o a ic (I ~I . [" 1 the Prf prC<Jk1. 1M , ing, -p1us-douhlc· t><,w s v.l... o f 11M: u ~ kno "' " (Dayrinl,'Cf and McLaflttl y 1977), ,md the Dumbe, r>f chlo. ;ue and hromm. atom, in pcak o!lUter'S o f 1M ~n.k .....wn , pc _Imm, by matching "-J!,,;nsl . ... !"""",ti_al i, otopic a b ~ndancc ..I..... t\'l~" <1.J 1 Y17~ The b.asio inr" rm" tiOll n~aila ble (rom l>"T IRS i. ill""" altd in Fi ~\l" 10.1 by t ile ~ mal.hing compo~n J . fo ~nd fo, Ih= of I h ~ !oo'Tl RS da t" ela, ,,,,, ~,in J!: th~ Unl:fIO"' " "Jl"l.'1I~m shown. nat~ cla.. 2-' .""'" t he f..... m ",t "b-undant even-ilia" and (our m<><.\ ~h\lnd allt odd-rna,. I""'k. in lhe IIlI1f';C m/z ~ .- ~~ , Tho 12 rc1'.;",,,,,,, <;ompotl,ld. ", hr""" dam in tbi, Cla ll m) ' ,'" hcool 11M: OOrre:ijXJnd ;nll dar" of tho " nl ...."" n aU roBta m a ph_nyl KIOUp 101 wbJmyl voup, n au ela, . 311 U>oL-. ~ n ti rel) difJere-n1 ' I"'<"ly l 1'....uP it. o;ontained in a va riely- ,,( (unctionalilies: .,.!et' , amid. , k~ooe, 1lCld, and ald ~b }-d<;. The ""I~rc of thi, fnn ~ tioll. I ;' t, i. m..... b.n er ind;"aloJ hy th. " .~­ lr"is loft (rom tM molecula' i"n (Chaple, S ~ da la do... ~ D oses tM fiv~ mo,t ab unolanl """h Ilvin~ ma " -!o," ".IU\-'S (If 34 75, H~", mO.l " f the \lOot mateh-

... ••, .'> , , zz: z <. •• .... . . . . . . ; 0h

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-,rum of p.>fO_ C,H, _ CO_ O_r>-C ,H ,

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oonlp" und , are prop}'1 0"010. "d dl ~ i tlle U>U ~ of ...."t:..!il..tod ~ ny l lIyJro.)1 ( 1 7~ carbon}'l (28), and p", p.... ) t~l gi"" a psodidw m"lec uls r "-.",,hl of 1&0 tor lhe", ,ub,tt\lctur.J UDlt.. ro<""'I'<'nJing 1<:> t/u; bigh..1 m U S peak in 1M unh own speclrum. inu;cKI;nll lhdt lhe rnoioruk i' a propy l ""l~"" ~ hyd ..." ,ylK:n.,.,ic ~<;'l. Th" int .rpN'l ~r JnJg.hl ~I ",-, n" l;~ th at l,M 291' IS moch larger tha.. 1M - 15)- , ~ . a nnll indic.Hlion Ihat thi' i. ~ct u ~lI y I~ c ..·prop,l "''''r (lin %-d:a.~ Scc1i" n 4, 6~ i lt l"' ''ah STI RS h", nol made lhi' dJfJy !IT1RS: lbese re,u U. are ' hown in Table 10 ~ 116~

l'rofICieIlCY;1I tbe in te'1''''I~li "n of rna" s!",ctra as tSe:'Cri"" d i~ (lfc,;O\lS cha pI..... k roquire. practice: ,0 d(le; dTie~n l u.. of PBM AndSTIRS lor ~~ l unlflOwIb. 1''''' d<.. ....... ription of these algoruhm. w~ , 1'.,,1"..... y Idt uoh! the .'n4 of IhlS book, lC in tho~ ... ntls of ' " bI>l ~l or ,eo; otI A "ide vAriety of un kn() w~. h , dcmo n" mted cooou1)1 <>pinion, tha t lhc<e progra m. <:"40 " " ~ reoJ ald to the interprel er, rapidly nitrro",ing the f>eid of p,,,..bl< rom po>~ nd,. and " ,mclime. providin ~ structural tnformation which rould nol "" di_I_ 1 " 'eu by experienced ;nl" rpr e l~ "', Becau,", P8M i, now avaiLtble on mOSl oomm.....:...1""'''''' pectrometer , yneUli. i nd bcc. u>c it> time requirom"'llI u e only ,.,.:c,n"" il 'h<.luld be run fin t 101 . , 'ery unknown . peclr um. II • wrw r ~ inlerl'felali.... plu, lhest da ta then d" nol produeo " 'ati 'factorl . ..." er, me $T1I1 S "",w I>. .h"uld M O be obta med and examined. It ha' ""on the ~ 'P"I' .nce of IIlO.ny iulerprtlen 1""-1 lhe "-eli.

'" STIR S al." "~ " be v. l"" hle in iI"',;1Urc:~fO."1 n1 corr c1ali"", evco lOT "' re rie<><:<:d m~", ~pec1J om« ,i , (,.

(raining"

~' pec l ~

10.5 Oe ne ral

ot ho lh P BM

~nd

r~e . &...,n

Ash I Y ~ S: C1upman IonS: Gra~ 19~ ~, Hile, 19S5, McLalJeny aDd SliOuJIe, 1989, lWI: Mc"ai..... 1987, 1 ~) : Royal Soci<;ll .1l Cbe m'OIJ) J')S3; Sh,,,,,r \986: Smil h 1\1n.

11 Solutions to Unknowns

A:> ha. been empha,ized in ot h ~f part, or this tx.lok. the m,,' t importan t way 10 loa,n how til lnl . rp ~l rna,S ' I'l'ctra j. by actually working out , tructur.. from unkuown l pe ~ tf a . Whe ther Ihi, bo ok i , u,od in a formal co~"c or I'm <elf. instrucrivn , ;1 i, 'm pu rt anl \<1 "" r. through a ,arioty of unknow n ,,,,, etra, In " n empting to solve I pIlrtlcula r uok nowlL use the , elut ion her. only w'hen you (Illut )'OU ' !lOw tilt an. """, o r when }'OU C,m Do l ~" fur th er. Wn..'1] }'OU ncc'ln~ to arr ive nr your OWll answer. Rcfere.n"" . pectra , hould nor be " Mod to .oh c 1 ~ . 9C unknowns. T he... unhowm "TO dc.ignc<1 to illu.,ITaIC principle. ~.l frJrlIl In the leU. M ost ore Co mmon molc.cul..; so litt le will be learned in lClCl\t1ll!t the'D In a mot"noc file of speelra that i. properl, ' iOOo,.d, f " II"" " II Ih" oppl k'ohk: ' l"l'" " r Ihe -S landard illlorpretat'o n procedure" OJl .ide the back CQ~ e r) co vered in Ihe toXl. Th e , olutions will foUow thi, Nder, " l!hOUa.h ' l' _ limiloti" n, l'Whihit 0 er) point (or oach

"0,"0"'0

The 1>,",lra h~" o been taken from the files of Ih i, labo ralOf) or from the bM oture. Th¢ dala ho,'c bco;n ~~, m;<,: u;d rn" ",, ~ I.- i h u li ,,", rrom ;ml"'n li<-" , ion_ mnle.:ule rcacl,o ni, and h a c~ s rou n d _ whore moh oo" ed,,,,,. appeared to be " " :"'>al)', Th e .bt\nd . ~ of a peal; du o rc the wnttilJulion of n.t uro! isoto pe, II uo;wr ~ t~ ";t h;lI lhc l , , ~cr .; 1. t.-.r::~ "'lali .... to l he ohun _ dan.,,, or I"" I'..k, ... ± O_2?_~ rt!ath'e 10 lhe a""" d.""" of tho la rgest pea k ill tl>e ~pooct Nm. Pea kl or Imoll a bullda noc tb . t "' ere tbou i bt to be inoollscqumtial I" l he ""lul;' .n ,,( ,II<: ' p<;<.1 . ..m ~ " ,,: !K>:n om ;l lC.J '11>i. includ "" unimport ant pU b belo,", 1% I reIa,, ~ 10 t~e m""t abuooant pea k) a t rt... lo.. end 01 ~ v .... r ,,( ""~ ~ . or uni, In . . . ,. " ",. . I;'.n, ' " ,,' I~. I" ..'_m" " end or "f'OClrum I I Tn;, •• Ihe mil .. opectru" , of "'ater, If any re' " in Ihe sptcrru m W rTe,po,xh lO the man of ,be IIWJ"'UIe (thlt i:s. ,ool...ul,,, .... tim pal< murt be

'--ma.,

t""

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~

". the ODe of b ighL"' l m,o " . T illi sp«:tr um, \110'«10<<:, ind"'alco \"~l lite
Icpn:>enl the ow k cular

fragmtn l ~

HO and O. re'p", li,'CIy_( WI U'I] J.2. r o r tlli' . pect ru m a molecuL., ""eight of 16 i' ind icated. which Q<.uld co rru pcod l<><:H . 11 , ~ h <"T "",,1..1 in ue SP.CllU1U suppo rt thi.. <:acll <>n atom to ", hleh i, . ([oched • r.malkr n()m~ of hy dr o;en a((lmo. LIoklh. ",, ]

/ 3. A .... ,~ Ula t ..·.igh! of 32 cor re, po nd,

1<.0 """ ' If to'S .... ygen alOm,. OJ i.

ru loNl OUl, as ill only po'l.ib!. fragme n t ",'0,,1d h l .-e a ma.. of 1" The element al

"""'''''''';Ii"" C H.U i> indicated. The only posubl. n ' i1n!l'--rrlenl for the' e i. C H, O Jl, 'Illd the other ('C ah in \he . pa.1r""" Clio ~11 be Ju,\ified 'IS picee, nf su ch a SlnlCturo, [ ).1 ct h ~n "l J 1,4, The howlodgo that I~ main i""OOu, components or ~ ir ar e nitro!!"", , ,, y~n , and ar gon idcnt; [... ,he J. ,J.'C 2K ]2, arod 40 pOllk. " ' 1'1 . , 0 •. Ilnd Ar. re, pee\i, 'oly. M"'''''. :!OJ ~nS"'" a nd ,,~)'­ lI. an d 20 ~ pr e se n t mon,," \om;" ~nJ .... u l>ly e ha , god 'l'\lL'k.." If" r c u mrJe. miz "' !iJ = 20), The r-:~h ~\ m/~ 11 u d 18 Me due t o} 'u ' " (Un k""wn I .I ~ m~" 44 i' di' cu, ,,,,d in Unk""", " 1.5, [l'l'" oll,;n, '''la, n. ~ r",n, ""'11:' ] 1 5 If lho ;solopie peah of rn a' .... 4.~ and % a. c iJlflorod, Ihe ba,e (1.\l a••I) I"'~L in tM "ll"lrum indicates a molerolar ..~'th1 '" 44, The major r-:al l 31 12 a nd II> int for m ula " r "arb o n d,o>;"" dQCS iii Ihe oboc,,"J p.:ak,. with lhe m.. .' 22 oo" c· <ponding to CO, ' · , [( :"'I:... n .b<" jtl . a l m,l. IJ I ndiu ", ~ m" ",.." le or rna" 38 which oould fOI1n an dbunJan\ It a~men\ ion hy "'" 10M 01 '....0 hydrogcu ato m, (.../z 36. ( M - 2)" ). TI>c hi" .. In In. le~t .hou ld lnd 10 lhoc " hocrn tion in T~hle 2.1 01 1M J!J ahu ndan", 11.1'0 ,of Ih ~ nalt" " l obk>n ... ' IOt OjX'!l, rna".. 35 and. 37, n..... lht spectrum i. ~ ",i"." ,, 01 H" O 811d H '''C~ in proportions CI). m.pood.ing I" the i",\o pic abunride 1

A,"

,11,.,

1"""''''''' ....

«>o'.,n

rna,,,,,

Ia,,.

2.2. lhe pc;\b a' m ~ ",<" ~4 and % ,hould .ro u~ ~ ""'T , u, picion" b'Olumc ...... ;...m" "" or ma" 79 and 81 an d of llClI rI, C<jual a~undam;es, Be· ""u'"" ....."""" \14 and % rop..... nl th<> lno le<:wa r iom., by dl lfe r~ n " e th<> mo lecule ,,,maIO' I ~ rna" \lnit' in addi li" n h' 1M bro mw alom: the JTk ..1 lugical assii.n~tll for I ~ i , i, CH". Pea h at ma _ 9~ aoo 97 2re du~ to io.ol, 'f"'lo l "k lh) l bromidel 2.3, Look flf' ! for tho - 1\ +2" elemenl$. In thi, ea"" [mi. 6611",1: 64J cqu al, ~.Il'/,: 1M iso(opic--.a bl,oda""" 1. 1>10.' , n" w. oni~' !wo elemenl' ,ot . ""h [(A + 2)-lf A· l uhono, S; (3 4 ~iJ an d S (4.4')1.), T he for mer i" "uloidt Illt al· low ed maim..", ",tali•.., er ro r ~ lIY>~, Tbul , ulJur j , ;ndic:Jud, wilh lhe >IS "b uml."", •.to X.gl'ft m ~ ,,' i !~ riA.. 1)+J- Allh<1 ugh S , would hau the cor= l rna... rD' thi<. llot m l ~ m.il y 01 the mi~ M peal would be &. ~~ Ji""" 11m ,' ",a uld be lwice Ih ~ proM~; li ly lhal one ~ tho t,,·o S a lOm. ,.," uld .... "'S.) With S, r-""",I in ",/, 1>4. the l'elidua i 3:1 ma,.. un; l' mu,l "" auigned; 0 , i' on obvi "u, I""'"l bil ily. E~ch of th~oo wou hJ ",' ntri !>ute O.Z"/, 10 lh~ proh bili(y 01an i'otopic "'it 66 pc" k. or wil h ~, a tOlal of 4. g~~ ap"~eiBl: ",011 "'i lll the o b'erved 5.00::';' Th< ma,,· :n dilTe"nc. between M · a nd " !> mig ht al' o be al silrned (0 CH . O . ~u t las wiDbe di""", ,,,,d in ~, ion ~) , llu . wouid c,m"" a 1.1 % oon lributioo I<> ~,/ . 6~ . whicn woo ld .... k~ Il ~ p1edictcd ~b u nd a n" . much too lu ",. ['Sulfur

»c

"c

Ji ,, ~l de]

f'C'l k ",.•~ due 10 C, H ,O" til<; " , pccted ..... ·4 ) mln.ll y ~ !Om . p-rc...." L Thus II>< <>b\oe r\'fll ' ali" ratio would he ~-;. h om Ill. two \ """....(.o..(b nlor~ cl~ly I" lhat l"mdk led for tim'" ",,-[ boo atom" ' uch U in the iOll fo""ula ( ""H, ' How.v"" one should " lw"Y" he a", art 01 l h~ po6$ible oon lri .... ci"n rtom "b a "ky o u n d~ in the ;n' lr umenl" wbieh is much mo,e lild)' 10 a hiGh ("0' low; whi l) indicatio n Dr the Dumk l cl caTbo n alomo, O n tbe other hand, ;f an ' ''l~ en alom i' p"""nl in , he "l;·• •.H i" n. the.. ,hould br a o.2~,~ ~"ntTi t>uti atl to Ihe mi z 45 pea k due In C , H, " 0, unfort una tely. thi, i. j U'1 " " th" iimit of the ,,""',lule ~rro, a<.sUmN po",hIe ill Ih~ ;n ten, ily dala or IhtK unknown ,pce lra To c~icubte tbr nwnhcr . o1' .."' "'On at " m, in the latir ~l/: 5 ~ f'<:lI l . nill" I.... . til~ in tensity .«I io of ma~' $'l:~G is 4.4~,;. From Ihi" 'h l'llo 2.2 i,odJcaln fo~ r Cl<' \><,11 ~ h..m; a <mallu n umber w",,,ld nnl be p<,,'; b;" .. " Ie'M Ift.'! YJ conloined a ~ impu rity or e.<1r"",'<.>u, Fragment_,,,,,, canrribmion. Thu....:: SMc.",<:sponds '0 C.H,o (bul a""). The rn" of 1S to !live the loa"" """~ ~I ....·' z 4 J is most ~ 'Ili,,,,lly a tntlhyl Group. confirm inll Ih<: I'm:l iction of the for m" ,", C, H; I ror Ihis rrnllm .3"'~ ..~ or""""nd, niceiy to IllWt rn.ln ah.n', " rr3'ok 2.2). By dillenm ce thac . ho'uld al'" be six hydro~.n ~l"m, in ,"--" 78, lo r n probable . lomenla l rompo:
If the

m ~..-4 3

'c

gi,..,

't~bi1ity, rBrnz~llC]

2.6. The "4"'<1 ral rt8ion ...,/= 71 74 indiCK\<" thOi "" ~A ... r oltm<"t. other t ...." 0 0)' #0 ,l ie POUi'*; " Iher"'i'" [ m,.'z 74l -r"'i ! 72] > )*4 f rom t ile

tt l _ _ .. O"_

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_

l 7J1T72] ,'. I~, T~ bk 2.2 j",lic,d c, three ca rbon Qtom. in tt.e hw.I: J'<'Ik II rna" 72; howe"".. " " Ihi.. lhe mi;; 74/72 ratio Iho~l d "" O_04~,~ ill comparison 10 IlK: O.5~,~ r" and Chtek tilt COmmon i,o(o!",< nl Tab le 2.1 for ~n " pI;ln . lio~ . The C, I CCOIIIIl. for only 30 ~mu Gf the molecul", ..~i~ht or n. &lh thi. dlfl~l en~" a nd 1'" ",i= 74,.'72 ra tio Can be aCCO0;;", ..-ill be ."',cel hoe p robabilit y lh al 0""' o f lbe <>llSens of the mo lecule .. u " '0. Thus. 'wm T abk 2.2 the mi, 7{·'?2 ral;O _!KIllld be 004~.'; + ~ I,noes Q.2U:',.. ", l).44~_~ eh, eklng the O, j ~,~ fotlnJ The moJ~ c"J u r fOlmuh. <:,11,0. ;s tbul in dic
t""

l,inuo,ie' c:lt bon al"m . which II consilient "..ith bt,th "If: a~i8~ nnd 50/51. The t(lm<1 h.......] ] ,9, The {OOL-': l.l4lilmi ' 1J2] ranc (sr. Table 11.1) ek.-... I ~ , howo lMt no ,ilicon. • ulr~ r. ch lo , ine. or bro mine a.tom, .re p.-= nl. 11>< ["'i: H3 }/[",i. U2] .'Illae ind icates C.l l>ow<'C,.. if lhe ", I "i,~ <'fro, hoot . hu.J ba;" _Iightl}' larger, botb C , and C" "' ''uld have to '" "",,
T_

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"

" f the mi. IllaU u h... ",!rich rnu,t be duo to ~ A~ elemen l", i. 8«.oUnted for by H•. fCoH. O. ' .. JI> _ 6) 1.11/ .n.. a"" nd.""" of rbc mi. 78 l"' ak (itt Tabla II .l l , Ito.... immediate!)' lllat no ~A -.j. 2- element. can be present , Fo. Iho ~ + l~ element' , Table 2.2 le1k uStha t thc ",... j b iht l~ l are C, and C ,~ •. For ,onl dlOC"," cd in Chprer 3. Il>c '"i. 76 molecu l ~1 IOn c"""". <:<mlam an odd o" mhe, of oitrogen .tom,.., th.t C , is "o, re",L A po osible romb,na h,m "f ~ A" e lem~nts il H, P. (C , H , l'. «>\11<1 no ' fragmem to yield "'-" H. j [ C , H. P, r + db '" 0] 2.11. If m,h 86 . Dd 8 7 '"'" on ly lso1ope peak> of miz 85, then llIe p~"" 01 One sJli",m atom e lplaIn< l Mtr rel" ';,·e a hundance' , 1llc: ;oh. .... .ce of "'!: 84 "" ,u ~ lly i. e.idencc t hai ,h ,.,.., .n: no hydrogen . tom , in "'!z 85. A k1I.......1 co mpo~ tlQfl rot- lhe ~A elr n..nll 11 F j . l SiF" T + db _ 01 W

1' 1. The moM101m"" pc~ k , miz 182 ( I~~ Table 1I.4)can conlain n,'~'" .. 2·· rl"""",,,I, ' ~ « pI " ' Jl:"n; the indie" t"d ~I:>un d .""", " f Ihe WA ... 1 ~ clementi i, ...1f...·."... J, I!'~...I tha ' these must be "l'P't".im. te:d hefore a calculatIOn for o. yI!"" "" n be made, T ile [mi. 1~ :\lI mi: 181J val of I ~. e ; indica,es C !J to C" (Ihe . ta red ""or limi' of ± 11:1;,; lneI> ' ha l •• 1 tile fan ge D,6 to 1 6 . 6~", m" ot be co lllid"t~d ), T he intcm ily ••1.... p<ediclN fot mil 1H4 fOT C ,, ---c .. :>.Ie 0.8, 0.9, 1. 1. and 1.3, respect;, ,,I, . if no " X),V"" i. pre.em , Experimmtally, ' hc ..I"" of [mit 184]'l P1!lr 1 ~ !] """ be (1.1) to \. 45, ;' lJo",i " g Inc fo rmulas C 12 0 "_" C" o,, _1. ( ',. 0.. ".nd C". How",,,,, (' ,,0, (ma.. 1 ~2~ c oo, {rna" 1SS), and C ..O lll1an 18Ill)'

"

Tol>Ie lU CbU 1m 1J»O.... _

.

..,.

,

~,

" " " "•.• J.±

•• '"

,.••

0,6

T. ... 11.

n.S) O,l

2 .2

"'''''._,e ••15,1 1 1.' 1.( .. 0. )6

, . ...". .. . . .100_

.'" ,. '" ..'". . ,." ••. , ree

,

0"

1'-'

' ..l

o.r. IOf'~2. 13.

., '. '"

,.... 0'

se

...'"., m

0,1

' 76

_

malize

,.

..

" "',

,

M.i OJ ''''. ~' 0

e.t

r u-

('.1

~

0.2

"c,

..

" o.

••

.,

.

O•

,.

.'.

I'CL' )

''''

l' ~.)

(0.21

fDr mi~ lSI witl> The uullkdy m" lccu.:" for mula C " II, (182 - 15 x 12 = 2). A,>ignill~ ~ ... " ckmcn", lhe remaining po,sibilitic, ~r" c.:" H, oN" C "B,. , C , .IH , f'. e n H ,~O. a nd C.. H ". Improved "'I',,,i",,-"1ll~1 acc" rAC)' or compmi--lion informa tion born <>11.;, ' f'\:..1.I.1 pea h would be U""",.;u y 10 l .:tIt""l th;.

ltn rurtocL LC" H,oN., C" II ,., C,.H, F. C, ., H '00. C,. H..] 2.11. InlenK p,,,h fcllmc" b~ lhe 1o" of H , a re UUl\ ""'~ the " bM-1K'C or ~ n 1\1 - 3.1+ .."uld c.,. ","",. Ihal lhe latter cnn al,., be du ived fwrn L175 ' 1'[ 174 +]. SI~ almo.l all inrn ...1 '" , mi" 174 rcak ha,', the "" mpo sit;on .. 'C." Br. Tb l$ ~I:JO) ""'~ ... Ih~1 Ih. [ 176- ].'1l74- } ratio ~an Illd,c"uc III< "A ( 2" clemen..... 11", Ihall Br" '" lhm at lea ' i on, o'},II'"1l nm.t be pr......·nl. ({'-.;H ,8.o, r -j. db _ 41 1.14. In I llempoll1tt 10 c J'C'l1< . .,."" ,,~>ence Ilf on. or mOle ,.'" .. r clemen.. •t..,ul'e Jbund.-.oc<:l> al " li. 131,

\I ""

,..,j",

... ..- ..... _--_

'"

I ll, and 13' . ,. Unpo6$lbly h i ~b to b< fitted by an y "'A +- I" ekmenll; IhlS .. ca b) ""c, lap"; n; t lll ~ ITI...nt' e ion, of the ..... in ...-i<:. (m,l. 112, 114, Slid 136). The n um be r of A +- 1 dcm.:n... i. indi o:e lN " Illy ind irccl ly by the [mil 1, 7Ji Lm,' z 1.\ 1>] vol"" of0 0 ± Q.2 ind ical t$ lflu llraph, ;ndi<;~ (i n" the"" i,,' \ol' ic co"trl Nl!io~. a ~ , ho"' o in S«I,on 2,7,) Tile maoo dilTeren ce du e to "A ... r" , 00 • A~ """"o l. of 25 11 'ltl ~ , '" l!! _ 2 ~) can ooI}' be d ue to C 1 H. with "" n<j""'a, i<)n "h alma: rrn riclions; l hi6 a..il:Jlmo.'Tll ;, ~l , ,, "on, i, lenl with the ~ b.., llU of ~ 1l1 M - 11- pt4t , [(~ , HCT" r +- d b _ 1] 3.1. C,H. ", "'/= 28; C , H ,O ' .l>I/r)Y', r . H.N··, .../z 7 1: C." . NO" m/: 86; C, H,Clflr ' . m"", ltlJ; C. H.OS · , "'.'z 124; C" r ,. ", ", it 1469; H,O I • m/: 19; and C, H.S;O · , rn,/' &9. 3.2, C 'QH" O · is an C1o'<:D-cl"" ITOn ion. al\d !I) Connot h. the molecu lar ion. ,l.l ( : , ~ H ..•· u. an " dd-elecl' on >On. The other ion. rop",,,,nl I",,,,,. of H, C , H" CH , . C , lI s • C ,H ._ ~nd C, H , . re, ,,,,cti,dy. ",II "I' which are l'O'SlIlle 10<._ 81'l) Ib<:1lZnI<' " ..... k! n hibil ' uch ~ ' peetlUIO J .4, Thc p...-.cnce "r tb< large mit. 96 and 98 pul. """,,. dout>l un tile a"'llJI mt1l1 01 "" : 100 a. th. molecular io n. N"" o or the COmmon isorol'"" COIfespoo"., 10 ,h" IYfM: "r i' Gl" pic du.rer , however, The iom or m8... gill<' hdpful hinl' lor el3,'6 1 •• 'i<>. lhe ch lor m" kl 2.1 or A.l . To c~lculate the Ci<. oo n <~, n l" nl of M " fro m .../2 'J1/96 , do nOT fOf ~~ \ lh l tho -"'CI" ( :I i"ot"pic ;01\ of (M - I)' .. ill CODlnbu' . 64~·~ 0/ the ",i. 9S to the 9 7 p"ak, (2.4 ~~ - 0.1>4 ~ I.S/~ ~6 1% = 2. 1 /~ OJ _ C, . T hl. caleulalJou i. suporlluOUS, ho",.,'cr. ";no:; the tt.olan~ of m o lo<:olar for mula of 26 am u (M +, - C I, _ % - 7'0) i, """'t lop:-aUy dlle 10 C , H, . II i. diffIC ult to di,lingu i, h !'Jtlwe.'D lbe possible I""mer.; 01 C.",(.1 , with.....t ....andar d '>. [ lrans- l ,2-Dichlo roa th)'k neJ 1.5. r ite is.uld hall<' alrudy ootcd Ihat the "'/, I3S and 137 peaks failed o.e.e~ WI"" /I'f.l un """", ,, ror a mo lecula r ion. Bocallse there I. 00 indi.cu ;on . '" ~ , n. ",' nl ~ i ninF. more than Two carbon alom, or ( m~ chlorine atom. tM rn<JS( prob.oble llrocl nre to " ccoun! for thi, ' pectr Ulll II Celf, e r, . (CItl<Jropeotaf)u"" ,,'ho ncJ

C,.,.

w-'

',

...6. l Cllrt>on

~1 '~c hl","dc J

4.1 l'Joe /Irsl ru le cm ptla. ~ . l he im po r t;Utce of pn,J u.t.io n " ability. The highl)' < tl b,~Md "'l m in obcn> ~ 1 i,m (Ii'l uatio n 1),) ) p. o du c ~1 by far the rn""t . bu nJ 'D t puk in Ih;,..pc..1 ,.ntl .

" ,--

.(l 1.1)

M

4.2. I\lphu cle''''~ae ~ ~n be Iniliated by ,~c ' lUJ.... I ,;\<: on ";l hcr the " ' ygcn the nitr" gon al<>m (Cquu ion. II 2, II 3~ The Me.:l ron-
........

,.- ~

~~

H,.NCI1t •

•

CI1,=6H

111.2)

"".31

"~-"' A H,N ~

--'--

.....=-. •

. CH. OH

ru.n

M'~

nitro>gon i, "'p"rio r 10 ' hoi or o. y~ n; w-niza, io n mould OCC1l' mOle lead;I)' al ni tlll ~ o n rrabk AJ l iODd ~h of f " "" Iw-n ' 1.2 . ~t>ukll>c ,\a bl~ Ihm ~ , " bt...ali.... Il. l ,\.;1 1, [ Itl/l )0] _ l 7% '" M al ioniu.tiun. he, ea, 311 "- 2. 'l/~ '(bir,;" also , " Itb Ste_ n'l Rule: IE(H.NCH, 'l =

r"'il

li. 1 c'l .and

I I<~H tlC H , ' J

_ 7 .1> . '1.

O . Tbe rallo [mh W I![ m'; 97] i$ m lJl of Mi; '»; ' hus "" ~ 9lI,h<>uld be con. ldoreling '; ",1 fur "" -+ 2" d em enl>, Ih. ' a l",. [m/% IOOllfm]z 981 ~ 4.3 is co......ent "' i1b S t . II miz 98 .ir; the moloeu!.u ion, mil 97 m..... mo co nwn »tUrn; ;" "s L, ,,,,ri!>u,i,,n ' 0 mi. <XI m",.1 he: . ",buleted before o no:: c.alcol.ales the "A -+ , - dc_ lit.. The •.,. idml1 al>undalUlO (1 3.6 0 ,8 - 1!J = 4,9) lS ron5lSlen. with - J) i, klg;"al (C. H t , S 8 i~ "" , -+ dh _ - 4). The ...... abunda nces of other peaks ma ke equi,,-nca lthe delermination of their elemenial com poon ;o"" r, om iWlO pi. abu ndan. ... alth ough C HS' ;, a l" g;"11 a",ignme-nl rt>r m,i, 45. Tbc mi; 98 """ ~ l"'''"'' " U tesls ror the mol..",l,,[ ion, "nd as . ueh . ho uld ~ l a , . Jati•• ly .t abl. ' l""' K::s. T he io.. 01 H i. the dominant """han;
•• •

'"

n ,I. Dltf1l lor Urllm" wn 4.3

,. ,.se

,..

"

aa ' ''" m o ll. .

'" OW 13.' - 1.< 4,3..l. 0,<

"

,.

"••

eo (",I I"~·)

lUI lUI

"

,. ""

- ... _......... -

.....

, ullur or u " .•y, t,,,, (r + db = .1. <1T bOlh. Pos, ibk: , ,, ucr ~ ,.., , con '; .I,n l with In.. arc 2_ "r )-mtllofllbi<>phcnc or th in-2,5-<;}'do""lIdoc nc, l 2· MClhf llhioplomc] 4 4 ,hrou.qh 4.S Ao ll hough the", Mr<:. .. sta ted, iil<wneric C. -amincx, ca ktl mtion oJ The elcnm lal ,xnn po, iti<'> n < lOll hli h in 'C>tral ' U e, iI Oil<' ...u e using the >IIi t 74.. 73 n lln, mainl)' bee. uoc , .( lhe pr od ucti on of (M • 1)' ~J' un ion -mole<:ulc , caCl;C>1\ (lite Secti"" 6:1). Note lhe 'ub,lunlial d;rrCT~l'Ce5 in ba",-pe"" . hunda nces ", th o p; lhi, i, useful in ev" lu nt i n ~ lhe ",!ali' e icn po (l ~ n cc of J"C-'lb in dilkn."fI 1 spoctr:a fG ril!"h ~ 19TIJ. Iu ' n' ''' C' 10 lhe qucstion in lhe 'c~l, 1011O ,,' :n ~· met b)'l gWlll' i. in cocnpctiri"" ",ilh Ibe lots., of "Ih.. ~ · ,u ~hr u<-n!>. The prol>arnlil}' 01 ~ -CH ., I" " i, m<1C b gre"ter I ~ an Ihat for x-b)d"'@I'll lo.., but Ie.. ' Nln th.J1 [(II ~_C ,H , 10". Thi, 11<11'" 10 ideunl y U,,' nO"" 4.8 . , C , H, C H{C H, )N H•. Of rhe Ih 'c ~ .(' H , . mines listed lsee lc~l~ onl y ~ CH.d ,C HNHCH, and C H,CII,N (CH , ,, ..... llIn unidrmifJed; W Iinl $bollld huve ~ 1" "'1 f '" -CH, nM ' n lk, . and Unl no..-n U .. The a"is nmenl of l he lilll e.,. "'N cture to l;nk no ..n 4.7 is bo rne out Il ~ the ",,'r 44 or lhlS speCfru m. il i. for med by Ihc d imil,. tion of C, H. f, om the ( M - l j ' ;o,, 'hwu~~ . f c.. m"'tomenl , imil.. 10 the lo" n.:ll i,,,, 01 miz >0 in C, H,NH C', H, (,c c ~ tio"". I (l~ Tk rcm~i~;n8 po<siblc ....."""" Jr, C H ,C H , ( :H. CII , NH " (CH, I,CHCH,"' H, . and CH,C H,CH, NHCH" Thc li..... 10010 lho uld yiel<1 aburnl.llll '..... ,,{ ",.i z JQ and ar<: Ih" , Unknown. 4,4 u d .. , ~. The.. . pccl r~ IlU . U'l'r";"8 1y simllar, ll:flc<:tirl8 ' he dornina~l d r"' l of tbe omiM fU1lct ion <>II the clc' ''' 8e; h"""'fl", lbe sm oll ...h "" i" le dlBe1cn"" in l~ abundafldan l;ft i ~ Unknown 4.4 lonl y . maOcootril>at k,n. \.hollid he prc",-"fI! f.om C, H , N' . "d C , H , N - ~ ",,,,,. pmible ....ith ~_ a nd ;"ooulyl..mi"" ",,,ignmeol' " ... 4 4 und 4.S, U l......ti.-dy. Nn , peot",m i. ai'~n for c-,H," n CH" it . hould " ve a base pc.a.I. al MI: 44, bUl . n insigni f",",nl !'t. k at (M ( :H , l' . [4,4, BUlyl' m;",, ; " ..1, iwbtll y'ami",,: 4.6, OOp.- "", l mcl hy l ~ m lllr; 4 ,1. d hy l di mct b yl ~minc: and 4 .8, s«-buI ) lamioeJ 41;1, 4.10. For l~ " ",'mmetric 3·pcn loo..,,,,e, ~- . nd 1",,1""'a8" oan gin only !he C , H,<.'O ' and C , Il , - io,,", mi' ~7 and 29, OD I h~ Olher hand, 3_ ~)'l·2­ b uL,."onc , Ilould ,icld CH, CO" (CH , J,C Hro., CH ,.. and C , H , · Ion> al ..i: 43, 1 1, .t 5., anJ 43, rc'fK'oti>dy. [4,'9. }-P e nt ~no ne ; " .10, :Hnclhyl·2bU lane M ) 4.11. hu il it. ol"",enlal W m/J""ilion ha <1 not bec1I gh -c... IOOSl 130 appea r< to be- a gundanl C. H , •• , O I ion. ; u.. IM · 41)' is Tbe m<xt . lrund_nt 01 th eoc bl Ill" a nd l hn. indica" , ooc o r . ...... !'fopyl i'oup" _u",",lluted On 0"" '" balh """r b" n alom.. The abt.ndao cc. of l~ - m ,l· and (M - C , H, )" arc ,1 and 9:;;. ' '''pcClj, dy, 01 tll..l '"

_

", 1M _ C, H. ) ', m.\m, ' h~

pi... ...,.;

,,4 melh.,.1 '" d hyl . "lJo.lit"""lI oa all

:0-

carbofld 10 )10:1<.1 I'" 11\ )1" ... .. ron Sl,. ;lM!icltcs a h l,1 ", he, ("l ' t }1;. uf C. II ,.O ",..'I \~. n t>o: " d,b..., 1 01,,"" IC.H . I i ill"" Icrmco1 by ind,,,,ti .~ dl~lIj"" of (;H, -o·C. H.1 The 1o,,,,,,1lI C,H-C H,OC.H. " ""l"ifed The abund"""" of fM CH, )" lad 1\11 - C, M. )· _ Icc C, H.( 11,OC H( ~H . IC',H , bo PfONI:>k. Ibnol. pernurwo ..hoorl O ~~~.~ ~.;. ruponn ely, l:>uJ I'" Sf*.'t1'..... of d'".1, 1d ha o.r~ ~ £D-+Utrl

co",,,,,

r.,..

-'

tlher]

~•

•

C....•

111.•• 4. /1. 4 /J TIw ro:tn>-[)od-. AkIcr ~ "' ~ lor . - - *"'I'C'''' " Tt T1Ic 10. 11l"lbl..-.'t "'ir 16-1 • , lot 1l'Co>noi ' pecTnlIn .. 1011- . 4 1). ,.I.-.nc] -",,,'0. btR

ru

or,be ....

or

1'Qt'I "'" ("'"

•

II

•

( lI j )

•

(11 61

"" '60\

,.._ ... -

..

_-

'"'

4 ./ 1, See f q,, ~ tjon, 1U and 11.8,

Oil!i
:j .

O=C>
(l l.7 )

....r 28.IOO'll.

.:"\

o

+ Ct~"

OCHz=

,,",r

28, '0&\>

4 . 1 ~ , See E Cl u a l ion. I I,~ l ,,1 1 13

v'~

-

'"

-'--

''''

c ,~

~

~~~. "' ~

""

~

.. '" ,

m'z 87

.....!!!- ......!L-

II ,

'1

r--', "'"' trI:z

---!tt..-

~

II

•

UI.91

'0'

): '("'~

\I 1.10)

"

'" "

~"

w

'd

"

II •

.~'" • • 00

1I1.1I)

"'0

'"

--'-

A... " "

']

0

"

II •

•

"t) ..

( 11 12)

' d

~

, ,,

tcA",o ,"

--'-

II •

::l" "

4.16, 0 7. Sa: ( q ...lI ion 11,14. L4. J 6. 2·pcnla n,me]

Jtl ~

~

"'I>

~,

~".

_

. . ""... ..

-"'-

0

00

4·Mel tl ~J- 2- pen l a ~ (Jne :

)

•

(ll.13)

4, J7, '-methyl.-

' '0

.J.-.-

. ,N

-"'-

0

II

•

~

{I I. H l

.,n

4./11. Tht " Wl'.."l moleculnr ion a t ...,'~ Dol (omaw. no "/I + r den'lt nl. (e"""p. ol~,. n h nJ I() or 11 c:lIl:>on . Il"",. wnml.lll witM C IoH ,.. Tilt W I ~·

' I"'ndlng r + dl> , al u. 014 i' Ihal e,pooled ror p/I. n~" : [hi. .. . uPf'<>l'ted I>y Ihe C, H, and C,H, m,illnment' for mi: 91 and 92.altd by 1M «a ro ma lic ion saiesw (So"' i,,,, .S.2), ,,,,,,,"Sling lh l Ih" mol<>:;,,\c i> a t :. H. C"H. ... omer_ v .... should lIa" e marked "'it 92, C,H" ... an important odd -de<:tro ll io n; ~ lhal iT is OD lhe h ;~h -m aSl sid. of the ba&c 1'",,1< (cuI< iii ScctI<>1l ) ,41. Dot h lho formation of C, H, · by n::.rran ~ltI<:n l and C, H, · 1» ' • .,;;Iea",!!" ind l<=l le Ihe """""';Ii"" i. u" snbstl!,,!ed (sre . lso T al>I< A.61 C. H,CH. - C , R, . "The low .. b uDdance .alio " r ",/ : 4V2'l il'Kli "" tel \hi<\ the nil )'1" ha in .. not b"",,"hed [Rul}Jh",-nn;J>C]

(11.1 5)

4./ 9 MaSin 4 ~. 13, and 87 prob.,b1y M \'r 1-..0. fo al l?l, . 00 five .arbo n ..tom , ",,,,I>, "lid \h" , <.'(In''''n " "" " ' Yl:"n al"''' "a, h. T ho: ri-Ap-plu. -do"ble, . 1"" "r «eh or,~ and n: i\ i! an e>en-dccrron ion. T he "" , .l l l ~ m i. a" ,>unobnu 1$ Wl I"'n e.penme nlal enol ol lhm n pccl.d for Ibe h... vy....,lope eOnl n hul,Oll '1(>Ill ";1 In . "The '00 lC lon lSo" ;on S,2j ",i. -'1, 4 S, 59. n , 117 ... ~ l l a hk A ·f'I1 I h~1 an ~"'"<)J,ol '" elher III""I;on II . domillnn! btu'" of lhe mo lt<:ulo: Ihe L, ck of tot · md ic! i, nOt It r.traidlt-clw.' D d hn . A . "".... n~"k h~p' ~ h", .... \ .... , mi. 1:Ill ;, lhe mokc" lar KMl, a nd lhat mf: 11 2 .. lhe \ tot _ 1&1· formed ~l lo S! <>I' H. O from an . k oho!. "The IDr llLll1011 of UOpor!3Dt DE" ' ion. from elhelh R 0 ' R', hy Ihe t".. or ROH i> un<:<.mmnn. F"'l h~..,., lhe 1,_ " r H, 0 from prim" ,y akoholl, RCIl , OH, .. so f~ tha i C.lI, . _, O· iom. are t """mtty of lower abundance. The "hundaDl 1M _. 43)· and 1M 57)' i"", intl;"a' . Ih" id':Tl (il)' "f lhe ,..·,yl alco ho l as C~ H~- CH OH---C>H , ; lilt lad 01 1M _ l ~l · Rnd 1M - 29t ion! iodle" l"" Iha l 1lteIe IS no cha in hranch mg, (A o extra cllK ;. the l"et~'I ..bl" io n or mi. ~h.S ; .... Section 6.4. Fo' II.e lJam'; li" n "'/. I:\()_ I I 2 a metan ab k! would be exf"'CIed 31 mi" %.4; "..,", 129 ---0 112 -..oukl appear at mi; 97.0, bot would in"",I" e Ihe uDllkriy 1_ of 17 am ll,) [4-OctanolJ 4,20. AJpha-<:lean gl: reaction. can r",ult in the I" " (b qualio" 1I.J6) of three difk " ,nl g ' ~: (: .,H , ', (:H , '. an d II·. The, e reactlom w;U pr oduce peakl ~t "'/ : J!ti, 114 , and 12 8, wllh abund ances decr.a,in~ in Ihi' ordcr a, prcdletcd by Ihe flOI< I", !IM' I<:J'" of the larb""l a;kyl gro up. Each of lhe"e lon' call underfo ~)'" of an olefin b)' cleavage <>I' aD N-C bond with hy d ro ~eD re..rn. ng. me" l \[.qllal;on 4,44~ See Fi~ \lf e 9,18 and Seclion 9.X f"r a m",. thorough discu« ian "r lh< ' ~ I ru m of Ihi' com pound. [Methylisopropylblllylam ine ] 4.1/ . Ma'" 1 7 ~ lh mi: 105 and 123 appear 10 contain , eyeD carbon atom. ,

"",nd>.

..

,

" , ....

_. -

" ""'-CI'~,---i.i-l-eM' 6H, ,

rrl z

+'"

y C-J<" CHt=N-----<:l1(CHsJ.

k

~,

.:ISI

, ,,,,,,,,- i.=cHCH 61-1:.

ee

r>.J- CoM" •

CH'4 -

'"'

(l L1 ~J

C~TCH,),

J

"" II.

"" l l Z!!

,..I-c....

'H!C.H ,

l+-t

CHCI1 •

H----7'=ClC">lt

'"

rri z sa

~, ~

Tbc Mi : 122 i , ,,[

~.

~n

que, ti ~na.bI<'

f'Knific.rn:c ~ ~ an ood-el. "tr on ion hcc,u<e of the " b andan! l1I/z- 1 Z~ i<>tl, h"...~",". lh. lWl.. -~ 6 pe~k . \M - J n t ', s.hould be

IIOted , A wea k alkyl. io ll ""t lfS IhrOllIl" C. is pTe""l , as is a u oromanc-ioo ""';n:

(\ •• S

(M •. , .\ 1' , (M - 29)'. an d

( M _ 4:1) ' , b ut instc:1J or 1M - 51)+ Ill.r< are th e m:lj. >t l<'N al (M - sst "",I /M ~ l · . ~' r om TaM. A.S U COm m on [,, " o f SS is 100J of C, H o from csu,-,; (d ~" bIo; .h ~ d ,, ~ rem ranKem
0
this; Tablt ,1,.6 imlica los a C<) ", s poll d in~ C. H. _ RV 1tn lclu,e. Two othcr ahundllnl Ions pro" j"" lhe final d "~ mi: n aod 105 ,"o" ld ~ phen}'l ",ld bon royl, lu g ~ • •ting t hat th e ooln )J<'llnd i, ~ bonyl ocn.llonl t ba n (M _ 4W, [But yl bl",""" tt:] 5.1. Altb o ul:h t n~ (lO"Slble m olecul;lr ' un I I mi t 128 prob~bly has tk wm~ , ilion C"H••• C. rOfmul~ ""nn" t he rllled Oul On tl>c h , i. of "",l"pi~ . bur>T he p w t...I>lc """",,ula, jou i, of hi\:h ' Iohilily: th. ", "'" Ic-w II'lIlP"<'hl fh bk A .6k The p"a k, of imporl ance , l lld t h c," rC"-'T1\ble the . ,oroa t oc lo.r,e also ly~, ".1 o r ~tomalic" The (o, mu/;o C , nH. JUl" ire, ,"ven m'lJ' p ial d o uble t<,n,J,. (10 - t + 1), Aga in , ,"",e" co: op<'<:l rn ,u lOId be occc " " r y In dootin lui, h he l ,",'Un the . ovorll1 i""""-·.... pn'iiSi b!c. [N l pb'l!,"'rn:J

da""",. M" "

"",N;,;

--_..._---

.1.1. M~" 86 appur . 10 hm'. the .l.m.llt~\ «,ml""'i l~'n C. H. O, Ie belte, dl«k .. ith iootupi. ~h Ulld u n ,, " , ( h~ n C , H , .O~ Ind for ""-'! 4 3 th. fOfmula C, H,C · j, definitely prefera ble. Moss I S should be C H ' . The "1'P<~Tano. 01 th. ' p'<':llum (tha t i•. domin"!«l hy rna.. 43 Ul ,u"e$l~ e . H,O and CH , KroUP» \hUL ~l'C readily 10.1. If th. ell , ,. f'Il ft ill ('l B, O. lh. bal" """ i. c o. TM ab~!\t. a S)'IIlfIlOWic "" toeIU",- ( :H ,(:O - ('O CII , (CH .,C O -C H- N'" H . , n, ,,, ld r rod""" addJli<>na l lrng.menl ionl), M0,1 other 0 , woul d be .~pcct.d tf 1M formulll fragm ent<. lbe i \l _. CH , I' iI. mu. h .... al.",. than C H, ' "'cau•• of ilS rc. d)' furl hel dii<S<><.iali" " by ""'" Co. When 1 ~ CII, _CO bo nd i••1.4 .~d, the charge j, p<.te, ab!)" ft'la.ned b) the C II, i ro n!'. [ 2,3- lIutancdiunt:] .1.3. Note th.1 1 d" a buooa l"X' of ",i, I ~ I 10 184 are identic.'ll to rbcee lc<:uJar io n t hat e ~n pwd uce the N ,i ; lOS fu g. mm t C, H,O ' ;0>. .. ell a. mi. 77 C.H , ' . T he abundance 0{ mi: I ~2 a >lahle molttular ion, in keeping with r + db '" 9, NoI iee th t the", ill a defuoi'$ m:emblance bet"" u n the . po.lra or u ~ ~ n"",·o, ~. I and 5.l; the pe.al« a l 39, SI, /)). ~o " n "'~I,'I.." t arn ma tle character. From The simpllcit y or Ihc "I'C'-'lJ"....... t he mulecu le ,h ould be generally nable, wil h o n~ 'If a fc,," h<>nds of mllch !li ~ h e r b bllit". T he "ompo,iti" m " f lhe majM fragment" C." , · and C, H,O ' , ... lKon "..mbin
<:."..

"r

'''"""l>I

ra. DZ<>p heno ocJ S .~. ""th the mi'" JJ9 and the III,'Z 1.'>6 re-k, COllu in """ n lind ""en C atoms. consi, teo! wit h the f{lfm ""'" C, H.UO and C, H,ClO" (r + db = 5,5 an_I S ~ KOhould rorrespond 10 C. H.O (r , dh '" 4. ~J. The miz 156 rulfi ll. tho rt:quirt:fIlMU fo r C\( +', Dl.ltl118 1he o the r t .. " t'"~k , (M - OHr and ('M _ CHO, l· • A cartx>~ rlI!f'l UP ...oold produce the<e and tho ", i : 45 peal< by ~. ~nJ i..."'le.I .a p The hi[th r + db n lu.. and lhe nq :lis ibk: ( :110, ' . uggeot thaI C. H. C1 is d llorOJ'lk nyl (ADlh= ,i ng i,o"","" ha,'" ncaTI ~ idmtk al m" SS spr<;tr",f [ ....<:h..' '''hcn''''''' acid] ' J, T he C.H ,_ . · inn ,or." i, strougly indi cated, "nJ ;t. ... i. tribuli..... • ho uld __ ' 1 Ihc .... Mi nched a lKane C I"H,. '" the wmpo.><.ln,J yieloli spec. trum ~.~ . IComp""$ t bL! &pccrrum to Figure, 3.2 and 5.2 )Of tbt C. " ,' ion. of Uol ..",.n 5.h. "'/ ' 2 11, lb9, nnd 85 are more ~hu~ < C,H , - C HlC,ll. ,-, roltp. bu l lbLS '" rrnJu" im pro bable by th. low ah~ndan"e oi lM _ C, H. t ; lhat n . tile II<"g
'.6.'.7.

C,., .oo

",_"_no llf'll"""iable I,," of C" C J ' C" or C., i, ver y ,, ~Iuable. T M H? and by IC ,H,j, CC 611 " (F or a ckt..lcd di" u"";I>n 'lee SecIio.m 9 I) [ Heu <J<,cl l\/:, ~ ·m et h }' lp ell l ad cc ~"", and , . prt'p}'llriJ e.:a ne] 5.8, lon-"" i.o int"rma li"n l Toatly tacil ita tes the ""Iulio n of ,"" un Ln" ..u, lle<:auS<' Ihen: i, M o~)·g.<-n p"'''n!, II>c poal<s a t mJr 13. ~ , 4), 51, and 71 ind icate lho ,orie, C.H , •• ,· for" '" ! - S. Thc is,'toj>Jc a blu>dallces of ",...-: 105. 92, and 91 indioale C. H. ' , C , H. ", and C , II . +, "" pect '~I) . , hi. and the P"'" euoe of Iho al kyl.;" " _iei ;tldic. '6 IT. !>" A.I» 11•• 1 tho ",n ..'ieo 11, 9 1, 105, 119, 133, 147, >nd 16 1 ' Cf'•..-:n'. <:. H ,(CH, l. ",II of tl><: C. H, . , , ' ion , orie. , The ~,y mJ ximum of "'iz 133 in tllo,: t' . H, ICIl , I, · ""ri o, i, not due lu eh~in hranch,ng: LtCI" ,...d in fun<:lionalia:d unt>ran , hed lox'" ...ao ;"", 'ICJ"',ated t>y - (0 1, 1, ~ Ik .",", ouch a. Im ty acid , (Fi~uIe ~.YJ. [Oclyl""n,one] '.9. $.10. ~ im por lanl ou - ,o rio, C.H , , · · in Ih, \lllf"-T flMI 01 bolh ' p"111 W\l.IlC' h (T a hle , 5.1, A.6) thai the UnkOO....ni " Ie C.:'H ,. , .. C. H boll Y m o1t_ ....1.... ""Le lhe.. ,or io, in FiguIe, 3,5. ~. K, .1 14. . nd 3.21. 'I1>c: OIoJ): real di rkI.n"" is !he prese nce OJ';1 .. -t 4 in dox" """. in Unkoo",n 5.9 wm.,rn.;nll'" jz ~ L 45, 59, 73. aD i, , he lugical candida t. 10 bot lhe "",lco,,!:" ion. which mean, lhal Ihe mol ecule conlaiDl> «II odd nllm""" ..! n it , o~en atom,. The ab undam ion. of nell ....... . w:b ~. 102 9!l, and 78 co uld In Ihll ",.. y be "'en_cleotr",, ion o, T he ~ il!h ."" ndl noe of th,. postubled mo leeul", ;ll n ,"" \lId 01", be lelll ",il h lhe J rOO" UIC·In:>c ltm ....-ric•. Agoin, ,ovora l j, onte n a~ po."bk: of doc formu la C. H .N I" " " ph.. d "u ~1c ~ , nd, 7), and roforell ~ lpoctra w<>"Jd " " , ~ mure """,Ii ,. idtllllrlc,llLCIl. [1s oq " i n o~n e ] j .l 1. lbe-r, un: ",w T..1 . ign, tha I this com po und i. q"ile .NT" renl r",m lhe p,«>:d i,,!! 1m.,.,. .\1a, ,,",, 76, 69, 50, 3I, a ud 26 lmvc a "", oleao i<m, OJ el"" l>as an odd nu m"", nil1'O!!en a l""' .. Simita d y, pr o... ,......" i" l,f M,/: 16, 50, and 26 are oitller od d·e lO1;\ru n i<~~m""l iu n.. OJ COJIlain an odd fium bl=r of ni lIO~en alom•. T h,," are fe.... or no 1l) ' ''OUpl of pea... in unit-rna" ,equenon, bke (l6.. t>1, M . I>'I~ l he pracl1cod nyn tn~y h...·c fou nd u ,'u luable due in I h ~ io n .. toe< or ma'<$O\ J l , 50, AIld W ('I<;e T a~k A 61 T he I ~ ok of hydrogen, 0'''''' lDal ... IM 1o"....... . J'C'lh of 12, 14, and 19 01,,« tn Iho OIom, ptOsellt. A.",mil>ll ....'I"~ 10 II< Ihe mo lecula, ion give, eorre, pon· d. nee b<:lw<."I:n w h. a l rna.""" l') . nd M - I ~, and al 26 and M - 26, , uW< tin~ ,he PIItl r - eF, eN. {T. iRue.......'C h .nillik) 5./ 5. Yo ur sn 10';(- 107), 91- 91. n - 79, nnd 63 6~ ; lh i, i, Ih" ehk"".l k)'1",n ..,ron. I..,tn pic abundon= indi
stlo....,

c,n,

""""i,-

_

"r

--__...... __.....

'"

fc~I ~~ ,.( TM .pectru....

romi n"DI wilM lh. dcm<:nl~1 Ct>Itll">Sll io,)n C . R 100 lor m ..... 14ll "" Ih" moJ""" la, iOD, AbLlnJanl pt~h oo r"",pondlDS I" (101 - C,H , l' I. "d 1M - CH ,t-1r . uU e' l Ill' , u b S lrt"~tu rc (; , H. -C_CII , O , fOl which a I<>v;i""l ", ,,k'.;~ ,,, would be (C , H , ), C{~ H , Cl . H" " ,,ver, tile fOIDld UCl < a r. con3idm ,d, (rM (', H. I - ] + [ C. II.."D> Ir(M C , H, )' ] + [C,H, ' l~ St.'·. llSOn', Ruk O(>prJo ri incon, isl"nl with Iho "h, "r..o:d a bundances, sinu Ihe i"n i ,~ti"n or an alk yl radi. al , h"\lld be lo d by U ........it.. ' ioD. 1I0w",'. r, bot h C.H. ' " "d C, H, • ean be Ionn. d at 1:>1 """"ndary docompo. i· tio n.. aod t"c i""" ' ( H(C',II, lCH , CI "nd ' C HIC. H.\C.ll,C'l can un derS" I,....a. ill HC I and C', H , CI (' e<; ~"" li" n ~.6 ). [J-(Chkl romC1hy l)""pt~"" J j,/ 4. Yo u , h,;>Ulol ha>. made The f~ IJowiag ~ "N h le auignmems: mi; 1.\ 1'\ M ' , (·. H. O CI: 107, (' ,11, 0 · , and!l4. C~H60 ' · . 0 [ " . A phenyl ring i, ind i· Cl iOy the aromali~·i"n .erie. . Ih<: h igh abundanc. of tho "'i: 77 i. a b irly ,. haN. ;n,(;~~li "n or ffi(>n""" b"""' lon ~ C, ".0' p"at indic,'.' th.u " , ) Il"n i , " l( a ~h o d to th. M g.1bo 1....1 Ihlt (M - ClIoCW i, m lll;" \.o, !",," IM O (M _ C11' is indi "",i "" Iobil< m . C'I il' 0u p; d Ct mi: 146 148 " pp"an ntt .hould SUl'lI"! ~IJ i""IOpic du ster, The IIIOSt proba bk ' U' I"'" " ul T d >k 2.1 ..... ..Iic< >n ~ nd ... lfu,. One atom "r . u\fur fit. thc rna' " 1 4~.' ' 1 46 Iatio belter, """ ,hi' l'O£lulalLOU Ieav., ~ re,iolual at "".-': 147 (cor recling r~r the "s ",'nlrihu rion from mi; U S), indicating . ight or Din<: carbon al"m, (c"T",...,.,ndm~y, SI, " '",,kl inolic~," approXimately C, ~ 5ulfu.r (or , ili. " n) I, al>o ind icalw in mit ~<;, t>ul '>ol iDma' ... . l l ~, <;~ , " r R4. A....m'''i tha i mit 146 i , 11><: m" ~~l a, ,a ll and ~~ nt ,, ; n , n" Itill'llgrn alom.. a "";.,., of abun.t. nt " J d...k.:1TUriI ion$ ;. .pp~ ron l ; ma.,,", 42, ~, Xl, 34, 'l ~ . ~ OO 112. Table A .~ ' USi"l'IS ao oItfut-ron ",rieo; the abu ndanl (M - M)<' aJld lM - ~Zl " indiu te a IhloL Th. i> , uJ1!"Ort.d by tho " U. yl·i on ".,ric< by 1M ",i l 4'). hI, 75, S~, I O ~ i, on ...it•. M ass 8~, more llg. "",m in u nbr~n chr:d nllyl Ih,ok (fqU li" n 4.42), For a dram~tic """fu mation of Ih" e~iole- ..... .. oom pm. Ihi, . peo;lr um rc Iho.. of , H.,,511 aDd ~-C,, " " O H, Figur"" J ~ I Knd 3.8. [OctanethtolJ 6.1. T he m.i: % .S lDef3OU1blc j> "id'ol """' .mal;On or tht mo lt]'oll: a bl",d. ace, of Ih.l ~r ge pco.ks indiQtc lhe ekmcnlaJ "am· ""';1;' _ CI-I. N, C,H,!'!, C: , H" N, altd C. H ..N . Th_ .re consi' tent "..ith

i"""

"""'fry

n.c

<"..

...c,

..vI

'" ,h. s.ol Uraled am Ine-ion serion, aDd a molec\ll~ l ~omp<>!Ili<m of C, H 10 N. The lartnl and _vnd l" rp pcah mrrL-."on "t C,". and CH" ~ 'JlO'.~ i> . I)~ 11>e1. -.b,mld be ethyl and m elhy~ but 110 la'llet alkyl, aroup' on the ca rbon alOJIJl ' ) alph a 1<> tho:; nil ro ~.n " lorn, H,,", c'-cr , m any ; '''mcTj~ C, H 1, N .min... til Ih... de""riplion . Th. lh,.. metastable ion peaks co, er, pon d to the decompo.iri un. 5 ~ I _ 3lJ' • 100' .• S ~ ·. and H6 ' --. 5H' _The m o.t "omm nn palh ",. ) C.H,. Io u from _ "h h un.. l« !ro n ions is l h. charge-sile rea,rang"mou! leOm On 4.44 in\'C)l~lll& c l .n~n 8 . ufth< C N b on d. Thu, the (M - C H , l' _ 4M_ C H ._ C , H.l' tn e!;on indi cate, lh. ,lnlclure CH , --C_ N __C , H" oIIxl 1M valh"", )'

r",

(1'.1

C, H, )' _ (M

C, H" -C , H.l ' in
N- C , H'" T he o nly C, H L , N i, o rner roDl llining bo th of Iht$e sII MINe"'.... ;. 1,NCII, CH,CH,. [ DiethyIprO(lyiantiDo]

tc.n,

6.1. (AI R, - K, - H, Y - II , ; (111 R, _ CH ,O. R, '" ca ; \' = HJ ; IC) R, _ CII ,O, R, _ CH" Y = 0; see Ilinnann 1% 2, p. .'OY, Th ~ peal< al

(M

~ ~J ' ;n A _nd H. a n'" 1M - 421' in C

", v

"

"''""

r:

J/

(

y

I,

~

-v

"

can t>r ~'rJ aintd "" 11 17.

_ rn H,~~V 11 1.17l

8.1. A , da li.d) abulldam (M _ 2)+ io n i, uu us ual iu moo, spoelra., SO lhe 164 /1 66 sho uld be cheeked 0111 a, Mp<,,,ibk: iMJ IOrHc dll","-, One hm min,: .hlm i, indi~alcd bl ,,-,"u'al . uch Ion [>I.;" T he ioo .....ies In,/z I ~, 29, 4lo H . H , and 85 indicate, aikyllo C. ' or !'O'lll>l y enboo)'l lo C " 1b< bro miru:-.:onlaill'PIl ;oll,e[ie, ,,,/;:; 79 ijl , 9 ~ ~ 5 , 107 IO'J, Ill-I n ""d I H- I J 7 gi ..,. .1rotI ~ ...... po rt 10 lhe pre""n"" Ol ,he I lkyl ~lIai n, . nd I., the IOnnula C.,H"Bt IOJ lhe "',/;:; 164 166 iOllS. The I"". or the: ...... U tll' yl , . dK>ol "h" old nm he f" "'f ed 0" ..- C. H, .Br ' k",< fro m the "me ca rbon; a I"" ,cal np" U1alion 101 1M l.r~t "'Iz 1J5 - 1J7 iotI< iJ; lhilt they u ~ I h r oo ~" Ihe d;' pl. ",m"," ,C,",-'1lt'n 4.42

11-Rromuhc. anc1 /1.1. The pr=uU'-Jepe"dtnl "";:; 180 pu t i> ploo. bly Ihu (M + I) ' ion (McLa fferty 1957b) and .. a pl'lo. imalcly ( ' , ,, flo{ ,. (In,." 1791 ,ncn co nlain, an odd nwn ba .>fni " ....g L"Tl .. ,om.. T h• ...iz 12(1 aoo 88 peab lon e ,'alues of 8 and 1, ""'l""'livdy. for lhei. mlU imulll number of c,u lxm atom,. Lo w-m"", peah ind ,cate 1M pl_n~ 01 ato mMOc ;,. ",I';llur ~..., J am ine (mi z 30) and oxygenaled r"l" 3 1.45) funOllt, nahtici. ... met hyl estel, - CO- OCH" i, a proba ble ~au ", tT . ble A,5) 01 the pea.. H;p,c'l(;nl;n s (M - 3 1)', (M - 321' , and (M - 59)',

-... _. ...._-_.

.....

'" mi.

I .... of , he IIl,,*"SI pe.Jb in lh. , peclrum.

~~

"nd 9l . cctlld arioe Ifom ctu""fe 01 ,he ""me "' ,nd (~ 8 + 91 _ 179); Iho mi: QI <: ('6 H .rn ,~ . The t"c~'c' c hal~ , etemiou by Ih. mi~ 88 , u"""to ...." bili...lior' by lhe a mi... moiely, - C}{( - /'I ' H , )(X I OC H .1 appears to be tbe onl y l"O"ibk Io?"up ron· I~m;ng ,Ioc =rM~ ymc lhyl func liolla lity; lhi' .liIo ;,. "" ""....en' with the hlllh ~ ooruia """ or m/: 120. Th. , n i~ 13 1 pea\; I"o ballly "rise$ from lbe <:omhin.d 1""0' of CH , O and NH•. [ I' i>cnylalanine met hyl CSIer] S.3. T h. ion or m,i: (0) should toe C" Ixt..... Oil the C. l:OmpoaillOD of mi: 88. Th< abundant 30, «, 51l, 72 lion .,... iI.. .... indiuall vc of a ...tllra l.d "min<:; lhe m/: 103 eompo,i(icm Ihu. ,hou!d be C , I I , . :S-O, and il pa""'-", the M " lem , Alph a clca , ag'" init ialed by lhe am me ' ho llkl Ix dominanl reaction, ; IhelM eH,)' a nd (M - CH ,O f' pea l . ,h... indicale lhe nwi.tie, /'I C .-(: H. and N C CH , O H. "",pM " hyd ro.• " l i, pre"nt, Th. l'," ' jble mole,"'b are M HOCli, CH 'CH"INH( :. H, . (h) HOC H, CH(CH , JN(CH , lr , (.1 11OC H,CK H. h NHCH , . (II) HOCH. CH,N HCH(CH,), . and (d IIOCH :(:H ,N ICH,lC,Il , ; no N ilo' a· lo", (M - H )" i' po, siN e fro'" ~ ..y ,,( ,hose. Th e 1>;0", m/z-]ll pc ~' ,hould ~ril e by the fllrth.r D 01 DJle oJ I I>< a .c1< . ,~ "" p,od UcTS {OIl' 88 '" 12) t h",..g h hyd ro l!'"D ""alfao",m" D' I( q ualion 4.44t thi' would not "" l'O" ible wllb tM I"rtlary amino>; " and e. h .><:I '(In ",; ~ uc n ... ro, the rem ainder ' hoold be.

".""pI

•

»:

HOCH,cH{CH,lN'H=<:H"

,"

......--- >oICQ1P;~ ~

"" »: "" , "" •

Y

~""~

~

-,"

........ =CHo

(m'z J(lI

~ H=WH.;,

1m', tilIl

CH,CH=N'''''

Im-'~ ""I

(11.18)

HClCH,C(ct<~~ ",C>i, ~ CI UIJ,I ,CtW~ · >
HOCH.;, G H .~ '

* -," --

H==(; HCH,

H >G~ ' HC H I G H , 1,

,"

+-Y>"===CHGl6. (""" "' )

-

(1l,20J 1".-, 301

I h~, " ' honid giw weal< tIIi ; .lOand « pc. h . The ",/<. 88 ion 01 a , hould ar tIe mainly b,.- I"", , ,( C H . rm m 1M more hL$ hly bm nchod ~--<:"rbon. ' 0 l h \ l",-.. " . ho uld be • li~nif,,:am ",-,. ·60 ipD. S" .....1 'l1'I' d cnr rcclly predict' Ih• • bulI· da nt "'.-'Z )0 and 44 pca1 0; no,e 1""-' ,he significant m/,-70 ion i' oon , i't\:DI wi,h Ih" >-Iahle . 1ruc1u l'e CI T, = CH- J'I'-- H - C HCH " l N-(2·h )dro. )'Clh)'I)- ,"I . tto propyl. ", i...]

m

"

,--.

--..

8.4 H~ " e you ""i~ncd the f"'m ula. C, H ,O, 1(> ",," H n d C, H, O 10 m,'z If ..." •. " " ""Tk th" problem assuming th. ... dlluo " . Ill JuWl;ro try. hig.... rno! u'i on mUI spectrometry. T h . ' >""trum ;. dim cu h beea .."" of t he .,• •"'Iy of ISONne ronnula. which "an I>c "I'l'ljc,d l!) each major ;OIL and been '" of rhe .bs< no;c oj a m,>Ic<:ullH ion. Y.l m Jny ~tud enl> a~ a\>le \Q 0'"'" at the "t>rrn.1. I t''''lu'''O un"qulvocaUy. How n er, ouch . "I><" gueu- u n ...r,m be >cry' ~.lu " bl •. F or , 11<-'11 \0\0" n!Ole.."lu·"";l(h1 co mpou nd s, th. liICk of M .' .uggcm • !.alurated , tructu r. (Ta hk ,'.4\ CH , O ' , C ,H ., O ·, and C,H ,O, · are lbr moot In4 ~~

>arab lc I'O"luLtl<'> lo r , h• • b undll nl >It/t 31, 45. Jnd 75 io ns, re,pc"ti ...~ y, T il....

m.l, 75 m""t ronl"'-D (" '0 fulKllon.:J ~ roup" ; tll«. i, no odd_eleot"'.. (M - IS)" ion w ind icale lha l ei1 l>cr" a "l'dr~ ,} sroup, The abundant CH , " . ,,"""" a C H,O moic1 y; ,d ali, " i,,,, 'lahiblies predict a low abundallCe ro. C H . " u..less il i. auached 10 an de c1 ron-J l traCl1n ~ ~w u p. Tho C H,O gro up ;'; prob:>b!j au"elled 10 CH , • • in"" il OaMol be par! 0( a C H , (X:HICH , l- VI C H , OCl C H., ), ..- gro up. If tm"e groupo \li . ~ r< . ~m.. tile aIIunJ,o....", OF lhe "'/: ~ 01 13 ioos, respectivd y, would he m..,-fI 8..... ler til. .. ;,; obsn" cd. J h. few ,,""" danl ;0", in lhe spectrum suU".;t . simpk molil£<J lha' ,lob " as nm " rigorous proof ot " ruolur. by rn"" ' ped m metry. bUI "" ' h", a .. ay 10 bypothe,i"" a pTOba ~ , trud ..1'e ...-bk" can lhe n be cbcclcd I;.,i ",\ rd cro""" ' ]'\I.",lt " 0' olhe, techniqun . [ Met b~ la IJ

(lUll

'\/

/ .;-" ~

CH,O -

"

CHl'J.

~

'OCI',

8,' , The rnass-12l ;'-"" "Pf'Ur1 1(> ha , e se,,,,, carboo atom, afid two ,"Yt"" ato m,. '0 it eould be C~ II.O : , T1fip·p1Il6·d.....l:>lc-txm d' .alue _ 5, The ../: . )04 i,m J'O"i bly ha' ""von calOOo a\orn.. u J 1\ .
_ . "' _00 __-

'"

t loc "",1<:<-1.11... i"n, .md it> at.u~d., JKX: indicate>. • hi~ld ~ >lab'" mol« . '" In lhe

low-m.. ..s "'t'On the ('!'Nomina nl ion "' " ... ;noo;

.'a)""

the rings-pluHI<Juble-1)ond, of S OJIlQJ'<.tIJ. 10 " '*""' J I ring 1'1". an ad ditional rin~ Or do.. blo be nd. l b e "' ril ing (M - W "... l indica!... 1h. pres· on"" of a lab ile bl'dro1:<'" atom, and 4M - 181' indi<:.' ln a rudy """ o f H ,0 (T"" " A5 "Im;",l' Inal thi, i. d oc I" a h},dr.... yl gm " r~ the (1.4 an d 1M - 29)- ion. are prob a bly C. IT. O " a nd C. II,O ", 1"l'5f'OdJ ~ly,
zat

~ 0-c: : ~ -

o=c

,./H

o~

;Y

';;c..

)

:

I

I

--L.

,-

H, O • C,.l-<.O

.

CO • C,HoO

(11.22)

~A The mi. \I'Ii9~ c~lio i, t<", l~rllC ror "'it 9~ to be Il>c ," o,"""l"r ion; t~e miz 84 mak e' "',i~ 99 a mllCb mo re like])' candida te. T his ouue>ts tha llh. mole,uk con t~im an ndd numbtI " f nitroi en atoms. conli , ten! WIth th. C. H. N a,,;gurnenl of m,i: 54 (EE- . r + db _ 2~ Bt:cau.. "'iz 59 . <mla;n. ox)'g.n (c E ' , r + db = OJ.lhe moM lolli, a] as"1I1lffiem lor m,i: 84 is C. H.NO (EE' , ' + db .. 2~ and lh"" C , H, N O 10' M " ' rhe , ignifi, ant rna". 31 , 4.\ ,,00 j9 ;'1nl , uU ,,.,1 ( h ble A.N an ak" b"l m elt", lunc\lonM>ly, For "'i: 54 Table: A.6 lu,~lt l­ C,H.CN. an d the pre..""" of a nimle grou p would . 1", e' rlain the unu. uaJ (M - J)' anJ [M - 17)' ;0_ n.c "'i: -59 i"" il most likel, H OC(CH sl. - , CH ,OClI (C1I, )---. or C, H,OCH , - , in ~gl" " r (1.1 - I ~ l ' .. (M - 2'W . The ""IJ of 11J<.,.., """p"!lbl. "'ith lhe ba.. ptak at ma.. 31 i\ C JH, OCH J - ' { /l-C ya nO<1 h)'1cl h) l d h...-]

<m.

'" r-... ,.

Gl-l,c..,ocH,CH.c'i

Il

-_. -

CH, .

+ CH, = OCH, CH,c N

( li B )

m,M (11 .24)

'1~ --.L!!..-

C,H. " HO= CH l ( ( !.H j

M.7. The mh -l50 ion appun to hJ" e C, and 0., co m p
tent ..,ifb C. a nd 0 . rom poncn l' ;~ nl,!: 165. Th. ma..-l04 peak !I... .. IOU 'm Um "I' ..,,,,,.... "" rbom a tom, . T ilt ",/. - 4~ 1011 i! OIOpo r ~\ ;(" p<J;n\ to u.., wrnl") ""'." tIC .. gnifi""~1 ,'en.:.. . ugp.'01" decl ron~ al i".. , ul>Slitu.ntl, Th e ubundant 1M - J ~t indical" ra.:1Ie 1_ of CH , . and lhc m/= 43 1M 4~J I m. k" the a"'tyl group, -COCH ... ~ p<)Wl tok "''''''''' " r thi, 1o... I[ the """t, '1 gr~\\p il Kttactml to I"" ph,:ny l. lben 12'l ~aI L"" 11.26 otfers an oxplaoatlon fur .ho a ~ ~ nJ" nl -..'z 104. Tbi<. """"mJl'O\lllOQ of an " ,'en _electro n inn to yield an I l>u nd om odd -<:lcn• • greup coma;", 16.\ - (76 + 4)) _ 4 ~ amu. and is probabl)' NO , . C·, II. NO, I"'.. .: I SH) - C , H. O (mi, 1(4), L<>.. <>I NO i. Iyri",,-l of ",t'.....""'... IT.~I" " .s~ mi' 120 may b. ()vi C H, - NOr , a nd",;z ~~ ....y be 1M - C H., CO - :-': 0) " , l l,· Nitm ac. tophelloDtl

",,
I"'.

Y--';~--eo·

-----!....--

y ••

c"H,cO' P U6)

IIII Th . mokenla, coml""'l'~ 'n , oI lb< ", Ir 148 ",,~k ooukl be C,-, H, OCI. from lh. l. ol<>pic 0bundan"", Tllli oorr~"". 1'-' Ihe ' eplaf the elem.O' l uf C H ,0 , in D O E by a n <>' Yl en awm. and an incroa", in the rin~,.pla •• ,h ,a C>le. bo nds \'alae r...... 'J I.. 10 . ')'1le m,'. 248 I"'ak po" ,,, ti><: le'" fOl' !II<' moleculor '''''. Ib= are n<> <>Ih", Pl''' l . ' I)m ~inin8 more than t..,o chlorino; ;u< """ SII'QfI@add nional C\'i,!<;nc-crot lhep,ese""" or OXY ~. ll i. p"OvXlM by the abaad.1nt OE ' i.... ~I mi' 22(; lhi, , houM repre:>\Onl tho [0 "" r,(CO, IliIlCt C, H. ""', '"'''akl .... a nlikely Irom a h' llhly ar"m alic molecale. No te , hI I~. p'''''''.... ckfnt'l\. l rom """ t", n of tbe O E - ' j"n or m,i. I SO is e , ." •. II can conlain n<>

--... _........

.....,.....

~.

cM<m "" (W "" /11<"'. 60 it mu,", be (M _ Cl, - CO)" , Thi, i. also evidenoe '''''1 2211 " (M _ C O ) ' . not (M - C, H. )· . f\ L,,~ ( XI I"... the o t - ' ion of pe~' a pheuol os endO<)'clic "" . oo o}'l group; ,he lauer would Mron,is. ten t ...il ~ t"" ,'~"m;"'U1 Iori",,1 molecule. [3,6-Dic hlorolllloreoonel

'UUC'"

m".

(11.27)

,he

S P. mi;; 303 peak eorr.""po nd, In _ " ...... i.... opOc a buod ances to the M" of eoc.,ine, a Dd th e relati, e a bundall(:e ." thO. ~ i. """,,
of thi, cyclic molecule, There is aD a' oma.!c-ioo ....-ies.: the I"omi""nt

(611~ &2. and % inn, arc c,,",i,t.cnt with IIJl

EE· l;>" ydo alkylaminc _ lOS and"'-", a.n (IE " cyd "" lkyl serie, (Table A.61: , hese are a l,..-, . 1.If'...." lal. by the ~1nm­ t"",,l'o "" to ,he k"" .... C tH. from th i, ion tEquation 4,311. rC<><:amel

-.-

--

1l1 .2l!)

ll.lO, TIle p f(>t m!: 177. There i . pro bably a , ulfur atom in the rcab at ",,'; 143, l .l I . 104. ,lid 61. To ca k ulate the ckmcnll C, H" . Nnnc of th. tom

". """,ma l•• mi. 177 a, the mol«ulu i<m, C , H, , NO, S. O ther odd ~ I" U ions au diffICult to idfmif)' \><:can"", . ... ' h. 1"" "'0"" of the n;tro!!,:;" a' ''''' The la[~. n uml!<'r " f fuOC!io '>aJ gr<>nps presco t "",k"" it ""'u ;, low-rna" ion "'"'" In lIoe all yl amine III:li<"Io M,/: J.O ap pears to be l ~. <Jnly ion of lmportaGCC; Th.. In''l pin. an aw'e.:lcilbk (M 11) I indi""tc a ru e amine gro up. or I ~. ;,m ",,,i.e, 01 T abk A.6 ront;u ni", ""If" •. the altyrltiol or , lI!fide """ic. "'iz 41, ~ I , 75 offer " Itro"t...-e ,,-,,"gn mem lor lbe . nU" r atnm in ll>c ......!ecu.., The rM _ 151' . (M _ N j". aDd (M _ 261 ' a TO r u ,, ~ lL I J a, e.0; due to a _ _by] , ulfide. nod ' hi, "'''''''' ''' lilt u , ignment o! CH, SCH . · n 1M >lruclUre " f lhe base peal 41",/, 1\1 arod for the aroul' k>" in m""I 11 6 T he 1M _. 731' i, expcelN (Eq u t,OI' 11 . 2~J far K_ CO OC , II , ....hen

-,.

l r*l,

R--c~ ,

1l.. .:t H:::.-cOClCA

R ' i••,. hili.red, " och .. ,"'cu,,,

(Dr

.. . ~

11 U ~)

" "I ,mno m;i ,h (Tab le A.S), The ,,~hle

It - al$O . """ uuh for Ibe lack of the e.p.",lc'\l (M - C,H . t · Mnd (M - C ,II ,,- ,

,Ii,

mu'JI h. w: a ma"$ of 177 102 _ 75. 3nd mu,1 "DOl "i n R_· CHi'; H,CO OC CH.,SCH, - , <0 tha t the m"k,cula, >trlleture CH )SCH,Cil>CH ~H ,cooe ,H, is illdic. ted. "The lionnalioo of ~i: ~ " ratinnoliud w Equal..... II.W [ Methioni"" < "I.it 75 p". k l;~n"'01 he ~ + ' , "'i: 61 wD ulJ then be l M - 14)' . TI>< """,ci ty " I " "t D-rna" pc.ah ind ICates Ih" t Ihe leu. M " i. at aB ~ ""n mil"' " ~ m be , , A, a«mHe...! '''H''" r""cT i ona ~ t y i, ind icated by ,he 3 L 4~. (59, 13] i" n u ric,; " , ec,,!O d D'U' h m ,J;e ~' cd b)' mi. 7 ~ and 61 (C , H , 0 , '; C,H.O ' , hn uld n,,1 occu, in th;, " bunola" e, wit h"ut ;('>/l"",,,I,,,,uk "'''''hOC!" "1' 0, lbo "liz 62 ednno, t>e C, H , .O' , TI1, mcla. l" b!<' io" pea k at 10.. : 111.4 indie. !.. Ih. l 10/1 M c~ ... 10'" 11 , 0 (30.4- _ 43'.. .6 1~ lht ...."'1 logic~1 ' tr ucture_ fo r it Il ~ -C1l1OC H,O H an d - ( :-I llO H1C H , O H, Th, ,. aro _ i~ 1f",. n , 0" ' - ;00$.' ".,iz 74. ~ 2, and 44 (and- 1! ' UMl YOG m",,~ 1""",'.0. The "'.,.. hhl ~ fTJ' lU-" " fo, m.i~ 74 [otm" lion" lito 1M' of H, 0 (or R OJt ~ 10 ",it n (74 + 1gj, C , H , O.\ , () f " higher h.....>olo/t- ;,. a ",,..,i l'> lt candidat, I'm , he M " . Compou~,l, , uel1 a, HOCII , C H, O<1--I , O H 3J1d CtI,a CH ,()(: H , O fl llh labl<) ,ho ul. a 101l",nl.l!rorn ativc; bydrO*"lI lt dllanllorncnt can expla in the ....z 62 and 44 pea ls IEquali"n 11 .3O\. f G lyttrolJ ~ / 2. Th " mit 141 he M O' if' l ~ " n ta i n< an odd nllmhL.. of nittOIi,n " I,m,, ; it ~pp"ars lo' ,~"'I~j" C.NO (n, C ,"', OI. and m f ; 126 corre ,poBd, ,<> C,NO. Tile P""'"""'~ of - 1\n ck'1l\O "!S F , ooi
" ".Id

·... .... y~

_.._._-_. r Ho a

00

0

Il.. •

'"

(' ~'Q

: .1<00

r

!.

~, ~

a nd mi. T!, C ,. The latt>:. l M .. 691' pea k lUll thus l<m ollly C , ; a I~ l a ""gn"",nl is (M - C F, IT, wh",h "I",. lI.""nunl, lo r the inloM ",}: 69~. C F, ' , Th". M" ' . I>ould beC ~ H . NOF " r ... db _ I. The unlll ua ltM - 211' ~' n mu. t be d ue III , he 1, .... of C , H, . nnt HCN , '" .. <:y,"" de "" ould lfll.ui.. r + d b >- I; Table A.5 ru U "'lO tllat an eth yl amide ,,,'uld """'...." I" , (~ - <-·. H , I' , . or .. IIWlecuL'lr ,truct:u re CF,CO NIIC,J t" Th i••bould . 1>0,.- In inl.........(M - CH, ," :mot! ... i. n by el"''''ah'''' ~lph~ to tl><: nit ru ll"" l" ocll('>O, . 00 at "'/ : '11 . 0<1 12 (a t a i,,! by ck,a , agcs alr ba to l b. carn.' n j'l rU" eli" " . N<.>le t""t Il><: h j' rear r. n,..,mellt de<:<>mpositio n of ..i. 12 by ~ eaCtlOl' 4.44 yield, "'if 44: H C H, CH , ",-H -C - o _ C , H ~ + H ,N ' ---C - o, [ £ Ihyl ln lh!oro" :Kctamierie< i' consistellt with an .Ih ne, and Ibe DE ' i£ E ' pe" k pa in ,ne o\wiou,l~' tl1 o"" al "'/: l 10i21I, B ~i239, aoo 2Nii261, cor res.ponding to " . ,·alue. of 15, 17. • n....}'lM"'. ,,,",c'D< , C"H" (tt>. R ' an d (R - lIj- ' pe.h ol'e not important). For the f()fm ur a R , R ' R T , l ,, ~ n ' + I -f tho probable M -' Lon al m,/> :"1:11) i, C,H oOllr. Don'l , kip lhe ' lcl" in the Standard Inl"tpt "la. lion Pl'Ooedlll"! T h. rean angem. nt 10" of C, II. eonnot C«ur if the C , II . moidy i, dir""II } attaeh<XI to the riog; tho 10" i' likel}, however. ift h. moiety i9 atlached to a nother olom (, uch os OX}'gcnJ ",Ili"h ;, a ltac hed 10 lb" ring . [po flromophenyl cth yl " ther] ,,3. Calculati on' (}n i, ol',pic ollundance, , ugge", ",,,m,,nlal e" ml" ",it i" n, " f C .H oO. and C . H,0, for Ihe peaks at mi. 166. a nd r49. re,pectively ( ring ~plu~ · dou hle_hond. ,'aluc ror e""h cqu" ls 6j, T he OF " m/: ·166 ion i9 " 10ii~" l "'lJId i -

w",

'"

J a le r", In. n", lc. ula, ion. T h. ,..,au cllarac ler i'li" low-rna" arom ali. ion<, 'm d the ;meow pea.. a, m.; 1 4~ [( '>1 - 17)' :1 ",iz 12 1 [ (M - 17 - 28)' ) , an d mi; 45 (C HU, ' ~ I"ov;,;,k ' ln1n~ cyi" ~i y ", mi, I22 and J 4h pcak , of much hi!.'". , .nandan,," (4~ ~'; and 5 '~,~). ( r. ~phlha ljc acid] ~,1, _ "'lpha de"." ~. of th. ll-;, omer k ad s to two r<'" il:>le radical ,pecic"~

\ (lUI)

(lUll

",'r 99

". ""i[h~r

of which " In abstract II byd",!!,," t tl give "',/: Y'I (C , H_O, ' ) l>y m"' i.._ Equ~l; "n Y.42. f or 1M I?·h lo d.ri" l flve. bo..." ',,r, .>-d ..... '. . or loc ","ake"l "" nd It ad' 10 lIIi: 99. 9,5, The i' N " p!C alm nJ ano;e, "I ll.e "', Z 1 ~ 4 ",d ICa l.. Ihe wmp<",;!i<m (\H coOS. , + db _ 4: [hi, pea k P ~ ISU lhe "' . 'es" .I "" ll>c '" i. an aro malicion , er ie,. and tho pea k, "I 6Q. 82, 9~ 7. un" ((~ ........ " "idc noe fur sulfur al1iKhod to an "rom " I;" rin~ (Tahle A.61, "lIh" u. h a Ib,opb.n.. ,,,t>.t,,ul~d ";I~ an un""l · urated or cyclic group is 31.., possib l ~. Th. "'/J 47 a nd /'II """k> indi ca, .. thal ;rn alkyl mo iet y i' al"" a\\,••:I...' tor'\> forma li"" md ude Equa· (ion 4.].6 wjt h a. and Ee of ,1 h ~ dlt" y l gr oup, JXl"ib!y in an ",lJ>" pt».iu""- is indiQl~ l>~ Ihe p;~l ~l ",i. 121,

ni,m, , imlla. to

•

•

(M - C H , - 11, 0 1- . The mfz 98 ,,1M!. pJ ."ti m~I:>I) , '17 l""ak lltjU,onlaill . ul!ur, and Ihus appd r~otlJ ...-c(M - (', H. - CO)" and (M C , R, C H()j' , con· -';, 1<... \ ...-iln ~ r nenolic-l)'p" hy<1rox)'1 ~"-'Ul', l Un) ! ,,.h~'d"-'>.Yrh"nyl ~u1fid~J "'./I. Ir rna.. 101 is rh~ mok cuT3T in" . il m uM cont. in ao odd numhcr 01 nil rof"'O ~ Iom .. Thc 1M ~ CIl , )' ion ~ppears to nay" JIi) mor" Iha n fou r car· 00 11 "1" ...,,• • JMl "'i: 59 10 h.. ... 1-"'0 ""loon ~I "m-, an J no mort Ihan 000 o. y;cn i I,,,,, , A llY ~""o--elCOlr(>n i~~ ",rica " r Tshle A,6 Ih~l jnclude, m/: 59 i, r uled (lUI t>, r~ M it""" "huoo~n=, In ract the jdenlit y of Ini, ion fragm"nl is a major h ') In It.< id",n iry ofUnkno-..'n 9.~. Wilh a max im um of C, and 0 " and " 'ilh t he rndJC81N vr<'" ,n.. ol' ~ i \TOgen_ lhe for m ula C,H"NO i, a logical JXlstu. LlIe 101 "'i: ,~Il. ,,00 i' all ndd-dectron 10". 1M - 42)-', T able A.7 sug~"'I' H , NC(X ' H , - Z -11 01 HO:-; -CHCH, - Z - H; for Z, 42 am u, T;< ,,""ihle an, Ide and m:j me str uclure' al"" requ ire> " " dy " f ' ....-crenee l l"'Clra of similJ r com pound" LJ- MOlh}'IMl lyrami
,"

(11.34)