Durga Nath Dhar Preeti Dhar
C0 2 Me
THE CHEMISTRY OF
CHLOROSULFONYL ISOCYANATE
THE CHEMISTRY OF
CHLOROSULFONYL ISOCYANATE
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A,
THE CHEMISTRY OF
^,.f A-
CH LOROSU LFONY tH ISOCYANATE Durga Nath Dhar Indian Institute of Technology, Kanpur, India
Preeti Dhar State University of New York, New Paltz, USA
\?Q World Scientific wb
New Jersey Jersey-London-Singapore' • London • Singapore • Hong Kong
J
Published by World Scientific Publishing Co. Pte. Ltd. P O Box 128, Farrer Road, Singapore 912805 USA office: Suite IB, 1060 Main Street, River Edge, NJ 07661 UK office: 57 Shelton Street, Covent Garden, London WC2H 9HE
British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library.
THE CHEMISTRY OF CHLOROSULFONYL ISOCYANATE Copyright © 2002 by World Scientific Publishing Co. Pte. Ltd. All rights reserved. This book, or parts thereof, may not be reproduced in any form or by any means, electronic or mechanical, including photocopying, recording or any information storage and retrieval system now known or to be invented, without written permission from the Publisher.
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ISBN 981-238-081-7
This book is printed on acid-free paper.
Printed in Singapore by Uto-Print
Dedicated to the Memory of Professor Derek Barton
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Preface
Chlorosulfonyl isocyanate, CSI, was discovered by Graf in 1952. Since that time it has become a subject of increasing interest and importance. It has served as a precursor for the synthesis of a variety of useful products such as pharmaceutical compounds, herbicides, pesticides, liquid crystals, sweetener intermediates, and bleaching catalysts for detergents. In this book we have woven the work of CSI investigators (references covering the period upto August 2001, through the Chemical Abstracts) into a unified treatment for researchers interested in the chemistry of chlorosulfonyl isocyanate. The book is divided into two parts. Part I deals with reactions and Part II focuses on applications. Introductory remarks about CSI, its properties, and the method of its synthesis are incorporated before Part I. This is followed by the outlines of the reactions of CSI with a wide variety of substrates. We have presented the substrates according to the established format, viz., aromatic and alicyclic hydrocarbons, alkenes (mono-, di-, tri- and tetra substituted), dienes (conjugated and unconjugated) including allenes, tri-and tetraenes (conjugated and unconjugated), conjugated pentaenes, alkynes, alcohols, vie. diols, thioalcohols, phenols, ethers, carbonyl compounds (and their derivatives), amines and their derivativies, and the substrates containing silicon, nitrogen, phosphorus, oxygen and sulfur atom(s). Amongst polyfunctional substrates only one functional group has been arbitrarily chosen as the basis of their classification. In part I, sequential numbers are assigned to each reaction to provide access to these through the author index I. Index is referenced to these numbers rather than to page numbers. The table of contents is organized to serve as a subject index. The significant applications of CSI in the preparation of useful
Vll
viii
Preface
products is the theme of part II. The data reported therein have been carefully extracted from the published patent literature. The material on the subject has been classified under the following headings: Herbicides, Pesticides and Insecticides, Anti-viral and Anticancer Compounds, Biologically Active Compounds, Antibiotics and Miscellaneous Category of Compounds. References are given to original papers and patent literature, and are accompanied with Chemical Abstracts (CA) references. An author Index (part II) is provided. Literature references are reported in the conventional manner and journal abbreviations correspond (with a few exceptions, vide infra) to those adopted by the American Chemical Abstracts. Some important journals have been abbreviated, as for example, Journal of the American Chemical Society (referred to as JACS), Journal of Organic Chemistry (JOC), Journal of Chemical Society Chemical Communications (JCS Chem. Comm.) and Liebig's Annalen der chemie as 'Ann.' In the event of our omission or citation with less emphasis than deserved, we ask for your indulgence and tolerance. In spite of shortcomings, if any, we hope that this book will not only be a source of information, but it will also serve as a stimulus for more creativity in synthesis involving the use of chlorosulfonyl isocyanate.
Acknowledgements
The writing of the book was financed by a generous grant, received from the U.P. Council of Science & Technology, (CST), Lucknow, and we gratefully acknowledge the same. In particular we thank Dr. A.N. Pathak, Director, CST, for evincing keen interest in the progress of the project. We appreciate the help of DND's former students who have assisted in various ways. They are Prof. Anil Kumar Singh of IIT Mumbai, Dr. Sajan P. Joseph of Eli Lilly Research Laboratories, Indiana, USA., and Dr. Pramod Kumar of Lupin Laboratories, Bhopal. We thank Dr. Mridula Saxena for literature searching and proof reading, Namita Sumbli for editing, and Dr. Amrika Singh for checking the references. A personal gratitude is due to Roopa Dhar and Surinder Tikoo, whose support and encouragement in the most critical moments was a real source of strength. We also thank Pankaj, Sonali, and Ravinder for their patience and understanding.
Durga Nath Dhar Preeti Dhar Lucknow, India New Paltz, USA
ix
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Contents
Dedication
v
Preface
vii
Acknowledgements
ix
Introduction
1
Properties
1
Synthesis
2
References
2
Parti C S I Reactions
CSI Reactions
7
Aromatic Hydrocarbons
7
Cycloalkanes
7
Mono-Substituted Alkenes
10
1.1 - Disubstituted Alkenes
14
1.2 - Disubstituted Alkenes
22
Tri-Substituted Alkenes
38
Tetra-Substituted Alkenes
48
xii
Contents
Conjugated Dienes
51
Unconjugated Dienes
60
Allenes
67
Conjugated Trienes
77
Unconjugated Trienes
79
Conjugated Tetraenes
82
Unconjugated Tetraenes
84
Conjugated Pentaenes
86
Acetylenes
87
Alcohols
91
Vic. Diols
104
Thioalchols
105
Phenols
105
Ethers/Epoxides
109
Peroxide
114
Ketenes
115
Thioketenes
115
Aldehydes
116
Acetals
118
Ketones
119
Ketals
133
Diketones
134
Contents
xm
Triketones
134
Acids
135
Esters
139
Thioesters
142
Amides
144
Sulfonamides
149
Chlorinating Agent
153
Acid Chloride
153
Amino and Imino Compounds
154
Nitrogen Compounds
167
Azaridines/Azirines
167
Nitrogen Heterocycles
170
Compounds Containing >= N -
176
Compounds Containing - N = O
182
Cyanides
183
Diazo, Azido Compounds
184
Oxygen Heterocycles
185
Sulfur Containing Compounds
187
Sulfur Heterocycles
192
Organo-Silicon Compounds
193
Organo-Phosphorus Compounds
195
Miscellaneous Reactions
196
Contents
XIV
Part II CSI Applications II-1
II-2 II-3
II-4
199
Herbicides, Plant Growth Regulators/Inhibitors and Plant Protection Agents
201
Pesticides, Insecticides and Fungicides
228
Anti-viral, Anti-cancer and Anti-HIV Compounds
233
Biological Activities
239
Analgesics/anti-inflammatory compounds
239
Anti-allergies
246
Anti-proliferative/anti-tumor agents
247
Neuroleptics
248
Anti-convulsants
250
Anti-degenerative agents
251
Anti-coagulants
252
Blood related problems
256
Platelet aggregation, induction/inhibition
256
Hypoglycemics
256
Brain related problems
258
Contents
Eye disorders
258
Heart related disorders
259
Disorders of stomach & gastrointestinal tract
262
Bioartificiai insulin distributor membranes
263
Bronchial asthma
263
CNS related disorders
264
Lipid/cholesterol lowering agents
264
Antibiotics
265
Growth hormone release promoters
267
Antagonists
269
Inhibitors
271
Chelation & diagnostics
276
Miscellaneous activities
277
Antibiotics
279
Azetidinones
279
Azabicyclo [3.2.0] heptenones
286
Carbapenems
291
Cephalosporins
296
Cephems
302
Beta Lactams
305
Contents
XVI
II- 6
Penems
306
Penicillins
308
Thenamycins
309
Miscellaneous antibiotics
311
Miscellaneous Applications
317
Author Index I
323
Author Index II
339
References
355
Introduction The reagent-Chlorosulfonyl isocyanate (CSI) was discovered by Graf in Germany in the early fifties. Since that time it has generated widespread research interest and a number of publications, including several review articles1"8, on CSI have appeared in the literature. Chlorosulfonyl isocyanate, C1S0 2 NC0, formula weight 141.5, is also known as N-Carbonyl sulfamoyl chloride. Properties •
Clear, colourless, mobile liquid.
•
Melting point,-43°C.
•
Boiling point, 107 - 108°/760 mm (38°/50mm).
•
Density, d 4 20 ,1.626.
•
Refractive index, n D 27 1.4435.
•
Infrared spectrum shows characteristic absorption due to : vas - N = C = 0, 2240 - 2220 cm"1 v a s S0 2 , 1390-1370 cm"1. v
a s S0 2 ,1190-1180
cm"1.
•
The dihedral angle of gauche conformer of Cl-S - N = C is 94° (~ 98°) and that NCO group is not linear for the lowest energy conformer of CSI (based on micro-wave spectroscopic data). 9 , 1 0
•
Thermally stable upto 300°C.
•
It possesses a choking smell.
•
Fumes on exposure to humid air, and reacts violently with water.
•
The following can be employed as solvents/diluents in reactions involving the use of CSI: CH 2 C1 2 , CHC13, CC14, C 6 H 5 C1, Et 2 0, (C3U7%0,
1
CH 3 CN and
2
CSI Reactions
and S03(1). Me 2 CO and MeC0 2 Et may also be employed as solvents for CSI, to a limited extent, but at low temperatures. Caution If CSI accidently comes in contact with skin, the area should be immediately flushed with a large quantity of water. Synthesis The first synthesis of chlorosulfonyl isocyanate was reported by Graf,1 '' 12 , and consists the interaction of equimolecular quantities of cyanogen chloride and sulfur trioxide: CI CN + S 0 3 -> C1S0 2 NC0 In this connection a spate of attemps 13 " 18 have been reported essentially based on the above reaction, but under different experimental conditions. The highest yield of Chlorosulfonyl isocyanate (87%) has been reported in a Japanese patent 14 . References 1.
Ulrich, H., Chem. Revs. 65, 369 (1965).
2.
Graf, R.,Angew, Chem. Int. Ed.,1', 172(1968).
3.
Rasmussen, J.K. and Hassner, A., Chem. Revs. 76, 389 (1976).
4.
Szabo, W.A,,AldrichimicaActa,
5.
Dhar, D.N., and Keshava Murthy, K.S., Synthesis, 437 (1986).
10,23 (1977).
6.
Kamal,A.andSattur, P.B.,Heterocycles, 26, 1051 (1987).
7.
Liu,Z.,Chen,D.,
8.
Yang,X., U,Z.,HechengHuaxue,4,3\
9.
Jo, O.L., Graybeal, J.D., Lovas, F.J., Suenram, R.D., J. Mol. Spectros. 152, 261(1992).
Huaxue Shiji,l 1,26 (1989)., d . I l l , 77460' (1989). (1996). C. A. 125,221381 (1996).
10. Durig, J.R., Zhou, L., Gaunev, T.K., Guirgis, G.A. Spectrochim Acta, 53 (A), 1581 (1997). 11.
Graf, R., Chem. Ber., 89, 1071 (1956).
CSI Reactions
3
12. Graf, R., German Patent 928, 896, C. A. 51,4419 (1957). 13. Niermann, H., Diskowski, H., Roszinski, H., Tiedermann, J., Martin, W. (Hoechst A.G.) Eur. PatentAppl. EP 294,613, DE Appl. 3,719, 305, C. A. I l l , 9240 w (1989). 14. Nakamura, A., Ono, M., Ataka, T., Noguchi, S., Shirakawa, H., Segawa, H., Japan Kokai Tokkyo Koho JP 01, 228, 955, Chem. Abstr. 112, 79957 e (1990). 15. Nakamura, A , Ono, M., Ataka, T., Japanese Patent JP 01463063, C. A. 117, 17079J (1992). 16. Schlegel, G., Lachhein, S., Berger, H.,Eur. Pat, Appl. EP 501, 369. C. A.,11$, 8613° (1993). 17. Cieslewski, T., Chuck, R., Gross, M., Galli, M.P., Swiss Patent CH 680, 292, C. A., 118, 23641 l r (1993). 18. Ogawa, T., Yano, K., (Sumitomo Chemical Co., Ltd., Japan), Japanese patent JP 2000053630, C.A. 132,167972, (2000).
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Part I CSI Reactions
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CSI Reactions
CSI Reactions Aromatic Hydrocarbons Reaction Number x
x i) CSI, AICI3
I
CONH2
> •
(1)
frjy
2o-3o°c ii) Hydrolysis
Graf, R., (Farbwerke Hoechst A.G.), German Patent 1010958, Chem. ZbL, 2569 (1958). (Farbwerke Hoechst A.G.), German Patent 1002331, Chem. ZbL, 10336 (1957). Chem. Ber.,92, 509 (1959). CONH2
sC^sd^sC^
m
i) CSI, Toluene
s£z^£s^s~^
OOO ^r^
TOO
ii) Hydrolysis
Graf, R., Ann., 661, 111 (1963)., German Patent 941, 847., C.A. 51, 14789(1957). Cycloalkanes
Me Me
(3)
wJ*
Me
A
CSI,CH 2 CI 2
rl
M e
**
~|
Me K \
f-»
.N—L
/ SO2CI
+ H
/
X
=
^o
Me
\ CH(Me)CONH2
<"'•) Mo/ Me
7
\
CONH2
CSI Reactions Me Me H
Me / - Me
Me_ CSI, CH2 Cl2
Me.
r.t.
1
A~S>
CIO2S
Mi
(74%) Me Me Me CSI, CH2 Cl2
Me.
—71
CMe3
Me3Ci
,N\ ~O . CI02S/ (65%)
Mi
<
H
CH2 CONH2 (22%)
Moriconi, E.J., Kelly, J.F., Salomone, R.A., JOC, 33, 3448 (1968). o
,a
i) CSI, CH2 CI2, - 7 8 u g
(4)
ii) NaOH - aq. Acetone Tricyclo [4.1.0.0] - heptane
NH
O
(37%)
(9%)
V i)CSI,CH 2 Cl2,-78 C
A/
t*
ii) NaOH - aq. Acetone
i) CSI, CH2 CI2, -
»
c
^ SOt- • <J(
ii) Ph SH - pyridine
Me
Methyl-substituted bicyclo [1.1.0] butanes Me i)CSI,CH2Cl2-78°C
/
O
ii) Ph SH - pyridine
P
Me
NH
(15.5%)
CSI Reactions
L
9
i) CSI, CH2 Cl2, - 7 8 C >•
ii) NaOH - aq. Acetone
•l>
Bicyclo [2.1.0] pentane
+
[
CONH2
NH
(31%)
(7%)
o
CSI, ether -78°C Hexacyclic bis bicyclo [1.1.0] butanes.
^A.... H
*
o
VA,„H ,H
+
^E
(33%) R = SO2 CI R =H
Paquette, L.A., Allen (Jr.) G.R., Broadhurst, M.J., JACS, 93,4503 (1971). Paquette, L.A., Lau, C.J., Rogers, R.D., JACS, 110, 2592 (1988). Borror, A.L., Chinoporos, E., Filosa, M.P., Herchen, S.R., Petersen, C.P., Stern, C.A., Onan, K.D., JOC, 53, 2047 (1988).
o
i) CSI, ether, - 78C ii) Na 2 S 0 3 / OH
M
O
?
Me
"• HN
Mi
^Me
(5) (90%)
(6.8%)
Sasaki, T., Hayakawa, K., Manabe, T., Nishida, S.,JACS, 103, 565 (1981).
10
CSI Reactions
Mono-Substituted Alkenes R
\
(6) v '
> /
/ < S.
H
CSI, hV or — — - — : — - » , (Peroxydicarbonate ester)
c i C H R CH2 SO2 N C O
H
(60-90%)
(R = H, Me, Et, Bu, C1CH-,, Cl 2 CHCH 2 )
Wegener, P., Riemenschneider, W., Ulmschneider, D., (Hoechst A.G.), Eur. Pat. Appl. E.P. 53, 331, C.A. 97, 1443592 (1982). Gunther, D., Soldan, F., Chem. Ber. 103, 663 (1970). /R (7)
CSI
CH 2 = CH R
-NH
( / (R = A l l y l , C H 2 C H 2 B r . )
Pfaendler, H.R., Rudolf, S.,Ann.,9\
1 (1987). H
(g)
AcO - CH = CH2
i) CSI
AcO—J-
ii) Hydrolysis
N \ /
<^ O (62%)
Mickel, SJ., Hsiao, C.N., Miller, M.J., Org. Synth. 65, 135 (1987). (9)
ROCH = CH 2
CSI
RO-CH-CH2
I
I
RS0 2 - N - Cv
R O - C H = CH
+
I RSO2 - HN - CV
Effenberger, F., Gleiter, R., Chem. Ber., 97, 1576 (1964) l)CSI,-40OC (.1UJ
.
Vinyl acetate ii) Na2 SO3 - aq. Na HCO3
/
.0 V NH (38%)
Crombie, L., Haigh, D., Jones, R.C.F., Matzin, Ab. R.,JCSPerkin
Trans.
CSI Reactions
(11)
H2C = CH
11
•Br
CSI, CH3 CN
(CH2)2 Br
>
-NH
f
r.t.
O
(9%)
Pfaendler, H.R., Strasser, R.,Ann., 911 (1987). H
(12)
"\ / / = H ^ %H2l
,CH2I ii)Hydr0lySiS
" J
NH
NH O
TL>
(Thienamycin Intermediate)
Tanaka, T., Miyavdera, T., Heterocycles, 19, 1497 (1982).
r
,Ph
CSI
(13)
O
N
_/
Hydrolysis
0
S 0 2 CI
^
Ph
%
Begley, M.J., Crombie, L., Raymond, D.H., Jones, C.F., Osborne, S., Webester, R.A.B., JCSPerkin Trans. I, 2027 (1993). Vorbruggen, H., Krolikiewicz, K., Tetrahedron, 50, 6549 (1994). i) CSI
(14)
CH2 - CH2 - CH = CH 2
I
Ph
23°C,40h
3 - Phenethy p - Lactam
ii) Na H CO3, Na H SO3 (CH2 Cl2 - H2 O ; 50 : 75)
Zablocki, J.A., Tjoeng, F.S., Bovy, P.R., Miyano, M., Garland, R.B., Williams, K., Schretzman, L., Zupec, M.E., Rico, J.G. Lindmark, R.J., Toth, M.V., Mc Mackins, D.E., Adams, S.P., Panzerknodle, S.G., Nicholson, N.S., Taite, B.B., Salyers, A.K., King, L.W., Campion, J.G., Feigen, L.P. Bio-organic & Med. Chem., 3, 539 (1995).
CSI Reactions
12
OSi Me3
CSI
•Si M e 3
(15)
CCI4, 0 C, 0.5 h
-Si Me 3
N SO2 CI
Si Me3
CSI.CCI4
o-25°c*
^
y — \ S0 O
2
Na 2 CO3 (aq.)
CI
Concentration in Cold
Si Me3
J
-NH (60%)
Me3SicT
^NS02CI
Colvin, E.W., Monteith, M., JCS Chem. Comm.,1230 (1990). CSI
(16)
Si Me 3
at 0 ° 0
• CI OSi03 : N SO2 CI
Pyridine at 0 ° C '
CN
Deleris, G., Dunogues, T., Calas, R., J. Organomet. Chem., 116, C45C48(1976). OSi Me3
(17)
y
Si Me3
CSI, CCI4,
0°C,0.5h
^ \ X ^ > N S 0 2 CI
Colvin, E.W., Monteith, M., JCS Chem. Comm., 1230 (1990).
CSI Reactions
13
-YX^"
i)CSI,CCl4, - 1 5 ° C
(18)
M
\
Si
/ *
^^• x/
18h
Cl
—N
Me
Me
>
ii) Na HC0 3 , Na 2 SO3
78%
Gehanne, S., Giammaruco, M., Taddei, M., Ulivi, P., Tet. Lett., 35, 2047 (1994).
(19)
CSI 6 o
X
o R = - CH - CH 2 O
O
X R2
>
H
X
n
OCSI.PhMe,-78°C } Jr
100 Min.
6 O
R1
NH
O ii) Na 2 CO3
(A) H
>l
R1
O (B)
f
O O (54%) > <
(46%)
O
X
Example compound: R1 = CH 2 OTIBS; R2 = OBzh. Kaluza, Z., Furman, B., Chmielewski, M., Tet. Asymm., 6, 1719 (1995).
CSI Reactions
14
l ^ \
(20)
cs.
^
N
O
^
*
°
\ °0
Hall, R.H., Jordaan, A., Lourens, GJ., JCS Perkin Trans. I, 38 (1973). Hall, R.H., Jordaan, A, De Villiers, O.G., JCSPerkin Trans. I, 626 (1975). 1,1- Disubstituted Alkenes
R
o= (21)
RR1C = CH 2
>• (Pressure bottle)
(Volatile alkenes)
N
(80
K
. 970/,,)
Hauser, F.M., Ellenberger, S.R., Synthesis, 324 (1987). 1 - Chlorosulfonyl - 4, 4 - dimethy azetidin - 2 - one
Me
(22)
_£?i
==y \Me
alkaline hydrolysis 4, 4 - Dimethylazetidin - 2 - one
Black, D.S.C., Boscacci, A.B., Aust. J. Chem.,30, 1109 (1977).
CSI Reactions
15 Me
(23)
I
Me
/
H2C = C - CH2 CONH S 0 2 CI (30% unsatd. N - chlorosulfonylamide
CSI
H2C = C Me
0=C
N-S02CI Me Me
(70%)
(3- lactam N - Sulfonyl Chloride
Graf. R, (Farbweke Hoechst A.G.), German Patent 941847, (1953), Chem. Zbl. 1297(1957). (Farbwerke Hoechst A.G.), German Patent 1119277, (1958), Chem., Zbl. 27-2304(1964). Ann. 661, 111 (1963) Org. Synth., 46,51 (1966). Clauss, K., Tet. Lett., 15,1271 (1974).
Me
Me
i) CSI, Et 2 O
Me
- 65 to - 5°C 3h
(24) CH 2
ii) Na 2 S 0 3 , NaHC0 3 pH, 7; 1/2 h.
Me
/
\
O
R
Schoen, W.R., Pissono, J.M., Prendergast, K., Wyvratt, (Jr.), M.J., Fischer, M.H., Cheng, K., Chan, W.W.S., Butler, B., Smith, R.G., Ball, R.G., J. Med. Chem., 37, 897 (1994).
(25)
i) CSI
^
ii) Hydrolysis
=
0
N
I H
Espie, J.C., Rassat, A., Bull. Soc. Chim. Fr., 4385 (1971). Espie, J.C., Ramasseul, R., Rassat, A., Tet. Lett., 19, 795 (1978).
CSI Reactions
16
Me
(26)
Me
^H
>=<^
M e
2
C / \
H
CMe3CSI, C H 2 C I 2
—
—**
0°C,'/ih
CMe 3
N
1
rCIS0 i e n /2
+
H2C
CH2-CO-NH2
^° (67%)
(22%)
Moriconi, E.J., Kelly, J.F., Salomone, R.A., JOC, 33, 3448 (1968). OAc
OAc I
i) CSI, Et 2 O, 0 ° C \
iONEta/CHsCN*
/
^
CONH S 0 2 CI
(27)
NEt3, CH 2 Cl 2 OAc T
/
^^N/VWVW
CN
Vorbriiggen, H., Krolikiewicz, K., Tetrahedron, 50, 6549 (1994). •CI
.CI i)CSI,4cPc > ii) NaHC0 3
(28)
N
O
H
(73%)
Methyallyl Chloride Clauss, K., Tet. Lett., 15,1271 (1974).
S CH 2
(29)
i)CSI,-60°C
-NH
1
<
Barton, TJ.,Rogido,RJ.,JCSChem.
ii) Hydrolysis
A
Comm., 878(1972).
(53%)
CSI Reactions
Ph.
Ph.
(30)
17
^f
> =
CH2
/ w w w CONH S 0 2 CI
CSI / CH2 Cl2 / \
(88%)
Bentel, P., Adolphi, H., Kiehs, K., Ger. Offen., 2, 249, 939 (1974); C.A. 81, 13108 b (1974).
^e:
(31)
CH 2
O
/ CSI
N-S02CI
<
\
Ph
(92%)
Ph
Isaacs, N.S., Chem. Soc. Revs., 5, 181(1976). Bertian,H., Pure Applied Chem., 27, 611(1971). Ulrich, H., "Cycloaddition Reactions of Heterocumulenes " Academic Press, Inc., New York, NY., pp. 135 -141 (1967). Ph
(32)
^>
:CH2 CSI
<5B
A, ^
Ph trans - 2 - phenylpropenyl Cyclopropane
S0 2 CI
o
Pasto, D.J., Chen., A.F.-T., Tet. Lett., 14,713 (1973).
(33)
'V
Ph CSI
> / ciso 2
Graf. R.,Ann., 611, 111 (1963).
V
CSI Reactions
18
SnBu 3
(34)
<
c
H2I
i)CSI,-4(Pc »
c DPh h ^ •S
H ^
ii) NaH S 0 3
Sn Bu 3
sSPh N
(85%)
Imanieh, H., MacLeod, D., Quayle, P., Tet. Lett., 30, 2689 (1989).
r
i) CSI, CH 2 Cl 2
4?
(35)
i ii) Na 2 SO3 (aq.)
-NH
Aue, D.H., Iwahashi, H., Shellhamer, D.F., Tet. Lett, 14, 3719 (1973). CIS0 2 - N
CH 2
f
CSI
(36) Me 3 C^ / /
Me
'
3
C
N
Dunkelblum, E., Tetrahedron, 32, 975 (1976) r£
^^r
-r
™
(37)
Ph
1—r o
x
so2ci
Et3N CH3CN 0
Ph-
(85)
s
Vorbriiggen, H., Krolikiewicz, K., Tetrahedron, 50, 6549 (1994). Ph
Ph CSI,Et20
(38) 0°C
NH
CH 2 (67%)
O
Barret, A.G.M., Betts, M.J., Fenwick, A., JOC, 50, 169 (1985).
CN
CSI Reactions
CH 2
.0
i)CSI,CH 2 CI 2
(CH2)n (39)
19
-70°C
v
LA
(CHty" 2)i
|j
NH N
ii) Ph SH-Py./Acetone
Spirovinyl cyclopropanes
0°C, 1 h.
Sarel, S., Felzenstein, A. Yovell, J., Tet. Lett., 17,451 (1976). Langbeheim, M., Sarel, S., Tet. Lett, 19, 2613 (1978).
J^
(40)
2
(CH2)n
i)CSI,0°C ^ X
^ " V
ii)Na 2 S0 3
>=0
\ A " ^ H
( X = CH; CC^Me)
Langbeheim, M., Sarel, S., Tet. Lett., 19, 2613 (1978).
,
S 0 2 CI
/ i)CSI,CH 2 CI 2 ^ •60°C
(41)
o
\ N = / \^
A
\ (84%)
Na 2 SO3
(53%)
.of
y\
Hogeveen, H., Zwart, L., JOC, 44, 1365 (1979).
20
CSI Reactions
y
(42)
! / i)CSI,-60uc » ii) Hydrolysis
NH
(75%)
O
Malpass, J.R.,Tweedle, N.J,,/OSCAe/n. Comm., 1244(1972). Sasaki, T., Eguchi, S., Yamada, H., JOC, 38, 679 (1973).
CSI 60
a -Fenchene
'- °C o ^ ^ HSQ 2
+
H02SN'
^
o
Malpass, J.R., Tweedle,N.J.,
V 0
V o 25 C
(44) N-O
CHCONH2 (6.5%) [X = SQ2 CI, H]
Sasaki, T., Eguchi, S., Yamada, H., JOC, 38, 679 (1973).
CSI Reactions
21
i) CSI, - 78 u c
(45)
» ii) Na2 SO3 (aq.) (48%)
Sasaki, T., Eguchi, S., Hirako, Y., Tetrahedron, 32, 437 (1976).
CSI, 60UC
(46)
Q
°^r
CIS02N^\
NSO2 CI
Doyle, T.W., Conway, T.T., Tet. Lett., 10,1889 (1969).
V
V i) CSI
(47)
ii) Hydrolysis
Longifolene O
NH 2
Mehta, G., Dhar, D.N., Suri, S.C, Ind., J. Chem., 16B, 87 (1978).
i) CSI
(48) ii) Na2 SO3
,§H
7 - Methylene quadricylane
Paquette, L.A., Broadhurst, M.J.,y<9C, 38, 1893 (1973).
CSI Reactions
22
i)CSI, CH2CI2, r.t.
>
(49)
ii) Na2 SO3 (aq.)
11-Methylene-9, 10-dihydro9, 10-ethanoanthracene
Ciganek,E.,yOC,45, 1505(1980). 1 , 2 - Disubstituted Alkenes hv,R» (50)
R1 CH = CH R 2
CI - CH - CH - SCb NCO
CSI
I
I
R1
R2
(R1 = R2 = Me; 92%)
2 - Chloroalkane sulfonyl Isocyanate(l) R2
R1
R3
2 (2- Chloroalkyl) - 3 - oxoisothia zolidine-1, 1-dioxide (II)
II
I R1
R2
Yield (%)
R1
R2
R3
H
H
84
H
H
C^H.2 CH^ CI
75
Me
H
90
Me
H
CH 2 C (Me)Cl
80
Et
H
70
C4H9
H
CH-j CH Cl C^ Hg 62
C4H9
H
63
a
H
11
CH 2 C1
H
73
CH 2 CI Cl 2
H
60
Cl 2 CH CH 2 CH CI Cl 2
H
3
Gunther, D. and Soldan, F., Chem. Ber., 103, 663 (1970).
Yield (%)
CSI Reactions
23
O Me
(51)
X. A.
CSI H
/
HN'
\
(Key Step) (CH2)6 OMe
Mi
(E-)
NH
\
(CH2)5 COOH
Jouany, M., Coustal, S., Frappier, F., Marquet, A., J. Chem. Res. Synop. J, 114(1982). Ph.
,Ph
V
(52)
Ph C H = C H Ph
CSI
»
N
^
Ph
Ph.
\
NaHCQ3 Na 2 S 0 3 - aq.
k
N
ciso 2 (47o/o) Friedrich, H.J., Tet. Lett., 12, 2981 (1971). R CH 2 CH = CH CH 2 R1-
CSI
4(RCH2-Substd.)-3(R1 CH 2 Substd.) - 2 - azetidin • one - 1 - sulfonyl Chloride
(53) R1 = H , Me R 2 = Me, Et, Pr.
Bestian, H., Biener, H., Clauss, K., Heyn, H., Ann., 718, 94 (1968).
(54)
R1 RV
,R1
CSI
Hydrolysis 0
S
\
CN
S 0 2 CI
Nativi, C , Perrotta, E., Ricci, A., Taddei, M., Tet. Lett., 32,2265 (1991).
CSI Reactions
24
R^
(55)
i)CSI
^
\ ^ \
S
i M e
R
w
^ ii)H 3 0 "*
3
Vinyl Silane
^
/x
y°
\ ^ N ^ NH2 ^
Page, P.C.B., Rosenthal, S., Williams, R.V., Synthesis, 621 (1988).
* (56)
©
<\ X>
r>
H
pi trans - P-Trimethylsilystyrene
\
H3 O -
OSi Me 3
Ns, /
NHo z
Ph
Barton, T.J., Rogido, R.J., JOC, 40, 582 (1975).
TrO. Me3Si
TrO. 10
i)CSI/Na 2 C0 3
^ f \
-78 °C. Toluene
]~1
H) Red-A.
O ^ N T ^
° ° -
H H^
(57)
U ± >
51%
Hydrolysis
..
HCL „. H H !
O
H
T
°Sylati°n
O^i
TsCX H
H
K 2 C0 3 /TBABr
H
0
o 0
H
Lysek, R., Kaluza, Z., Furman, B, Chmielewski, M., Tetrahedron, 54, 14065,(1998).
CSI Reactions
-Si Me2R1
(58)
25
i)CSI, CH2CI2.0 C^ (2hj *
Si Me 2 R 1 -NH
(R = C 3 H 7 ; R1 = CH 3 )
'') N a 2 SO3 - NaHC0 3 (aq.)
(40%)
Nativi, C , Perrotta, E., Ricci, A., Taddei, M., Tet. Lett., 32, 2265 (1991).
(59)
Me3 SL
_^j.
. si Me2 Ph
i) CSI, CCI4
Me 3 Si :
1 Si Me2 Ph
ii) Na2 SO3 aq. -NH
/
Colvin, E.W., Monteith, M.,JCSChem.
(50%)
Comm., 1230 (1990). Et
(60)
CSI, CH2 Cl2 0 0UC, 2H
w w w OAc
OAc
^ -NH
/
{Cis/trans; 48%) Kametani, T., Honda, T., Nakayama, A., Sasakai, Y., Mochizuki, T., Fukumoto, K.,JCSPerkin Trans., I, 2228 (1981).
X
i) CSI
(61)
=JWWVWOAC
ii) Na2 SO3
OAc
-NH
(R = H, Me)
/ (44%)
Kametani, T., Honda, T., Nakayama, A., Fukumoto, K., Heterocycles, 14,1967(1980). Ph
Ph
Ph
(62)
SMe
I
i) CSI
MeSv
ii) Hydrolysis
H N
HN.
cis - p - Methyl thiostyrene
1
ir O (12%)
ph
Ph .SMe
\ / \
^ IT O (2%)
I
-°
HN^^NH
Ph
Y o (1%)
Hirai, K., Matsuda, H., Kishida, Y., Chem. Pharm. Bull. Jpn.,2\,
1090
26
CSI Reactions
(1973). Matsuda, H., Hirai, K., Kishida, Y.,Ann. SankyoRes. Lab, 24, 96 (1972), C.A. 79, 5207P(1973).
(63)
V
CSI
D-A=,
°
(X = H; CI; Me)
X = CI; Yield, 63% X = Me; Yield, 66.4%
CSI (X = H) SPh
~©-' -N. \ <" S 0 C I 2
SPh
CONH2 H (12%)
H (10%)
(25%)
(40%)
Hirai, I., Matsuda, H., Kishida, Y., Chem. Pharm. Bull. Jpn., 21, 1090 (1973).
(64)
Matsuda, H., Hirai, K., Kishida, Y.,Ann. Sankyo Res. Lab., 24, 96 (1972), C.A. 79, 5207P(1973).
CSI Reactions
27 OR2
(65)
t i)BuOH(11.5eq.) BF3. OEt2(1.2eq.) r.t., 1 day
C02Et
«C02Et OR1
1 ii) CSI (1.5eq.)CH 2 CI 2 - 78°, 30 Min. H 2 0, 70°, overnight
R1
= H; R 2 =
BU'
1
R =CONH 2 ; R 2 = H R 1 = CONH 2 ; R 2 = SiEt3
Mi) CI Si Et 3 (1.1 eq.) imidazole, DMF, r.t.
R1 = CONH 2 ; R 2 = Si Me 2 But
Hirama, M., Shigemoto, T., Yamazaki, Y., Ito, S., Tet. Lett., 26,4133 (1985). Me2 Bu* Si
(66)
Me 2 Bu1 S i CSI
II x
x
NhK
0
! -SPh
SPh
CSI Me2 Bu4 Si O
H
H
?
SPh
MeoButSiO 1
H
S Ph
V
/ /
H
-NH
-NH
S
O
O
Nakatsuka, T., Iwata, H., Tanaka, R., Imajo, S., Ishiguro M., JCS Chem. Comm., 662(1991). O CSI
(67)
N
h
so2 ci
Berge, J.M., Roberts, S.M., Suschitzky, H. Kemp., J.E.G., J. Chem. Res. S, 255 (1978).
(68)
CSI
-NH
\ ,O DL - cis - azabicyclo [3.2.0] - heptan - 3 - one
Gomes, A.S., Coutinho, F.B., J.Polym. Sci. Polym. Lett. Ed., 20, 423
28
CSI Reactions
(1982). O CSI
(69)
Bicyclo [2.1.0]-pentene 1,3- Dinethyl bicyclo [1.1.0]-butene Me
CSI
Me
Volz, W.E., Paquette, L.A., Rogido, R.J., Barton, T.J., Chem., Ind. (London), 771 (1974).
(70)
i) CSI
Fp"
ii) Et 3 N F p = n5 - C 5 H 5 Fe (COg
CN
Giering, W.P., Raghu, S., Rosenblum, M., Cutler, A., Ehntholt, D., Fish, R.W.,JACS,94, 8251 (1972). H CSI - ether
(71)
/
S 0 2 CI
N
-30°C
\ (40 - 50%)
Dunkelblum, E., Shaviv, A.Jsr. J. Chem., 10, 971 (1972).
O
CSI Reactions
29
/ S 0 2 CI N Hydrolysis
(72)
-NH
(Na 2 S 2 O3) O (90%) >
CONHS0 2 CI
Gomes, A.S., Figuiredo, A.M., Org. Prep. Int., 5, 13 (1973) Graf, R.,Ann., 661, 111 (1963). Tabak, D., De Oliveira, P.A.M., Org. Prep. Proced. Int., 8, 243 (1976). / (73)
+ CSI
CI
hV/R« S 0 2 NCO
» •
(50%)
0 /
CI
Gunther, D., Soldan, F., Chem. Ber., 103, 663 (1970).
i) CSI / ether
(74) ii) Hydrolysis (35%)
30
CSI Reactions
Moriconi, E.J., Mazzocchi, ?.H.,JOC, 31, 1372 (1966).
/
i) CSI
(75)
CN
ii) Et 3 N, CH 2 Cl 2
Vorbriiggen, H., Krolikiewicz, K., Tetrahedron, 50, 6549 (1994).
(76)
/
CSI
CO NH S 0 2 CI
O
Dhar, D.N., Unpublished results.
S0 2 CI CSI, ether
(77)
-60°C
o
O
Fliri, A., Hohenlohe - Oehringen, K., Chem. Ber., 113, 607 (1980).
( C H 2 )
(78)
[^
^ J
+ +
rs,
CSI
Et2
°or » CH 2 Clo Cl 2 * CHo
(CH22))^n (CH I
^|
f N
(37%)
S
°
2 Cl
i) 4M NaOH/Acetone, 0°C or i) 25% Na 2 SO3 / 1 0 % KOH, 20°C
(CH 2 )n
CSI Reactions
31
Gocdgame, D.M.L., Hill, S.P.W., Lincoln, R., Quiros, M., Williams, D.J., Polyhedron, 12, 2753 (1993).
(79)
CSI — NS02CI
Jandralla, H., Laumen, K., Chem., Ber., 116, 2136 (1983) CH 2 OAc
o
(80)
CH 2 OAc i) CSI
) O /NHCO2 £*>
1 ii)KI
AcO
AcO
-. \
f
r
CSI
Tri - O - acetyl - D - glucal
o
OAc
AcO
CH 2 OAc
I —O AcO
Jordaan, A., Lourens, G.J., JCS. D. II, 581 (1971).
OAc O
OAc -O
(81)
OAc
Nl
CSI
}
.
^
(Lewis acid)
•
OAc
AcO
OAc O
>
AcO AcO
CSI Reactions
32
I
) | /
CSI K U
>.
RO
o
OR °
<
OR
OEt
)
(R = Ac, Me)
»•
< RO
NHCO2 Et + | OR
° > OH
Hall, R.H., Jordaan, A., Lourens, G.J., JCSPerkin Trans. I, 38 (1973). Hall, R.H., Jordaan, A., DeVilliers, O.G., JCSPerkin Trans. 1,626 (1975). Me
Me
(82)
4
Me
.0.
\
Me (40%)
Drew, M.G.B., Mann, J., Holland, H.J., Lewis, T., J. Chem. Res. Synop., 389(1987).
i) CSI/ether -78°C-r.t. > •
(83)
ii) Na2 SO3 / ether
0°C-r.t.
J>—NH O 40%
Mann, J., Overton, H.J., Tet. Lett., 26, 6133 (1985).
33
CSI Reactions TrO-
TrO
(84)
H
/ \
CSI / PhMe / Na2 C 0 3
.(X
H
^
/ \
-78°C
-NH
#
o9
O
(80%)
7^
Furman, B., Kaluza, Z., Chmielewski, M., Tetrahedron, 52,6109 (1996). OBn
OBn
" i OBn
CSI, Ph Me
(85)
/
- 50° C -NH [A] 56% [A : B ] : : 98 : 2
Ito, Y., Kobayashi, Y; Terashima, S., Tet. Lett., 30, 5631 (1989). Kobayashi, Y., Ito, Y., Terashima, S., Tetrahedron, 48, 55 (1992). O
(86)
0 ^ 0
\=l
(100%)
•20°C
1,3- Dioxole O
O
CSI
O
o
CIC7:/ CSI
Dihydro - p - dioxin
Lattrell, R.,Ann., 722, 132 (1969).
o
o \
CONH S 0 2 CI
34
CSI Reactions
(87) +
csi
Benzvalene
A
N-R
N yy s o 2 ci Christl, M., Brunn, E., Lanzendorfer, F., JACS, 106, 373 (1984).
V
f
i) CSI, ether
(88)
ii) Na 2 SQ 3 (aq.)
V
3
47%
A - Carene Sasaki, T., Eguchi, S., Yamada, U.,JOC, 38, 679 (1973).
(89)
o
i) CSI, CH 2 0 2 , - 7 8 " ^
(
&
ii) NaOH-aq. (51%)
Paquette, L.A., Allen (Jr.), G.R., Broadhurst, M.L,JACS, 93, 4503 (1971).
CSI Reactions
(90)
cK
35
VzJb
CSI
ciso2 Moriconi, E.J., Mazzocchi, P.H., JOC, 31, 1372 (1966).
CSI - Et 2 0
(91)
S0 2 CI
0°C-r.t.,6h
(86%)
O
Moriconi, E.J., Crawford, W.C., JOC, 33, 370 (1968).
(92)
N - SQ 2 CI
CSI
O (I)
(II )
Katz, T.J., Nicolaou, K.C., JACS, 96, 1948 (1974).
-NS02CI
CSI
(93)
,/
R/
Vo ^
(R = H, MeO, Me, CI, NO2)
,/
\
o so 2 ci
36
CSI Reactions
Mazzocchi, P.H., Harrison, A.M., Isr. J. Chem. , 2 1 , 164(1981). Harrison, A.M., Dissertation Abstr. Int. B., 42, 4423 (1982).
i) CSI - Et 2 0
(94)
•78°C
0
ii) Na 2 SQ 3 / OH
(69%)
Sasaki, T., Hayakawa, K., Manabe, T., Nishida, S.,JACS, 103, 565 (1981).
i) CSI
(95)
ii) Na2 SO3, KOH (aq.)
f (16%)
Syn-benzo-homobarrelene
NH
(4.0%)
(1-3%)
Volz, W.E., Paquette, L.A., JOC, 41, 57 (1976).
•
CSI Reactions
37
i) CSI
(96)
ii) DMF
VC0
2Me
CQ 2 Me
(50%)
N
I CO2 Me
CN i) CSI ii)DMF
N
I
CQ2Me
(22%)
N I CO2 Me
Natsumi, M., Kumadaki, S., Kanda, Y, Kiuchi, K., Tet. Lett., 14, 2335 (1973).
(97)
i) CSI I
C O N H
0
o
2
^ ^ ^
C=N
0
-H2O
ii) Hydrolysis
O Me N - Acetyl-1, 4benzo-oxazine
O
Me
O
Bartisch, H., Schwarz, Q.,Arch. Pharm., 315, 545 (1982).
Me
38
CSI Reactions
Tri-Substituted Alkenes
Me Me
Me Me
(98)
Me H S=<' +2CSIEt<0 N 'Me
OEt
N
[Q]> ~y
y
HN
NH
N
Y
CK^Y" SC ^ CI
Matterstock, K., (Farbwerke Hoechst, A.G.), unpublished results. Graf. R., Angew. Chem. Int. Ed. Engl., 7, 172 (1968).
(99)
CSI, 30 u c
>
U
CIS0 2
Si Me3
CSI, CCI 4
>
Si Me3
«o p
so2ci
Prenyl trimethylsilane
Deleris, G., Pillot, J.P., Rayez, J.C, Tetrahedron, 36, 2215 (1980).
3
woo v^/ '" I
63
2
''^r •
ii) Na2 SO3 (aq.) R=H R=H
R' = Me; R' = Si Mes;
Si Me3
f
O
•N
V
Yield (product): 36% R-R1, Me 2 C =
Nativi, C , Perrota, E., Ricci, A., Taddei, M., Tet. Lett.,32, 2265 (1991).
CSI Reactions
39
-SiMe 3 CSI,CCI 4
(101) >
0-25°C
Si M e
~[
#
H^
3
Na 2 SQ 3 (aq.)
so2ci
r
Concentration in Cold
N
O
Me 3 Si C r ^ N S 0
2
Si Me3 H
CI
Colvin,E.W.,Monteith,M., JCSChem. Comm., 1230(1990).
Me
(102)
Me
Me
CSI.CH2CI2 0 ° C :,'/2h
M«f~
Me
Me.
/
N
^
CIS0 2
O
(70%)
Me
^CHO\ CH (Me) CONH2 (8%)
Moriconi, E.J., Kelly, J.F. and Salomone, R.A., JOC, 33, 3448 (1968).
(103)
o
OMe
i)CSI, CHCI
Si Me3
(
0°C ' ii) HCI, H 2 O P
NH2
(48 - 52%)
R= n-C5Hn\
= n-C4H9 f
Page, P.C.B., Rosenthal, S., Williams, R.V., Synthesis, 621 (1988).
CSI Reactions
40
N.
(104)
. OR1
^\
CSI
Si Me3
NH2
Imanieh, H., MacLeod, D., Quayle, P., Peter, D., Gareth, M., Tet. Lett., 30,2689(1989). Me OAc
AJ\.
(105)
A
i) CSI, CH2 Cl2 Me
atO°C
Me
ii) Na2 SO3 (aq.)
O ^ N ^ M e H (28%) 5, 6 - Dihydro - 4, 6 - dimethyl -2(1H)pyridone
Bateson, J.H., Quinn, A.M., Smale, T.C., Southgate, R.,JCSPerkin Trans. 1,2219(1985). Et
CSI, CH2 CI2
(106)
N2 atm.
> Et-
OAc
\
OAc
E'
/
Et-
i c e - ethanol bath—>• r.t.
-N
s (70%)
O
\ i-
H
Shah, S.K., Dorn (Jr.) C.P., Finke, P.E., Hale, J.J., Hagmann, W.K., Brause, K.A., Chandler, G.O, Kissinger, A.L., Ashe, B.M., Weston, H., Knight, W.B., Maycock, A.L., Dellea, P.S., Fletcher, B.S., Hard, K.M., Mumford, R.A., Underwood, D.J., Doherty, J.B., J. Med. Chem.,2,5, 3745 (1992).
R^
(107)
R
0
AcCSI'CH2c|2
> = ^
o°C 2h-
R
' 5 days °
-/ J?
OAc Na2S03
N
NaHC03 S
0 2 CI
OAc R"
/ jr
N
°
Firestone, R.A., Barker, P.L., Pisano, J.M., Ashe, B.M., Dahlgren, M.E., Tetrahedron, 46, 2255 (1990).
CSI Reactions
R ' - C O C H =
(108)
41
R2
R2 R3
CSI
R3
X HN-
O
Q
+ •
%
R1 CO2
O
Clauss, K., Grimm, D., Prossel, G., Ann., 539 (1974).
R2 R2 ^tS
(109)
R1
V
R1 i) 2 CSI
D
ii) NaHCC-3
(R1 = R2 = R3 = alkyl, Aryl)
H
I
Y° R2' R3
o
v
Hollywood, F., Suschitzky, H., Hull, R., Synthesis, 662 (1982). Cis-1, 4- Polyisoprene
(110)
CSI, C6 H6
Me CH2CIO2SN
CH2
TCH = C (Me) CH (CONH SO2 CI) CH2 ^~
^ O
2M -NaOH refluxed
[CH = CMe CH - (CO2 Na) C H 2 I -
—fcH2 CMe (NHSO3 Na) CH (CO2) Na CH2] L
n
Jm
Van der Does, L., Hofman, J., Van Utteren, T.E.C., J. Polym. Sci. Polym. Lett. Ed., 11, 169(1973).
CSI Reactions
42
Me
Me
(111)
- £ CH 2 — C = CH — C H ^
+ CSI
». _ /
C
H 2 — C — CH — C H 2 X N —C = 0
so 2 ci Van der Velden, P.M., Smolders, C.A., J. Appl. Polymer. Sci., 20, 1153 (1976). Me (112)
- f CH2-C = CH-CH2-V
+
_^CH2-C-CH-CH2^
m
0° - 20°C
CSI
^CH2 - C = CH - CH 2 A -
N-C = 0
I
SO2CI
Hydrolysis 2N-NaOHat100°C
1.65N-NH40H at r.t.
Me
Me
_^CH2-C-CH-CH2-^ Jz V, I I n HN C
< C H 2 - C = CH-CH2
A-
K
J n
s
\ ^Na©
sof N ©
Polyelectrolyte
Me
Me
_^CH2-C-CH-CH2^j \ , i O 'a NH 1
c
£CH2 - C = CH - CH2 A V /n-
\ ^ NH2
SOrNH4
Van der Velden, P.M., Smolders, C.A., J. Appl. Polym. Sci., 21, 1445 (1977).
CSI Reactions
43 Me
Me
Me
Me
Me
(113)
+ csi
Me
\
X,
/"—V o
CISO„ CSI
Me CH
2
=
O
Me
C
C=
CH
C
NHS0 2 CI
Barton, T.J., Rogido, R., Clardy, J.C, Tet. Lett, 11, 2081 (1970).
,n4)
CX>
^ c^ Q£>=< • H
CONH S 0 2 CI
•Ph
Ph
Carey, F.A. and Neergaard, J.R.,JOC, 36, 2731 (1971).
CSI, - 70°C
(115) &
V warm
/
O
CIO2S
(50%)
Malpass, J.R., Tet. Lett, 13,4951 (1972).
(20%)
S 0 2 CI
CSI Reactions
44
i)CSI, - 60°
(116)
ii) NaOH
7
NH (53%)
Furst, G.T., Wachsman, M.A., Pieroni, J., White, J.G., Moriconi, E.J., Tetrahedron, 29, 1675 (1973). Sasaki, T., Eguchi, S., Yamada, U.,JOC, 38, 679 (1973). Malpass,J.R.,7ef.Zett., 13,4951 (1972).
P
i) CSI, rt l""i^\
/-. HCI/EtOH
ii) KOH, Na 2 S0 3
\"'*i~
v
H
Reflux
<
i^COOEt ^<
""M'-I^NI | " " ' * E > NH:
(117)
<S-o„
a**•'Vao,
^ , e ^ (e
ne
^ - ^ C O O E t
LAH/THF
— O ^ - L | "»-^f*NHCOOEt
Reflux
H
-£T |
0H
''*^T*NHMe
Szakonyi, Z., Martinek, T., Hetenyi, A., Fulop, F., Tet. Asymm., 11, 4571 (2000).
CSI Reactions
45
H
CN
.STol
(118)
I
j^
I
^
g C |
^
0 A c
STo
|
I
j
^
(39%)
N
OAc
Takemoto, Y., Ohra, T., Yonetoku, Y., Imanishi, T., Iwata, C , JCS Chem. Comm., 192(1992).
( 1 1 9 )
,
,
„
DCS. ii) Hydrolysis
Thujopsene
Mehta, G., Dhar, D.N., Suri, S.C.,Ind. J. Chem., 16B, 87 (1978). H
H E COOH
O
(120) Me
^
*
E Me
\
H = COOR ROH SOCI2
(^J S*"<+*
. ^ NH2 Me
j^NH2 Me
H
H l S*'«-m'
^^ ( ^ , ALJrrLJC :
N
OH
t^ NH2 Me
Szakonyi, Z., Fiilop, F., Bernath, G., Evanics, F., Riddell, F.G., Tetrahedron, 54,1013(1998).
CSI Reactions
46
Me
Me
(121) CSI
3 - Chlorosulfonyl - 1 , 8 , 8 trimethyl - 3 - azatricyclo [5.2.1.0] nonan - 4 - one.
Me (Structure based on X-ray Crystallographic data).
Waschman, M.A., Crowley, J., White, J.G., Z Kristallogr., 156, 137 (1981).
NH2
(122)
CC - cedrene
Mehta, G., Dhar, D.N., Suri, S.C, Ind. J. Chem., 16B, 87 (1978).
CSI - ether
(123)
)
reflux-120 h.
/
i)
< (63%)
r
O (R = S02 CI, H)
Moriconi, E.J., Crawford, W.C., JOC, 33, 370 (1968).
A i) CSI H
(124)
ii) Hydrolysis — H
Isolongifolene
CONH2
Mehta, G., Dhar, D.N., Suri, S.C, Ind. J. Chem., 16B, 87 (1978)
47
CSI Reactions
(125)
NSO2CI
+
Me O2 O" Methyl photolevopimerate
MeO — 6
H O
(12%)
Mehta, G., Dhar, D.N., Suri, S.C, Bhadbhade, M.M., Venkatesan, K., Ind. J, Chem., 20B, 193 (1981).
48
CSI Reactions
Tetra-Substituted Alkenes
>n<
i) CSI
(126)
^
ii) Hydrolysis
rf
\ .N
O'
H
(100%)
R. Graf. Angew. Chem. Int. Ed. Engl, 7, 172 (1968); Cossio, F., Roa, G., Lecea, B., Ugalde, J.M., JACS, 111, 12306 (1995). R1
(127)
Rt
.R3
i) CSI
> R2-
•R4
ii) Hydrolysis
R3
R4
R2-
V
,/
R1
R2, H2/
R 3
„„
I ,,R4
I
\
COOH
Meyers, A.I., "Heterocycles in Organic Synthesis " John Wiley & Sons, Inc., New York, NY., pp. 285-286(1974). R1 •
(128) R
4^
R 2
CSI - CH2 Cl2
"""1
•R3 PhSH - Py. Acetone
R1 R4
R4
\
CIC^S^
R2
Et R3 I + CH3 CH = CH - CH - CONH2 \ O a = 82% b = 85 c = 47 d = 74
R2 /.. R 3
Na = 96% b = 88 c = 68 d = 80
a; R1 = Ph; R2 = Me; R3 = R4 = H b; R1 = Ph; R3 = Me; R2 = R 4 = H c; R1 = R2 = Et; R3 = R 4 = H d; R1 = R3 = Et; R2 = R4 = H
Moriconi, E.J., Kelly, J.F., Tet. Lett., 9, 1435 (1968). JOC, 33, 3036 (1968).
CSI Reactions
49
R1 ,R2
(129)
I SO2CI CSI
^R3
[M] — CH2
R2•
^
R3
O
Pyrrolidones
Transition metal 2- alkenyl
[M] = n5 C5 H5 Fe (CO)2 -; n5 - C5 H5 Mo (CO)3; Mn(CO)5 -
Yamamoto, Y., Wojcicki, A; Inorg. Nucl. Chem. Lett., 8, 833 (1972); JCS Chem. Comm., 1088 (1972);Inorganic Chem., 1779(1973). Me Me
(130)
Me
Me
>
/
Me-
CSI, CH2 CI2
N-
> Me
0°C, 30Min.
Me
V
CI O2 S
Me
o
(70%) Me
H^=V
CH (Me)CONH 2
(8%)
Moriconi, E.J., Kelly, J.F., Salomone, R.A., JOC, 33, 3448 (1968). /r
(131)
y=
CSI
\ " S02 CI
0
(80%)
NHSO2 CI (20%)
Graf, R., Angew. Chem. Int. Ed. Engl., 1, 111 (1968).
CSI
(132) [ > = < ]
o
^
A
• 78 - * - + 20°C
N-X (15%)
(85%)
Weber, W., Erden, I., de Meijere, A., Angew. Chem., 19, 387 (1980).
CSI Reactions
50
(133) [ > = < ]
CSI, CH 2 Cl 2
-
-78°C
^
\
Hydrolysis
,/
V
CI0 2 S '
o
C\
Y
H/
N(~10%)
55o/o
de Meijere, A., Erden, I., Weber, W., Kaufmann, JOC, 53, 152 (1988). Ph
Ph
(134)
y = ^ \
O
^ O
* •
ii) PhSH/Et3 N
Ph
Ph
i)CSI,-30°C Ph
P"h
N
N H
SO2CI
(45%) warm -0
N SO2CI P h ' x Ph (85%)
Barton, T.J., Rogido, R.J., Tet. Lett., 13, 3901 (1972); Dunkelblum, E., Tet. Lett., 13,1551 (1972). Ar
(135)
Ar
i)CSI,-30°C ii) Hydrolysis
Ar. HN-
\
O
Clauss, K., Tet. Lett., 15, 1271 (1974). Barton, T.J., Rogido, E.J., Tet. Lett., 13, 878 (1972). Aue, D.H., Iwahashi, H., Shellhamer, D.F., Tet. Lett., 14, 3719 (1973).
CSI Reactions
/
(136)
51
f
i) CSI, CH2 Cl2 i
\
NH
ii) Na2 SO3 (aq.) (39%)
Aue, D.H., Iwahashi, H., Shellhamer, D.F., Tet. Lett, 14, 3719 (1973). Conjugated Dienes
(137)
C H 2 : CH. CH: CH2
CSI
H2C: CH. CH: CHCO NH SO2CI + 4 - Vinyl - 2 - oxo - 1 - azetidine Sulfonyl Chloride
Goebel, P., Clauss, K. Ann., 121, 122 (1969).
i) CSI
(138)
R2
ii) AIH3
(R = Me; R1 = R2 = H; R = R1 = Me, R2 = H; R = R1 = H, R2 = Ph)
Hassner, A., Wiegard, N., JOC, 51, 3652 (1986).
i)CSI,-10°C
(139)
1 ii) PhSH, py., H2O
Moriconi, E.J., Meyer, W.C., JOC, 36, 284 (1971). Baxter, A.J.G., Dickinson, K.H. JCS Chem. Comm., 236 (1979).
CSI Reactions
52
(140)
/ " CH2 = CH —C Me % QH/
Me
i) CSI i
[i:
ii) Hydrolysis O'p
-NH
[I] = 7 - oxo - 1 - aza - bicyclo [3.2.0] hept - 2 - ene- 2 carboxylate system (olivanic acid) Bateson, J.H., Baxter, A.J.G., Roberts, P.M., Smale, T.C., Southgate, R., JCSPerkin Trans. I, 96, 142521 (1982).
i) CSI, ether
(141)
*•
-10°C ii) Na2 SO3, - 5°C (71%)
Hauser, F.M., Rhee, R.P., Ellenberger, S.R., JOC, 49, 2236 (1984).
(142)
CSI
NHSO2CI
Hoffmann, H„ Diehr, H.J., Tet. Lett.,?, 1875 (1963). CSI
(143)
> * - ^ ^ >
• 5 0 ° _ » . 0°C
Hassner, A., Wiegard, N., JOC, 51, 3652 (1986).
53
CSI Reactions
CONH SO2 CI
(144)
«^N-
(R = H, Me)
/
N
' CIS0
\>
2
Moriconi, E.J., Meyer, W . C , Tet. Lett., 9, 3823 (1968). o.
v
i) CSI
(145)
<"
/
K^-
ii) Na2 S 0 3 , KOH
^ ^ >
-N•
(R = H, Me)
Depres, J-P., Greene, A.E., Crabbe, P., Tet. Lett., 19, 2191 (1978).
(146)
CSI
<^V
>
2 — Oxo — 1 — azetidine sulfonyl chloride Polar Solvents (rearranglement)
6 — Chloro-sulfonyl imimo — 5, 6 — dihydro — 2H — pyrans + 1 — Chlorosulfonyl — 4 — alkyl — 2, 6 — dihydro — 2 (1H) — pyridones + Chlorosulfonamides
Goebel, P., Clauss, K., Ann.,122, 122 (1969)
1 ~y (147)
CSI
0v
T
H 2
°.
N
\ SO2CI
Clauss, K., Tweddle, NJ.,Ann.,
722, 142 (1969).
CSI Reactions
54
CH-, CH,
(148)
CHc
i) CSI
C H 2 = C H — C = CH 2
ii) Hydrolysis O
NNQ
O
Haug, T., Lohse, F., Metzger, K., Batzer, K.,Helv. Chim. Acta, 15, 2069 (1968). i)LAH
^ \ .
(149)
<
ii) EtNO, HN-
\
at 0 C
O
^
02 N'
Hassner, A., Keshava Murthy, K.S., Tet. Lett., 28, 4097 (1987). H
(150)
C H 2 — CH— C ^
i) CSI,CH 2 CI 2 , 0°C
C H 2 C 0 2 C H 2 Ph
»> ii) Na2 SQ 3 , K 2 HPQ 4
I H [E/ C-
J—\ °
CH2 CO2 CH2 Ph
^ H ,
f
O
(90%)
-N H
CO2 CH 2 Ph
Benzyl-3, 7 - dioxo - 1 - azabicyclo [3.2.0] - heptane - 2 - carboxylate.
Berges, D.A., Snipes, E.R., Chan, G.W., Kingsbury, W.D., Kinzig, C M . , Tet. Lett., 22, 3557 (1981).
CSI Reactions
55
CH3 CH = CH - CH = CH CO2 C H g - ^ T J ^ - N 0 2
(151)
1— CH2 CH = CH CO2 CH2-<^3^>— N 0 2
CSI CSI
C0 2 CH2 — C6 H4 NO2 (P)
S
o
p - Nitrobenzyl carbapen - 2 - em - 3 - carboxylate.
Uedo, Y., Damas, C.E., Vinet, V., Can. J. Chem., 61, 2257 (1983).
CN
(152) OMe
NMePh
O
i) C S I , C H 2 C l 2 - 7 § C ii) MeOH
OMe
CN
MeO
NMePh (54%)
2 - (N- Methylanilino)- 4 • methoxy penta - 2, 4 - diene nitrile
Wang, Y.W., Fang, J.M., Wang, Y.K., Wang, M.H., Ko, T.Y., Chemg, Y.J., JCSPerkin Trans. I, 1209 (1992).
(153)
'
yCN N N Me Ph
i) CSI, CH 2 CI 2
o *"
ii) PhSH Y = SPh; Yield, 1;78% Y = OMe; Yield, 1;68%
CN Et
Fang, J-M, Yang, C-C, Wang, Y.W., JOC, 54,477 (1989).
^
NMePh
56
CSI Reactions
H
Me
Ph
(154)
6
CSI.CH2CI2 atO°C
V^
/S°2
PAA Me Me
2 - Isopropylidene 3 - phenylmethylene cyclopropane.
CI
Me Me
=
X
N S02 CI a) X = O; Y = NSO2CI b)X = NSGCI; Y = 0
Pasto, D.J., Smorada, R.L., Turini, B.L., Wampfler, D.J., JOC, 41, 432 (1976).
(155)
a
i) CSI
-N
k
ii) H2O
Hauser, F.M., Rhee, R.P., JOC, 46, 227 (1981). 1
(156)
o
CSI \^A
NSO2CI
Berge, J.M., Roberts, S.M., Suschitzky, H., Kemp, J.E.G., J. Chem. Res. (S), 255 (1978).
i) CSI
/
(157) ii) Na2 S2 O3 0
Archelas, A., Morin, C , Tet. Lett., 25, 1277 (1984).
57
CSI Reactions
R3
(158)
R2
R2
AX
/S02C,
CSI dry ether R1
R
4'
V
^Rl
Narasimhan, K., Kumar, P.R., Heterocycles, 22, 2751 (1984). Me
(159)
Y
CSI Mi
NSG2CI
Askani, R., ^wgevv. Chem. Int. Ed. Engl, 9, 167 (1970).
(160)
Bicyclobutane bridged-diene
Hogeveen, H., Zwart, L., JOC, 44, 1365 (1979).
(161)
CSI, CH2CI2
H 3
f l \ ^ 0
e° " Acetone
^.
N SO2 CI
Konkel, M.J., Vince, R., Tetrahedron, 52, 799 (1996).
(36%)
NSO2CI
CSI Reactions
58
CSI, CH2 Cl2
(162)
—
'
a) X = SO2CI b)X = H
X-N: O
CISO2 N v
O
-o
+
a) X = SO2CI b)X = H
Malpass, J.R., Tweddle, N.J.,JCS Chem. Comm., 1247(1972).
(163)
f(CH2)^
( CH 2>rK,
CSI
/
(L
N-SO2CI
(n = 1,2, 3)
Malpass, J.R., Tweddle, N.J., JCS Perkin Trans. I, 874 (1977).
(164) r.t., 1h CSI / CCI4 r.t. Longer Xn. time
(41%)
(37%)
CI2 OSN,
—o
i y "
i
r
X = SO2 CI ; H
Malpass, J.R., Tweddle, NJ.,JCS
Chem. Comm., 1247 (1972).
59
CSI Reactions
(165)
NS02 CI MeO NS0 2 CI
MeO
Barends, R.J.P., Speckamp., W.N., Huisman, H.O., Tet. Lett., 11, 5301 (1970). CISO2 HN
,0
(166)
Me02C Me02C Methyl levopimarate
(55%)
G. Mehta, Dhar, D.N., Suri, S.C, Bhadbade, M.M., Venkatesan, K., Ind. J. Chem., 20B, 193 (1981). NHS0 2 CI
(167)
c MeCr
"\>
.•"S,
MeCr
o
(70%)
Metha, G., Dhar, D.N., Suri, S.C, Bhadbhade, M.M., and Venkatesan, K., Ind, J. Chem., 20B, 193 (1981).
60
CSI Reactions
Unconjugated Dienes
(CH2:CH2)2CH2
(168)
1
i) CSI ii) Hydrolysis
f O'
R1
-NH
R = HR-i = C H 2 C H 2 : C H 2 R R 1 = CH 2 CH: CH CH 2
Baxter, A.J.G., Dickinson, K.H., Roberts, P.M., Smale, T.C., Southgate, R.,JCSChem. Comm., 236 (1979).
(169)
CH 2 = CM — CH 2 — CH = CH 2
CSI, 0°C 24h
S
-NH (25%)
Pfaendler,H.R., Strasser, R.,Ann.,
(170)
911 (1987).
i ) C S I , C H 2 C I 2 , r.t. 1 14 days
V \ / % 1,5- Hexadiene
ii) Na 2 S 2 O3
/\y% j"
-NH (75%)
Aida, T., Legault, R., Dugat, D., Durst, T., Tet. Lett., 20,4993 (1979). i) CSI
(171)
/
W
1,6- heptadiene
^
ii)NaSO , CH CI 2 3 2 2
f
R
/
X -NH O // (49%) R = [ (CH2)3CH = C H 2 |
Barrett, A.G.M., Graboski, G.G., Sabat, M., Taylor, S.J., JOC, 52, 4693 (1987).
61
CSI Reactions
,0
S
i) CSI
(172)
ii) PhSH, pyr.
V
Paquette, L.A., Kakihana, T., JACS, 90, 3897 (1968). Paquette, L.A., Kakihana, T., Hansen, J.F., Philips, J . C , JACS, 93, 152 (1971).
(173)
CSI, 80" C
HJVWW
fwwv H
4h ^—NH O (58%)
Singh, R, Cooper, R.D.G., Tetrahedron, 50, 12049 (1994). -SiM^R
SiMe2R
(174)
62% Roberson, C , Woerpel, K., Org. Lett., 2, 621, (2000).
i) CSI
(175)
ii) Hydrolysis
J
N '
HN-
bis - Si- lactam
Biener, H., Farbwerke Hoechst A.G., unpublished results.
V
CSI Reactions
62
(176)
i) CSI
» ii) Hydrolysis
HN'
O
Mehta, G., Dhar, D.N., Suri, S.C, lnd. J. Chem., 16B, 87 (1978). Me Me
(177)
i) CSI
>
/ / — Me
j
'/
ii) Hydrolysis 0
O
i) CSI, CH2 Cl2 ii)Na2CO3at0°C (48%)
Parson, P.J., Camp, N.P., Underwood, J.M., Harvey, D.M., JCS Chem. Comm., 1461 (1995).
Me (178)
\
Me 3 Si.
Me
/
-Si-
i) CSI • Si Meg' ii) Na2 S 0 3 / Na HCCg
Me 3 Si,y -NH Me
/
Me N -
\
O
Nativi, C , Perrotta, E., Ricci, A., Taddei, M., Tet. Lett., 32, 2265 (1991).
63
CSI Reactions
NH
y
(179)
i) CSI 1
^>
ii) Hydrolysis
Caryophyllene
Mehta, G., Dhar, D.N., Suri, S.C, lnd, J. Chem., 16B, 87 (1978).
CSI, Et 2 Q
(180)
•40°C-r.t.
^ R (94%)
H
N SQ 2 CI O
Moriconi, E.J., Wheeler, C , Crawford, W . C , JOC, 33, 370 (1968). Ph.
Ph
(181)
(15%)
Mazzochi, P.H., Halchak, T., Ammon, H.L., Tet. Lett., 20, 2953 (1979).
CSI Reactions
64
i) CSI, Et 2 0
(182)
>•
-30 C Me
ii) Ph SH - pyr.
L>~ H—>^.,. MeN - R
R = SO2 CI,
0 Yield, 86%
R = H;
Yield, 36%
Moriconi, E.J., Jalandoni, C.C, JOC, 35, 2073 (1970).
CSI, E^O 0°C—r.t.:
(183)
(R = SQ2 CI, 78%) CISO2-N CSI, Et>0 >
r H
— * •
0°C—r.t.
o'
H
(71%)
Moriconi, E.J., Wheeler, C , Crawford, W.C., JOC, 33, 370 (1968). o NH
(184)
i) CSI
0 ii)Na2S03/OH
o
Sasaki, T., Hayakawa, K., Manabe, T.,Nishida, S., JACS, 103, 567 (1981).
65
CSI Reactions H
CN
i) CSI ii) DMF.A
(185) Benzobarrelane
Paquette, L.A., Volz, W.E., JACS, 98, 2910 (1976).
(186)
(8.3%) H
(2.6%)
Volz, W.E., Paquette, L.A., JOC, 41, 57 (1976). CH;
(187)
CSI, CH 2 Cl 2
N-R
r.t
R = S 0 2 CI, R = H (64%)
Paquette, L.A., Broadhurst, MJ., JOC, 38, 1893 (1973).
CS1 Reactions
66
(188)
Q f ^ L ^
ii) Na2 S03, OH I r S
Paquette, L.A., Broadhurst, M.J., JOC, 38, 1893 (1973).
(189)
OCOMe
OCOMe
OCOMe
Skuballa, W., Raduechel, B., Vorbrueggen, H., Tet. Lett., 29,4285 (1988).
67
CSI Reactions
Allenes
(190)
> =
•
CH2
CH3 „
C—C=CH2
CSI
CSI
f
O
CIO2S
I
H2 C = C — C — CONH SO2 CI CH2
Note: The following allenes are reported to react with CSI in a similar way: .CH
;0
>
CH 2 ;
(CH2)6 •CH
Moroconi E.J., Kelly, J.F., JACS, 88, 3657 (1966). R1 R1.
(191) R2
/
,R3
<
R3
R2.
R4
CSI R4
af
-N
\
SO2CI
Moroconi, E.J., "Mechanism of Reactions of Sulfur compounds", vol. 3, Intra-Science Research Foundation, Santa Monica, Calif, p. 131 (1968). Bestian, H., "Cycloaddition with Sulfonyl - Isocyanate ", Pure Applied Chem., 27, 611(1971).
68
CSI Reactions
R3
R2 R3
R2.
(192)
R1> —
CSI, ether
• = < R4
y*
R1-
w
ice Cooled
+
%r &
CONH2 R2
^
> = ^ R1
CO2H
R3 +
Me2 C = C — CH2 N CONH2
R4
I SO2CI
K
Moriconi, E.J., Kelly, J.F., JOC, 33, 3036 (1968).
(193)
^
< ^ /
CSI
^
-N
o-f
\
Cossio, F., Roa, G., Lecea, B., Ugalde, J.M., JACS, 117, 12306 (1995). R
(194)
CSI
ciRor
^RI
Cl
R1
2 P(0 N - S0 2 CI
H
|~ R = Me, R1 = Me, Et, Pr., RR1 = (CH2)5 1
°
Mondeshka, D., Parashikov, V., Angelov, Kh., Synth. Comm., 19, 3113 (1989).
69
CSI Reactions
R1 R2 R2
i) CSI
(195)
CR1CR = CH 2
>
iijAIHa 1
HN— R = Me, R1 = R2 = H; R = R1 = Me; R2 = H; R = R1 = H; R2 = Ph.
Vinyl azetidines
Hassner, A; Wiegand, N; JOC, 51, 3652 (1986).
(196)
R2 R4 C = C
K
S C6 H4 CI R3
4
i) CSI ii) Na2 SO3
SC6 H4 CI
-1—R3 -NH
SC6 H4 CI R3
~V^ f
O
R2
CSI Reactions
70
Table
A
S-Ar >
Yield (%)
Product
Allene
-
•
=
<
Me
S-Ar
1<
#
Me
55
Si Me3
87
-NH
O
S-Ar | \
^
—
<
Si Me 3
# O
A
S-Ar
< „
S-Ar
Me
/Ar S S
S-Ar
^ > = Me3Si
•= < ^
20
-NH
Me
Me3 S i _ l
^ Si Me3 NH
Si Me3
f
54
O Me
>= -^c
Me3Si
•Ar
"A
/
\
>
c„, Si Me3 °
S-Ar
Me
Si Me3 +
sf NH f// . . O (a)
A o <->
S-Ar
#~
-NH
10%(b)
(a : b : : 1 : 2) S-Ar •Ar
" \
> Sn Me3
A O
-J—Sn Me -NH (22%)
Buynak, J.D., Rao, M.N., Chandrasekaran, R.Y., Haley, E., De Meester, P., Chu, S.C, Tet. Lett., 26, 5001 (1985).
CSI Reactions
(197)
_/\
i)CSI,CCl4
-Si Me 3
>
71
ii) Na2 SO3 (aq.)
^ 0
,SiMe 3 H >
H
DCSI.CCU ii) Na2 SO3 (aq.)
Si Me3
NH (22%)
A
A
Si Me3
-NH
J
O
+
H
SiMe3 -NH H Me3 SU
,Si Me2 Ph
i) CSI, CCI4
Me3Sk,
r
Si Me2 Ph
»
ii) Na2 SO3 (aq.)
H
y
-NH
Colvin,E.W.,Monteith,M.,JGS'CAem. Comm., 1230(1990).
Me
(198)
R1
i) CSI
S C6 H4 CI - p
> = —C
ii) Na2 SO3 iii) HF - MeCN iv) (MeO)2 C Me2
R2 Si Me3 S C6 H4 CI - p
Mel
f
O
0
(51%)
Buynak, J.D., Mathew, J., Rao, M.N., Haley, E., George, C , Siriwardane, U.JCSChem. Comm., 735 (1987).
72
(199)
CSI Reactions
Me2C:C:C
( S C6 H4 CI - p)
CH2 CH2 OSi Me2 CMe3
CSI
Me S - C6 H4 CI - p
Me-_1
i — CH2 CH2 OSi Me2 C Me3
S
-NH
O
Buynak, K.D., Rao, M.N.,JOC, 51, 1571 (1986).
S - C6 H4 CI - p
RMeC
(200)
Me R>
-R1
4— R1
CSI
-NH
"S C6 H4 CI - p
• Alkylidene -
R1 = H, Me, Si Me3, Sn Me3 )
Buynak, J.D., Rao, M.N., Chandrasekaran, R.Y., Haley, E., De Meester, P., Chu, S.C., Tet. Lett., 26, 5001 (1985). Buynak, J.D., Rao, M.N.,7C>C, 51, 1571 (1986). Me
H
•Me
Me
i) CSI
Me
ii) Na2 SO3 / KOH
(201)
>
Ph H'
Gompper, R., Lach, D., Tet. Lett., 14, 2683 (1973).
=0 H
CSI Reactions
(202) P
73
CSI
^ > = (26.4%)
Ph
N S02 CI
Ph.
CN-SO
2
CI
I
° 2 CI
\ = S 0 2 CI
(17%)
o
(19%)
s
(30.5%)
Gompper, R., Lach, D., Tet. Lett., 14, 2683 (1973). Pasto, D.J., Chen, A.F.T., Ciurdaru, G., Paquette, L.A., JOC, 38, 1015 (1973). Pasto, D.J., Borchardt, J.K., JACS, 96, 6220, (1974). Me Me Me
CSI
(203) ""Me
X = O; Y = NSO2CI1 X = NSOCI; Y = O j
Ph .Me H' •Me
CSI - CH 2 C l 2
H2C:
0°C;1/2h
a; X = NSO2CI; Y = O") b; X = O; Y = NSQ2CI I
c; X = NH; Y = O
J
Phi , / \ X H3C'' CH3 a; X = NS0 2 CI, Y = O b; X = O; Y = NSO2 CI
Pasto, D.J., Borchardt, J.K., JACS, 96, 6937 (1974).
74
CSI Reactions
Tr<X
i) CSI/ Na 2 C0 3
(204)
-60°C ,Toulene ii) Red-Al
TrO
TrO
\
\ O
O
^ H
O
O
^
H
O n
O
2.3:1 de= 39%
Lysek, R., Furman, B., Kaluza, Z., Frelak, J., Suwinska, K., UrbanczykLipkowska, Z., Chmielewski, M., Tet. Asymm., 11, 3131, (2000).
CSI Reactions
75
CSI
(205)
o N
I
S0 2 CI
Gompper, R., Lach, D., Tet. Lett., 14,2683 (1973).
CSI
(206)
(50%)
SQ 2 CI
Poutsma, M.L. Iberbia, P.A. JACS, 93,440 (1971).
(207)
Me CH2 CH Me2
Ph
Me
O
/
Ph
H ^ t > = ' ==•, (E) 1(81.3%)
> -CH2CHMe 3
W
, \ ^ \ ^ SO2CI
Me
Me2HCH2C
_.
Me
CH2 CH Me2
Ph CH 2 CH Me3 CSI, C H 2 C l ^ 0°C,
"Me
(Z) 1(18.7%)
I
PI^\ 5
x
Vib* pf)
Me2 CH CH2 Me
H 2 C=<
+
H 2 C
so2ci
,H
S02CI
CSI Reactions
76
Me
CH2CHMe2
Me2CHCH2Me NSO2 CI
Me CH2 CH Me2
X/
Me2 HC CH2 Me
NSO2 CI
NSO2 CI
J'
H 2 C=<
Ph.
I
+
/\ Ph
/\ H
Ph
8 Pasto, D.J., Borchardt, J.K., JACS, 96, 6937 (1974).
Me
(208)
Me
H
9
Me2C CSI
and / or
Alkylidenecyclopropane
R
Me
Me
N
I
SO2CI
Pasto, D.J., Chen, A.F.T., Paquette, L.A., Ciurdaru, G., Prep. Div., Pet. Chem., Am. Chem. Soc, 18, 131 (1973).
77
CSI Reactions
Conjugated Trienes
(209)
C — NH S 0 2 CI (cis)
(trans)
Moriconi, E.J., Hummel, C.F.,JOC, 41, 3583 (1976). SO2CI
(210)
//
/
A
CSI, CH2 CI2
N
r.t.,6h O
Cycloheptatriene
Moriconi, E.J., Hummel, C.F., Kelly, J.F., Tet. Lett, 10, 5325 (1969).
CSI, CH2 Cl2
(211)
//
\ 25°C
N
>=o
+
^
I
SO2CI
c&Malpass, J.R., JCSChem. Comm., 1246(1972).
NSO2CI (90%)
a) X = SO2CI b)X = H
CSI Reactions
78
Q
o
OMe CSI
(M\
J CISC-2 N — OMe
(212)
(in CH3 CN) O MeO—C\N/S02CI
/
(in CH3 CN)
Pilidis, G., Chem. Ber., 116, 3516 (1983).
(213)
//
R1 R2
CSI - CH2 Cl2 1 r.t., 6 h NS02 CI
R2 R1 R1
CSI - CH2 Cl2
R2
r.t., 36 h
1 ^3
XS
°2CI
Moriconi, E.J., Hummel, C.¥.,JOC, 41, 3583 (1976).
(214) '• H
o
O CI02S/ (cis)
Moriconi, E.J., Hummel, C.F., JOC, 41, 3583 (1976).
CI02S/ (trans)
CSI Reactions
(215)
79
CSI
CIS - Bicyclo [ 6.1.0 ] nonatriene
(I) R = H (60%), R = CH3 (56%), R = CI (15%) Paquette, L.A.,Broadhurst, MJ., Lee, C , Clardy, J , JACS, 94,630 (1972). JACS, 94, 632 (1972). JACS, 95, 4647 (1973). Baldwin, J.E., Bryan, D.B., JACS, 96, 319 (1974).
CSI
CIS02-N^>-^
(216)
O
Baldwin, J.E., Bryan, D.B., JACS, 96, 319 (1974). Unconjugated Trienes
(217)
i) CSI, CH2 Cl2
G* ii) Na2 SO3 - OH (52%)
Paquette, L.A., Broadhurst, MJ., JOC, 38, 1893 (1973).
80
CSI Reactions
(218) Barrelene
R = S02 CI; R =H
Yield, 74%
Paquette, L.A., Volz, W.E.,JACS, 98, 2910 (1976).
i) CSI, r.t.
(219)
ii) Hydrolysis Bullvalene
(I)
+
X
S
(31%)
O
V
>
?JSL :Q
*= o
N
+
/^r ^H
(II)
(15%)
(III)
(19%)
(IV)
Paquette, L.A., Kirschner, S., Malpass, J.R., JACS, 92, 4330 (1970) .0 N —R
CSI, CH2 Cl2
(220)
i
(r.t.)
9 - Methylene • barbaralane
Paquette, L.A., Broadhurst, MJ.,JOC,
a) R = SC-2 CI b) R = H (77.5%)
38, 1893 (1973).
CSI Reactions
81
CSI
(221)
CISO2 N
Propellane
Scott, L.T., Erden. I., Brunsvold, W.R., Schultz, T.H., Houk, K.N., Paddon - Row, M.L., JACS, 104, 3659 (1982).
(222)
(2.4%)
Paquette, L.A., Broadhurst, M.J., JOC, 38, 1893 (1973).
(223)
J (51.5%)
!
Paquette, L.A., Broadhurst, MJ.,JOC
F H
38, 1893 (1973).
CSI Reactions
82
CSI - CH2 Cl2
(224)
r.t.,95h
(80%)
Moriconi, E.J., Hummel, C.F., JOC, 41, 3583 (1976). Conjugated Tetraenes
i) CSI
(225)
^=0 ii) Na2 SO3
Ferber, P.H., Gream, G.E., Kirkbride, P.K., Tet. Lett., 21, 2447 (1980). i) CSI, CH2 CI2
Vo
>
(226)
r. t. ii) Na2 SO3 (20%) 7 - Methylene cyclo octa - 1 , 3, 5 - triene
(R = H ; S 0 2 C I ^ R 8 - azabicyclo [ 5, 3, 1 ] undeca 1, 3, 5 - trien - 9 - one.
Ferber, P.H., Gream, G.E., Kirkbride, P.K., Tiekink, E.R.T., Aus. J. Chem. 43,463(1990). /S02CI (227)
N •^ N
Erden, I., Kaufmann, D., Tet. Lett., 22, 215 (1981).
0 i)OH ii)oxidn.
o
CSI Reactions
i) CSI, 50
(228)
83
' VNH^
c >>
I CO ^/
v;
ii) NaOH
(68 - 88%)
Paquette, L.A., Krow, G.R., Barton, T.J., in "Organic Petrochemical Synthesis ", Vol I, Srinivasan, R., (Ed.), John Wiley & Sons, Inc., New York, N.Y., 67 (1971).
(229)
( ^ ^ 3 i) CSI, CH
2
Cl 2 , 0UC
:
>
ii) PhSH - pyr.
Fe (CO) 3
Fe (CO) 3 (80%)
Paquette, L.A., Levy, S.V., Broadhurst, M.J., Truesdell, D., Foyos, J., Clardy, J., Tet. Lett, 14, 2943 (1973). o
OMe Me
I
i) CSI
(230)
•_. ^
„
Hw |
Me
NH
i
OMe
ii) Hydrolysis Methxoymethylindene
Gibbard, A.C., Moody, J.C, Rees, C.W.,JCSPerkin
Trans. I, 145 (1986).
84
CSI Reactions
Unconjugated Tetraenes
(231)
(73%)
Paquette, L.A., Broadhurst, M.J., JOC, 38, 1888 (1973).
(232)
R3
CSI
Bicyclo [ 4.2.2 ] deca 2, 4, 7, 9 - tetracene deriv.
Paquette, L.A., Broadhurst, M.J., JOC, 38, 1886 (1973).
85
CSI Reactions
J? NH
(233) "X (R2 = CH2)
(80%)
R2
= H2
Paquette, L.A., Broadhurst, M.J.,JOC, 38, 1886 (1973).
(234) 2 - Methylene - bicycio [ 3.2.2 ] • nona - 3, 6, 8 - triene
53%
O
^AN-H // (3.2%)
86
CSI Reactions
< M M H
+
(6.9%)
Paquette, L.A., Broadhurst, MJ.,JOC,
38, 1893 (1973).
Conjugated Pentaenes CONH S0 2 CI
(235)
CSI
Effenberger, F., Klenk, H., Chem. Ber., 109, 769 (1976).
i) CSI, CH2 Cl2
(236)
0°C ii) Hydrolysis 7 b - Methyl - 7b H Cyclopent [cd] - indene
McCague, R., Moody, C.J., Rees, C.W.,JCSPerkin
Trans. I, 175 (1984).
87
CSI Reactions
Acetylenes
(237)
C4 Hg C ^
CSI
C.H
», C4 Hg C ^
C - C - NH SO2 CI (Low yield)
Et2 N - CH 2 C ^=
CSI
CH
»,
H C ^ C CH2 NEt. CI SO2 NCO (95%)
Moriconi, E.J., Shimakawa, Y.,JOC, 37, 196 (1972).
R1
R2
\ (238)
R i c =
CR2
U SI CSI
/
Na2 CO3 N \ _ c ^i . C I _ — * .
g//
„
R
H2O *"
\sc—0
^. \ /
/v
II
\R2
0
2 (I)
Substituents R1 R1 R1 R1 R1 R1 R1
I; % yield
= R2 = Me; = R2 = Et; = R2 = n-C 3 H 7 ; = nC 3 H 7 ; R 2 = Me; = Me 3 C; R2 = Me; = Ph; R2 = H; = C 3 H 7 , R 2 = MeCH = CH 2
42 95 86 92 51 48 90
Kobelt, D., Paulus, E.F., Kampe, K.D., TetLett, 12, 1211 (1971). Kobelt, D., Paulus, E.F., Kampe, K.D., Tet.Lett., 12, 3627 (1971). R1 (239)
R1C = =
R22. R CR2
1
R2
R 1 JL
'
An) 0 2
CK/Vv^O''OU2
Moriconi, E.J., Shimakawa, Y.,JOC, 37, 196 (1972).
02 nAoJ CI ^0-' /
CSI Reactions
88
(240)
Etc
CSI, CH2 Cl2
=
CEt
• r.t.
• CI
N/
\ SO2
Moriconi, E.J., White, J.G., Franck, R.W., Jansing, J., Kelly, J.F., Salomone, R.A., Shimakawa, Y. Tet. Lett., 11, 27 (1970). NEt2 (241)
MeC ^
< ^ — o
CSI
CNEt2
CIS02 - N
(100%)
Moriconi, E.J., Shimakawa, Y.,JOC, 37, 196 (1972).
C02R3 (242)
C 0 2 R3
I
I C
C
i)CSI
c
ii) Hydrolysis
I
CH2 O CO N
CH2 0 H
R2
\
R1
(I)
R1 = R 2 = H
R3 = Me;
R1 = R 2 = H
R3 = Et:
R1 = R 2 = H
R 3 = CH 2 CH 2 OC3H7(n> 85%
Yield, I = 80% 83%
Suzuki, K., Ushijima, R., Miyano, T., Nakagawa, S., Heterocycles, 29, 497(1988).
89
CSI Reactions
R (243)
[M]-CH2C =
CSI
CR
»
r
O
//
n
\
•5
Transition metal - alkynyl
/ \ - Pyrrolidones
M = n 5 C 5 H 5 Fe (CO) 2 -; n 5 - C 5 H 5 Mo (CO) 3 -; Mn (CO) 5 -. Yamamoto, Y., Wojcicki, A., Inorg. Nucl. Chem. Lett., 8, 833 (1972); JCSChem. Comm., 1088 (1972); Inorg. Chem., 12, 1779(1973). Giering, W.P., Raghu, S., Rosenblum, M., Cutler, A., Ehntholt, D., Fish, R.W.,JACS, 94, 8251(1972). i) CSI, CH CI3 (244)
R
_ =
_SiMe3
O
oc
R- =
ii)HCI,H20^
^
(54-71%)
^
NH9
Page, P.C.B., Rosenthal, S., Williams, R.V., Synthesis, 621 (1988).
N
02s" % /
(245, > - C ^ ^ ] ^
i
J Cl
A
o
^
J^B-CH^] (62%)
(96%)
Kobrich, G, Merkel, D., Thiem, K-W., Chem. Ber., 105, 1683 (1972).
90
CSI Reactions
N Me2 Ph
(246)
Ph C ^ =
i) C S I , - 2 0 C
C N Me2
» ii) Hydrolysis Me2N/^N \ (55%)
Ph
MeS Ph C ^
CSI
C S Me
N'
•)—CI
so 2 -6 (16.1%)
Me Me
0~sc
=
CMe
CSI
„ S
Me
\
N'
\
/ •>—CI
S02-0 (34.9%)
Me
i)CSI
( ^ V - S02 C = CMe
ii) PhSH - Pyr. Me
Me
SO2
rv
"-} HN
SPh
So 2 -6 (1.4%)
Hirai, K., Matsuda, H., Kishida, Y, Ann. SankyoRes. Lab., 24, 108 (1972); C.A.,78, 159569z(1973).
CSI Reactions
91
Ph
Ph
\ (247)
CSI
PhC=CPh.
CIS
»
/
°2N
^ N
O
o
SO2 CI
(57%)
Moriconi, E.J., Shimakawa, Y., JOC, 37, 196 (1972).
Alcohols (248)
CSI
ROH
»
CISO2NHCOOR
R = Et, CI CH2 CH2, Me2 CH, Ph CH2, Cyclohexyl Graf, R., Chem. Ber., 96, 56 (1963). Graf, R., Angew. Chem. Int. Ed. Engl,
7, 172 (1968).
o (24^)
ROH
CSI
^
T R-O-C-NHSO2C1]
~C°2 ^
RNHSO2CI
Timberlake, J.W., Ray (Jr.), W.J., Stevens, E.D., Klein, C.L., JOC, 54, 5824(1989).
i)CSI,CH2Cl2
(250)PhCH2OH
^^^ 0
p h C H 2 a
C-r.t. R
A
N H
R
/'
S
\
N
xk
C 0 2 R l
H R = H, R' = Et R = R' = Me (Yield : 83%)
I CIH3N
O
C02R1
Muller, G.W., DuBois, G.E., Grant, E., JOC, 5 4 , 4 4 7 1 (1989).
CSI Reactions
92
CSI, PhH
(251) v
Me OH
•
CI S02 NH C02 Me
1/2 h
(99%) Et3 N - PhH o (17 C) Et3 N SC-2 N C02 Me + Et3® HCI (92%)
Duncan, J.A., Hendricks, R.T., Kwong, K.S., JACS, 112, 8433 (1990).
n«i^ K^-3^)
Me OH
CSI, PhH o 25-30C
Me O2 CN SO2I1 Et3
Me O2 C NH SO2 CI
Me(CH2!feOH
(84 - 7%)
Et3 N - PhH 5 »• (25 C)
Me O2 CN H fo H5) Me *"
(55%)
Burgess, E.M., Penton (Jr.), H.R., Taylor, E.A., Williams, W.M., Org. Synth.,53, 1857(1973). Burgess, E.M., Penton (Jr.), H.R., Taylor, E.A., Williams, W.M., Org. Synth., 56, 40(1977).
(253)
Me OH
CSI, Cyclohexane
CI SO2 NH CO2 Me (100%)
r.t, 2h
Carbomethoxysulfamoyl chloride Et3 N / C6 H6 (r.t.)
©
©
Et 3 N S 0 2 N C 0 2 Me
Duboudin, J.G., Minh, D.T., Synth. Comm., 19, 285 (1989).
CSI Reactions
93
C02Me
i) CSI
(254)
EtOH(BuOH)
i i ) M e 0 C 0
JH(RNH2)
>•
R-CH
SO2 COOEt
^NH/
(t-Bu)
CO-NH i)TFA
R-^CHI
\
0 ii)OH
NH - SO2
(77 - 84%)
R = Pro; Asp; Met; Phe; Ala; Va. Aouf, N., Dewynter, G., Montero, J.L., Tet. Lett., 32, 6545 (1991).
CO2 Me t (BuOH)
t
csi
O R '
CI SO2 NH CO2 Bu
(255)
Q
NH3, CI
ii) Et3 N C02Me R•
/
, H •NHSON^ 2 ^ C O Bu 2
C02Me
TFA
- <
NH SO2 NH2
^—NH R
t.
^S02 N
Dewynter, G., Aouf, N., Regainia, Z., Montero, J.L., Tetrahedron, 52, 993(1996).
CSI Reactions
94
(256)
H
H
I t-BuCL,N
I
H
t-BuOH
I . N ^A / C I
t-BuCv
TNoo —oo
>
cs,
RNH 2
—
s/N-R TTr" *o ' ~o
ft
R: OBn OtBu °'HNEt3+
^OH CI'
„ , / \ / O
x
. N ,
.CI
BnONH2
9
>
H
o" ^o
Hajri, A., Dewynter, G., Criton, M., Dilda, P., Montero, J.,Heteroat. Chem., 12, 1 (2001). CC2Et (257)
C s l
BuOH
>
H 3 C
ci SC2 N H CC2 BU'
^ X ©
H
g
CH2-Ph C02Et H3 C
~X
T F A
N
/ NH-SO 2
Ph Chj2 OH^ NH
•• 3 0O — < H
_ B0E
"
H3 C
^
<
\
X
C02 Et
^
/ NH-S02
X
Boc
B0C
CC2Et N
"
.
N H C
^
P h
NH-SC2
Dewynter, G., Aouf, N., Criton, M., Montero, J.L., Tetrahedron, 49, 65 (1993).
CSI Reactions
95 O
(258)
^
^
•
k
V
ii) (L) - Phe - OMe. HCI
^
«» %
„ [I
(90%)
Groutas, W.C., Kuang, R., Venkataraman, R., Biochem. Biophys. Res. Comm., 198,341 (1994). i)CS
' ii) R1 R2 NH, TEA
(259)
^
iii) HO CH 2 CH 2 CI iv) PPh3, DIAD
R
R1 \ ^ /
N
M O \\/y
i) TEA
o x
\
N
/ \ /
C
I
^
ii) [NO]+
| Boc
L°
V >N
Sf
r,
I
NO
2 - Chloroethylnitrososulfamides (CENS) Abdaoui M., Dewynter, G., Aouf, N., Favre, G., Morere, A., Montero, J.L., Biorg. Med. Chem., 4, 1227 (1996).
(260)
Me 3 COH
CSI „
r Me 3 COC (O) NH SO2 Cll
h e X ane
'
(- C 0 2 ) Me3CNHS02CI
R1 NH2
Me 3 CNH S 0 2 NHR1
Timberlake, J.W., Alender, J., Garner, A.W., Hodges, M.L., Ozmeral, C , Szilagyi, S., Jacobus, J.O. JOC, 46, 2082 (1981).
CSI Reactions
96
O (261)
CSI
RCH2CH2OH
II »
RCH2CH20-C-NHS02CI
(R = CI, Br)
Agoh, B., Dewynter, G., Montero, J.L., Leydet, A., Imbach, J.L., Bull. Soc. Chim.Fr., 867 (1987). (262)
CSI
PhCH(CH2OH)2
>
2 - Phenyl - 1 , 3 - propandiol
PhCH(CH2OCONH2)2 Felbamate
Walker, D., Babad, E., Tann, C.H., Tsai, D.J.S., Kwok, D.L., Belsky, K.A., Herczeg, L.J., (Schering Corpn., USA). PCTInt. Appl., WO 940 6737, C.A., 121, 204976 (1994). (263)
Cl CH
2 CH 2 OH
csi
^
CI CH 2 CH 2 O CO NH S 0 2 CI
RNH
2^
CI CH 2 CH 2 0 2 CH NH S 0 2 NH Ph + CI CH 2 CH 2 O S 0 2 NH CONH Ph Sulfamoyl Carbamate
(Sulfonyl urea)
I Et3 N O
i CIHNO2SN
O
Montero, J.L., Dewynter, G., Agoh, B., Delaunay, B., Imbach, J.L., Tet. Lett., 24, 3091(1983).
97
CSI Reactions
? i)CSI f 2 6 4 ) B r C H 2 C H 2 0H
^
——
r^ NH, TEA ii)
*-
\
°-v ^
Y
N —
°
O
°
I
s
Ii
J^ —
N
vuO
°
(80%) Sulfonyl bis - N - oxzolidone (SBo)
Dewynster, G., Abdaoui, M., Toupet, L., Montero, J.L., Tet. Lett., 38, 8691 (1997). o (265)
Q ^ ^ ^ O H Wang resin
CSI, THF, OC^ 30 Min.
*
s^ Of
(
°v
J^
XS
O
NH
CI
Fitzpatrick, L.J., Rivero, R.A., Tet. Lett., 38, 7479 (1997).
CSI
(266) H O / ^ ^ ^
/\
**
H NN
O^
s
Y
Y / ^ S
°2Ci
o Agon, B., Dewynter, G., Montero, J.L., Leydet, A., Imbach, J.L., Bull. Soc. Chim. France, 867 (1987). ,_,_..
1 - 2 or 1 - 3 haloalcohols
(267)
+
CSI
^
Nitrogen mustard + Et3 N R.1 / R2
>
O^
-Z— R3 \R4 ^NHv
0
NH
(65-95%)
N - Carboxylsulfamides
98
CSI Reactions
Halo-alcohols Chloro - and Bromoethanol, R1 = H, Me, CH2C1, H, H, H 1 - Chloro - 2 - propanol, R2 = H, H, H, H, H, Me 1,3- Dichloro - 2 - propanol, R 3 = H, H, H, Br, H, Me 2, 3 - Dibromo - 1 - propanol, R4 = CI, CI, CI, CH 2 Br, CH 2 CI, CH 2 CI 3 - Chloro - 1 - propanol 2 , 2 - Dimethyl - 3 - Chloro - 1 - propanol. Dewnyter, G., Abdaoui, M., Regaima, Z., Montero, J.L., Tetrahedron, 52,14217(1996). (268)
i) CSI
CI 3 C.CH 2 OH
*.
CI3C. CH2 0 S 0 2 - N = C = 0
>80°C
Lohaus, G.,(FarbwekeHoechstA.G.), DAS 1230017, 1965.
(269) CSI
/=\ H3CO—<\
h— OH
U^/0H
/=\ -H3CO—(^
h— OS02NCO
Glycidol Q /T~\ PH n ' U ^ - ^ O ^ N H S O a O — ( V0CH3 CH 2 CI 2 \\ \=/ O 0. ,0 Q^SI ,
/
//
\
Et3N, 12h, THF Reflux
o J //
J O
^
'
5
AiKanne Alkaline Hydrolysis"
™ ^ ~ X
>-°CH3
HO^A^OH
OH H3CO
Gautun, H., Bergan, T., Carlsen, P., Acta Chem. Scand., 53, 446 (1999).
99
CSI Reactions
CSI
(270)
^ CH3CN, N2atm. 20°C, 4h
GG-OH
G Q
O NH y S N/" S
/
O
CT
NH2
N
0
[ GG. = All trans geranylgeraniol 1
Macchia, M., Jannitti, N., Gervasi, G., Danesi, R., J. Med. Chem., 39, 1252(1996).
(271)
CH2OH
i) CSI
COOH
ii) Na SO3 2
CH2 - O - C - NH2 COOH carbamoyl acetic acid
Battistini, C , Scarafile C , Vioglio, S., Perrone, E., Franceschi, G., Tet. Lett, 27, 513(1986).
Me
Me
(272) Me-
-CH2OH O
Me
i)CSI,Et20 0
°c
Me-
-CH20-C-NHS02CI
o—o
O
O
Me
(76%)
Adam, W., Bhushan, V., Fuchs, R., Kirchgaessner, U., JOC, 52, 3059 (1987). (273)
HO (CH 2 ) 2 Si Me 3 -C2H4 (vacuum)
CSI / CCI4 ^
CI S 0 2 NH CO a (CH 2 ) 2 Si Me 3
CI S 0 2 NH C 0 2 Si Me3
Durham, P.J., Galemmo (Jr.), R.A., Tet. Lett., 21, 123 (1986).
100
(274)
CSI Reactions
O ^ l
CSI/THF •NH
H 1
H -40°C
CH2OH COOH
UUk
NH
H
H
:
;
//-
CH2 O CO NH2 COOH
Firestone, R.A., Fahey, J.L. Maciejewicz, N.S., Patel, G.S., Christensen, B.G.,7. Med. Chem., 20, 551 (1977).
OMe (275)
i) CSI, MeCN
R CH2 CONH
ii) Acid hydrolysis C02H OMe R CH2 CONH
r
OCONH2
O C02H
Rasmussen, J.K., Hassner, A., Chem. Revs., 76, 389 (1976). Graf, R., Angew. Chem. Int. Ed. Engl., 7, 172 (1968).
CSI Reactions
(276)
HO
H >
HN j H2N
N
N
\
H 2 N CO'
H
*--~ \
101
H
H
I
© V=NH2
|
N
HN I
i)CSI 1OH2O
v ©
j)=NH2
H2N
---OH
"--OH
OH
OH
Tanino, H., Nakata, T., Kaneko, T., Kishi, Y.,JACS, 99,2818 (1977). CH2 R 1
CH 2 R1 ( 2 7 7 ) R 2 * « / o R 3 V « w O H CSI.CH2CI2 RZ^U R4 O
O
o
O R 3 W * O - C - NH - S - CI O
R4
5'- O - [ [ [ [ Hexapyranosyl) oxy] carbonyl] amino] sulfonyl] - 2', 3' - O - isopropylideneuridine deriv.
HN
O HN
CH2 R 1
J~°\ _*.
R2«WV/ O R 3 \ « M W
H
(AN
O-C-NH-O—I/°\|
X Fiandor, J., Garcia - Lopez, M-T., De Las Heras, F.G., Mendez - Castrillon, P.P., Felix, A.S., Alarcon, B., Carrasco, L., Eur. J. Med. Chem., 22, 59 (1987).
CSI Reactions
102
O °Ac
(278)
CSI, CH2 Cl2
OA\
20°C,2h'
AcO
OCO NH2
AcO
Protected 6 - ethynyl mannopyranose R = H;C=
CH
//
T
NH
N-—^N^NHAC AcO
OCO NH S02 - O—|
o
y^
(30%)
Elloumi, N., Moreau, B., Anguiar, L., Laziri, N., Sauvage, M., Hulen, C , Capmau, M.L., Eur. J. Med. Chem., 149 (1992).
103
CSI Reactions
i ) M e 2 S O - C S I , CH2Cl2^ -78°C
(279)
< :
*
^>=0
ii) Et3 N, 25°C , 1/2 h (I)
i)Me2SO-CSI,CH2Cl2^ \\
- 78° C ii) Et3 N, 25°C, 1/2 h
HO H
Yield (I & II ) = 69-90%
Olah, G.A., Vankar, Y.D., Arvanaghi, M., Synthesis, (2), 141 (1980). Ph S02 NH CH (OH) CCI3 or Ph SO2 NH CH (OEt) CCI3
(280)
CSI,CHCI 3 orCH2Cl2
»« CCI3
CCI3
PhS02-N-^^0 I -S0 2
PhS02-N-^0
° 2 SA 0 H (I)
N
o
H (ID
(Yield, 1,11 = 53-83%)
Bryuzgin; A.A., Levkovskaya, G.G., Mirskova, A.N., Zh. Org. Khim., 30 (I), 63 (1994), C.A. 122, 10005^ (1995). (281)
R
R3
V°
>k OH R1 Ph Bu l Ph
R i) CSI - PhH
V°
R? R3>
ii) H2O
R3 Me Me
R2 Me Me -(CH 22>)
Graf, R., Chem. Ber., 96, 56 (1963).
5
NH2
-O^^o
104
CSI Reactions
HO
(282)
_
C02 Et
V
i)cs, •R
ii) H2O
Wrobel, J., Dietrich, A.,Heterocycles,
38, 1823 (1994).
Vic. Diols O R2
(283)
R>
i)CSI
ii) HO
'
(fc
/S
OH
R4
R1
R1-C-C-R3 \ R4 (a-k)
R2
R3
R?
R1
R3 R4
o^ ^o
Yo
O (i)
O
II / R 2
,R4
+
R4_c-C-R2
\ R3 (k)
R R1
wR3 R4
OH
(f-k)
a)
R\
R2,
R3,
R 4 = Ph
b)
R1,
R2,
R3,
R4 = 4- MeC 6 H 4 .
c)
R1,
R2,
R3,
R4 = 4C 6 H 5 C 6 H 4 .
d)
R1,
R4 = Me;R 2 ,
R3, = Ph
e)
R1,
R4 = Ph;
R2,
0
R1,
R2;
R3,
R 4 = -(CH 2 ) 5 -
g)
R1,
R2;
R3,
R 4 = -(CH 2 ) 4 -
/R1
||
R 3 , = 1 - naphthy 1.
o I
c=o (h,j)
I NH 2
CSI Reactions
105
h)
R2,
R4 = H;
R1,
R3, = -(CH 2 ) 4
i)
R1,
R4 = H;
R2,
R3,= -(CH2)4"
J)
R2,
R4 = H;
R1,
R3,= Ph.
k)
R',
R2, = Me; R3, R4 = -(CH 2 ) 5 -
Joseph., S.P., Dhar, D.N., Synth. Comm., 18, 2295 (1988). Thioalcohols (284)
RSH
CSI
».
RSCONHSO2CI
( R = C1 2 H25)
Graf, R, (Farbwerke Hoechst A.G.), German Patent 931,467, 1952; Chem. Zbl, 11094(1954). Graf, R., Chem. Ber., 96, 56 (1963). Sheers, E.H., US Patent 3,113, 857 (1963)., C.A. 60, 5395 b (1964). Phenols CSI ,*o^ (285)
PhOH
»r.t.
ArOH
CSI, 10(Pc
CI S 0 2 NH COOPh ArO - S O 2 - N = C = O
Lohaus, G., (Farbweke Hoechst A.G.), DAS 1230017, (1965). Rasmussen, J.K., Hassner, A., Chem. Revs., 76, 389 (1976). Graf, R., Angew. Chem. Int. Ed. Engl., 7, 389 (1976).
CSI Reactions
106
O CI SO2 - N / \ OR H
ROH + CSI
(286)
(R = aryl)
ROSO - N = C = O 2
Warm, A., Bernardinelli, G., JOC, 59, 3540 (1994).
/
(287)
/
.OH
OCO NH S02 CI
r.t
CSI
^ ^
O SO2 NCO
H
/
2Q
.O SO2 NH2
100°C (62 - 79%) [ R = 3 - CI, 4 - CI, 4 - Me, 4 - OMe, 4 - Ch]
Hedayatullah, M., Hugueny, J.C., Phosphorus and Sulfur, 19,167 (1984). Lohaus, G., Chem. Ber., 105, 2791 (1972). OH
(288)
OCO NH S02 CI CSI, ether
N02
I NC-2
(100%)
Barret, A.G.M, Betts., M.J., Fenwick, A., JOC, 50, 169(1985).
CSI Reactions
107
O
(289)
O
OH
CSI, Et3 N *> 0°C,THF
O
EN-O-i-N-V^O o
Sliskovic, D.R., Krause, B.R., Picard, J.A., Andreson, M., Bousley, R.F. Homelehle, K.L., Homan, R., Julian, T.N., Rashidbaigi, Z.A., Stanfield, R.L., J. Med. Chem., 37, 560 (1994).
ci (29Q)
C\-JcL-
ci
°
O H - ^ ^ C I - ^ - O - C - NH S0 2 CI X CH2 CH2 OH ^'CI CI ci
CI
^ CI o O - C - NH - SO2 - O - CH2 CH2 X
X
CI
Montero, J.L., Dewynter, G., Agoh, B., Delaunay, B., Imbach, J.- L. Tet. Lett., 24, 3091 (1983). ZH
(291)
CSI
CI S02 NH CO Z
Z = 2, 4, 6-CI3C6H2OCl = P h ^ - 0 -
Lattrell, R., Lohaus, G., Chem. Ber., 105, 2800 (1972).
CSI Reactions
108 (292)
R 0 H
CSI
CISO2NHCO2R
*•
H2NSO3R
R = Pentachlorophenyl, = Pentabromophenyl, = 2,4, 6- tri-iodophenyl. Hedayatullah, M., Brault, J.F., CR herbd. Seances Acad. Sci., Ser.C, 285,153(1977). /
m
UH
(293)
i) csi
[ Q ] R1 ^ ^ COOR
\
OOCNH2
rv-vr
N) Hydrolysis*
R
A A ^ C 0 0 R
2 - Carbamoyl benzoates
(R= Alkyl, Aryl; R'= H, Halo, Alkyl) Kamal, A., Rao, M.V., Diwan, P.V., Rao, A.B., Sattur, P.B., Eur. J. Med. CAe/w.,23,487(1988). o OH
H
OH
(294)
^ \
X)-C-NH2
CSI, CH CI3
MeO(A^ 2 Methl - 4 - hydroxybenzoate
MeO 2
31 %
Parameswaran, K.N., Shi, G-Y., Klotz, I.M., J. Med. Chem., 30, 936 (1987).
OH
(295)
K ;1
^ . . O C O N H
-
^ (QJ
Uc,
o
*
NH O- S O 2
Hedayatullah, M., Brault, J.F'., Phosphorus and Sulfur, 11,255 (1981).
CSI Reactions
109
Ethers/Epoxides (296)
CSI
HC(OCH3)3
„
M e O - C O - N - S 0 2 C I + H COOMe Me
Biener, H., (Farbweke Hoechst A.G.), German Patent 1186044, (1963) Biener, H., Ann., 686, 102 (1965). CH2
f 2971
(°Me)2
CSI
MeO CO - N - SO2 CI CH2 OMe
Graf, R., unpublished results.
o \ S OEt j)2CSI (298)
, ?
'
I
ii) Hydrolysis
Ethylisobutenyl ether
oEt
I
HN
N
o.
V ' .0
[O] ^ NH
*"
HN
T
^NH
Y
Graf, R., Angew. Chem. Int. Ed., Engl., 1, 172 (1968). BnO .
(299)
o
LT)>
BnO
Bn0
^ s ^
y1
O/NH
^ ^
Bn O
Sugar vinyl ether
Kaluza, Z., Abramski, W., Belzecki, C , Groder, J., Mostowicz, D., Urbanski, R., Chmielewski, M., Synlett., 539 (1994).
CSI Reactions
110
i) CSI, Na2C03, 21 days
= o
r.t.
(300)
Me
ii)Na2S03 (64%) Na OMe, Me.OH
NH2
(r.t.) ..CO2 Me
(31%)
Buckle, D.R., Houge - Frydrych, C.S.V., Pinto, I.L., Smith, D.G., JCS Perkin Trans. I, 63 (1991).
(301)
MeO
CSI, PhH
PhOMe
-o-
S02
Effenberger, F., Gleiter, R., Heider, L., Niess, R., Chem. Ber., 101, 502 (1968). OMe i)CSI,DMF
(302)
A
•
ii) NaOH, EtOH OMe
OMe
Q
OMe
(86%)
Iio, H., Zenfuku, K., Tokoroyama, T., Tet., Lett., 36, 5921 (1995). OBn
(303)
MeQ
CSI, Et 2 O
QD^T I H
20 Min.
MeC.
iQ (97%)
NH SO2 CI
H
Moody, C.J. Swann, E., JCS Perkin Trans., I, (21), 2561 (1993). Moody, C.J. Swann, E., Tet. Lett, 34, 1987 (1993).
CSI Reactions
111 O
~ /
N
CSI P h H
~.
.
(304)
O
S
n
(r.t.)
-PEG
Jl
Polyethylene glycol (PEG) Et 3 N
O
II
n
|T
i
-PEG
Wipf, P., Venkataraman, S., Tet. Lett., 37, 4659 (1996). CSI
*> O^
(305)
Rl R2'z
Rt
R4
R
R3
o
S02 CI I
,S02 CI
0
\
/
R4
• R1-)
4-
R2
(>
R4
•R3
(B!'
H2O im
H2O / OH
o O^ i) CSI
R* \
^ O
°
^R4+R1-)
Q
/ ii) H2O, OH R 2 '
X
R 3 " R 3
R ' , R = Ph R1,R4 = H
R2, R 4 = H R2, R3 = Ph
c)
R1,R4 = H
R2,R3=
d) e)
R ' , R 2 , R 3 =H R'= COPh
R4 = Ph R2, R4 = H; R3 = Ph
f)
R',R2=
R3, R4 = H
Me
R3
(20.5 - 30.6%)
a) b)
P—^ivie
^- R 4 N
RT RZ
(61 - 73.5%) 3
NH Nl
-ecH2)g
112
CSI Reactions
Table : 1.3 - Dioxolan - 2-ones(A) and 1,3- Oxazolidin-2-ones (B) Yield, %
Epoxide
B Trans - Stilbene Oxide Cis - Stilbene Oxide Cis - Cyclo-octene Oxide Styrene Oxide Chalcone epoxide
73 61 74 61 67
23 23 20 30 28 o
V°V
Ph/
II
CSI
Ph 3 - C - P h
\ Ph
Keshava Murthy, K.S., Dhar, D.N., Synth. Comm., 14,687(1984). Keshava Murthy, K.S., Dhar, D.N., J. Heterocycl. Chem., 21, 1721 (1984). Q O
(306)
CSI, CH2 Cl2 o (-78)
Ph/
o
pfT
"°
pfT~^
(i)
NH
(II)
1,11(1 : 1); Yield, 60%
Lorincz, T., Erden, I., Synth. Comm. 16, 123 (1986).
(307)
\ R1-
_y \'<5/
R1 _
i) CSI n
)H20
- ^ :
^
o
H/
^O (48%)
Daniel, J., Shukla, D., Dhar, D.N., Chem. Lett., 1575 (1992).
CSI Reactions
&
AcO
(308)
www R
csi^
113
AcO"Q? C H K X X ^ _
ether"
Ac0 CH2
(ID
(I)
AcO AcO C Ho H 2- -V^
=
= NH CO2 Et R =p
AcO AcO CH2
OH (IV)
Dimers ( V & VI )
CH2 OAc
=^A
AcO
CH2 OAc
ivwww R
(III) CSI, MeCN r (II - IV ) +
0
X ^
AcO CH.2 EK>2 CH
o: AcO CH2
CH 2 OAc
VoAc
OAc (V)
(VI)
Hall, R.H., Jordaan, A., De Villiers, O.G., JCSPerkin Trans. I, 626 (1975).
CSI Reactions
114
BzO—
BzO— BzO <
309
>
-O
BzO'
CSI, CH2CI2
BzO-
" ^
O
BzO-
low temp
BzO OCO NH SO2 CI
OH
O BzO V
BzO
H2O
O
BzO—
r.t. BzO
H0
OCO NH2
CAN
-y0vl
R = Me, H
BzO-
O
BzO
\
O BzOBzO
O OCO NH SO2 O—. O I
R = Me;
Yield, 67% ^
R = H;
Yield, 60'
\
/
*
Pere'z- Pere'z, M-J., Bal zarini, J., De Clercq, E., Camarasa, M-J., Biorg. &Med. Chem., 1,279(1993). Peroxide
t BuOOH
(310)
CSI
CI SO2 NH - C - 0 0 --Bu
0
•78 C
(I) 0
H2O
II H2 N C 0 0 Bu R1
RR1 NH
I
t
R - N - SO2 NH COO Bu
(I
0 ROH, Et3 N
RO SO2 NHC - 0 0 - Bu
Hoft, E., Ganschow, S.,J. Prakt. Chem., 316, 359 (1974).
CSI Reactions
115
Ketenes Cl S
CSI, CH2 Cl2 (311)
CH2 = C = Q
O
°2^
10%
f
O'
Mundloss, E., Graf, R., Ann., 617, 108 (1964).
p - Tolyl Ph
(312)
Ph C = C = N — < ( ) > — Me V-
9
-V
Diphenyl Ketene - p - tolylimine
CSI, ether o ' -30C
2C K V ^
p-Tolyl/
NL
^
C P h 2
^NH
Y
O (84%)
Romming, C , Skatteboel, L.,^cta Chem. Scand., 43, 819 (1989). Thioketenes R1
(313)
:R2: > c = cs
CSI
R2 •
f
O
R1
S -N
\
J
R2-
f
SO2CI
O
-N
\
H
Schaumann, E., Moller, M., Adiwidjaja, G., Chem. Ber., 121, 689 (1988). R1
> C = CS
(314)
R
1/
Thioketenes R = Me2 CH, R1= Me3 C
o CSI, 100- 150 C 12-48h Me3 C;
R-
f-
O
f -N
\
SO2CI
(29 - 83%)
Schaumann, E., Roehr, A., Adiwidjaja, G., Tet. Lett., 21, 4247 (1980).
CSI Reactions
116
Aldehj'des CSI
RCHO
(31b)
RCH = N - SO2 CI + CO2
at >0C
O 0-^V-N-S02CI
CSI 2RCHO at < 0°C
t
R / ^ O - ^ R
(R = Ph; p - Me C6 H4; Bu)
Graf, R., Angew. Chem. Int. Ed. Engl., 7, 172 (1968). Clauss, K., Friedrich, H.J. Jensen, H., Ann., 561 (1974). CSI
// CI3C-C
(316)
\
H
CI3 CCH = N SO2 CI
Et3IH -20°_.120°C
Schmidt, E., Kuehlein, K., Ger. Offen. 2, 645,280., C.A. 89, 5908 (1978). JL O P h ^ ^ f
(317)
I
i) CH2 12, 2n, Ti Cl4 •
>=o
ii)CSI, r.t., 12h.
H
S02CI
< 60% )
Black, H.T., Olson, J.T., Abt, C D . , Synth. Comm., 22, 2729 (1992). H
H
I
X1
.c = o
(318) \ ,
CSI (>100C)
•OH
J
X2 (X1,X2 = H)
O
X2 (X1=CI, X2 = H)
Kamal, A. and Sattur, P.B., Synthesis, 272 (1981); Synth. Comm., 12, 157(1982). Dhar, D.N., Bag, A.K., Ind. J. Chem., 22B, 627 (1983).
117
CSI Reactions O H . OH
(319)
CSI
o 0-5C CSl/PhMe
N - S 0 2 CI
y
\c//
C-H
o
.0-C-NHS02CI
Q
100-105
cop: (89.4%)
Dhar, D.N. Bag, A.K., /«
H
^,0 0
(320)
i) 2 CSI
N.
ii) H2 O H
Ar
i) 2 CSI
© ii) H2O / OH r, O
o2s N
^ > ^ / N - H H
Ar
(64%)
Daniel, J., Dhar, D.N., Tetrahedron, 48, 4551 (1992).
^ / > NH
CSI Reactions
118
OTHP
R
© »»" iii) CSI
F
iv) H2 O
OHC
,321)
V ^ Me
i) (Et 2 0 ) 2 (O) CH2 CO2 Et / NaH
*-
KOBu
Et02
H2 N ^ \
c
Kitazume, T., Kobayashi, T., Yamamoto, T., Yamazaki, T., JOC, 52, 321 i (1987). Acetals O
(322)
II
CSI
CH3 O CH2 OCH3
CH3 O - C - N - SO2 CI
I CH2 O CH3
Clauss, K., Friedrich, H.J., Jensen, H., Ann., 561 (1974). R
(323)
0
0
CSI
r,
0.
Y
RAOAR
R
.N-so2a
0
in
(R = H, Me)
CSI
»
I'"1
R (R = H)
Graf, R., Angew. Chem. Int. Ed. Engl., 7, 172 (1968). Clauss, K., Friedrich, H.J., Jensen, H., Ann., 561 (1974)
119
CSI Reactions
Ketones o
o
R2
i) CSI R 1 - C - C H 2 - R2
(324)
ii) Na2 SO3 R
(
1'
NH
if
NH I ^S02 O'
R AoA 0
R1 = Me, Bu, Ph, Ph CH2, 4CI - C6 H4, 4 - Me C6 H4; R2 = Me, Et, Pr', Ph)
Hassner, A., Rasmussen, J.K., JACS, 97, 1451 (1975). o ,11C>
OH
R-C-CH2R
1
cs|
.
ether/CH
2Cl2
R-C-CH-C-N-SO2CI
KiZi>)
©
i
-
©
R1
~ 0
r
0
II
ll
II II R-C-CH-C-
rsi
N H - SO2 CI
^J'
O
O
II
II
"
*^
R1
"
x
"
R-C-CH-C-N-CNH-S02C 1 1 R1
*
o
II S 0 2 CI
O
O
°v
O
O
NH
C T ^ H
NH3
3, 4 - Dihydro - 4 - oxo 1, 2, 3 -oxathiazine 2, 2 - dioxide
NH O
O R1
X HN
R1
R1
uracil. (R = Ph., R1 = Me Yield : 28.4%)
Rasmussen, J.K., Hassner, A.,JOC, 38, 2114 (1973).
CSI Reactions
120
Ph.
>=o
i) CH2 12, Zn, Ti CI4
(326)
!
Ph
ii) CSI, r.t., 12 h.
(65%) SO2CI Et
\
i) CH2 l2. Zn, Ti CI4
=
ii) CSI, r.t., 12 h.
.*K*
0
.N 1
PrT
(74%) SO2CI
Black, H.T., Olson, J.T., Abt, C D . , Synth. Comm., 22,2729(1992). R2
I (327)
R1-C-CHR2R3-
R1 - C - C - CONH SO2 CI
II
O
o
DMF R2
R3
I
R1 - C O - C - C s N R3 (I)
R1 Ph
R2 Me
R3 H
% yield(I) 90
Ph
Et
H
82
Ph
Me
Me
80
Et
Me
H
71
Me
Me
Me
87
Me
Me
H
63
Me
COMe
H
70
-(CH 2 ) 3 -
H
54
-(CH 2 ) 4 -
H
69
Clauss, K., Friedrich, H.J. Jensen, R.,Ann., 561 (1974).
CSI Reactions
121
Rasmussen, J.K., Hassner, A., JOC, 38, 2114 (1973). Rasmussen, J.K. Hassner, A., Synthesis, 682 (1973). t (328)
MeCOCH2C02Bu
CSI
t CI SO2 NH CO CH (CO Me) CO2 Bu
*~
Yarmenko, V.V., Drach, B.S., Drogovoz, G.K., Nagurnaya, N.A. Babin, N.A., Kalita, E.V., Berezina, V.F., Sergeev, S.A. Chichetkin, V.I., Priputina, L.S., Russian patent, RU 2035457 C.A. 124, 146207(1996). (329)
CS ' low temp *
MeCOCH2C02R
+.
Me CO CH C 0 2 R I CO NH SO2 CI (II)
(I) 1(a) (b)
R = Me
II (a)
=87%
R = C4Hg
H(b)
=91%
[ || b]
Pyrolysis
Me c o CH2 c o
NH S 0 2 c, + C 0 2
+ CH2 = C (CH2)2
Clauss, K., Friedrich, H.J., Jensen, U.,Ann. 561 (1974).
0
0
0
II II (330) Me-C-CH2-C-OCMe3
QC| ».
0
II II M e - C - CH - C - OCMe3 CONHSO2CI
Me o=<
0 N—S= O
O
1
O
II H
O
Me - C - CH2 - C -NHSO2CI
(Hoechst, A.G.), German Patent, 2, 327, 804 C.A. 82, 171097 (1975).
CSI Reactions
122
CI
O
I
O
02 S
2 CSI
(331)
SO2 CI
(84%)
Clauss, K. Friedrich, H.J., Jensen, H., Ann., 561 (1974). R3^
o (332)
HIM'
i) CSI
R2 ^>=CH-C-R1
„ R2
K
ii) Hydrolysis
R3'
w
O'
R1
oxazines (I)
R1
R2
R3
%yield(I)
Me
Me
Me
54
Ph
Me
Me
39
Ph
H
Ph
57
Me
H
p-MeOC 6 H 4
55
Ph
H
p-ClC 6 H 4
45
CMe,
H
Ph
54
PhCH=CH
H
Ph
44
Clauss, K., Friedrich, H.J., Jensen, H. Ann., 561 (1974).
O. )>
CSI, CH2 Cl2 ( 3 3 3 ) (Me3SiMe)2CO
». - Me3 SiCI
/
Me
N O Si Me 3
Me-N. S0 2 — N
(100%)
Barton, T.J., Rogido, R.J., JCS Chem. Comm., 878(1972).
CSI Reactions
123
Ph
(334)
Ph2C = O
CSI
N
130° C
so 2
I
(28%)
Clauss, K., Friedrich, H.J., Jensen, H.,Ann., 561 (1974).
• S02 CI
(335) " - © - l " ® - " ' ^ L . R - O - l - O - * !* R1
R = R1 = Me, OMe, CI R = H; R' = CI
. SO2 CI N-
O
MAO/
C - C (C6 H4 - R)3
r©
CSI
(R - C6 H4) - C - C - (Ce H 4 - R)3
H2 N SO2.
/
R - C6 H4 - C - C = (C6 H4 - R)2 . ,
so2 N 2
(RC6H4)-C
"0 C
(0)~R
^b
Joseph, S.P., Keshava Murthy, K.S., Dhar, D.N. Synth. Comm., 19, 417 (1989).
CSI Reactions
124
(336) R II ( a - e )
R
a
H
H
b
H
c
H
a a
d
Me
e
Me
X2
X1
Compd. No.
-|
J
H
a
Yield, % I
II
H
66
8
H
72
6
a
70
7
H
78
5
H
81
5
Kamal, A., Rao, K.R., Sattur, P.B., Synth. Comm., 10, 799 (1980).
(337)
R2
R1
N
OC°
CSI
R2
to
hAo I
R (61 -81%) (R = H, Me;R 1 ,R2 = H,CI)
4 - Phenyl - 2 - (1H) - quinazolinones
125
CSI Reactions
Ar
Ar i) CSI
00:
>•
ii) H2O iil) Base
NH
I
N'^0
Ar
Ar
Ar Ar
i) CSI >•
0^°
ii) H2 O / Base
@
&N
^O
Ar
Kamal, A., Rao, K.R., Sattur, P.B., Synth. Comm., 10, 799 (1980) Synth. Comm., 12,157(1982).
(338)
CSI
Acetyl isocyanate
3- chlorosulfonyl - 6 - methyl - 2H - 1 , 3, 5 oxadiazine - 2, 4 - (3H) dione (40%)
Sridhara, N.S., Latscha, P., Z Naturforsch., 30(B), 969 (1975).
02
o (339)
R-"
o ^,r
N
O
^R
N-H i) CSI
-NH 0-25°C _R1
%A(o
ii) H2 O / OH
-R1
— R2 R3
R
-R2 R3 (35 - 45%)
CSI Reactions
126
O
RI^
O
"rT
O
^ R2
RV
O ^f
"N^
%A 0
N i) CSI o 0-25C
o
o
0
o
R
R2 N.
+
XONH 2
o R3
R3
R3
N
(40 - 75%)
a)
R1 = Ph; R2 = Me; R3 = CI
b)
R1 = Ph; R2 = Me; R3 = H
c)
R 1 ,R 2 = Ph;R 3 = Cl
Daniel, J., Dhar, D.N., Synth. Comm., 21, 1695 (1991). Ph
Ph
(340) Ph
H
CSI
O
A
O
R (R = S02 CI, H)
Dhar, D.N., Mehta, G., Suri, S.C.Jnd. J. Chem., 14B, 477 (1976).
127
CSI Reactions
R1
R2 -R3
CSI Ph Me, reflux
(341)
o
i
<J
*> R4-
kWJ— R 2 R3 (65 - 85%)
a)
R ' , R 2 , R3, R4 = H;
b)
R ' , R 2 , R4 = H;R 3 = C1
c)
R 2 , R 3 = H ; R 1 , R 4 = C1;
d)
R ! , R 2 , R4 = H;R 3 = OMe
E)
R \ R 4 = H;R 2 , R3 = OMe
Dhar, D.N. Bag, A.K. Ind. J. Chem., 22B, 627 (1983).
— R
(342) SO2CI
a)
R = OMe;
R1 = H
b)
R = H;
R1 = OMe
c)
R = Me;
R1 = H
d)
R = C1;
R1 = OMe
Dhar, D.N., Suri, S.C, IndJ. Chem., 18B, 281 (1979).
CSI Reactions
128
(343)
^
^
J
L
^
v
CSI, CH2 Cl2 15°C
O
z/
1 - Aryl - 2 - benzoyl Cyclopropane
(I)
a) b) c) d) e) f) g)
X, Y = H X = OMe; Y = H X = OEt; Y = H X = Me; Y = H X = OMe; Y = CI X, Y = OMe X = CI; Y = H
Z = S 0 2 CI; Yield (I) = 50-68% = H; Yield (I) = 20-53%
Sampath Kumar, E., Dhar, D.N., Synth. Comm., 25, 1939 (1995).
(344)
A
(TO
^O
CSI, Me CN
*k S02CI
O
Sampath Kumar, E., Dhar, D.N., Ind. J. Chem., 34B, 63 (1995). H ^ ^ N H
2
H
i) CSI, CH2 CI2 - MeCN
(345)
o 10C ii) H2 O / O H Ar
© iii)H
Ar = Ph, p - MeO C6 H4; p - Me C6 H4; p - CI C6 H4
^ > Pramod Kumar, Dhar, D.N., Synth. Comm., 25, 1933 (1995).
129
CSI Reactions
(346) CSI
o Pyridazinone
Chloropyridazines
(R = H; R1 = H, Me, MeO, CI;
R = R1 = Me)
Srinivasan, T.N., Rao, K.R., Sattur, P.B., Synth. Comm., 16, 543 (1986). Ph
Ph
(347)
CSI
l>=°
![>="•\
Ph'
SO2CI
Ph' CSI
I \
\
S02CI
Moriconi, E.J., "Mechanisms of Reactions of Sulfur Compounds'', Vol.3, Intra - Science Foundation, Santa Monica, Calif, p. 131 (1968). Ph Ph
Ph
(348)
Ph
I J \\
Ph
Ph
O
^
CSI
(2 + 2)Cyclo- Ph
SI
addition
Ph
\
••
O
O
I
S S' O , />^< N/ N. N
SO2 Ph'
Ph [I]
CSI / AICI3 (4 + 2) Cycloaddition
Kumar, P.R.,Selvi,T.K.,JW. J. Chem., 23B, 1046(1984).
CSI Reactions
130
S
(349)
O i) CH2 12, Zn, TiCl4 =
0
ii)CSI,r.t., 12h Me Me
S 0 2 CI
Black, H.T., Olson, J.T. Abt, CD., Synth. Comm., 22, 2729 (1992). CSI / PhH CISO3 el
»
(350)
+
80°C
5H - Dibenzo [a, d] Cyclohepten - 5 - one
(51%) SO2CI
Rokach, J., Girard, Y., Atkinson, J.G., JCS Chem. Comm., 892 (1979).
(351) >PCSI, PhH
> -CO2 2 - Phenyl - 5 - oxo - 5 H naphtho [ 1 , 8 - be] thiophene
(94%)
Neidlein, R., Kraemer, A.D., Tet. Lett.,17, 4713 (1976).
CSI Reactions
131 O
(352)
HO
CSI / CH2 Cl2
OMe
I
i°\J
... K \ ^ NH ^ \ /
-s'b 1
'-OR1
o
•0R1
1
•OR3
0
[
-OR3 (4%)
0.
y
"NH
OMe
K ''OR1 O'
I
1
'"-OR3 (6%)
Baker, W.R., Clark., J.D., Stephens, R.L. Kim, K.H., JOC, 53, 2340 (1988).
(353)
CSI,
( Q
4 - Chloroaniline
O
CL
O
S02 NH - C -
O
N H
- \ C j ) — CI
O
Loewe, W., Matzanke, N., Ruetjes, T., Arch. Pharm. (Weinheim, Ger.) 327,819(1994).
N SO2 CI
o CSI, MeCN
(354)
» - r.t. ,1 h. Ph'
~0'
N
Ph
Ph'
O \ Ph 72 - 92%
Van Allan, J.A., Chang, S.C., Reynold, G.A., J. Heterocycl. Chem., 11, 195(1974).
CSI Reactions
132
^ \ ^ (355)
Enaminone + H2 N—(QV" C I
CS
v.
O
'. L ^ - ^ L J L SO2NH - C - NH Ce H4 - CI (p) O (Chromone - 3 - sulfonylurea)
Loewe, W., Metzanke, N., Ruetjes, T.,Arch. Pharm., 327, 819 (1994).
(356)
(Q
R = H, Me, OMe, 3, 4 (OMe)2
Tripathi, M., Dhar, D.N., Ind. J. Chem., 26B, 1082 (1987). (357) 5, 7 - Dimethyl - 8 - methylene tricyclo [3.2.1.02-7] oct - 3 - en 6 - one
CSI
CIO2SN
X M >
•Me
^ O
(70 - 75%)
Fischli, A., Mayer, H., Oberhaensli, W., Helv. Chim. Acta, 57, 57 (1974).
CSI Reactions
133
Ketals
(358)
(31%)
Hall, R.H., Jordaan, A., Lourens, G.J., JCS Perkins Trans. I, 38 (1973).
BnO-
(359)
BnO
i) CSI
>C 0N
»> ii) HCI
(67%) a -Aminonitrile
W
BnO
N
01
> — C ^ N H
i) CSI
BnO
>•
ii) HCI 2
O
X
(40%)
Sano, H., Sugai, S., Tetrahedron, 51, 4635 (1995). Sano, H., Sugai, S., Tet. Asymm., 6, 1143 (1995).
CSI Reactions
134 Diketones
O (360)
M e c o CH
CSI
2 CO Me
o -60C
Me - C - CH = C - Me I O O = C - NH SO2 CI
CSI, r.t.
(87%) (warm)
Me Me
r
0 H
O
o. /
O H
O
Me-C-CH-C-Me
I CONH SO2 CI
SO CI 2
Clauss, K., Friedrich, H.J., Jensen, H., Ann., 561 (1974).
CSI
(361)
o-» -50C
Clauss, K., Friedrich, H.J., Jensen, YL.,Ann., 561 (1974). Triketones 0 HN
N — CH2 CH (OH) CH2 O Bu
j) C S I
ii) Hydrolysis Ph
Ph
H N I ^ N — CH2 CH (O2 C NH2) CH2 O Bu
p/
p^
Pyrimidinetrione deriv.
Siegfried, B., Vachta, J., Valter, K., Hugentobler, S., (Sapos. SA. Switz.) PCTInt. Appl. WO 9112244 C.A. 116, 21067 (1992).
CSI Reactions
135
Acids O
o (363)
II
CSI
H-C-OH
H-C-O-C-NH-SO2CI
II H20
o
o H i - C l - O - C l - N H - SO2 - OH
CO2 + CO + NH2 SO2 OH
:
:
11:
II
+HCI
o
Graf. R., (Farbweke Hoechst A.G.) German Patent, 931,225, 1952., Chem. ZW., 3995(1956). i) CSI, PhH (364)
H-C-OH
Ph NH SO2 NH2
o 0-5C
(37%)
ii) PhNH2 iii) NaOH
Lee, C.H., Kohn, H., JOC, 55, 6098 (1990). ( 3 6 5 ) RCOQH
CSI
R COO CO NH SO2 CI
[A]
R CO NH SO2 OR1 + HCI
R1
DMF/ Et3N PCI5
R CO NH SO2 CI + CO2 [A]
ROH HN
•
RCONHSO2N /
'
R1 _ „ +HCI R2
R CN + CI SO3 H - DMF t (63 - 87%) [R = Bu, C - Hex; CI CH2 CH2, Ph CH2, Ph CH = CH, 1 - naphthyl) R - C = N - SO2 CI + POCI3 + HCI. CI
Graf. R., (Farbwerke Hoechst A.G.),German Patent, 931,225,1952., Chem. ZW., 3995(1956).
136
CSI Reactions
Graf. R., (Farbwerke Hoechst A.G.), German Patent, 940, 529, 1952., Chem.Zbl., 13257(1956). Lohaus, G., Graf. R., (Farbwerke Hoechst A.G.), German Patent, 1218448 A.G.), 1963. Lohaus, G., Chem. Ber., 100, 2719 (1967). Graf, R., Angew. Chem. Int. Ed. Engl., 7, 172 (1968). Moriconi, E.J., "Mechanism of Reactions of Sulfur Compounds", Vol.3, Intra - Science Foundation, Santa Monica, Calif, p. 131 (1968). Vorbruggen, H., Tet. Lett.,9, 1631 (1968). Botteghi, C , Chelucci, G., Marchetti, M., Synth. Comm., 12, 25 (1982). Wittmann, H., Beutel, P., Ziegler, E.,Monatsh., Chem., 100, 1624 (1969). Vorbruggen, H., Krolikiewicz, K., Tetrahedron, 50, 6549 (1994).
O
II
R1 - C - O H
R1-C^
- > •
R1-C^ •o
(366)
R1-C-OH
CSI, Et3 N
ROH
Rl-C^
o •OR
O R3>"» - > •
R1
-c
.R2 -N;
PS
Keshava Murthy, K.S., Vankar, Y.D., Dhar, D.N., Synthesis, 506 (1982).
CSI Reactions
137
CSI, pentane (367)
(+)-[S]EtCH(Me)COOH
EtCH(Me)C= N
40 C, 2h
(57%)
CSI, pentane Me3 C CH (Me)
(-) - [R] Me3 C CH (Me) CO2 H • 40°C, 2h
(60%)
Botteghi, C , Chelucci, G., Marchetti, M., Synth. Comm., 12, 25 (1982). (368)
Me3 C COOH
CSI
- [CI SO2 NH CO2 O C Me3 H20^
H 2 N C 0 2 O C Me3
R1 OH
R1 0 S 0 2 N H C 0 2 0 c
Me3
R2 R 3 NH
(R1 = Ph, or,4 - CI C6 H4) R2 R3 NSO2 NH CO2 OC Me3 (R2 = Ph, 4-NO2, NCCH2 CH2" R3 = H, Me, NCCH2 CH2" or N R 2 R 3 = morpholino - )
Hoft, E., Ganschow, S., J. Prakt. Chem., 316, 569 (1974). o ^ - * ^ , COOH
(369)
>_-oi i1;) i.2 C SI^
ii) 2 NEt3 OH
Hi) H2 O
^ ^
%x0 0& O
COOH NH2
i)2 CSI »•
ii) 2 NEt3 iii) H2 O
Vorbriiggen, H., Krolikiewicz, K., Tetrahedron, 50, 6549 (1994).
CSI Reactions
138
^701 K '
Ph CH = CH - COOH
CSI.CH2CI2-DMF ». reflux, 1.75h
C6 H5 CH = CH - CN
Lohaus, G., Org. Synth. 50, 18 (1970).
(371)
,—v i) CSI, CH2 Cl2 M e _ ( Q ) - C H = CH-COOH •
x^y
/ ^ \ M e t f J V c H = CH-CN
reflux, 4 min
—
(49o/o)
Brown, F., Bernstein, P.R. Cronk, L.A., Dosset, D.L., Hebbel, K . C , Maduskuie, (Jr.), T.P., Shapiro, H.S., Vacek, E.P., Yee, Y.K., et ai, J. Med. Chem., 32, 807 (1989).
(372)
RCH(COOH)2
CH 2 (COOH) 2
CSI
^
pci ° & l ».
N, N 1 - b/s (Chlorosulfonylmalonamide)
Malonic bis (Chlorosulfonyl carbamoyl) anhydride.
Wittmann, H., Sroka, P., Ziegler, E.,Monatsh., Chem., 99, 1962 (1968)
^
CN
CSI
(373) (X = COOH)
Mathe, S., Rassat, A., Tet. Lett., 39, 383 (1998).
O
O
CSI Reactions
139
0
CSI
(374)
R-CH2CT
~
(- C02)
^O®
Qf:
© R = Me3 N - ;
&
N SO2 CI
\ O
- N SO CI
/ M H©
e
*
R CH2 - C = N SO2 CI
CSI
R CH2 C.
e
R CH2 CO N SO2 CI
I
O
(- C0 2 )
0
2
EtOH
^
R CH2 C
N SO3 Et " N SO3 Et 0
Hoft, E., Ganchow, S., J. Prakt. Chem., 316, 569 (1974). Hendrickson, J.B. Jaffee, 1., J ACS, 95,4083 (1973).
(375)
Me3 N CH2 CO2 ') C S I '
(Betain)
PhH
Me33N N CH2 C (: N SO3 Et) N - S03Et
») EtOH
Wittmann, H., Beutal, P., Ziegler, E.,Monatsh. Chem., 100, 1624 (1969) Esters
(376)
CH
3 CH = CH . CH = CH CO2 CH2-
CSI
. CH2 CH = CH CO2 CH d
•NO2
^ N H
CO2 CH2-- NO2 p - Nitrobenzyl carbapen - 2 - em - 3 - carboxylate
Ueda. U., Damas, C.E., Vinet, V., Can. J. Chem., 61, 2257 (1983).
CSI Reactions
140
i) CSI
(377)
\ =\.
^
/
R-
ii) Na2 SO3 or Na H CO3
OCOR1
-NH (40 - 65 )
( R = H, Me; R1 = Me, Et, P r ' ; Bu ', Ph)
Clauss, K., Grimm, D., Prossel, G., Ann., 539 (1974). Ph
I CH2 i)CSI,CH2Cl2 (378)
Benzyl salicylate
I
i r.t., 2h ii) Cold water
o
o
o =c
II
6
0-C-NH2
Parameswaran, K.N., Shi, G.Y., Klotz, I.M., J. Med.(85%) Chem., 30, 936 (1987).
COOR
(379)
O-
i) CSI
(H2C) n
NHR
ii) 5% KOH
(n = 1 or 2)
Wamhoff, H., Ertas, M., Synthesis, \90 (1985).
(380)
0 C>= N I (CH2) n CO2 Me
CSI
C , ^ = NH N I (CH2) n COOH 2 - Imino - 1 - pyrrolidine alkanoic acid
Burden, P.M., Allan, R.D., Synth. Comm., 23, 1195 (1993).
CSI Reactions
141 0
(381)
Q
0CSI
OR
ee
Base
OR
ii) H2 O 'OH
(R = Me; Ph)
NH2
Q&. Kamal, A., Sattur, P.B., Thyagarajan, G., Indian Patent Appl. 178/Del/82 (1982)., European Patent Appl. 833011745(1983). Kamal, A., Ph.D. thesis, Aligarh Muslim University, India (1982). R1 ./
C02R
(382)
R1
/
CSI
CO2R
H2O
100-1051
(5 — 1 0 C)
OH R1
OSO2 NCO
C02R Rat Liver microsomes 22-25°C
SO2NH2
(R = Me, Et, Ph;
^^
-0-
R1 = H, CI, Br, Me)
Kamal, A., Rao, A.B. Sattur, P.B., JOC, 53, 4112 (1988). O
II
OH
O-C-NH2 CSI / CH CI3
(383)
> •
S
Me02(/ S/^ Methyl - 4 - (OH) - benzoate
rt
-
3h
Me02OA (31 %)
Parameswaran, K.N. Shi, G-Y., Klotz, I.M., J. MedChem.,30, 936 (1987).
CSI Reactions
142
(384)
/
OMe i) CSI
[O
CO2 Me
NH
base
ii) H2 O
'O
O CONH2 R (R = H, Me)
Kamal, A., Ph.D. thesis, Aligarh Muslim University, India (1982). O O
(385)
Q
/
SO2CI
CSI
o NR1
R1/
\
O
R1
R ^ c - C g H , , , t - C 4 H 9 , i - C 3 H 7 C H 2 C H 2 ; c - C j H , , ; PhCH 2 . Capraro, H.G., Rihs, G., Martin, P., Helv. Chim. Acta, 66, 633 (1983).
Thioesters
(386)
Me I
i)CSI,CH2Cl2, 60
Me I
»
onr
ii) Al CI3 r.t. — . 60°
(16%)
Me
Me I
I
®?
„; Or"T Me
I
O (2%)
Y o
(13%)
o
(12%)
Iwakawa, T., Sato, T., Murabayashi, A.,Heterocycles,
38, 1015 (1994).
CSI Reactions
143
Me
(387)
Me
/Q\-N-C-OMe
OMe
CSI.OC ((}>—
N — C — N — S02 CI
r.t., 1/2 h.
o Me
Me NL
,OMe
COS
V
AICI3 CI02S/
O'
N
OMe
0
Iwakawa, T., Tamura, H., Murabayashi, A., Hayase, Y., Chem. Pharm. Bull., 39, 1939(1991).
Me
(388)
i) CSI
N - C - S R ii)Z\
Me I
f CISO2
Me I N^
.SR -S
C= 0 Me
I
^SR
II
-COS
N
,A> CI
SR
AICI3, Z \
s- N
.A,
(R = Me, Et, P^, X = H, 5 - M e , 7 - M e , 7 - OMe)
Iwakawa, T., Tamura, H., Hayase, Y., Chem. Pharm. Bull., 38, 1075 (1990).
CSI Reactions
144 S
N Me2
(389)
J
^
1
- 0 - C - N M e
j 2
)CSI
ii)AICl3.A
*®y - ^
-s' 02 Dimethyl aminobenoxathiazine dioxide
(R = H, 5 - Me, 7 - Me, 5 - CI, 7 - CI) S
II
N Me2
i)CSI
r^V
(R1 = H, 5 - Me, 6 - Me, 7 - Me, 5 - CI, 7 - CI)
Y °
2
Iwakawa, T., Tamura, H., Murabayashi, A., Hayase, Y., Chem. Pharm. Bull., 39, 1939(1991). Amides (390)
Ri C0NH2
csi ^
R1 CN
(74 - 87%) R1 = Ph, p - MeO C6 H4, p - CI - C6 H4, C5 Hi 1, C6 H5 CH 2
Olah, G.A., Vankar, Y.D., Garcia - luna, A., Synthesis, 227 (1979).
<
(H)R-C = 0
(391)
CSI CSI
r<*
R - C1 - 01 N-C=0 I SO CI 2
^ R - 1C 1 N I SO CI 2
Hydrolysis ^
r<*
A midines
Graf. R., Giinther, D., Jensen, H, Matterstock, K., (Farbwerke Hoechst A.G.), German Patent, 1144718, Chem. Zbl, 20282(1963). Matterstock, K., Jensen, H., (Farbwerke Hoechst A.G.), German Patent, 1168896,1962.
CSI Reactions
145
Me
<
Me^
!. . N — -Si. Me3 |\ — Ol IVIG3
/
^ QSi Me3
>
< \
CSI
» ° = < /NH N-SiMe3 */ N — H Me Me o ° N, N" - Dimethyl - N, N" - bis [ trimethylsilyl ] urea
Roesky, H.W., Zamankhan, H., Chem. Ber., 109, 2107 (1976). Ph PU—L
(393)
Ph .
o =C
CO NH SO2 CI
Ph-
CS
V " Ph
'» O = C > - Ph
"N
N
I
I
Me
Me
Ph Ph-
Ph I Me R1
(50%)
R1 CO NH SO2 CI +
-N' I
'
n
'N' I
R3
Ph
R3 R1
o^O<
. CO NH2 ^Ph
N'
I
R3
(37 - 55%)
Foucaud, A., Gouriou, Y., Bull. Soc. Chim. Fr., 1500 (1971). Me
(394)
^
K.
N
Me
Y
I (CHa)^
°
i)CSI ii) Hydrolysis
•>
f
'
Y
NH
I (V*lW
(79 - 92%)
Rao, K.R., Nageswar, Y.V.D., Srinivasan, T.N., Sattur, P.B., Synth. Comm. 18,877(1988).
CSI Reactions
146
o
O
(395)
o
Me-N^Tr^NHSCteCI
Me-N'
A
N
H2 Q
^NNH2
Me
Bennett, G.B., Simpson, W.R.J., Mason, R.B., Strochschein, R.J. Mansukhani, R., JOC, 42, 221 (1977). O
(396)
1 -Phenyl-1,4-" dihydro - 3 (2H) • isoquinoline
N - CONH2
CSI
o
Zara - Kaczian, E., Deak, G., Acta Chim. Hung., 116, 89 (1984). o 11
(397)
|\"j£
i) excess CSI
N-i O'
1-""" \ /
M e
ii) Na2 S2 O5 (aq.)
""< CO2 Me
rvv: HN
M~^y
II O (37%)
NMe
" CO2 Me
Campbell, M.M., Harcus, R.G., Nelson, K.H. JCS Perkin Trans. I, 817 (1978).
CSI Reactions
Me
(398)
Ph CNHV 3 \
r
>
I Ph C-N i) CSI, MeCN 3 N^
Me
/ s
Penicillanic acid
147
-COH 2
ii) Me N 3
H ; \ S^
S (45%)
.O
'CMe 2
Faubl, H., JOC, 41, 3048 (1976).
BoC - HN
J-
M
^
(399)
CSI, CH2 Cl2
NH
\
N
-NH
&
O' BoC - HN
<X"IfX
t R1 = CH2 COO - Bu t CMe2 COO - Bu
NH.
\
S_
o
N
aS
I R1
^^NHS02CI O
Barbachyn, M.R., Tuominen, T.C., J. Antibiot., 43, 1199 (1990) Me
I
(400)
R1
S
R1
CSI <
0
T C02 R2 R1 = Phthalimido; R2 = C6 H5 CH2;\ R1 = Trityl ; R2 = C6 H5 CH2;
CI ^
s CO 2 R2 c / s t r a n s (2 :
'
3)
Ponsford, P.J., Baxter, A.J.G., Southgate, P.M. East Eur. Pat. Appl. 3740 (1979); C.A. 92,76280(1979). Smale, T.C., Eur. Pat. Appl. 2564 (1979); C.A. 92,76279 (1980).
CSI Reactions
148
i)CSI,0°C
(401)
Silyl*-protected deoxy guanosine
ii) Et3 N
(tert. butyldimethylsilyl)
(R = TBDMS)
K(J
(41%)
Camus, P., Lhomme, M-F., Lhomme, J., Tet. Lett., 30, 467 (1989).
Ph
I (402)
r^rs\
Ph |
0 0 I. © /I
— N
©'>-C<->C-C6H5 —'N N CSI.CH2CI2 Ph
~
O
O
II
II
'© N | > - C -^N I
x
Ph
/C-C6H5 N I C=0 I , "v0 N//
o = s -~o (71%)
Schossler, W., Regitz, M„ Chem. Ber., 107, 1931 (1974).
(403)
ZH + CI SO2 NCO
CI SO2 NH COZ
HC — O 2i
N-
HC — C O 2
Lattrell, R, Lohaus, G., Chem. Ber., 105, 2800 (1972).
I CI
CSI Reactions
149
Sulfonamides
(404)
CSI
R S02 NH2
R S02 NH CO NH SO2 CI _ R SO2 NCO + CI SO2 NH2 (I)
is.
% yield (I) = 75 - 92. % yield (I) = 18-30.
L r - j , U^ rig, L^g W]7>
R = Ph, p-Me C 6 H 4 , Me;
Appel, R., Montenash, M., Chem. Ber., 107, 706 (1974). Roesky, H.W., Tutkunkardes, S., Chem. Ber., 107, 508 (1974). R SO2 NH2
(405)
CSI
R SO2 NCO
(R = C F 3 , C 4 H 9 , C 8 H 1 7 )
CF3 SO2 NCO
H2O
CF3 SO2 NH2
ROH CF3 SO2 NH CO2 R Ph NH2 BzH
t (R = Me, Bu, Ph)
CF3 SO2 NH CO NH Ph
CF3 SO2 N = CH Ph
Behrend, F., Haas, A., Chem. Ztg., 95, 23 (1971). C.A. 76, 58900 (1972).
CSI Reactions
150
O
(406)
RSO2NHR
CSI, 0 - 8 0 C^
CISO2-N
-A,
SO2
>100 C
R
R SO2 NR SO2 NCO + HCI O
Me Me \ N — SO2-NH
i) CSI, 80° C
I
SO2
'k ^
I
ii) HCI
I
^
/
I
Me SO2
Me
Me N
SO2
I Me CSI Me \
Me ^ N — S02-N =C= 0
I
N — SO2 - N = C = O
I MeSQ2
MeS02 Me NH SO2 Me
Warm, A., Bernardinelli, G.,JOC, 59, 5340 (1994). (407)
R SO2 NH R1
CSI
R SO2 N SO2 NCO
I R1
Farbwerke Hoechst A-G. DAS 2257240; Angew Chem. Int. Ed. Engl, 13,748(1974) Lohaus, G., Midenberger, H., U.S. Patent 3, 931, 277 (1976). (408)
Me SO2 NH Me
CSI, Ph Cl
Me SO N Me NCO
100°c
(98%)
Schlegel, G., Lachheim, S., Berger, H. (Hoechst. A.G., Germany). Eur. Pat. Appl. EP 501369. C.A. 118, 8613 (1993).
CSI Reactions
* / (409)
'•"
° |l
Me CSI 8cP
SO2
151
'
I
C
^ N
*
-
S 0
2
- N h / ' ^ N /
I
Me
I
Me — SO2
SO2 — Me
Warm, A., Bernardinelli, G.,JOC, 5, 5340 (1994).
(410>
MeSONH 2
i)CSI,PhCI,100C 1.5h ii) Quinuclidine
52 62 50 65 62 52
R =Et = Pr = Me 2 CH = Bu = PhCH 2 = 2C1-C 6 H 4 CH 2
=
Sulfonyl isocyanate
% yield
Sulfonyl isocyanate (RS0 2 NCO)
c|
Me SO NCO 2 (47%)
-<0^ c H 2 -
—
or
_ cl ^O^- CH 2 CI
Mengel, R., (Celamerck G.m.b.H. und Co., K— G.) Ger. Offen DE 3, 228, 101, C.A. 100, 174264" (1984). (411)
CF3SO2NH2
wal
».
CF3S02NCO
Behrend, E., Haas, A., J. Fluorine Chem., 4, 83 (1974).
CSI Reactions
152
(412)
CSI
RR1NS02NH2
R R1 N SO2 NH CO NH S 0 2 CI Hydrolysis R R1 N SO2 CO NH2
(R, R1 = Me, Et, Ph,
NRR1 = Piperidino or Morpholino)
Appel, R., Motenash, M., Chem. Ber., 108, 616 (1975). O Me (413)
I /S02
I
I
~* N — SO2 - N = C= O
CSI
I
S
°2 \ Me
H
SO2 Me^ Me
Me
NH ^
N — SO2 - N = C= O
+
SO2
SO2
'Me
Me •
Warm, A., Bernardinelli, G.,JOC, 59, 5340 (1994).
SO2NH2
(414)
SO2 NCO
CS|
-*-
R-
95-100°C,2h Aryl Sulfonyl Isocyanate
(R = H, Halo, N 0 2 , Lower alkoxy, CF 3 etc.) Celamerck G.m.b.H. und Co. K-G., Ger. Offen DE 3,132, 944., C.A. 98, 215319 v (1983). (415)
p - Me C6 H4 SO2 NH (Et)
CSI
CI SO2 NH CO N (Et) SO2 C6 H4 - Me (p)
Lattrell, R., Lohaus, G., Chem. Ber., 105, 2800 (1972).
CSI Reactions
153
(416) Chlorinating Agent CSI acts as a chlorinating agent when allowed to react with an alkane (under free radical conditions,viz, UV irradiation or thermal initiation). Tertiary hydrogens are selectively replaced by chlorine compared to primary hydrogens (120 : 1) and the H- abstracting entity in the isocyanate radical. Mosher. M.W. Eates, G.W., JOC, 47, 1875(1982). Med MeQ
(417) ^ > N — Me >N — Me
CSI
MeO MeO
C02 Me
C02Me
C02Me
C02 Me
(81%)
Giger, R., Rubenstein, R., Ginsburg, D., Tetrahedron, 29, 2392 (1973). Acid Chloride
i)C SI
(418)
ii) Et3 N, H2O
i)CSI ii) Et3 N, H2O
CSI Reactions
154
Compd. No.
R1
R2
R3
Yield, %
la lb lc 2a 2b
H H Br -
H Br Br -
H Br
92 85 86 91 88
Dhar, D.N. Bag, A.K., Ind. J. Chem., 21B, 366 (1982). Amino and Imino Compounds
(419)
Ph NH 2
CSI - PhH
Ph NH SO2 NH2 (37%)
N - Phenyl Sulfamide
Lee, C -H., Kohn, H., JOC, 55, 6098 (1990).
o (420)
-€r
NH2
NH — C — NH SC-2 CI
CSI
- @ "
V H 1, 2, 4 - benzothiadiazines
Ejmocki, Z., Ochal, Z., Rodakowski, K.,Przem. Chem.,12, 449 (1993). C.A., 121, 57471 a (1994).
CSI Reactions
NH
2
nr
i) Obi < 4 2 1 )
^ ^ N 0
^
2
^
155
^ ^ / N H C O N H C/^\T ^ ^ N 0
2
Redn. "
2
Ws> Hoechst. A.G., German Patent 2, 855, 884. C.A. 94, 15413 b (1981).
(422)
a
-
^ ^ ^ -
C - OMe
_-u ©3? ^ ^
II
^ r <
H>
0
Cohen, E., Klarberg, B.,JACS, 84, 1994 (1962). CSI
Et3N
ROH
RNHSQCI
I RN =SQ> I -78 °C
( 423)
Hj^CQPh,
R1
* NHSQNHR
d^ocHj
NaH
0.5-1.0 n
*
N"
cr"N R
Xiao, Z., Timberlake, J., 7. Heterocycl. Chem., 37, 773 (2000).
CSI Reactions
156
Cyclization
i) CSI, §Q tr.
^•v.
"N
CH3 CN
NH
A
CIO2 S N H " ^
(424)
(tert. base)
0
i) CSI, 0°C
1
CH3CN
°2KH^
N
N"
^NH2
^A
O
(50%)
NH
o
Karady, S., Amato, J.S., Dortmund, D., Patchatt, A.A., Reamer, R.A., Tull, R.J., Weinstock, L.M. Heterocydes, 12, 815,1199 (1979). Y CSI
(425) hT
N"
^NH
EtN (C3 H7)2
I
^NH2
[ Y = CH, N]
CI SO2 - H N K
C= 0
""N' ^ N 2 ^
N
-^o
Karady, S., Amato, J.S., Dortmund, D., Patchatt, A.A., Reamer, R.A., Tull, R.J., Weinstock, L.M. Heterocydes, 12,815,1199(1979).
CSI Reactions
CI N
(426)
157
CI
-<^
I
i)CSI,Dioxane
N
d
C K ^ N
N'^N
70-80°C,20h
L
\NH2
o
I
II
C K ^ N
\NH-C-NHSO3H
N - (2, 4 - Dichloro - 2 - triazin - 6 - yl) urea
Rainer, R., Swiss Patent 580, 608 C.A. 86, 29891 (1977). Ar
Ar
(427)
^* ©CI
OAL \ - / \ N ^ \ N H 2 2 - Amino - 4 - aryl quinazoline
ii)base
^ - ^
^N "^N 02S^ ^1 . O
Kamal, A., Sattur, P.B., unpublished work, 1982. N3
H
(428)
V H N
N - ^ \
DCS!
N
il)EtN(Pri)2»
/
^>-NH2
,
^
c^N^S02
H
L
N-—N NCO NH2
Pasto, D.J., Chen, A.F.T., Tet. Lett.,14, 713 (1973).
^
H2O
"
CSI Reactions
158
S.
(429)
. NH2
C Y" I
i) CSI ii)EtN (Pr-i)2
M
c
SO, H (50%)
Karady, S., Amato, J.S., Dortmund, D., Patchatt, A.A., Reamer, R.A., Tull, R.J., Weinstock, L.M. Heterocycles, 12, 1199 (1979).
C02Et
C02Et
5% KOH (aq.)
(430)
Q^NH 2ii)H2O 0CV
NH CO NH 2 . C 2
H5
OH
O NH
A,
S'
^N
(91%)
H
I
Wamhoff, H., Ertas, M., Synthesis, 190 (1985). SMe SMe
i) CSI
(431) Ph -
N
^
NH2
Ph-N^^NH
ii) Et N PH2 O H (22%)
Karady, S., Amato, J.S., Dortmund, D., Patchatt, A.A., Reamer, R.A., Tull, R.J., Weinstock, L.M. Heterocycles, 12, 815 (1979).
CSI Reactions
159 MeO
(432) MeG
ii)H>0/ft
o w
(R F6 = CONH CONH)
Menendez, J.C., Diaz, M.P., Bellver, C , Sollhuber, M.M., Eur. J. Med. Chem., 27, 61 (1992).
CSI
NH
(433)
O
X = H, X = R,
^ Y/
Y = R; Y = R;
X NHC - NH SO2 CI
+
N-C-NHSO2CI
X = H, X = H,
NH
Y = R-CO Y = R-CO
/
\ R" (H)
O
R1 X-NH-C-NH-SO2-N/ \
+HCI R"(H)
(X = R, R - CO, R - SO2)
Graf R., (Farbwerke Hoechst A.G. 1952), German Patent, 931467, Chem. Zbl, 11094(1955). Graf. R., (Farbweke Hoechst A.G. 1952), German Patent, 940292, Chem. Zbl, 12973(1956).
(434) N
X
i)CSI, CH3CN, 0 C NHR
» ii) Et N (PH)2
[ R = Ph, C6 H5 CH2]
2
^N^Z>0 1
(50%)
1
CSI Reactions
160
Karady, S., Amato, J.S., Dortmund, D., Patchatt, A.A., Reamer, R.A., Tull, R.J., Weinstock, L.M. Heterocycles, 12, 815, 1199 (1979).
R1 i) CSI, Me NO2 (Method A)
(435)
AICI3
ii) CSI, EtN02 (Method B) NHR2 [I]
R1
0
V'
0
R1
$x
?
^•. ^ SO2 NH2
1
© H / H2 0
^
>•
NHR2
(III ), Sulfonamide deriv.
(ll)R2
Yield,% Adduct I Product R1 II, R1
Product III, R1
R^ (I-III)
II Method A B
III Method A B
H
H
H
H
85
67
90
4-Me
7-Me
5-Me
H
92
66
96
2-Me
5-Me
3-Me
H
87
66
73
4-Cl
7-C1
5-C1
H
65
69
70
3-Br
6-Br
4-Br
H
50
42
77
4-MeO
7-MeO
5-MeO
H
83
61
84
-
H
H
H
Me
74
64
89
-
H
H
H
Ph
89
89
Girard, Y., Atkinson, J.G., Rokach, J.,JCSPerkin Graf, R.,Org. Synth., 46, 23 (1966).
-
42
Trans. I, 1043 (1979).
CSI Reactions
NH-R
i) CSI
(436)
161
N - ^
>
NH
ii) Et3 N .NH-R
o
N
-S02
I R
R
I
NH
i) CSI 1 ii) Et3 N
NH
R
o
K—-^
NH N- -S0 2
I
R (R = Alkyl, Aryl)
R
Otto, E., Durkheimer, W., Muschweek, R., German Patent 2,409, 355. R i) CSI, CH2 Cl2
OAc
.o
R /
(437) ii) IN HCI, reflux 3-6 h. \
/
--ON
iii)AC2 0 , pyr., DMAP
^•OAc
r.t, 1 6 - 2 4 h
t, t - 2, 6 - Diacetoxy - r - 1 - tert - butoxy Carbonylamino -
V
O NH
RO O (63-71%)
•
X = CH2; R = Ac\ X = O; R = Ac )
1 - Cyano Cyclohexane
Santoyo, G.F., Robles Diaz, R., Calvo-Flores, F.A.G., Vargas Berenguel, A., Gimenez, M., Synthesis, 631 (1992).
162
CSI Reactions
Ph.
/
O
n
p
(438)
N
C —NHSO2CI
\ vN ^ C N
HCI (aq.)
CSI, CH2 CI2 N N 1 - Benzyl - 4 - anilino • 4 - Cyanopiperidine
\Pn (100%)
.CO2 Na Ph-N Na OH (aq.)
[
" x
|
<S (82%)
•Ph
Ph
(60%)
Feldman, P.L. and Brackeen, M.F., JOC, 55, 4207 (1990). SMe Pt
SMe
(439)
i) CSI PhN
ii) Et N Pr2j
NHPh
JL
V
, Ph
o's X (40b/o)
Karady, S., Amato, J.S., Dortmund, D., Patchatt, A.A., Reamer, R.A., Tull, R.J., Weinstock, I.M. Heterocycles, 12, 815 (1979).
(440)
/T}>
i) CSI, CH2 CI2 -15 —
o -10 C
CN
ii)DMF
H
(40%)
NCX
i.y
CN
CSI Reactions
163
O "
* - x
CIO 2 S-NH-G;
N l CSI H (X = Electron withdrawing substituent)
.
N==C
Ox
—)^Ux
| H
(
H
Barnet, G.H., Anderson, H.J., Loader, C.E., Can. J. Chem., 58,409 (1980). Loader, C.E., Barnet, G.H., Anderson, H.J., Can. J. Chem., 60, 383 (1982). Anderson, H.J.,Loader, C.E., Foster, A., Can. J. Chem., 58, 2527 (1980). Loader, C.E., Anderson, H.J., Can. J. Chem., 59, 2673 (1980). Floyd, A.J., Kinsman, R.G., Roshan-Ali, Y., Brown, D.W., Tetrahedron, 39,3881(1983).
R1
(441)
CSI
X
R1
R2
R3
% yield, I.
NH
Et
Et
H
62
NH
Me
Et
H
56
NH
CH 2 C0 2 Et
CH 2 C0 2 Et
H
46
NH
Et
Me
Ph
35
NH
H
H
3,4 ,5(MeO) 3 C 6 H 2
42
NH
H
H
F5C6
39
NH
H
H
4-t-Bu Ph
32
64
CSI Reactions
NH
H
H H
NH
H
H
H
39
O
H
H
H
70
t4
- ( C 0 2 Me) C 6 H 4
37
Boyle, R.W., Karnaratne, V., Jasat, A., Mar, K.E., Dolphin, D., Synlett., 11,939(1994). ci
^>CH^<"ecP
(442)
N^
^
Me
JJCS^
rA V
ii)DMF
H
C H 0
hT
^ M
(50%)
Anderson, H.J.,Loader, C.E., Foster, A., Can. J. Chem., 58, 2527 (1980). CONH SO2 CI NEt 3 i H
oc
i H CN
Vorbruggen, H., Krolikiewicz, Tetrahedron, 50, 6549 (1994).
(444) ( Q T ) ^
^
K
N
CSI MeC
> ^ O C N J ^.PhMe^Ly^N 0rSh
Lo
CI S02 - NH'
"^Ao (H
(23%)
Borror, A.L., Chinoporos, E., Filosa, M.P., Herchen, S.R. Petersen, C.P., Stern, C.A., Onan, K.D., JOC, 53, 2047 (1988).
CSI Reactions
(445) f O T V
165
R CSI.MeCNor
N
»
H
ether
(R = H, Ph)
"-NHSO2CI ' CH3CN/DMF
9N
_
CH3 CN or ether
^
f V
-
^"^e H
Me
-N- Me
(70%)
CSI
/Me
CH3 CN or ether v
N^\Me H
rf^-iT^ L ^ U ^ N S^^S ^ ^
CSI
" N ' NMe CV // NH SO2 CI O (60%)
.(gipn^^^
CH3CN or ether ^^Ny^^ "
H
aq. Acetone
N
/^NH OOCCII /fr NS HS 0
|C
°
2
y
2
Mehta, G., Dhar, D.N., Suri, S.C, Synthesis., 374 (1978).
H2 NT ^
^
^
P h
Xh ^ // ^^ •W^ -^^NK^. ^J P R I
^
i)CSI,CH3N02 in Al CI-, i')AICI 3
*"
^
NH
(55o/o)
^
^ o /
P n
R -a^ /Y ^^ r^ T ^Ph , . OS 2< ^ N A 0 H u H (32%)
2
CSI Reactions
166
R1 R1
Ph N^\ph H
Ph
i) CSI N
N
nitromethane
Ph
I
CIO2S - NhK
C=0
R1 Al CI3
Ph
R.
N
N H2N'
%
Ph
O
(27%)
Kamal, A., Narender, A.V., Sattur, P.B., Heterocycles, 24, 3397 (1986).
i) CSI
ii) - CO2 Ni) H 2 L/www CO2 Me |v) oxid n
(447)
v) Redn
C ^ \
F-
H Et aza - ebumamonine
Hammer, H., Winterfeldt, E., Tetrahedron, 37, 3609 (1981).
(448)
[0
CSI
Milanese, A., (Trifarma, S.R.L., Italy)., PCTInt. Appl.,WO C.A. 125, 195448(1996).
9621649.
CSI Reactions
(449)
167
u
CSI
\^S^NHR
,CN
^
V
/M = vT
- (Substituted amino) azazulenes
NHR
/CI
—1
•
- ^
^
^NHR
Abe, N. Matsuda, H, Sugihara, Y., Kakehi, A., J. Heterocycl. Chem., 33, 1323(1996).
Nitrogen Compounds Aziridines/Azirines N-S°2CI
A
Ph
n Ph i)CSI,(Tc i ) U b i , u c \^ N N x'
I N N
(450)
H
\ /
P h /
\ y
H X
Ph
ether-CHCbH-\ (4:1)
/-H
p^r
(Cis) 1
™A
o Acetone-H2O O Acetone-H2O
(KOH)
X^
N N
* H-\
^ P h
O
Z_ H
Ph^
^Ph
(2)
(3) SO2CI
I N H11C 6 , 8, R = H
H
C 6 H-|-| I N N H
CSI
9
= Me
10
=CI
11
=F O
C/s - 1 - Cyclohexyl - 2 aroyl - 3 - phenylaziridines
H11C6
^ A ,
—'
N
=H =Me =Cl =F
N
12,R 13, 14, 15,
=H =Me =C1 =F
ph
A
M
N
Nl'
H\
/ H
/^n^
^pn
H-A—^-H _ ^
/fS)ii 4,R 5, 6, 7,
H11C6 N-S020
16,R 17, 18,
=H =Me =C1
168
CSI Reactions SO2CI I N
z_V H H>
Ph
;A0
C6H11 I N
* -
23, R = H
CSI
C6 H4 - R (p)
C 6 H 4 - R (p)
_,
PhH
24,
= Me
VC6H11
19, R = H 20,
= Me (p)
21,
=CI
22,
=F
O H11C6 V
/S°2CI
A
/
H-
25, R = CI
C 6 H 4 - R (p) 26,
=F
Ph—U—o
Keshava Murthy, K.S., Dhar, D.N., J. Heterocycl. Chem., 21, 1699 (1984). O
o (451)
Me
i)CSi,CH?Cl2 O^
Ar - C - N
Me
Ar
Me + iu
ii) Na2 SO3, OH
Ar =
, Me
(0 C) M
ANA
'
N (1), 53%
-X :-0-Br O'
<.y
X = H, Me, CMe 3 , Br, CI, OMe, N 0 2 Y = H, CI When
O
Ar = Ph; Products (I) and (II) are :
2 - Phenyl - 5, 5 - dimethyl - 2 - oxazoline. 3 - Benzoyl - 5, 5 - dimethyl - 3 - imidazolidin - 2 - one.
NH •Me
Me ( II ), 34%
CSI Reactions
169 O
K %A
i)CSI,CH2Cl2 R1
/
\
N'
/R3
©
R2^ oxaziridines
"0 R3
RZ
ii) Na2 SO3 / OH
R1 = H, Me, Et; -x (Where X = H, Me, F, CI, Br)
R2 = Me, Et,
R>3J =_ C 4 H 9 , P h C H 2 , C 6 H n Pramod Kumar, Ph.D. Thesis, I.I.T., Kanpur, India (1994). CISO2
R1
\
CSI
(452)
* \ / \
R1
•78°C
(2 moles)
R2
f-^x fi^-:
R2
H NSO2 CI
CSI
R1 = Ph, p - Me C6 H4, " 7 8 p - CI C6 H4.
,N
R1
C
O
R2
R2.
R2 = H
- CSI (extrusion reaction) oxidn. R2
R1
X
R r ^ r r
R
2
H
O X
i) CSI N:
N ^
(.
NH
ii) Hydrolysis
(2 moles)
HT R Triazocinones (84 - 96%)
CSI O R = Ph, p - Me C6 H4,
Rv
,°-«
p - CI C6 H4, p- Me C6 H4
//^ H/'
Rv
^N
NH H
(55 - 60%)
R oxadiazocinones (33 - 40%)
Daniel, J., Dhar, D,N., Synth. Comm., 21, 1649 (1991). Daniel, J., Dhar, D.^., Synth. Comm., 23,2151 (1993).
CSI Reactions
170
Nitrogen Heterocycles
1
(453)
N'
i) CSI, Et2 O ii) Hydrolysis
*"
Me i)CSI, Et2 0
»ii)KOH/aqacetone C02Me
Pindur, U., Kim, M-H., Tetrahedron, 45, 6427 (1989).
OBn
(454)
MeO
MeO
NH SO2 CI CSI, Et2 O Me
(97%)
Moody, J.C. Swann, E., Tet. Lett., 34, 1987 (1993).
(455) CONH2
ii) DMF
Yasuyoshi, M., Yagi, S., Hachiken, H., Ikeba, M., Heterocycles, 38, 1881 (1994).
CSI Reactions
171
(456) CSI
Pyridazinones
Chloropyridazines 1
(R = H, R = H, Me, MeO, CI; R = R' = Me) Srinivasan, T.N., Rao, K.R. Sattur, P.B., Synth. Comm., 16, 543 (1986). Meq
(457) MeC/' CSI
Meq MeC/~
o -30 NO'/
\
©
o • 80 C
H2 0, H
r
NH
\ i
OH
(56%)
MeQ
o O'
*'/
/ (76%)
Menendez, J.C. Villacampa, M., Sollhuber, M.M., Heterocycles, 32, 469 (1991).
CSI Reactions
172
R4
o
R4
CSI, CH2 Cl2
58)
R2
0
-10C
i 00 1 a -e
2a -e
la
R ! , R 4 = Ph;
R 2 , R3 = H;
R5, R6 = H
lb
R 1 , R 2 = Ph;
R3, R4 = H;
R5, R6 = Me
lc Me
R^C^N;
R2, R 3 = H;
R4 = Ph;
Id
R 1 ,R 4 = Ph;
R2, R 3 = H;
R5, R 6 = "fCH2J5
le
R ! , = Ph;
R 2 ,R 3 ,R 4 = H;
R 5 , R6 = Me
R5, R6
Me
Me /
CSI
(—
Me
Me^^rvTi
1
00
H
Joseph, S.P., Dhar, D.N., Syrcf/z. Comm., 18, 1743 (1988). Joseph, S.P., Dhar, D.N., Tetrahedron, 44, 5209 (1988). O i
|N
i) CSI ii) Et3
(459)
~C
a) R = Me; X = S b) R = Me; X = 0 c) R = H; X = S
N-H I SO,
N-^N-H
CSI Reactions
173 NH2
N
I
N
X
N
i) CSI Ph
SO2
ii) H2 O
X = S;
Yield, I, 40%
X = O;
Yield, I, 86%
Daniel, J., Dhar, D.N., Synth. Comm., 23, 121 (1993).
Me
Me
© SO2
CSI
(460)
R-
N0 -N(i)
•N.
Me'
\
R1
R = H; Me
( I ) R = H;
R1 = Si Me3
< A
o
Yield, 84%
R = Me;
Yield, 9 1 %
I = 1, 2, 3, 5 - Thiatriazolo - [1, 2 - b] pyrozolium - 5, 5 - dioxide Friedrichsen, W., Boettcher, A., Debaerdemaeker, T., Heterocycles, 20, 845(1983).
H
I
(461)
02
Nv
y N
\
^ CHNO2
R (R = H, alkyl)
i) CSI
I
r
NH
ii)pr 2 NH NO2
Reddy, A.V.N., Maiti, S.N., Singh, I.P., Micotich, R.G., Synth. Comm., 19,3021 (1989).
CSI Reactions
174
/
Me
Me
_/
(462)
CSI Me'^'^SCfc
Me' 0 Na*,©
-N
3, 5 - Dimethylpyrazole
(100%)
©
>
Meso-ionic pyrazolium thiatriazole
(sod. Salt)
Grandberg, I.I., Nam, N.L., Khim Geterotsikl Soedin,l34 (1994). C.A. 122, 9953 h (1995). R2
f
(463)
,H R3.
R1
R2
CSI
r
R3.
2 - Pyrazolines
[1 -10]
R2
R1
R3.
l
CI02 SHN - C = O
H2N-C = 0
[11 -20]
[21 - 30]
R1
= Me; R2, R 3 = H
a)
1, 11, 21
R2, R3 = H
b)
2, 12, 22
R2, R3 = H
c)
3, 13, 23
R2 = H; R3 = p - Me
d)
4, 14, 24
R2 = H; R3 = p - Ph CH 2 0
e)
5, 15, 25
R2 = H; R 3 = p - MeO
CSI Reactions
175
f)
6, 16, 26;
R1 = Ph.;
R2 = H; R3 = o - CI
g)
7, 17, 27;
R1 = p-MeO C 6 H 4 ;
R 2 , R3 = H
h)
8, 18, 28;
R^p-ClCgH^
R2, R3 = H
i)
9, 19, 29;
R1 = p-Me C 6 H 4 ;
R2, R3 = H
j)
10, 20, 30;
R ' R 2 = Me
R3 = H
Dhar, D.N., Raghunathan, R., Ind. J. Chem., 23B, 1187 (1984).
/ N—N
//
(464)
N02
\
02N-.
o
N
N02
<3 CSI, CHCI3
^^ N'
r.t., 1 h. N02
vV
J, "N'
NO2
.N— NO2
S
(R = Bu, CH2 Ph, CH Me2, CH2 Si Me3,
Picrylimino thiatriazolines
CH2 CH2 CI, CH2 CO2 Me)
L'Abbe, G., Brems, P., Albrecht, E., J. Heterocycl. Chem., 27, 1059 (1990). I (465)
R
)QrV c H 2 x y^^~~-H
CSI, CH CI3
Et3N
r.t., 10 f R, X = H, CO2 Et = Me, CO2 Et
Badawey, E-S.A.M., Rida, S.M., Soliman, F.S.G., Kappe, T., J. Heterocycl. Chem., 26, 405 (1989).
176
CSI Reactions
Compounds Containing
R 1
(466)
\
/ R2
>==
N
-
csi, CH2CI2
cio2&^ ]p
N
so 2 ci
O Triazinediones (I ) 1
2
R
R
% yield (I)
Ph p-MeC 6 H 4 P-C1C6H4 p-N0 2 C 6 H 4 Ph Ph Ph Ph Ph Ph Ph
Ph Ph Ph Ph p-MeOC 6 H 4 ^-C1C 6 H 4 ^ - N 0 2 C6H4 m-N0 2 C 6 H 4 o-Cl C 6 H 4 C 6 H 5 CH 2
100 86 73 50 50 60 0 78 50 60 65
C
6H11
Walrond, E.R., Suschitzky, R.,JCSChem. Comm., 570 (1973). Suschitzky, H., Walrond, E.R. Hull, R., JCSPerkin Trans. I, 47 (1977). NC6H11
U
( 4 6 7 ) H-11 C6N = C = NC6Hn
CSI
C
C I O 2 S - N ^ ^ N ~ c 6 H11
H
N 6 H
/A
H2
Q
S0 2 CI
C
H-N"^N- 6H11
c^Ao H
Suschitzky, H., Walrond, E.R., Hull, R., JCSPerkin Trans. I, 47 (1977).
CSI Reactions (468)
177 2CSI
RCH = N - N = CHR
». R
o
T
^ | CISO2-N
(R = Ph, p - MeO - C6 H4)
^ | ^N
"NSO 2 Q I k
R
Walrond, E.R., Suschitzky, H., JCS Chem. Comm., 570 (1973). Me
Ph'
HN HN.
JJ<^< •Ph
Naser - u d - din, Riegl, J., Skatteboel, L., JCS Chem. Comm., 570,(1973). p-MeC6H4N
(470) v '
p-MeC6H4^
,,
^
N
Me.
/
\\
> C
Me^ \
o
J>— OEt
Q
/
Q
N
CSI, 70 C
c6H6
#
/
» » CIS0 2 N=/
\
\
y. Me
J<
Q
- ^ ^ M e
(33%)
L'Abbe', G., Destexhe, R., JCS Chem. Comm., (22) 1614(1985). R2
(471)
H-
R2
X.. —** nrrx y. j\—o
cAoAR1
NSO2 CI
Q
0'
5 - oxazolones
a) R1 = Ph;
R2 = Me
b) R1 = Ph;
R2 = PhCH 2
c) R1 = Me;
R2 = PhCH 2
U
R1
Dhar, D.N. and Raghunathan, R., Ind. J. Chem., 23B, 761 (1984).
CSI Reactions
178 O
(472)
O
O
HN I I N-H I ' , N - S 0 2 o ^ r
o
^Me
^
i) CSI 0 - 5 C N
*. NH
Me
ii)H20/KOH C 6 H 5 SH (37.5%) 0 110C
Me
HN
°2W°2 I CI
Daniel, J., Dhar, D.N., Heterocycles, 32, 1517(1991).
Ar'
(473)
@ /
P h
J
A> <S
l)CSI,CH2CI2 o atOC
0 || Ph II Ar - C - N • \ Ar'
(1 a - h)
O ||II + Ar' - C - N :
Ph
•Ar
(70 - 90%)
la
Ar, A r J = P h
lb
= 4 - Me C 6 H 4 ;
lc
=4-MeOC6H4;
= 4 - MeO C 6 H 4
Id
= 4 - CI - C 6 H 4 ;
= 4C1-C6H4
le
=4-N02-C6H4;
= 4 - Me C 6 H 4
If
=4-N02C6H4;
= 4 - MeO C 6 H 4
lg
= 4 - N 0 2 C 6 H4;
= 4 - CI - C 6 H 4
lh
=Ph
= 4 - N 0 2 - C6 H4
Ar',
= 4 - Me C 6 H 4
CSI Reactions
179 O
Ar'
©.Ph N<^Q
H
l)CSI,CH2CI2 ».
°
Ar P
|| ^ M ^ > M Ar-C-NHPh+ N ^ N
-30°C
N ^ / ' V Y^ Ph
(2 a - h)
r
2a; Ar = 4 NO2 - C6 H4
2b;
= 3 NO2 - C6 H4
Joseph, S.P., Dhar, D.N., Tetrahedron, 42, 5979 (1986). C8H-17
^
(474)
C8H17
^ (enamide)
^ 5;
Me V© | O0
R = H; (33%) = Me (38%)
=Me R
CSI 6; R = H 7;
= M e
N—^ I R = H(51%) Me = Me (44%)
Joseph, S.P., Dhar, D.N., Tetrahedron, 44, 5209 (1988).
CSI Reactions
180
CI (475)
R-<( ^
i) Et3 N - PhH
))~c "
N-NH
ii) CSI
1,3- Diarylnitrilimines
2
N
(44 - 75%)
NSO2 CI
e) R = H;
a) R, X = H b) R = 4 - CI;
X =2-CI
X=H
f)
= 3 - N02;
=H
=H
g)
= 4 - N02;
=H
c)
4 - Me;
d)
4 - OMe; = H
Dhar, D.N. and Raghunathan, R., Synthesis, 1095, (1982). Cl
0
/
i) Et3 N, MeCN, 1-2h
N NH
-
"N°2
„ mw
*
m>° N
N. \C6H4-N02(P)
(38%)
Dhar, D.N. and Raghunathan, R., Synthesis, 1095, (1982).
(477)
R
\
D?
R2—/
> = N R
2
/
; N H
H-N
I
- E ^
/ N
R3_N/
WN
<( X
>5
R3 4 - Arylthiosemicarbazones
S v°5 - 95 k)
CSI Reactions
181
a) R1, R2 = Me, R 3 = Ph
f) R1, R2 = Me; R 3 = p - CI C 6 H 4 ;
b) R 1 , Me, R2 = Et, R 3 = Ph
g) R1 = Me; R2 = Et, R 3 = p - CI C 6 H 4
c ) R \ R 2 = ~iCH2h
;R 3 = Ph; h ) R ! ' R 2 = ~iCH2h
;R3 = p-ClC 6 H 4
d ) R 1 , R 2 = -^ C H 2>4 ;R 3 = Ph; i ) R ! ' R 2 = ~iCH2h
;R3 = p-ClC 6 H 4
e) R 1 , R 2 = Et; R 3 = Ph;
j) R1- R2 = Et; R 3 = p - CI C 6 H 4
Tripathi, M., Dhar, D.N., Synthesis, 1095, (1982). R1 KI^
(478)
N
^ M R2
RNHCRl:NR2_2fL.|
I
Hydrolysis
RN ;CR1 NR CQNH SQ
H
H (37-99%) [I]
R1, R2 = Me; R1 = H, Me, Ph
R, R2 = Ph;
R, R2 = Me; 4-MeO C 6 H 4 ; R1 = Ph
R, R2 = 4 - MeO C 6 H 4
R = Me. R ' , R 2 = Ph
R1 = Me
[I] = 1, 2 4, 6 - Thiatriazazinum- 5 - olate, 1 , 1 - dioxide Friedrichsen, W., Moeckel, G., Debaerdemaeker, T., Heterocycles, 22, 63(1984). (v 4 7 9 ) '
p bc li °
RCH = NOH
^
„
RCN (75-86%)
Olah, G.A., Vankar, Y.D., Garcia - luna, A., Synthesis, 227 (1979). o (480) Ci \(~))- C H
=NOH
CSI
Hydrolysis
^
-
CI \ ( ~ ) ) - CH - NO - C - NH S Q CI
C,
C^N
Gerwalt, Z., Helga, R., Chem. Ztg., 96, 287 ((1972).
CSI Reactions
182
Compounds Containing - N = 0; =
(481)
R1'
N —» o
R 2
Rt
i) CSI 1
N-N = 0
NH
ii) ••/ H2O • * ~
s
R 2
Dhar, D.N., Bag, A.K., Ind. J. Chem., 22B, 600 (1983).
(482)
SO2CI I N
ci 02 s.\
Ar-CNO Aromatic nitriloxide
-O
N
CSI
Ar
ArN Oxadiazole
(Ar = Substd. phenyl)
N Dioxazole
Esipenko, A.A., Fetyukhin, V.N., Kramarenko, F.G., Chernega, A.N., Samarai, L.I., Pirenzhenkov, V.V., Zh. Org. Khim., 27, 1262 (1991). C.A. 117,26439(1992).
.R1 CSI (483)
R 3 V ^ S \ _ C = N ^ O ^R2
H2O
o 0-5C SO2CI
,R 1 R3-
C O ) — ^R2 H/'
C
\ O
60 - 70%
Rao, K.R., Srinivasan, T.N., Sattur, P.B., Heterocycles, 27, 683 (1988).
CSI Reactions
183
Cyanides
(484)
Me CR (OH) CN
')
(R = Me, Ph)
csl
>i) H2
M
o ££ +
A
W
o
NH
or 2, 4 - oxazolinedione
Garcia, M.V., Menendez, J.C, Villacampa, M., Sollhuber, M.M., Synthesis, 6978(1991). NH CSI.CH2CI2
(485)
2R1NHC 6 H 4 CN
[ r ^ T ^
^
ik-jJL
(R1 = H, alkyl, PhCH2 CH2)
N
H
jL R1
Reddy, A.V.N., Kamal, A., Sattur, P.B., Synthetic, Comm., 18, 525 (1988).
(486)
CSI
(Me3CN!)3S
Me3 CN
,// Me3Cf^
Excess
CMe3 I N.
\
RSO2 N
N
(Me3CN : ) S
S RSO2
//
N
/
I SO2R
CSI
!N-S02R
?=0
\
N
'
(58 - 63%)
CMe3 Azetidinones
Tesky, F.M., Mews, R., Krebs, B., Udupa, M.R., Angew. Chem., 90, 722 (1978).
184
CSI Reactions
Diazo, Azido Compounds /4o7x 4 7
t » )
F
CSI
(F3C)2C:N2
». o 100-60 C
fi/s (trifluormethyl) diazomethane
3 C CF3
yC^o
O' | CI - S ^ ^ N 11 O
Steinbeisser, H., Mews, R., Glemser, D., Z. Anorg. Allg. Chem., 406, 299 (1974).
^SS^ (
8 8 )
°l CI S 0 2 NH - C - C - R H y d r ° l y S i s t
H- C- R
II
-70°C
N2 R (a) = PO (OMe)2
H2N-C-C-R
'I H
II II
O N2
O
N2
I (a) = 86%
(b) = PO (OMe) Ph
(b) = 95%
(c) = C02 Ph
(c) = 40%
Regitz, M. Weber, B, Heydt. A., Ann., 305, 323 (1980). o SAO{\\ (489)
II 0 © R-0-C-CH-N= N
o pel
U b l
„
II RO-C-CH —N
I
II
.C
N SO2CI
Biener, H., Farbwerke Hoechst, A.G., unpublished results Graf, R., Angew. Chem. Int. Ed. Engl., 7, 172 (1968).
CSI Reactions
185
V s<* a
(490) RI . „ . t A - 2 L . * - 1
Na2 s 3
° '
H2
°-
N—N 1
R1-N
/
^
N-H
R1 = n - B u , C 6 H n
(90%)
Suschitzky, H; Walrond, E.R., Hull, R., JCS Chem. Comm., 16, 570 (1973). Suschitzky, H., Walrond, E.R., Hull, R.,JCSPerkin
Trans. I, 47 (1977).
Moriconi, E.J., Datta, C.P.,JOC, 35, 2448 (1970).
N
(491)
RN3
CS| phH
-
„
RN
N
-N-S02CI
^
ft (95%)
Vander Sarel, J-M., Smets, G., L'Abbe, G., JOC, 38, 675 (1973). Oxygen Heterocycles
i) CSI, CH2 Cl2
(492) * - ( 0 ) -
5 — " *
O
15-30 C ii) Hydrolysis
*
<® ^
x
'
•
•
HN
O
o (X = H, CI)
Sampath Kumar, E., Dhar, D.N., Synth. Comm., 25, 1939 (1995).
CSI Reactions
1S6
(493)
-«* Q
Q
\
CONH SO2CI
Graf, R.,Ann., 661, 111 (1963). Graf, R., German Patent, 941,487, C. A., 51, 14789 (1957).
(494)
J!\ o
i) CSI
•V
X
ii)DMF
(50 - 70%)
(R = H, Me, CH2 OAc)
/
i) CSI
// V Me -U
O
Me
\ > - Me
-CN
X
H\ X
ii)DMF
o
CN -Me
X
(49%)
Floyd, A.J., Kinsman, R.G., Roshan, A.Y., Brown, D.W., Tetrahedron, 39,3881(1983).
(495)
^00
H I N
i) CSI, Na2 CO3, 21 days
\ ^ Me Me
r.t. ii) Na2 SO3
oo
Me
0
'Me
(64%) NaO Me, MeOH r.t.
NH2 - CO2 Me
(31%)
Buckle, D.R., Houge - Frydrych, C.S.V., Pinto, I.L., Smith, D.G., JCS Perkin Trans., I, 63 (1991).
CSI Reactions
R2
R2
(496)
187
H-
•N
NS02 CI
s
CSI
J.
o
5 - Oxazolones
o
-o R1
a) R1 = Ph; R2 = Me b) R1 = Ph; R2 = Ph CH2 c) R1 = Me; R2 = PhCH2
Dhar, D.N., Raghunathan, R.,Ind. J.Chem., 23B,761 (1984).
(497)
P"MeC6H4N
p - Me C6 H4
O
\
CSI, PhH
Me. OEt
Me.
Me
CI S02 N
ET^
70 C
O
1 - Imino - 1, 3 - 4H - oxazole
^Me
(33%)
L'Abbe',G.,Destexhe,R.,yC5CAeiii. Comm., 1614(1985). Sulfur Containing Compounds Me
(498)
i) CSI
Me
ii)H2 0
Me >
^> s = o Me (+K9)
Keshava Murthy, K.S., Vankar, Y.D., Dhar, D.N., Ind. J. Chem, 22B, 504(1983).
(499)
M
%S=
Me /
0
CSI
Me
\
S = N - SQ2 CI + CO2
Me
Appel, R., Rittersbacher, H., Chem. Ber., 97, 852 (1964).
188
(500)
CSI Reactions
CI-SO3H
CSI
„
CIS02NHS02CI Imido - bis Sulfonyl Chloride
Appel, R., Eisenhauer, G.,Ber. 95, 1753 (1962). AH, F.E., Krell, R.D., Snader, K.M., Eur. Pat. Appl. EP 34462 (1981), C.A. 96, 34857(1982). Ali, F.E., Eur., Pat. Appl. EP 38177 (1981), C.A, 96, 68845 (1982). Gleason, J.G., Eur. Pat. Appl. EP 40990 (1981), C.A. 96, 142723 (1982). (501)
Rl-N:S!NCMe3
CSI
»
R1 N : S : N SO2 R + Me3 CNCO
Sulfur dimide (R1 = Ph; CMe3)
Appel, R., Montenash, M., Chem. Ber., 109, 2437 (1976). (502)
S(:NCMe3)3
CSI
».
(Me3CN:)S:NR Sulfur triimides (52 - 83%)
Tesky, F-M, Mews, R., Chem. Ber., 113, 2183 (1980). (503)
AgN(S02Me)2
CSI - PhH
(Me S02)2 N SO2 NCO Hydrolysis
(Me S02)2 N + CO2 + NH4 + SO4 (MeS02)2 N SO2 NCO
ROH
(MeS02)2 NSO2 NH COR (R = Me, Et, CHMe2)
Blaschette, A., Dalluhn, J., Proehl, H.H., Jones, P.G., Bubenitschek, P., Phosphorus, Sulfur, silicon related Elements, 70, 91 (1992).
CSI Reactions
(504)
R
1
-
N
=
.... /NMe2
CSI,Et2 0
\
z
C^C.KJ_
X
189
-^L. r T ^SCH3
o
SMe
.
7 0 "C
"Q^
NS02CI
N Me2 ^ N
U s
Me
Me R1 _ N = C = 0
A
6/
Nv
2
+
> = N - S02 CI MeS'
\ SO2C1
Schaumann, E., Kousch, E., Imbert, J.P., Chem. Ber., I l l , 1475 (1978). O
1 G (505)
Vinylene trithiocarbonate
S
CSI
\
O
^
/
11
S/^N-S0
N - SO2
/ 2
CI
C =
N
S +
Pajouhesh, H., Mahkam, M., J. Sci. Islamic Repub. Iran, 7, 169 (1996); C.A., 125,328618(1996).
r^Ofn puoj
C1-SO2N. .x 2 S t C4H9-N^ Sulfur triimide
C4H9 I N
-
C
4
H
c, s o
t
9
Excess CSI w ^
N
N
^ „ / \ _ t X/b\ y*^ N CAHg-N^ N X I t C4H9
Tesky, F.M., Mews, R., Chem. Ber., 113, 2434 (1980).
n
CSI Reactions
190
(507)
1 N = S— N 1 1 1 SI ISI
Mono - addition product
CSI
1 1 1 N— S = N
(100%)
^"
Appel, R., Montenash, M., Ruppert, I., Chem. Ber., 108, 582 (1975). CMe3 CI S 0 2 N (508)
(Me3CN:)3S
Excess CSI
N
%
'
CI S02 N '
N = O | CMe3
^5 -Thiadiazetidone
Tesky, F.M., Mews, R., Chem. Ber., 113, 2434 (1980).
. CO NH S02 CI
=
(509)
I \ Ac-N^
l=\ ^S
CSI „
Ac-Nv
/le Me 2, 3 - Dihydro - 2, 2 - dimethyl - 1 , 3 - thiazole
Me
.S Me
Vorbruggen, H., Helv. Chim. Acta, 74, 297 (1991). c
CONHSO2CI
<510)
cs,
r\ Ac-N c
S
\
y
/=^ -.3
».Ac-N.
\
S
y
i={ >-Ac-N.
MeCN
=
,6
\
/
Vorbruggen, H., Krolikiewicz, K., Tetrahedron, 50, 6549 (1994).
N
CSI Reactions
(511)
SCF 3
F 3 CS
191
f 3 C
SCF 3 \
y
CSI /
F3CST ^N-
/N
F ^ s '
SCF3
^N"
^SCF3
SO2 NCO Hydrolysis SCF3
F3CS
XJ
F3CS'
"NT
SCF 3
SO2 NH2
Reich, K., (TerosonG.m.b.H.) Ger. offen. DE 3,235,045., C.A. 101, 38216s 1984).
CSI - PhH
(512)
v\ /
EtOH
r.t.
\ *
*
S03Et (61%)
Potts, K.T., Baum, J., Datta, S.K., Hughton, E., JOC, 4, 813 (1976). f C t / T|-|F
(513)
2 Amino - 5 - methyl thiazolin - 4 - one
>.
o ^
NH
N _»NHCONH2 S'
H
^
N CO NH2 Me
"S
5 - Methyl - 1 (4 - oxothiazolin - 2 - yl) urea (75%)
Hurst, D.T., Stacey, A.D., Nethercleft, M., Rahim, A., Harnden, M.R., Aus. J. Chem., 41, 1221 (1988).
CSI Reactions
192
Sulfur Heterocycles
S
N
CONH S02 CI
Graf, R.,Ann. 661, 111 (1963) Graf, R., Ger. Patent, 941,847., C.A. 51, 14789 (1957). (515)
// \\ C/ \) \ g /
O-
i)CSi »•
V D— CN Xgx (72%)
ii)DMF
Gronowitz, S., Liljefors, S.,Acta Chem. Scand., 31B, 771 (1977).
s
s
s
Vorbruggen, H., Krolikiewicz, K., Tetrahedron, 50, 6549 (1994). H H
(517)
-o-d-b-
i)CSI,CH2CI2(-30C)
2, 2 ' : 5', 2" - terthiophene
H H
s
s
s
(75%)
Soucy - Breau, C., Mac Eachern, A., Leitch, L.C., Arnason, T., Morand, P.,J.Heterocylc. Chem.,28, 411 (1991).
CSI Reactions
193
Organo-Silicon Compounds (518)
(Me3SiN)2S
On N
CSI ^
| OoS
(Me3SiN2)SO
|
y ^ -N^^OSiMe3
Appel, R., Vhlenhaut, H., Montenash, M., Z. Naturforsch, Teil B, 29, 799(1974). ~o,
(519)
CSI
(Me3SiO)20
Me3 Si O3 SNCO » (60%)
Buss, W., Kaannich, H.J., Sundermeyer, W., Chem. Ber., 109,1486 (1976). Me (520)
CSI, CH2 CI2 *•
(Me3 Si N Me)2 CO
-N
^ Me-N^
-Me3SiC
>>-OSiMe3
S0 2 — N
(100%)
Barton, T.J., Rogido, KJ.,JCS Chem. Comm., 878 (1972).
i)CSI(1.7eq.) iM
*3
cC, 4 ,atO°C* ii) HCI / H2O / Acetone
w ]
r i Pn
, / ^
T
VNH2 O
(61%)
3-Benzyl - 4 - phenyl - 6 - (trimethylsilyl methyl) -3, 4- dihydro - 2H - 1 , 3 - Oxazine - 2 - one Esch, P.M., Hiemstra, H., Speckamp, W.C, Tetrahedron, 48, 3445 (1992).
194
CSI Reactions
PhMe 2 Si
SiMe 2 Ph CSI
N
PhCH3 25 °C PhMe
S02C1 2 Si
Red-Al (522)
N H
-78 °C to 25 °C
68% 95:5 Stereoselectivity
Roberson C , Woerpel, K., JOC, 64, 1434 (1999).
(523) Ph
O-
Ph
\
CSI, Et2 O
Si
Ph
/
\
Me
Me DCCI3
-
(I) (I)
,S02CI
Ph
€
O Xph
sr
/
\
Me
Me
s r
Me
o°c
Ph SH, Py
Ph
0
40 C
Barton, J.T., Rogido, J.R., JOC, 40, 582 (1975).
S02CI
Me
(43%)
CSI Reactions
(524)
(Ph 2 CH)Me 2 Si
195
n-Bu HC1
(Ph 2 CH)Me 2 Si //
n-Bu
i-BuCOO,
PhMe 2 Sis^(^X o — = ^ ^
n-Bu
^V^o
Peng, Z., Woerpel, K., Org. Lett., 3, 675 (2000) Organo-Phosphorus Compounds CSI, PhMe (525)
frans-(n1-C3H5)Pt(PEt3)2CI
trans Pt (PEt3)2 Cl2 25°C CSI / Ph Me o -78
trans - Pt (PEt3)2 Cl2 and / or
|
CK
SO2 CI | N \ _
0
^ PEt3
Hu, Y.R., Wojcicki, A., Calligaris, M., Nardin, G., Organometallics, 6, 1561 (1987). R1
(526)
Me
R1 Me
' - Me
CSI
MeMe % N 0 Phosphetene oxide
Me
Me(R = H, Me, R1 = Me, H)
Hall, C.R., Smith, DJ.U.,JCSPerkin
Me
N
NS02CI
Trans., 2, 1373 (1977).
196
CSI Reactions
F2
F2
F Phosphoramide
Roesky, H.W., Janssen, E., Z. Naturforsch., Teil B, 29, 174 (1974).
(528)
r
/ \ ^
p
OH i
OMe £ 0 M e
CSI
I ^OMe O
^ *-
^
0
f
<^ N
N
S 0 2 CI
Neidlen, R., Mosebach, R., ,4rc/z. P/zarm. 309, 724 (1976). Miscellaneous Reactions (529)
C I S 0 2 N = C = 0 + HF
».
FS02N = C = 0
Hahn, H., German Patent, 1,083791., C.A. 55, 17509 (1961). o (530)
CSI
'
2 0 C >
H2NS02Cl
Dry MeCN, HCI
Peterson, E.M., Brownell, J., Vince, R.,J. Med. Chem., 35, 3999 (1992). ,_„.,. (531)
Gas phase, 400 C 0 = C = NS02CI
S 0 2 ( - N = C = 0)2 + Cl2 + S02 FeCI 3
Matterstock, K., Graf, R., (Farbwerke Hoechst A.G.), German Patent, 1152093, (1961); Chem.Zbl, 14-1957 (1964).
CSI Reactions
C60
(532)
CSI
197
Iminolactone
Fullerene
Muthu, S., Maruthamuthu, P., Fullerene Sci. TechnoL, 4, 1066 (1996)., C.A. 125, 300804(1996).
(533)
SC-2 N = C = 0
SnR3
o
CSI
(R = Me, Bu)
Araswald, M., Neumann, W.P., Chem. Ber., 124, 1997 (1991). SO2 N = CH - NMe2
S02 NCO
SnR3 CSI, - 20°C
(534)
- R3 SnCI *~ ^
R1
^
DMSO 1
(- co 2 ) S02 - N = S - Me2 (82%) R1
Amswald, M., Neumann, W.P., JOC, 58, 7022 (1993).
R1 (80%)
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Part II CSI Applications
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201
CSI Applications
II-l
Herbicides, Plant Growth Regulators/ Inhibitors and Plant Protection Agents
General Name and Structure of Compound
Applications
l-[2-(Cyclopropylcarbonyl) 4 fluorophenyl-Sulfamoyl] - 3 [4, 6 - dimethoxy -2- pyrimidinyl] urea
Herbicides OMe N H — SO2 - NH - CONH—(/
\ OMe
•
1 - a - Cyclopropyl - a - (subs.) - hydroxy o - tolyl-sulfamoyl - 3 - (4, 6 - dimethoxy - 2 - pyrimidinyl) ureas
Example compound: Herbicides OMe
OR NN H — SO2 - NH - CONH—(/
\)
NOMe
(R = H)
•
Pyrimidinyl ureas SMe
(Cj)—
C = N— SO2NH - CONH—&
OMe
^ OMe
Herbicides
Ref.
202
•
CSI Applications N-Sulfonyl -N 1 - (2- pyrimidinyl / or 2triazinyl) ureas OMe
Herbicides
OMe
•
Pyrimidinyl (and triazinyl) ureidosulfonyloxybenzoates CO2R1
Herbicides
OS02NHCONR3R4
(R4 = Pyrimidinyl/triazinyl) •
As an intermediate for the preparation ofherbicidal sulfonylureas.
Sulfonylisocyanate R X S 0 2 NCO Rj - S 0 2 NH - CONH - R2
•
1
N - azinyl - N (2-alkylsulfmylbenzenesulfonyl)urea SOR1
Herbicides SO2NH-CON OMe
A = CH/N
6
203
CSI Applications
•
Purine derivatives Y
RINHO2S—
o-
fykN
N
R2o
OR3
Herbicides
k.
R1 = R 2 = H; X = H; Y = H •
Adenosine herbicides
Y
R1N— SR2
°
vr
v\-°
06
t
N
Herbicides NT
\)
X
OR4
Ri = R 2 = H ; X = H ; X = C1 Trifluoropropylthiazoline - moiety containing triazine derivatives (CH2)2CF3
OMe
N—SO2NH - CONH—^ N OMe
Herbicides
10
204 •
CSI Applications Pyrimidinyl urea derivatives
Example compound: .NHEt
OMe
N
X
Herbicides
11
Herbicides
12
Herbicides
13
"w
S^NSC^NH-CONH—ft
^S 'OMe
•
Thiazol (in) ylideneaminosulfonyl amino (thio) triazolinones
R5 _ ^ " N
RJ
o2
°
FT
•
Thiazolylimino sulfonyl urea derivatives •NR1 ^
•
s
NSO2NHCONHR2
R1 = alkyl, alkenyl, alkynyl R2 = subs, pyrimidinyl, triazinyl bond b = satd. or unsatd. Sulfonylammocarbonyl triazolinones o R 3 Q S 02N H C O N T " NR 1
R2
205
CSI Applications
Example compound: / \ /
R 3
Me
Herbicides
14
Herbicides
15
Herbicides
16
Herbicides
17
R ] = Me R2 = OEt R 3 = C 0 2 Et •
N- (2-Chloroethoxy) thiazolidine derivatives
N
/
OC2H4CI OMe
I—
N'/ S / ^'NS02NH.CONH—(/
^
NOMe
•
Ureidopyrimidine derivatives
[
J\C0 2 R
(CH2)n\OS02NH.CONhf-^/
N
/
X
\\ N
Y
R = alkyl X, Y = halo, alkyl etc. n = 0 or 1. [Pyrrolylamino) sulfonyl] ureido-] - azines OMe \
N—NHSO2NHCONH-V
Z OMe
(Z = CH/N)
206
•
CSI Applications
Phenylsulfonyl ureidotriazoles
/
NMe2
R1
\ . SO2NH.CONH-
R2
ON = CMe2
Applications in agriculture, increases the leaflength of corn.
R1 = CI; Rz = H •
Substituted arylsulfonylamino (thio) carbonyl triazolin (thi) ones Herbicides NR1R2
/7~( (f
X
QI
Q 2
II
/^NR4
V - SO2NH - C — N N ^ \
R
5
R3
(For the control of Cyprus, Setaria, Solanum, Xanthium, Echinochloa etc.) 1
R1, R2, R 3 = H; Qj = O; Q 2 = O; R4, R5 = H •
Pyrimidinyl and triazinylurea derivatives /' QS02NH.C - NLr
Herbicides
\, Q = Ph (CSMe) : N, X = O, L = H, B, D = OMe, A = CH or N Sulfonylaminocarbonyltriazolinones 0
x
R3QS02NH.CO— N f ^ N R I N<
1
R2
R ^ R ^ H , R 3 Q = CH. O
Herbicides
207
CSI Applications Pyrimidine - triazine containing sulfamides R2 R3
/A
R4
1
IN
M^
R5
I
S0 2
Herbicides
22
Herbicide
23
Herbicide
24
•R6
o
R J ,R 2 , R 3 'R 4 -, R5, R6 = H Example compound: N
NN
\ •N' > ^ \ ^ / \ ^
N H
O Y
•
^S
S
°2
NH
2
N-(Heterocyclicaminocarbonyl) arylsulfamate R6
yv
R 5
R7
R2
N-/
— ( O ) — 03SNCONR—^ R4
R3
\ R1
R = H; R1, R2 = Me; R3 - R7 = H; X = N •
Heteroaryl aryl sulfonyl ureas w QSO2NH-CNH—(/
R1
^Z R2
Q = (Un) substd. condensed hetero-aryl having a bridge head nitrogen W = 0 ; R 1 , R 2 = Me;Z = N
208 •
CSI Applications Benzothiophene/and benzofuran sulfonamides S02NH.CONR1R2 R3-
Herbicides total control over cocklebur and morning glory.
25
Herbicides useful in controlling undesirable plant growth.
26
Heribicidal activity- 100% control of Eschinochloa crusgali
27
R = H; R1, R2 = OMe; R 3 = H Example compound: OMe
J
-SO2NHC O N H — / /
\ OMe
3,4, 5, 6 - Tetrahydro -1,2,4,6 - thiatriazine - 3, 5 - dione 1 , 1 - dioxides O
R1N"^NR2 I
- A M ^
o
R, R1 = H; R2 = Ph Phenoxybenzoic acid derivatives 1 CONHS CONHSO2R
CI
CF3
\ 0 / ° \ 0 / N°2
Example compound: 1
R = NMe,
209
CSI Applications Sulfonamides
Herbicidal activity
R1 R2
R6
^WR3 N R4
\ R7
Compound I completely controlled nutsedge in pre-emergence applications.
28
I : R1 - R5 = H; R 6 , R 7 = Me; X = CH 1- [(Azinylureylene) sulfonylamino] imidazoles xi
_/ N ^ N — NHS02.NHCONH-/v
Z X
COR1
X2
Example compound (I)
As Herbicides. Compound (I) completely controlled weeds e.g. Digitoria adscendens, Stelloria neglect a, Set aria, viridis etc. 29
X 1 -X 2 = OMe;COR1 = 5 Ac. •
Indolyl Substituted uracil derivatives Me
f
>HT^P>-
CI
HN
•
Herbicides - Gave more than 90% control of Echinochloa oryzicola,Monochoria vaginalis, Scirpus juncoides. 30
Fluoropropylthiazoline derivatives OMe a
NSC2NH.CONH-(s
N
Useful herbicides OMe
Y = (CH2)2 F
31
210 •
CSI Applications Difluoropropylthiazoline derivatives
a
OMe
NCH2CH2CHF2 NNSO2NH.CONH—{/
\
N
NOMe
Pre - emergence Herbicide (90% herbicidal effect for Avena fatua, Stellaria media, Amaranthus viridis).
32
Herbicides (strong activity against weeds).
33
Herbicides (II) Showed strong herbicidal activity but was well tolerated by cotton.
34
Cycloalkylsulfonylaminosufonyl ureidoazines
K'
Z N
R1 SO2 NR2 SO2 N R3 CONR4
Y
Example Compound: Rl=
[ > - , R 2 = M e ; R 3 , R 4 = H ; X , Y = OMe,
Z = CH •
Phenylaminosulfonyl ureidoazines R1 N^ NH SO2NH.CONK
A N
N
R2
(I) Example compound: OMe
NH SO2NH.CON /
(II)
•k
\
OMe
211
CSI Applications
•
Sulfonylureas with fused heterocyclic moiety 1-Heterocyclysulfonyl - 3 - (4,6 - dimethoxy- Herbicidal activity pyrimidine - 2 - yl) ureas
•
35
Sulfonamide R2
I Herbicides R
1'
N
O
J
36
^ S 0 2 - N R 5 R 6 Salts
O
Example compound: R1, R2 = Me; R 3 = - C (CH 3 ) 3 ; R4 = H; R5 = H; R6 = Me •
Thiadiazalopyrimidines and sulfonylthioureido - pyrimidines R3
s
N""^X
J^ <^\
N
N
N
R4
(I) R3 R1S02NR2S02NHCSNH—(/
Example compound gave > 90% control of Cyperus microisia, Rorippa indica and no damage to wheat, soyabean and corn crops. 37
^X
\ R4 (II)
Example compound: (II) R 1 , R2 = Me; R 3 , R4 = OMe; X = CH •
2-Alkylphenyl sulfamates .CH2CH=CH2 N / ( (Cj)—OSO2NH.CONH—-//
R
/> V V
V
Example compound is an effective herbicide and does not cause any damage to rice. 38
CSI Applications
212
Example compound: R = H; X, Y = MeO; Z = H •
N - Heterocyclosulfonyl - N ' - Pyrimidinyl triazinyl ureas Me , S 0 2 N H.CONH—(/
ITS •
\\
\ N
C02Me
Herbicide (total control of Stellaria and Digitaria)
39
Herbicides
40
Herbicides
41
OCH F2
Sulfonamides Et2NS02NH.CONH
OMe
N
YY Me
•
Arylsulfamates R3 RO3SNHCONHRI —(/
^X R2
(X = CH; N) Example compound: R = Ph; Rl = H; R2 = Me; R3 = OMe Herbicidal benzothiophene and benzofuran sulfonamides R3 SO2NH.CONR — f t R2
3
N (I)
\
1
R4
213
CSI Applications R5 S0 2 NH CONR—//
X
V_^
-V
'«?.
R2
S02NH.CONR • R2 *
X R
(III)
1
Example compound (I) in rice cultures inhibited barnyard grass and water chestnut with small effect on the rice plants. 42
Example compound: (I) R = R 2 = H; R1 = 2 - C 0 2 Me; R 3 = Me; R 4 = MeO;X = S;X ] = CH •
Triazo compounds OMe Me02Ck/v. M e C T ™ ^ ^
NHCONH.S02NhK<::;i/ (I)
Herbicidal activity
43
Me
..X (II)
•
Lepidopterical Isothiourea compound
Herbicides, fungicides RN : C (SR ) NR CONR R and plant R 1 , R 2 = C 2 . ] 0 alkyl; R + R1 contain 12-22 bactericides C; R 2 = Cj . 4 alkyl, C 3 . 10 alkenyl, C 3 . 4 alkynyl, R3 = H, C, 2 2 alkyl, (Un) substd. phenyl; R 4 = H, C M 4 alkyl, Ph. 2
1
3
4
44
214 •
CSI Applications 5-Phenoxy - N - Sulfonyl benzamide CONR2S02R 3
Herbicidal compounds R1 R
(l) CONHS02NHMe
F3CH
O^°^^-N02 %
•
CI
(II)
Compound II gave a complete kill of Chenopodeum album premergent.
45
Inhibit the growth of weeds and also possess herbicidal activity. Compd. II gave total control of Amaranthus retrqflexus.
46
Herbicidal
47
Diphenyl ether Compounds:
_ /
.CONR2S02R 3
r
/^
• R
V
R1 (I) CONHS02NHMe
o
H2r ^S^
No
2
CI
(II) •
P h e n o x y e s t e r s of N - [ ( h e t e r o c y c l i c ) aminocarbonyl] sulfamic acid R2
• R1
H—(Cj)—OSO2NH.CONH —(/
V R3
R
Example compound: Me
OCF3 H — ( C j ) — OSO2NH.CONH —(/
\ Me
215
CSI Applications •
Triazinylurea derivatives
Z'
w
^—NR3CONHS02NR4R5
R2
Herbicides
Example compound MeO Z'
48
2 - [ M e C ( O M e ) 2 ] (C6H4)
^—NH.CONHSO2N
X
~"N
^ H
Me •
Sulfamoyl urea Herbicidal activity Rl / R2
^ —
NR3CONH.S02NR4 COR6
/ R5
Example compound: R 1 = Me; R 2 = OMe; R 3 - R 5 = H; R 6 = Me •
These herbicides cause moderate to severe injury to a variety of broad leaf and grassy weeds, both pre and post-emergent.
49
Herbicides
50
1- [ 2 - ( C y c l o p r o p y l c a r b o n y l ) p h e n y l ] sulfamoyl - 3 - (4,6 - diakoxy - 2 pyrimidinyl) urea
Y CO
OR
JHSO2NH.CONH—A. (-70%)
)) OR
Y = H, halo, alkyl, haloalkyl; R = alkyl.
216
•
CSI Applications
Pyrimidinyl urea derivatives
R1
R3
NO2
_/
S02NH.CONH
/\
y)
R2
Herbicides/plant growth regulators
51
Herbicides/ plant growth regulators
52
Herbicides/ Plant growth regulators
53
Herbicides/ Plant growth regulators
54
R4
•
Heterocyclosulfonyldiamide Me
OMe
Me
N — SO2 — N — SO2 NH . CONH -M N- \
Me
•
\ OMe
Sulfonyl ureas
R1 SO n ANR 2 S 0 2 NHC : (Z) NR 3 R 4 R1 = Me; n = 2; A = (CH 2 ) 2 ; R2 = Me; Z = O; R3 = Me OMe R4
'/
•A
\i OMe
2 - Heterocyclylureido sulfonyloxy benzoate ester CO2R 1
OSO2NH.CONH— R3
217
CSI Applications R4
R6
N
R3=
//
N
\\:_1^. R5 R5
•
2 -Alkophenoxy sulfonyl ureas OEt
OMe
O N
II
^\
OSO2NH-C— NH — / /
\\
Herbicides/ plant growth regulators
55
Herbicides/ plant growth regulators
56
Herbicides/ Plant growth regulators
57
OMe
•
N - Phenyl - N - pyrimidinyl ureas
R3
CONH 2
N R 4
R1 - R 3 = H; R4 = OMe; R5 = H. •
Heterocyclic substituted phenoxysulphonyl ureas OR1
v
OS02NH.CNR3R4
Example compound: R 1 = C H 2 C H 2 CI; R 2 n = N 2 O; Y = O; R 3 = H;
R4
N—'
218
•
CSI Applications
Carboxyaryloxy sulfonyl ureidoazines COOR1
R5 N
'OS02NH.CONR3—V R2
X
~ R4
Example compound: C02Me
or
Herbicides/ Plant growth regulators
58
Plant growth regulators
59
Herbicides/ Plant growth regulators
60
Me OSO2NH.CONH—(/
OMe
\
I CI
•
1 - (Benzenesulfonyl) -3 - (2- triazinyl) ureas NMe2 R1 H' R2
~
'S02NH.CONH/
N
is
N
N
O - N = CR3R4
Example compound: NMe2 CI
L II
S02NH.CONH/^N''^ 0-N = C
\ •
/ Me
Sulfonyl heterocyclyl urea N
N
oA\
OMe N-
,
'/ W
SO2NH.CONH—0
OMe
219
CSI Applications N - Phenyl - N - pyridylureas Herbicides/ Plant growth regulators NR4CONH2
Example compound: R1 = Et; R 2 = CF 3 ; R 3
H;
4
R = 2 - N 0 2 - C6 H4
Example compound gave complete control of Avena, Setaria and Stellaria (pre-emergent).
61
Growth hormone release promotors
62
(Tetrazoylbiphenylmethyl) benzazepinones and related compounds
(CH 2 )P NR6COANR4R5
R7
R8
Example compound: 3- Amino -3- methyl -N- [2, 3,4, 5 - tetrahydro -2- oxo - 1 - [2- (IH - tetrazol -5- yl) [1, 1'biphenyl] -4- yl] methyl] - IH -1 - benzazepin 3R - yl] butanamide trifluoroacetate. (89%)
220 •
CSI Applications N- (Azinyl carbamoyl) Sulfonamide
Example compound: Me SO2NH.CONH —(/
\S OMe
Herbicides and plant growth inhibitor The example compound is claimed to have exhibited complete control of Echinochloa crus-galli. 63
N - Phenyl - N - pyrimidinyl ureas
(C\_
Pre & postemergent herbicides
N C O N H - ^ " V R^
64 R 1 ,R 2 = alkylene Pyrrole sulfonamides and sulfamyl chloride intermediates R3 S02NH.CONR1R2
R4 R5
Herbicidal at pre and post emergence
Example compound: Me SO2NH.CONH— &
// w H
Me
\
Me
65
221
CSI Applications Herbicides for post emergence foliar application.
Fluropropylthiazoline derivatives
• S ' ^ N R
OMe
NR=—SO2NH.CONH—ft ^N OMe
Exerts 90% control over the following weeds, Amaranthus retrofleuxus, Stellaria media, Polygonum blumei, Chenopodium album, and Avena fatua. (Claimed to give no damage to beet). 66
[(Methylthiophenyl) amino sulfonyl ureido] pyrimidine SMe
R1 I
\ N-SO2N H.CON—0 R4
R3
Post emergent herbicidal activity
67
The example compounds had more post emergence activity than pre emergence and were more active on dicot than on monocot weeds.
68
R2
Example compound: R1 R 2 = OMe, R3, R 4 = H •
2- Pyrazolines R1
R2 * N — CONHSO2—ft :
N
Example compound: R 1 , R 2 = Me;R 3 = Cl;n = 2
^ n R ^
n
222
•
CSI Applications Phenylsulfamoyl (triazinyl) ureas
R1
X^
R3 X1
R4
R7
^>—N — C— NHS0 2 — N—(/
R2/
y
RSO-^CT R6
Example compound: R 1 = M e O ; R 2 = Me; R 3 , R 4 , R 5 , R 7 = H, R 6 Me, X = N, X 1 = 0 . •
Herbicides Provides preemergence and post emergence control of broad leaf and grassy weeds (severe to moderate injury).
69
Sulfamoyl chlorides Herbicidal R2 RSO2N H.coNRi—V
R3
y— R4
Example compound: Me Me2NS02NH.COH—0
In postemergence application (the example compound) damaged bush-beam and cocklebur but did not damage wheat. 70
Me
•
Herbicidal Indole sulfonamides
Pre - emergence gave 100% control of nutsedge.
Example compound: R 1 = Me ; R 1 = C 0 2 Me; R 2 , R 3 , R 4 = H; R 5 , R 6 = Me.
71
223
CSI Applications
•
Indole Sulfonyl ureas
•
Sulfamoyl urea derivatives
N
/\— N
/ ^
Herbicides
Herbicidal activity
NR3CONH.S02NR4R5 (I)
R2
Example compound: Me N
/V)— NHCONH.SO2NH—((
^ 0
72
The compound (II) was effective against 8 weeds in both pre and post-emergence.
73
Selective herbicides
74
Selective herbicides
75
))
Me
Fluoropropylthiazolidme derivative CH2CH2CH2F OMe N =
N OMe
•
N-Azinylino - (2- ethylthiophenylsulfonyl) ureas -SEt
_/'
x •SO2NH.CONH—ft
^Z Y
Example compound: SEt /
o
OMe IN
SO2N H.CONH — / /
^
^ Me
224
CSI Applications
1- [[2- (cyclopropylcarbonyl) phenyl] sulfonyl] - 3 - (4,6-dialkoxy -2- pyrimidinyl) urea compounds
Crop - selective herbicidal compounds
76
Selective herbicide suitable for rice plants.
77
H
Example compound: Y = H; R = Me; Yield = 70% •
Fluoroethoxythiazolidine derivative
o^
(A
1
S^'NSOaNH.CONH—V
OMe y 'Me
•
1- [[o- (Cyclopropylcarbonyl) phenyl] Selective sulfamoyl] -3 (4, 6- dimethoxy -2- herbicides especially pyrimidinyl) urea for cereals. (totally controlled barnyard grass and cyperus serotinus with no damage to rice).
78
225
CSI Applications
•
5- Amino -4- Cyanopyrazoles R2
R3
CN
/Nv ^ N H C O P h
y
N' ^ N R ^ R S
Me
R1
(I)
(II)
R1 = alkyl; R 2 = H, R3 = CN; R4, R5 = H
,
•
/
NOCH2CH2CH = C H - / /
Herbicide softeners II reduced the damage to zea mays caused by herbicide III.
79
Plant protection agents
80
Useful for plant protection against injury from herbicides.
81
^S-
(HI) 2 - Aminoalkenylsulfonyl ureas Me
Me NH CMe = C — SO2 NH . CONH—V
I
N
C02Et
•
Sonfonamide (herbicide antidote composition) Me S 0 2 - S 0 2 NH 2
\ Me
226 •
CSI Applications N-Alkoxy and N-alkylsulfonylaminosulfonyl ureas and pyrimido (triazino) thiatriazine oxides as their intermediates R4
R(R1Z)NS02NR2C0NR3 — V
X
R5
Example compound gave 80-100% control of Echinochloa crus - galli (post emergence tests).
82
Potential fungicides
83
Herbicidal and fungicidal Organisms tested include: Echinochloa crusgali, Amaranthus retroflexus, Piricularia oryzae.
84
Example compound: R, R1, R4, R5 = Me; R2, R3 = H; X = CH 2 ; Z = O •
1 - N - Hydroxyhydantoin 5 phosphates o
N-f
H O - P - O - I CH2I r - < . OH
,N~
H
O
(n=l,2) •
Sulfonylureido derivatives F
Me
3Q
y
NH SO2 NH.CON
^3 OMe
227
CSI Applications •
2- (Alkoxyimmoalkoxycarbonyl) phenyl sulfonyl ureas R1
Prevents artificial infection of rice by Pricularia oryzae.
85
Were tested for their -oxo-1,2,4-triazolo 4,3-b fungicidal -1,4,2,6-dithiadiazine 6,6-dioxide derivatives activity.
86
— SO2 NH C (! Z) NHR CO2 C R2 R3 CR4: NOR5
Example compound: Me 1^.
S02NHC(:0)NH—/^ Me
5-(2-aminoalkanoyl)-8-aryl-4(5H)
COCH(NHR1)(CH2)nMe ( R = H, 4 -CI, 4 -Me, 4 - MeO, 4 - N02, 2-CI; n = 5,9,13; R1 = H)
228
CSI Applications
II-2
Pesticides, Insecticides and Fungicides
General Name & Structure of Compound •
Ref.
Pesticides based on CSI (CI S 0 2 N = C = 0 )
•
Applications Pesticides
87
Pesticides
88
Pesticides
89
Endo and ectoparasiticides
90
Plant protective agent/pesticides
91
Pesticides based on perfluoroalkane sulfonyl isocyanate R S02 N = C = O R = Cj - 8 perfluoroalkyl
•
Phenyl Amino Sulfonyl Ureidoazines R2
R
S|^R102 l R&5
•
R6
H
N
° H
,^G
H
Pyrrole derivatives Example compound:
H
R K
•
N (Chlorosulfonyl) carbamoyl phosphate CI S 0 2 NH COP (0) OMe) 2
•
1 -Arylpyrroles X
/CN
X/V^3
Pesticidal activity (100% control of aphids, mites, southern army-worms, etc.)
92
CSI Applications
229
Example compound: R1 = NCCH 2 CH 2 ; R 3 = X 1 = X 4 = CI, X = F 3 CSO; Y = F 3 C; X 2 = X 3 = H •
1 - Phenyl - 3 - phenylaminosulfonyl ureas
H
R = 7-Me, 5,8 = Me 2 ; 7-Cl, 7 and 5-Br, 7-Iodo, 5-MeO •
Useful as potential pesticides for protecting crop plants.
93
Insecticides: 100% Nephotettix cincticeps.
94
Dimethyl benzofuranyl - N - (Sulfonyl carbamoyl) - N - Methyl carbamate.
R = CONHS0 2 CI Lepidophericidal activity (organism tested: Salt RN : C ( S R 2 ) N R ' R 3 .... (I) marsch caterpillars, Example compound: cabbage loopers and tobacco budworms). Et N : C (SPh) NC 1 0 H 21 CONH Ph* Several I showed * = Substituted bactericidal and fungicidal activity. 95 Insecticidal and Haloalkylthio, - sulfinyl and sulfonyl aryl acaricidal agents pyrrole (these compounds X gave complete kill of southern armyworm, tobacco budworm etc.) 96 •
Isothiourea compounds:
CSI Applications
230
Example compound: S02F3
c* H
Isecticidal, acaricidal and molluscicidal x agents. Example compound shows 100% kill against Spodoptera eridania 3rd instar larvae and Example compound: Tetranychus urticae B = H; X, Y, Z = 2, 4, 5 - Cl 3 ; W = 3 - cyano. P resistant strain. 97 • N-Unsubstituted (Carbamoyloxy) nitrostyrenes •
Pyrrole carbonitrile and nitropyrrole
<&?&
R1
Molluscicidal and fungicidal activities 98
R = H; R1 = OH R = OH;R J = H , OMe Phenyl pyrrole derivatives: w
~\W/ A
M
for controlling phytopathogenic fungi
R
Example compound: CN
\YJ
H H
99
CSI Applications
•
Pyrimidines derivatives R3
O
X =
R1 SO2 R2 N - C — / v
// R4
Example:
CH3SO2HN-C—V
•
N
1
I NH2 COOH
101
NH 2
COOH
Haloalkylthio, sulfinyl and sulfonyl aryl pyrrole Example Compound: X
YJ^>W
K
•
Agrochemical, fungicides and herbicides (Very good control of Pseudoperonospora cubensis) 100
cis - 2 aminocyclopentane - 1 - carboxylic acid; cis -2- aminocyclopent -3- ene - 1 Fungicides carboxylic acid for the control of Plasmopara viticola
u
•
231
Subst. Ph / + > HCF2 S02
Fungicidal agents
102
Plant fungicides
103
H
4 - Halonaphth [1, 3 - d] imidazole, 2, 5 dione derivatives
CSI Applications
232
Example compound:
•
2, 4, 6 - Trichlorophenyl chlorosulfonyl carbamate CI
Cl
•
~\
/— °2
CNH s
°2
Cl
Fungicides/ bactericides
104
Potential fungicides
105
1-N-hydroxyhydantoin 5-phosphates HO
o
II HO - C - O -
\ CH2
N
r ^f \
I
OH
.0
H
O
(n = 1,2) Derivatives of P-aminopropionic acid
Fungicidal activity > 90% control of vine m Udew (Plasmoparaviticola) and cucumber mildew (Sphaerotheca fuliginea). 106
•
2 - Aminocyclopentane - and cyclopentene Fungicides: - 1 - carboxylic acid derivatives Controlled Plasmopara B D viticola on grape and R 2 R1 N—* ' — COVR3 Phytophtora Example compound: infestons X = O; A, B, D, E = H; R1, R 2 , R3 = H; V = O lycopersici on tomato.
107
CSI Applications
II-3
233
Anti-viral, Anti-cancer and Anti-HIV Compounds
General Name & Structure of Compound
Applications
Ref.
•
Uridine - 5 - diphosphate glucose analogues
Antiviral activity
108
•
Glucosyloxy carbonylaminosulfonyl derivatives of nucleoside
Potential antiviral activity
109
Antiproliferative antiviral, antifungal activity
110
CH2 OR1 I
V p R 3 \ — CONH SO2 R5 R20 N /
IR4
Example compound: R1 = R 3 = CH 2 Ph; R2 = H; R 4 = OCH 2 Ph; R 5 = 5 1 - 0 - bound- 2 1 3 1 - 0 - isopropylidene - 5, 6- dihydrouridene. •
N-Hydroxysulfonamide H H 1-BuCX.NU ^N-R s
To" *o
O Example compound: R = OBn, 0~HNEt3+ , OtBu
CSI Applications
234
•
5 1 - 0 - (glucosylureidosulfonyl) uridine derivatives
R1 - N H . C O N H . S O 2 . O . C H 2
R2d
* R3
Potential antiviral activity
111
Example compound: R1 = 2, 3, 4, 6 - Tetra - 0 - benzyl - a Dglucopyranosyl R2 = H; R2 R 3 = CMe 2 0. •
Orotidine - 5 1 - monophosphate decarboxylase inhibitors and analogs including 6-azauridine 51 (ethylmethoxyalaninyl) phosphate (a 5 1 mono-phosphate drug)
RO
OR
R = H, Ac; X = Y = 0 , S; X = 0 , Y = S; X = S, Y = 0
Antiviral {in vitro/ in vivo) The five RNA viruses include : Japanese encephalitis (JE), yellow fever (YF), sandfly fever (SF), Puntatora (PT) and Venezuelan equine encephalomyelitis (VEE). No in-vivo activity was, however, obtained in the case of JE, PT and VEE infected mice. 112
CSI Applications
235
51 - 0. sulfamoyluridine derivatives
R1 OC (O) NH SO2 OCH2 .0^
Antiviral activity
113
Antiviral activity
114
X Me
Me
R1 = cyclohexyl, 1 - hexadecyl, Ph C 0 2 CH 2 - CH ( 0 2 PH) CH 2 tetra - 0 benzoylglucopyranosyl] to give sulfamoyluridines • Hexose - modified analogs of uridine - 5 1 diphosphate glucose derivatives
RO CONH SO3 CH2
k°N
v Me
•
Me
Alkanediol disulfamates H 2 N S 0 2 O (CH 2 ) n O S 0 2 NH 2 (n = 6, 8)
Useful in the treatment of malignant cell growth in mammals (mice). 115
CSI Applications
236
•
Sulfamoyl nucleosides related to carbovir and AZT X
° z ^ V ^NH2N-S-O-
O , / ^
N
H2N-S-O-
Q
II
O
-N II
-N II .Y
I
N
d (ID
(I)
O
Some analogues exhibited significant in-vitro anticancer activity.
HN O
o
(HO)2 - P - CH2 O - C - N H - S - O -
a
II
O N3 (III)
I
II
(X = OH; Y = CH; Z = NH 2 ) ") X = NH 2 ; Y = CH; Z = H X = NHMe; Y = N; Z = H X = NMe 2 ; Y = CH; Z = OH (X = NH 2 ; Y = CH; N, Z = H)
•
Azatidinones R1
# O
N.
x8 •v "0-X5
T
O X6
HN.
X7 Me
Useful in the treatment of leukemia.
CSI Applications
237
Example compound: R1
R
# 0
0
r ^ r N
\ / 0
HN.
•
2 - Chloroethyl nitrososulfamides (CENS)
•
2, 2 - Difluoro - 3 - carbamoyl ribose sulfonate RO
- V ~ * o S0 2 R3
These compounds show a significant oncostatic activity towards both A549 and MCF 7 cell lines. 118
Antiviral and anticancer agents
119
Antitumor activity
120
N r R1 R2
Y
I)
o [R = hydroxyprotecting group; R1, R2 = H, (Un) substd. alkyl, (Un) substd. Ph.; R 3 = alkyl] Compd. ( I ) 2 ! - d e o x y - 2 1 , 2' - difluorobetacytidine and other beta anomer nucleosides • Platinum (II) complexes
CSI Applications
238
R1, R2 = Phosphorylcholine, Un (substd.) famoyl or carbamoyl; A 1 H 2 = amine, cycloalkylamine, (Un) substd. diamines, diamino compounds etc.) Preparation of Phorboid Compounds as Anti-inflammatory protein kinase modulators and also exhibit activity against T-24 5'-Sulfamoylated purinyl carbocyclic human bladder nucleosides carcinoma cells (i.e., anticancer agents). 121
NH2
Antitumor and antibacterial
OH
122
OH
(X = N, CH) •
Glycosyl oxycarbonyl amino - sulfonyl - 2 1 , 3 l - dideoxynucleoside derivative
•
2 - Heteroaryl - 5, 11 - dihydro - 6H dipyrido [3, 2_ b : 2', 3 ' b ] [1,4] diazepines Anti-HIV activity. H
123
O
Ar/
0^0 ~N'
^N'
(Ar = 4 - Pyrazolyl)
Used in the prevention or treatment of HIV infection.
124
CSI Applications
II-4
Biological Activities
General Name & Structure of Compound Analgesics/anti-inflammatory compounds
Applications
Ref.
•
Useful as antiphlogistics or analgesics.
125
(3-Phenylthioarylamide derivatives p-R C 6 H 4 S CH = CMe CONH 2 R = H, Me, CI N 0 2
•
Lysine salt of 6- Chloro - 5- fluoro-3 (2- An anti-inflammatory analgesic agent 126 thienyl)-2 oxindole -1- carboxamide
•
Nitrosulfonamido pyridine derivatives R2
V%/N°2
IJ
R1 SO2 -
\Y~^^
CO (CH2)n NHR3
Anti-inflammatory, antipyretic and analgesic agents 127
Example compound: 2 I. HCl[R 1 = M e ; n = 1;R3 = H ; X = 0 ; R = cyclohexyl]
•
4-Nitro-2- phenoxy - sulfonanilide derivatives P h 0
Me S02 -
\^\/N0
2
K ^ ^
I CO (CH2)n NHR
Example compound: I. HC1[R = H] •
Substd. alkalimetal 1 -arylalkyl -4- arylamino - piperidine -4- carboxylate MO2CN/ y
ArNH \_J
\ r
"
Useful as antiinflammatory, antipyretic and analgesic agents.
128
CSI Applications
240
Example compound: Na02 C /
\ N
PhNI-r\ •
- CH2 Ph
/
Opionoid analgesics
1
Useful as antiinflammatory, antipyretic and analgesic agents
1
1- Substd. Oxindole -3- carboxamines CONH R1
COA
Example compound: X,Y = H; A = NH 2 , R1 = 2, 4 - Cl 2 C 6 H 3 . •
O-Carbamoyl salicylate esters COR1 OC (O) NH2 R-
Analgesic and anti-inflammatory, activity 1
Example compound: C02Et OC (O) NH2
•
2-Oxindole - 1 - carboxamides and their intermediates
CONH2
Example compound: X,Y,R = H
Useful as intermediates for analgesic and antiinflammatory, agents. 1
CSI Applications •
3-Substd. -2- oxindole - 1 - carboxamides COR1
CONH2
Example compound: I; X = 5.CI; Y = H; R1 = Thienyl •
241
Useful as intermediates analgesic and antiinflammatory agents (mice & rats). 133
Azaoxmdole -1 - carboxamide wo Y—\
Anti-inflammatory, and analgesic 134
Example compound: A = N; B, D, E = CH; X, Y = H; R1 = Alkyl, R2 = Alkyl, W = H •
2-Carbamoyloxy benzoates R1
C02R
\ Example compound: R = alkyl; R1 = H.
02 CNH2
Analgesic and antiinflammatory agents 135
CSI Applications
242
Example compound: R 1 = C O N H C H Ph 2 ; R 2 = Cyclopentyloxycarbonylamino • 4- [(4 - Oxo - 2 - azetidinyl) oxy] benzenealkanoatcs OCH2 Ph
Et
/
Et-"NH°
o
O
•
Aryl-IH- thiopyrano-[2, 3 , 4 - cd] indoles R21
R22
R5x
R1
i
(CR2 R3) m - y (CR2 R3) n - A (R2 R3) p - Q
ZR4
Example compound: H H
ArH2C
I CH20-CH2-C6H4-CH20H COH
Useful in the treatment fo asthma, rheumatoid arthritis, osteoarthritis, bronchitis, chronic obstructive airways disease, psoriasis, allergic rhinitis, atopic dermatitis, shock and other inflammatory diseases.
136
It shows elastase inhibition, so it is used as antiinflammatory agent as well as an antidegenerative agent. 137 Inhibitors of leukotriene biosynthesis. Useful as antiasthamatic, antiallergic, antiinflammatory, cytoprotective agents, treating anginal pain, cerebral spasm, glomerular nephritis, hepatitis, endotoxemia, psoriasis, uveitis, and allograft rejection and in preventing the formation of atheroclerotic plaques. 138
CSI Applications •
243
7-Methanesulfonylamino-6- phenoxy-4H-1 benzopyran-4- ones and analogues
R1S02 R2 N ^ A o " V j f z
u
J^l
R3 MeS02H
Example compound:
Anti-inflammatory agents and antipyretics 139
PhO
Ar S 0 2 HN
•
(3, 5-Di-tertiary-buty 1-4-hydroxy phenyl) thiadiazoles, oxadiazoles. andtriazoles (CH = CH) n - W
-
& CMe3
Antiinflammatory
Example compound: Me 3 C^ ^ ^
140
. (CH = CH) - R
(0) CMe3 R = Substd. 1 , 3 , 4 - oxa-group. •
Oxime-carbamates and oxime carbonates RO
Me1
CR1 = NOC (O) R2
Useful as antiinflammatory and as bronchodilators.
CSI Applications
244 Example compound:
N
o
CMe = NOC (O) NH
* / MeO •
/1 \
(significant activity in inhibiting phosphodiesterase is associated with I.
141
Antiinflammatory activity
142
Treatment of inflammatory processes
143
Oxindole - 1 , 3-Carboxamide Example compound: CONHR1
^ \
^CONH2
NA> CONH R2
•
CONH 2
3-ureidopyridofurans and -pyndothiophenes R
Example compound: R = NH2. •
Dipeptide derivatives R2 R 1
\ /
? iff
N
N^ R3
R
4
>H
Example compound: CO2H O
O
P h N / \ N H ^ ^ \
i U
U
Inhibit and prevent cell adhesion-mediated pathologies. Also useful for the treatment of many inflammatory and auto-immune diseases. 144
CSI Applications
Useful as antivirus, antiinflammatory and immunoregulatory agents. 145
Thiophene compounds
•
245
Preparation of heterocyclyl carbonyl substd. benzofuranyl Ureas as antiinflammatories NR1 C (L) NR3 R
Anti-inflammatory 146 Example compound:
R = [Unsatd. substd. benzalnellated heterocyclyl group] •
Derivatives of Isothiazolidin -3- one - 1 , 1 dioxide and 3-oxo-l, 2, 5- thiadiazolidine 1, 1 - dioxide O
R1
Useful as antiinflammatory and anti-metastatic agents.
sr^ o
o
(Serine protease inhibitor)
Example compound: O
Ph
o2
cAo
Ph
147
CSI Applications
246
Anti-allergies •
Imidodisulfamide derivatives R1
R1 — Z NHSO2 NHSO2 NHZ-
Anti-allergic activity
148
Anti-allergic activity
149
Anti-allergic (antagonism to the slow reacting substance of anaphylaxis).
150
Example compound: R1
R1 (K
^ ^ - C H PhNHS02 NHSO2 NHPhO
//
(R,R' = benzo) •
Iminodisulfamides R1 NSO?
-NH
Example compound: R = H; R1 = 7-(3-Cl C 6 H 4 N HS0 2 ) •
Imidodisulfamides
NH
Example compound: R = R1 = H, R2 = 7- CI; R3 = 8- CI
CSI Applications
•
247
N.N'-tfisCsubstd.-l,^^ tetrahydroisoquinolyl) - disulfonylimides
R3
\RS02-4PJ
1
-NH
Useful in the treatment of allergy and asthma.
151
Anti-allergic activity
152
Antiproliferative activity (in eukaryotic cells).
153
J 2
Example compound:
(R = R1 = R2 = R3 = H). •
Imidosulfamides
NSO2NHCON R1
R1
Example compound:
R = 7-C1;R 1 = 8-C1 Anti-proliferative/anti-tumor agents • Phosphorus and sulfur containing geranylgeranyl derivatives
f
Me
Me.
f
Me
H /P(0)(OH)2
f
Me
r
Me
(I)
Me
Me
OH
^\/VS02NH2 Me
Me (II)
Possibility of these Geranyl geranyl diphosphate inhibitors of compounds being post-translational Geranyl geranylation of useful as antitumor agents. 154 cellular proteins.
CSI Applications
248
Neuroleptics • Triazaspiro [4.5] decan - 4- one derivative O •NH - CH 2 -
N
Neuroleptic activity
J
N
Ph
•
4-(Polyalkyloxyphenyl)-2- pyrrolidinones H
a' -Gf
MeO MeO
•
Useful as tranquillizers.
8a-(Acylamino) - ergolines H,
NHCOR4
Useful as neuroleptic, antidepressant and prolactin secretion stimulators.
,iU 3
R1-N R2
Example compound: R ^ H , R2 = CN; R 3 ,R 4 = Alkyl. •
2-Substituted ergolme derivatives
R6
Useful as neuroleptics and antidepressants.
1
CSI Applications Ergoline derevatives
R6
Neuroleptics
H-N
Ergoline [I], Single or double bond at 8 or 9; but no cumulative double bond. R8 a or p when bond at 8 is single; R 2 = CN, SR, SOR, C(0)R, CH(OH) (R = C,_4 alkyl); R 6 = C,_4 alkyl; R8 = Me, NHCO NEt 2 , NHCS NEt 2 •
8a-(Acylamino)- ergolines NHCO R4
Neuroleptic and antidepressant agents R1-N
Example compound: R1 = H; R2 = CN R 3 = Me; R 4 = Me, C 5-[(4-benzylpiperazine) sulfonyl) -2methoxybenzoic acid -4- benzylpiperiazide Neuroleptic PhCH2-N
\so2^p)-
OMe
CON
N - CH 2 - Ph
CSI Applications
250
Anti-convulsants • Diastereomeric 9, 10- dimethoxy-1, 3,4, 6, 7, 1 lb-hexahydrospiro [benzofa] quinozolin2,4'- imidazoline-2', 5' -dione Example compound exhibited anticonvulsant activity.
MeO
MeO'
R
R1
Example compound: RR1 = CONH CONH •
Adamantane - spirolactams
Useful for anti-microbial anti-convulsant anti-hypoxia anti-Parkinson anti-colinergic activities.
H N R2
O R1
1
2
R and R = Adamantyl group •
Phenyl and phenoxy ethylsulfamates and analogs Useful as anti(HO)p A (OS0 2 NR1 R 2 ) Z convulsants.
Example compound:
A = A r y l ; R ' , R 2 = H;p = 0, 1, Z = 1. •
O-Alkylsulfamates. 2, 3 : 4, 5-bis-0-(lmethylethylidene)-b-D- fructopyranosesulfamate and related compounds .CH2OR Me, Me', / N O - - -
\
Example compound: R = S0 2 NH2
/
M e
Potent anticonvulsant activity
CSI Applications Anti-degenerative agents • 2-heterocyclyloxymethyl - and -2heterocyclylthiomethyl-1,2, 5 thiadiazolidin - 3 - one 1,1 -dioxide R1
.o
R2-
^ ~ ' " ^
rf
A
\
HN.
4
R
^Nv
o
o o
1) Useful for the treatment of degenerative diseases (elastase inhibitor). 1
X
o
(R = Un (Substituted) tetrazolyl.) Pr O .Ph
^
S \
O
•
N /
" O
V-N ^
N N^ N
Substituted azetidinones X3 R1
R2
R1 •R3
r/
-NA
R-
/
O
(I)
X^
f
-NCONHCHM (II)
X7
,X5
NCONH CHM-
0/
(III
Example compound: Me Me-
,<#>
X6
r >-©
N-C0NH.CH2 ^
>
Anti-inflammatory and antidegenerative agents 1
CSI Applications
252
•
Substd. 2- (phosphinyloxymethyl) - 1, 2, 5thiadiazolidin -3- one 1,1- dioxide R2.
U
R3-Nv
X
,NCH2OP(0)(OA)(OB)
•
Useful as proteolytic enzyme inhibitor in the treatment of degenerative diseases. 168
^NCH2 0 P ( 0 ) ( O H ) 2
2-(2, 3, 5, 6- Tetrafluoro-4-pyridyl) -1,2, 5-thiadiazolidin -3-one 1,1 -dioxide
Useful for the treatment of degenerative diseases (emphysema, rheumatoid arthritis, and periodontal disease). 169
Anti-coagulants • Aminosulfonylphenylalanine derivatives
R1 R3 N . S -
o
As oral antithrombotic agent - useful for the treatment of thrombosis.
CR2
Example compound:
NCOMe
170
CSI Applications
•
•
253
Polylectrolyte produced by the reaction of cis 1, 4- polyisoprene & CSI, followed by Anticoagulant activity the addition of NaOH. Synthetic polyelectrolyte Anticoagulant (Natural rubber + CSI, followed by treatment activity with NaOH)
• •
•
171
Gaseous CSI treated styrene - isoprene- Antithrombic activity styrene block polymer. Unsaturated polyurethaneureas were modified by treatment with CSI to produce sulfamate and carboxylate groups on the film surface.
Useful for the prevention and control of thrombosis.
172
173
174
Hydrogels by irradiation of synthesised heparinoid polyelectrolyte i) CSI
Cis 1, 4-polyisoprene
ii) NaOH Soln
heparinoid polyelectrolyte
7 -irra
ia
^
The polyelctrolyte hydrogels do not deplete antithrombin III from blood. 175
Hydrogels Fibrinogen receptor antagonists having substd. (3-aminoacid residues and pharmaceutical compositions comprising the same N-R1 Y1 R2HNV
Y2
R3
N .
-
'YYNJ R4
O
(CH2)m-C02R5
Useful for inhibiting platelet aggregation, blood coagulation in extracorporeal circulation, occulusion of arteries and reoclusion of coronary arteries.
176
CSI Applications
254
Example compound: O
Et
O
H2N
\y
C02H
NH
•
Preparation of an asymmetric semipermeable membrane with anticoagulant activity.
The membrane has a potential use in Semipermeable styrene - isoprene styrene insulin delivery and hemodialysis. 1 block - copolymer membrane •
Asymmetric membrane with hemocompatible properties A styrene polymer contg. a p- pendant vinyl function was modified by the gaseous CSI to give a membrane contg. A and B Units. Anticoagulant • CH2 - CH •
o Na S03 NHCH CH2 CO2 Na [A]
•
— CH2 - CH —
o CH = CH CONH2 [B]
Asymmetric membrane having blood Heparin like compatibility compound with enhanced blood A new asym. membrane synthesized from compatibility. an ABA poly (Styrene-isoprene) (SIS) block co-polymer + CSI (g) • heparin like compound
CSI Applications
255
A asymmetric membrane prepared from styrene isoprene - styrene block co-polymer
Anticoagulant styrene - Isoprene - styrene block polyner + property CSI(g) ». modified polymer (Heparinoid type Surface modification of polycarbamate with compound).
180
synthetic polyelectrolyte NaOH
Natural rubber + CSI
poly
electrolyte
Activity similar to heparin.
181
Posesses heparin like properties.
182
Useful as heparinoid material.
183
A asymmetric membrane with hemocompatible properties Poly (p-vinylstyrene) + CSI membrane
desired
Heparin - like polymeric bio - materials Polybutadiene/polyisoprene
CSI
(I)
Heparin like material CIO2S /
V
Fibrinogen/platelet interaction changes due to surface treatment on polyvinyl chloride. The polyelectrolyte may be useful in Poly (cis - 1, 4-isoprene) + CSI •» making polymer polyelectrolyte non-thrombogenic. 184 The synthesis of some polymeric biomaterials Potential utility with potential blood compatibility. in blood CSI (g) Polybutadiene/Polyisoperene contacting prosthetics. 185 Modified polymer
CSI Applications
256
Blood related problems • Assymmetric membranes from a styrene isoprene - styrene block co-Polymer Membranes have blood (Styrene-isoprene-styrene) block copolycompatibility CSI (g) Modified polymer mer •
o-Carbamoylsalicylates o NH 2 C 0 2 C 6 H 4 C 0 2 H
Platelet aggregation, induction/inhibition • Thiophene and Pyrrole derivatives Rl R 2
186
Agents for modification of hemoglobin
187
Useful for inducing platelet aggregation.
188
AN R4 R5
-F^-R3
Example compound: y AC AN \
// w
H
A = Alkylene Potent inhibitor 5-(4- Amidinophenyl)- pentanoyl -3- (3of canine platelet pyridyl) - propanoic acid. aggregation (in vitro); orally active. Hypoglycemics hypoglycemics, • N-l-(Methyl-2-pyrrolidinylidene) CNS depressants sulfonamides and diuretics •
ex.
NSO2 R
Me
Inhibitors of aldose reductase
189
190
CSI Applications
•
257
Chiral hydantoins (R = CI) showed hypoglycemic
activity.
191
(R = C1,F) •
Substituted 3H-1, 2, 3, 5- oxathiadiazole 2oxides Hypoglycemics
192
RCH2 S = 0
o (R= l-chloro-3,4-dihydro-2-naphthyl) •
Chiral hydantoins .0
Example compound: R = F (Sorbinil); R = CI •
Oxazolidinedione derivatives
The chiral hydantoin (R = CI) possesses greater hypoglycemic activity than sorbinil (R = F) in rats. 193
Useful as aldosereductase inhibitors and hence used for the treatment of diabetes.
194
CSI Applications
258 Example compound:
CH2 C6 H4 Cl-p
Brain related problems •
Carbazole
For ischemic brain 1 9 5
O
MeOOC v
Me/
X
N H
NH2
.CO2-CHMe2
^C02-0-C0NH2
NB818 is described as a patent and selective amehorant of the cerebral circulation. 196
(NB818)
Eye disorders •
Sulfamates
•
useful as antiglaucoma agents
Thiadiazolo [3, 2-a] pyrimidme sulfonamides and thiadiazolo [3,2-a] triazinesulfonamides
O
*kA
x.
RN S02NH2l
N I
N SO2 NH2
197
Topically effective carbonic anhydrase inhibitors (ocular hypotensive agents). 198
CSI Applications
Heart related disorders • 4-Aminoqumoline and 4 aminopentinopyridine derivatives
Improves brain disorder and heart function. Inhibits 5-lipoxygenase acetyl choline stearase and anoxia, shows isotropic action and useful as cardiotonics and the treatment of heart failure, cerebral arteriosclerosis and Alzheimer type senile dementis. 199
NH2
NH2
(H2 C) 5
N (I)
259
(II) NH2
Y
(General Structure) •
Isoquinolines derivatives
The HC1 - salts were more effective than MeO verapamil in the inhibition of ventricular fibrillation induced 1 2 Ar = Aryl; X and X = Divalant alkylene by reperfusion C,_4 chain optionally substituted with lower after coronary artery ligation in dogs. 200 alkyl groups
•
Carboxyalkyl dipeptide derivatives and pharmaceutical composition containing them RCOR 1 R 2 NHCHR 3 COR 4 CR 5 R 6 COR 7
Example compound: RCOCH 2 NH CH 2 COHCH 2 COR R-R7 = optionally substituted alkoxy
Antihypertensive 7
201
CSI Applications
260
•
2-Substituted or Unsubstituted aminocarbonyl - oxyalkyl - 1 , 4- dihydropyridines Increase the coronary blood flow 74% (in dogs).
202
R = 2 - N 0 2 ; R1 = R2 = Et; R3 = Me; R 4 = CH 2 OH. 6, 7, 8, 9- Tetrahydro - 3H - Benz[a] indole Centrally acting compounds. These heterocyclics also show the effect on blood pressure, heart rate and rectal temp. (rats). 203 7- Amino -2- (hydroxymethyl)-s-triazoles (1, Useful in the treatment of cardio5-a) pyrimidine derivatives vascular disorders, NR1 R2 especially cerebral R3. ischemic diseases such as arteriosclerosis, R4 N CH20R5 cerebral and Example compound: myocardial R1, R2 = Et; R 3 = H; R4 = Me, R5 = Ac. infarction, senile dementia, hyperlipeniaetc. •
AA A
Example compound shows vasodilatory activity. 204
CSI Applications
•
261
2- Carbamoyloxy alkyl - 1 , 4 - dihydroxy pyridine derivatives and their intermediates
R2 CO2R 3
R1 O2 C
R /
N
\ X O2 CNR4 R5
H
Example compound: NO2
C
A1-O2C
XT H
•
°2
NO2
Ar
Et 02 C
CH2 O2 CN H2
205
Useful as coronary vasodilators and antihypertensives (experimental animal: rat).
206
C02Et
Me'
N H
(I)
Useful for increasing cardiac flow and decreasing blood pressure (coronary vasodilators & Hypotensive).
\ CH2 O2 CNH2 (II)
Carbamoyloxyalkyl -1,4- dihydropyridines. Cl
R1 O2C
Me^
N
\ z O2 CN H R3
Example compound: .CI •CI . CO2 Br
Me02
Me
N
^ C H 2 0 2 CN H2
CSI Applications
262
3- Aminopropoxyaryl derivatives R1 OCH 2 CH(OH) CH 2 Z (CO)m R R = Un(Substd) alkyl; R 1 = arom. or heteroartom. radical Z = piperidinylamino, 4-piperazinylamino, NR 2 (CH 2 ) n NR 3 .
Useful as cardiotonic, antiarrthymic and a and P-sympatholytics.
207
Cardiotonics
208
Useful for the treatment of peptic ulcer.
209
R2, R 3 = H, alkyl; n = 2-4. (Aryloxy) hydroxypropyl heterocycles OH CH (OH) CHN
J
\
-O
N-CH-
J 2
CN
H
Disorders of stomach & gastro-intestinal tract • 1, 2, 4- benzothiadiazine - 1 , 1 - dioxide derivatives 02 N'
I
II V
N-ZAOBNRl^^N' R2
Example compound:
R3
CSI Applications
•
263
Amorphous cefuroxine oxetil Useful for improved bio-availability from gastrointestinal tract. 210
H
NO Me
cf
^
\ C H 2 02 CN H2 CO2 CH Me OAc
Bioartificial insulin distributor membranes
•
Styrenic asymmetric membrane with The membrane homocompatible properties could be employed Poly (p-Vinylstyrene + CSI »- modified as an artificial insulin distributor. 211 polymer
•
Styrenic asymmetric membrane with Membrane can be hemocompatible properties used as substrate for culturing islets Vinyl substd. polystyrene + CSI «• of Langerhans for Polymer membrane. a bioartificial insulin distributor. 212
Bronchial asthma
•
Pyrido [2, 3 -d] pyrimidine derivatives
R
\ ,K
R4
'-
X
R5
Example compound:
R 1= Cycloalkyl optionally substd. by OH group.
These compounds possess phosphodiesterase inhibitory activityuseful for the prevention and treatment of the respiratory disorderbronchial asthma. 213
264
CSI Applications
CNS related disorders • Thieno [2, 3-b] indole derivatives
COT COT
\
•
4 - ( 3 , 4 - dimethoxyphenyl) 2 - pyrrolidinone -1 - carboxylic acid derivatives OMe MeO
Example compound: R = PhO
r^
CON
Useful in treating diseases in the CNS- related to the metabotropic glutamate receptor system. 2 Possess central nervous depressant, apomorphine antagonistic and antinociceptive activities similar to that of chlorpromazine but with less tranquilizing and narcotic properties.
Lipid/cholesterol lowering agents •
(Aminosulfonyl) ureas and oxysulfonyl Lipid carbamates lowering activity
•
N-acyl sulfamic acid esters (or Thioester), Useful for the n-acyl sulfonamides, and N-sulfonyl treatment of hypercarbamic acid esters (or thioesters) cholesterolemia PhO - S02 NH - C - OPh and II atherosclerosis. O
2
CSI Applications
•
265
(Amino alkyl) substituted benzoheterocyclic compounds
1
T
[Dotted line : optional double bond]
Q
M = (Un) Substd. heterocyclic atom grouping
Compounds associated with antimycotic and antihypercholesteremic activities.
218
Q = Unsubstd. Cycloalkyl T = H; R = (Un) substd. aminoalkyl] Antibiotics •
N- (2- ethoxyethyl) -N- (4Phenoxybenzyl) dichloroacetamides.
R
CH
~(f~j)-X-((~J)-
2 N (CO CH Cl2) CH2 CH 2 OEt
Example compound: R = AcNH; X = O •
Useful as potent antiamoebic agents. - activity comparable or better than Etofamide and Teclozan. 219
Substituted benzenesulfonic acid esters. / NHC (C = S) NH C02 R
NH CO NH2
R = Alkyl
Anthelmintic activity
220
CSI Applications
266
•
2, 5- Dioxabicyclo [3.2.1] octane -3.4.5 tricarboxylate sequalene synthase inhibitors
HO2C
HO H0 2 C ^ | HO2O'
Me K
J ^ \ ? > O
H
.Ph
^ ^
•— R3
Me
i) Used as anticholesteremics and ii) Active against fungi - e.g. Candida albicans 221
Q2:
R
3
=
Q1/Q2/Q3
Diphosphate modified antiviral analogs of Potent antiherpes uridme - 5 - diphosphate glucose derivatives activity
222
Uridine - 5 - diphosphate glucose analogs Inhibitors of protein glycosation that shows antiviral activity
O - CO NH SO3CH2
(I)
Example compound: (I) R = PhCH2.
[I] Showed antiviral activity
223
CSI Applications
•
4- (o-substituted thioallophanates
aminophenyl]-3-
o [AcNH] C 6 H 4 NH CS NH C 0 2 . Growth hormone release promoters • Benzofused lactams
Me
O
Me
y^NH2
(II)
•
267
Useful as fungicide and mite ovicides.
224
These compounds release growth hormones in humans and animals. This property has been exploited in producing efficiently the edible meat from animals. These compounds are also administered to the humans to overcome the deficiency in the production, by the body, of growth hormones. 225
Benzo - fused lactams O
o -CH?
NH - C - (CH2)3 NH2
Where L, K =
Useful as growth hormone release promoters.
226
268
•
CSI Applications
Benzo - fused lactams O
NH2
NH-C-CH2-CMe2
Promote release of growth hormones 227
\=j •
Substituted dipeptide analogue Ph CH2 CH2
NH CO CH2 C Me2 NH2
Growth hormones release promoter 228
•
Heterocyclic fused lactams
\ — NH-C-A-NH2
A = Unsubstd. C ] 7 alkanedinyl R'(R 2 ) Het. = Disubstd. 5 or 6 membered heterocycle contg. 1-3 hetero atom selected fromN, O, S.
Promotes the release of growth hormones (humans) to increase stature, and in animals to render the production of edible meat more efficient. 229
CSI Applications
•
269
3-Substituted benzazepinone
NH COCH2 C (NH2) Me2
Stimulates release of growth hormones. 230
Antagonists • Triptophylphenylalanine derivatives
•
5-Chloro-2H-l, 2, 5- benzothiadiazme (HH) - one - 1 , 1 - dioxide
•
Substituted (pyrrolidin-3-ylalkyl) piperidines
Useful as tachykinin antagonists for treating asthma. 231 Non - competitive NMDA receptor antagonist 232
229 N (CH 2 )
R2
N
V'
N-CH2CH2Ar2 Ar
R1, R2 = Substd. Spirocyclyl
Tachykinin antagonists
233
Thromboxane A2, receptor antagonist
234
Ar1 = Substd. aryl Ar 2 = Substd. phenyl •
Substituted sulfonamides CH2 COOH
NH SO2 •
(Trans)
•CI
CSI Applications
270
•
Benzodioxide acetic acid and phenylacetic acid derivatives
R4-
'N
N
Andothelin B receptor antagonists
R1
Example compound:
+Oi-o ^ £ s / HO2C
N
x
Pr
1 , 3 , 8 - Triaza and 3,8- diaza - 1- oxaspiro (4, 5) decane derivatives (R1)P
-v (V_j)-
C0
^(R 2 )m
CH
( 2) n -N
Y —NR3
Xl
imple compound:
As selective 5-H2C receptor antagonists
8-[5- (5-methoxyphenyl) -5- oxopentyl] -2-
thioxo-1, 3, 8-triazaspiro [4.5] - d e c a n i one. •
[(Tetrazolylpyrrolyl) benzyl] imidazopyridines and related compounds
Angiotensin II antagonists.
271
CSI Applications
•
3- and 5- (Bicyclo ether or bicyclic alkylene thioether) alkylenamino - thiatriazines o2
R
'~k A
Show histamine H 2 - receptor antagonism and antiulcer activity.
238
Useful as leukotriene antagonists
239
Example compound:
R1 = H; R2, R3 = OH •
Heterocyclic amide derivatives R 2
\ ^
A"! Q A2 M
Example compound: R 1 = Acylamino; R 2 = H; Q= (Un) substd. Phenylene; A 2 = CH 2 ; M = C02H Inhibitors •
Thiatriazepinones Ph
Ph
O N
^
^
NH
These compounds are diuretics, carbonic anhydrase inhibitors. 240
NH
Ph
Ph
N-(Aryloxysulfonyl) analogues OMe
carbamates
MeO
j S02 NHC02—ft OMe
MeO
y
& Inhibitors of cholesterol acyltransferase - therefore useful as anti-atherosclerotics and anticholesteremics. 2 4 1
CSI Applications
272
Arylaminosulfonyl Carbamates P h - O - CO NH S 0 2 NR 2 R 3 Example compound: CH Me2
02 CNHS02 N H — ( C j )
MeO-
CHMe2
•
Me2 HO
As cholesterol acyltransferase (ACAT inhibitors)
242
ACAT inhibitor
243
p38 kinase inhibitor
244
Me2 H C '
Aryl aminosulfonyl Urea R1 R 2 N CONR S 0 2 NR 3 R4
Example compound: ,CHMe2 ft
^ —
NH CONH SO2 N (Me CH2 CH Me)2
^ CH Me2
Pyridyl Aryl Urea Example compound:
CSI Applications
273
• Imidazole derivatives Histamine H3 receptor Ugands 245
• N-(Aryloxy sulfonyl) Urea derivatives R1 R2 N CONR S 0 2 OR 3 Example compound: H 2 N CONH S 0 2 OPh
Useful as ACAT inhibitor
1
Ph1 = Substituted phenyl •
7-Oxo - 1 - azabicyclo [3.2.0] hept -2-ene carboxylic acid esters and their derivatives R1
/
cT
R2
CO2R
Example compound: R = Ester function; R1 = R2 = H •
246
Exhibits p-lactamase inhibitory activity against Enterobacter p99. 247
Sulfonyl alkanoylamino - hydroxy ethylamino sulfamic acid
// W
N
Effective as retroviral protease inhibitor and in particular as inhibitors of HIV protease. 248
CSI Applications
274
•
Pyrrole derivatives
•
Azetidinone Compounds
Inhibitors of TNF; useful as antiretroviral agents 249
O II Et-
/
/
v
OCH2-C-N
N-Me
Elastase inhibitors
250
Inhibitors of topoisomerase II
251
- N. CONH CH2 . N . COCH Ph2 • HC1
/ CH2 (CH2)3 Me
•
Synthesis of n a t u r a l l y indolequinone BE 10988
H2K
^
occurring
y— CO NH2 N
Disopropylphenyl sulfonyl analog
•
Highly selective inhibitor of AC AT (Hypocholesterolemic agents) 252
Substituted 3-oxo-l, 2, 5- thiadiazolidme 1, Potential inhibitors of human leukocyte 1 -dioxide elastase and cathepsm G. 253 \ R1 -
I N ^
NC NCH2F
"
Example compound: R = C 6 H 5 C H 2 ; R ' = H.
CSI Applications
•
Indolequinone BE 10988
CONH2
» 2 \
•
Inhibitor of topoisomerase
2
3,3 Diethyl - 2- azetidinones Et Et-
/-Q
•COOH
-NCONHR
As highly stable inhibitors of human leukocyte elastase inhibitors 2
Inhibitors of GDP - mannose dehydrogenase of Pseudomonas aeruginosa mucoid stains Guanosine, 5 ' amino - 5 1 - deoxyguanosine, GDP- mannose 5 1 -(3- hydroxyphenyl) - amino - 5 ' - deoxy- dehydrogenase inhibitors guanosine
Benzocycloalkyl amines
Inhibitors of HIV Protease
2
CSI Applications
276
Chelation & diagnostics • Polyethylene glycol Carbamates. RO ( C H 2 C H 2 0 ) n ZNH(CH 2 ) 5 N(OR ! ) COCH 2 CH 2 CONH (CH 2 ) 5 N (OR 2 ) COCH 2 CH 2 CONH (CH 2 ) 5 N (OR 3 ) Ac. Useful as chelating and diagnostic R = C ] 4 alkyl; R1"3 = H; acyl group; agents. 258 Z = - CO (NHS0 2 ) m m = O, or 1 n = average value ^ •
9
Useful as chelating agents in treating XNH (CH 2 ) 5 N (OX 1 ) OCH 2 CH 2 CONH diseases (CH 2 ) 5 - N (OX 2 ) COCH 2 CH 2 CONH associated (CH 2 ) 5 N (OX 3 ) Ac. with excess Fe (III). X = Org. acyl group. N- Acyldesferrioxamine B derivatives
259
X ' , X 2 , X 3 = H; •
Porphocyanine and cnc-expanded porphrins
These compounds are useful in photodynamic therapy and diagnosis. The metalated forms when the metal is paramagnetic are useful as MRI contrast agents. 260
CSI Applications
277
Useful in the treatment • P y r a z i n o b e n z o t h i a z m e d e r i v a t i v e s and and prevention of inflammatory analogs immunol. diseases, Example compound: autoimmune diseases, (Syn) -3 ( l O H - P y r a z i n o [ 2 , 3 - b ] [1,4] rheumatism, collagen benzothiazin-8-yl-methyl) - 3 - azabicyclo disease, asthma, [3,3.1] nona -9-yl acetic acid nephritis, ischemic reflow disorders, psoriasis, atopic dermatitis or rejection reactions following organ transplantation. 261
Miscellaneous activities
Benzoyrano [4, 3-c] pyrazolones R4
N
NR 1
Example compound: R 1 = R 2 = H; R 3 = R 4 = CI. •
Useful as immunodulators, especially active as immunosuppressantsuseful for the treatment of e.g.; kidney rejection, rheumatoid arthritis, psoriasis and melanoma. 262
4 - ( 2 , 1 , 3-benzoxadiazol -4-yl) 2- Carbamoyloxymethyl - 1 , 4-dihydropyridine - 3 , 5 - dicarboxylates Exhibit smooth muscle relaxant activity (rabbit). Me O2 C
'N H
^CH2 02CNH2
263
CSI Applications
278
•
3,4-Disubstituted benzenesulfonamide OR1
R2 0.
Useful in therapeutics (or have therapeutic utility). 264
• SO2 NR3 R4
Example compound: N-(indan-l-yl)-3,4dimethoxybenzenesulfonamide •
Substd. 2-acylaminopyridines
Useful in the treatment of nitric oxide synthase mediated diseases and cLisoiriexs. 265
279
CSI Applications
II-5
Antibiotics
General Name & Structure of Compound
Applications
Ref.
Azetidinones
•
N-Substituted Sulfonylammo - carbonyl azetidinone derivatives H2N
_/
V
CH2 OCO CH2 NH2
\N
O'
(CONH)2 SO2 R 6
R 6 = [Pyridinoyl - carbonyl amino] Antibacterial agent 266 imidazolidinone Q
O
H2N—^
'C-C-
II
(Q)
•
NOMe
Isoxazolylamino sulfonylamino carbonyl azetidinones
General structure R2
R1 NH-
//
O'
4? -NCO NH SO2 NR3 A (I)
Antibacterial agent 2 6 7
(General Structure)
Example compound: OMe N
H2N
jrf]f X
< s5
X
N-CONNaS02
O -
(II)
o
N Ns
>-Me
CSI Applications
280 Azetidinones OR1
OSiR2R3R4
/>
NH
A
Me'
tert.
?SiMe2nB" Rtert. OSi Me2 Bu
Me/\ J
o R1 = Si R5 R 6 R 7
1 NH
O
Intermediates for antibiotics
268
R 5 - R 7 = C!_ 4 alkyl R 2 - R 4 = Cj. 4 alkyl, Ph, aralkyl. •
4-Mercapto - or - hydroxy - 3 - (1 -hydroxyethyl) azetidin -2 - one derivatives OR1 Me
A
AR2 NR
O
Example compound:
Used as intermediates for (3 -lactam antibiotics. 269
OR OSi Ph3
Me/\
/>
NH
O
R = Hydroxy protecting group •
N-(Sulfonamido carbonyl) azetidinones RHN
)
-NCONHSO2NH2
R = Carboxylic acid derived acyl
As antibacterial agent
270
281
CSI Applications •
2-Oxo-l-[(Substituted sulfonyl) amino carbonyl] azetidine R2
R1 HN
\
R3 -NCONHSO2R
//
O
Example compound: Antibacterial
271
CH3-C-NH
CONH SO2 NH
•
o
O II
O NH-C
OH
N H
N-[(Heterocyclylsulfonyl) carbamoyl] azetidinones R1 R3HN R2 A
NCONHSO2R
O Example compound:
Antibacterial agent 272
NOMeC - NH^i
^
H
\
s NH2
H
Me
I
r
-N—COC-S02NH-NH
^
OH
CSI Applications
282 •
l-(Aminosulfonylaminocarbonyl) azetidin-2ones O R1 NH- N - CONH SO2 ANH C O - i
#O
OH N H
'
Antibiotic Example compound: Acyl N H
yf
O
•
O - N - CONH SO2 NH - N H C O — ( f \— N—" H
OH
2-Oxo-l-[(subtd. sulonylamino] carbonyl azetidines R2 R1 N H .
S~\
R3
CONH SO2 R
Antibacterial
Example compound: AcNH
/y- N
OH /N-NHCH2—/f~^-0H
Y
CONH - SQ2 NH -fg v
CSI Applications •
283
3-(l-hydroxyethyl -4- (tert.-silyloxy) azetid2-ones R1 OCHMe
OSi R2 R3 R 4 NR
/>
As intermediates for bactericides
275
Intermediates for carbapenem antibiotics
276
O
R = H; R1 = Hydroxy protective group; R2 - R4 = CI - 6 alkyl, Ph, aralklyl •
Azetidinone derivatives MeCH (OSi Me2 CMe2 CHMe2)
QS
R
i
R2 R
3
f
-NH
/ Example compound: MeCH (OSi Me2 CMe CHMe)
f
OAc
-NH
l-Sulfo-2-oxoazetidine carboxylic acid derivatives Antimicrobials: Inhibits the growth of micro-organism NOR1 -NS03H // viz, Proteus mirabilis Or R = Amino - substd. 5-or 6-membered P. vulgaris. 277 heteroaryl contg. 1-2 N and an optional S or O. R J r R 2 = H
r
R C CONH II \
R2
1
2-Oxo -1-[(acylamino) sulfonyl] azetidines. R1 RNH ^ i J 0
R2 i— N
Bactericidal R3
- SO2 NH CO R4
278
CSI Applications
284 Example compound: H
H H
AcNH —
-N-SO2NHR
(R = alkyl) •
1 - Sulfo -2- oxoazetidine derivatives R2
Bactericidal RON = CR1 CONH—<
N SO3 H
Y
Inhibits Proteus mirabilis
279
o Example compound: R = R1 = R 2 = H • 1 -Sulfo -2- oxoazetidine derivatives H2 N Z C CONH
Bactericidal
r
.R2
(inhibitory action against Proteus OR1 ° mirabilis 1028 and Escherichia z = 5 - or 6 - membered arom., 1 or 2 -Ncoli 1346) contg. optionally with addnl. O, Se or S atom; R1 = substd. alkyl., R2 = H, Org. group., oxime group at least partly syn.) N
-NS03H
280
3-(l-methylethylidene) - 4- acetoxy azetidinones CH2OH Me
X S
O
• s
y%y
XOOH
NHAc
Synthesis of (±) asparenomycinic antibiotic
281
285
CSI Applications
•
4-(Substd. methyl) -2- azatidine -1 -sulfonic Highly potent acid derivatives. (Synthesis) antibacterial activity against R1 Gram-negative C . CONH/ bacteria including H2N -N-SO3M NOR 0 ^ Pseudomonas (I) aeruginosa.
-A3
282
Modified derivative of sulfazecin •
Sterically uniform 2- azetidinones H
H
Me /•NH
J>
S (O) R^ n
(I)
R = H; acyl, trialkyl silyl,
Useful as intermediates for penems and Carbapenems (antibiotics).
283
Bactericidal activity
284
Intermediates for thienamycin antibiotics
285
R2 = Ph substd. in o - and (or) p- position by halo, alkyl, alkylthio, alkoxy; n = 0, 2]. 4-Thiazetidinone
y -N
//
O'
•
x
Me
C02 H
3 -(1 -hydroxyethyl) -4- siloxyazetidin-2- ones R1 O CHMe
W
^—
o
N H
QSi R2 R3 R4
CSI Applications
286
Azabicyclo [3.2.0] heptenones • 6-Amino- 3-substd. amino - 1 - azabicyclo [3.2.O.] hept -2- ene -7- one - 2- carboxylic acid R2HN
/>
r
.SR1
Antibiotic
286
Antibiotic
287
'COOR
O
Example compound:
R1 = (4-Methylpiperazinyl) R2 = PhCH 2 CO•
6-Amino -3- substd. amino - 1 - azabicyclo [3.2.O.] hept -2- ene - 7- one -2- carboxylic acid RN
NR1 R2
CO2H
O Example compound AcNH.
(4 - methylpiperazinyl)
V #
-N
O
CO2H
5-Substituted -3- (2-aminoethylthio) -6- (1hydroxy ethyl) -7- oxo -1 - azabicyclo [3.2.O.] hept -2- ene carboxylic acid MeCH(OH) Me
>
O
SCH2 CH2 NH2
CO2H
Antibiotic & bactericide 288
287
CSI Applications •
6-Azabicyclo [3.2.O.] hept-2- ene derivatives C02Me 0
V Ac /
N
Potential antibacterial agents
289
Bactericidal.
290
Inhibition of Escherichia coli.
291
B-Lactams (Azabicycloheptanones).
J
I^ SR CO2H
Example compound:
I
r V - sc H3 C02H
Derivatives of 7 - oxo -1- azabicyclo [3.2.O.] - hept -2 -ene -2- carboxylic acid R2.
SOR1
CO2R
Example compound: Me /
O
SOAryl
CO2R
CSI Applications
288 •
3-(2- Amino ethylthio) -6- (1 -hydroxyethyl) 7- oxo- 1, 2-azabicyclo [3.2.O.] hept -2- ene carboxylic acid Antibiotics HO CH Me
/> •
S CH2 CH2 NH2
C02R
6-( 1 -Hydroxyethyl) -7- oxo -1 - azabicyclo [3.2.0.] - hept -2- ene-carboxylic acid derivatives Me CH (OR4)
y-
SR1
Antibiotics CO2R 2
Example compound: Me CH (OH)
O
•
SH
CO2H
3-Substituted -6- substituted. 7- oxo - 1 azabicyclo [3.2.0.] hept -2- ene carboxylic acid R2
SR3
R1-
/ o Example compound:
Antibotics CO2R
SH
J
COOH
CSI Applications
6-Amido - 3 - substituted - 1 - azabicyclo [3.2.O.] hept -2- ene-7- one- carboxylic acid AcNH
R
.0
AcNH
Bactericides //
C02 H
C02H
R = CI, OAc, OMe or OCH 2 CH 2 NEt 2 •
Substituted -6- substituted. -7- oxo - 1 azabicyclo [3.2.O.] hept -2- ene- 2carboxylic acid R1
SR3
J
Bactericidal
CO2R 3
Example compound:
R, R1 = H; R 3 = Alkyl group. •
6-and 4-Substituted -1 - azabicyclo [3.2.0.] - heptene - 3 , 7 - dione -2- carboxylates. R1
R2
Antibiotics Example compound: Me HOH-
/r
Me
Me
o CO2 CH2 C6 H4 NO2 p
O
•
p-Lactam acetic acid derivatives
CSI Applications
290
SR1
/>
CO2R 2
O
Example compound: HO.
SR1
0 ©
S
Intermediates for 1-azabicyclo [3.2.0.] hept-2ene antibiotics
298
Antibiotics
299
Inhibitory action action agenst Proteus vulgaris.
300
C02Na
O
(R1 = hydrocarbyl) •
6-and 4-Substituted - 1 - azabicyclo [3.2.O.] - heptene - 3 , 7 - dione -2- carboxylates R1
R2
R3
/
C02R4
o
Example compound: R = HOCHMe, R1 = R2 = H, R3 = Me, R4 = CH2C6H4N02-p •
3- Pyrrolidinylthio - 1 - azabicyclo [3.2.0.] hept-2-ene carboxylic compounds R2
R3
R4
// O'
NR
-N
' R1
Example compound: OH
Me
o-<-
S—i
C02H
,/N-NH
CSI Applications Carbapenems
•
1,6- and 2- substd. -l-carba-2- penem- 3 carboxylic acids
OH
Used in pharmaceutical CH {J)— 2 NH2 compositions
OMe
Me-
/r
COOH
/f O
6-Amido-l- carba -2- penem -3- carboxylic acids R2
y
R1 - H N -
' CO2 R3
O
Antibiotics
R^PhCHjCO R2 = Unsubtd. Cj alkyl. R3 = Trichloroethyl P-Lactam as penem and cabapenem OR1 i
^ S ^ / CH2 NH R2
Me'
/>-
R3
O
Antibiotics
R1; CH 2 = CH-CH 2 0 2 C.CO, R 2 ; C 0 2 C H 2 C H = CHPh R \ CH 2 C-H = C
f R1 = Ac
f
-NH
OSi Ph3
Antibiotics
292 •
CSI Applications 5- Methyl carbapenem compounds Me
R1
V >
/
R2
N
O
CO2R 3
Example compound:
Broad spectrum antibiotics
3
Inhibitors of the bacterial enzyme leader peptidases.
3
Useful against staphylococcus aureus in mice.
3
Antibiotics
3
Me HOCHl2
V
Protected
•SH
^ O
CO2H
5 S- Penem derivatives
r
R\
.^
/R2
S^
' CO2 R3
O
Example compound:
//
>,
N
O
•
U.
\
CO -CONH2
Cephalosparin analogs On
R1 NH
.^
o
a
CHCHO
CSI Applications Carbapenems antibiotics Synthesis of trans- (+) -4- carboxymethyl 3- ethyl-azetidin -2- one and it's conversion into natural carbapenem antibiotic (+) - PSAntibiotics 5 [I] H
Et
S (CH 2 ) 2 NH Ac
s CO2H (I)
•
Broad and potent antibacterial activity. (staphylococcus aureus compartable to cilastatin/ imipenem)
Carbapenem derivatives OH
H
t1
H
R1
COO
R 5
Example compound: R1 - R 5 = H •
1 B-Methyl carbapenem antibiotic, S-4661
Me'
OH 1 H
H
^
Y
Antibiotic
Me
s—
S
N HSO2 NH2 N-H
O
C02H
P-Lactams
Useful as intermediates for the synthesis of carbapenem antibotics.
3
CSI Applications
294 5-Methyl carbapenems OH
Me SR
Antibacterials
313
Antibiotics
314
Antibiotic
315
Me #
CO2H
•
O
1 -, and 1, 1 -Disubstituted -6- substituted -2carbam-imidoyl -1 -7- carbadethiapen-2-em -3 carboxylic acids R5
f\4
R3 SXC (= R) NR1 R2
R6-
/
CO2H
o OH Me
Me
/
S CH2 C (= NH) N Me2
Me #
•
O
CO2H
[X = bond, aliph., alicyclic, arom., heterocyclic; R - R2 = H, aliph. cycloalkyl, aryl, heterocyclic and may form rings with each other or with x; R3 - R6 = H, (Un) substd. alkyl, Cycloalkyl, aryl, heterocyclic, R 3 ,R 4 = alkylene] •
Carbapenem antibiotic (±) -6- epi - PS - 5 S CH2 CH2 NH Ac Et-
/>-
C02Na
295
CSI Applications
•
6-, 1- and -2 substd. 1- carbadethiapen-2em-3- carboxylic acids R2 SR R3
Antibiotics
316
Antibiotics
317
Antibiotics
318
CO2H
Example compound: SH
N
O
•
COOH
6-, 1,1-disubstd. l-carbadethiapen-2-em3- carboxylic acids R1
R3
R2
R4-
of
•C02H
Example compound:
%
O
COOH
6-(l- hydroxyethyl) -2- (2- amino-ethylthio)1,1 - disubstituted -1- carpede thiapen -2- em -3- carboxylic acids NH2
CO2H
Example compound: OH
x_
Me
Me 'NH2
Me'
^
CO2H
CSI Applications
296 •
2-, 5- and 6- Substd.-1- carbadethiapen -2em- carboxylic acids R1
R2
SH
s/
O' 1
Antbiotics
319
Antibiotics
320
Antibiotics
321
-C02H
2
R = R = optionally substd. hydroxy alkyl. •
6-( 1 - Hydroxyethyl) -2- (Substd. mercapto)1- methyl - 1 - carbadethiapen-2- em - 3 carboxylic acid esters Me HOCH Me
SR1
/>
O'
C02R
R = Ester, R1 = Un (Substd.) alkyl, alkenyl, alkynyl, Cycloalkyl, Ph, pyridyl Cephalosporins •
Cephalosporin compounds:
cv
R1 CH2 CONH
y
r CH2 O2 CNH2 CO2R
Example compound: OMe
O-
CH2 CONH
•
r CH2 O2 CNH2 CO2H
297
CSI Applications
Cephalosporins RNH-
N
/
O'
^K Broad spectrum antibiotics
CO2R 3 Me
322
I; R = R' CO - N - CONH CH Ph CO
R 1 = Ph CH = CH, Ph, PhCH 2 CH 2 , Me CH = CMe. R 3 = Na, R 4 = CONH 2 •
Cephalosporin Ph
O
OMe
I
II
1
R NH - CH - C NH—,
S N
^
O
"i
CH2 OAc
CO2H
Antibiotic - active against Serratia lutea. 323
O R = [Ph CH = CH - C - N (Me) CO - ]
•
Cephalosporin Compounds
o-
OMe
R1
r
CH CONH-
^
Useful as bactericidal agents.
324
Useful as an antibiotic.
325
" CH2 O2 CNH2 COR1
•
3-Propyl derivative of cephalosporin PhOCH2-
0
OH
7 C02R
(R = alkyl)
CSI Applications
298 Example Compound:
o-
CH2 - CONH
J>
r CH = CH CH2 OH C02 CH Ph2
•
Cephalosporin derivatives Cephalosporin molecule
Antibacterial
326
Example compound: R 1 = H ; R 2 = Ph. •
Cephalosporins
Example compound: 7 p-[(z) -2 (2-tert. butoxy carbonylamino - Antibiotics 4- thiazolyl) -2- pentanoylamino] -3c a r b a m o y l o x y m e t h y l - 3 - c e p h e m -4carboxylic acid •
327
Cephalosporin derivatives
R1 C - CONHN
\ ,OR2
cT
S
O
CH2 O2 NH2 CO2R
Example compound:
Ph - C - CONHN
\
CH2 O2 NH2 OMe
CO2 CMe3
Antibiotics
328
CSI Applications •
299
Cyanoacetamidocephalosporanates NC CH2 CON
V
O
tf
^ - ^
N
Antibiotics
329
Bactericides
330
Useful as bactericides against staphylococcus aureas.
331
Active against penicillin G-Sensitive Staphlococcus aureus.
332
CH2 OAc
7- (or 6) - Substituted - 7 - (or 6) benzylideneamino cephalosporin (or penicillin) compounds R3 CH = N-
R1-
y
"CH2 R 4 CO2R 5
Example compound: R1 = N 0 2 , R 3 = Me; R 4 = OAc; R 5 = Ph 2 CH; R = R 2 = H •
3 -Vinylcephlosporin analogs R1 NH
>
o
CH = CH NR3 R4 C02R2
3 - Vinylcephalosporins On S„
RNH
//
CH = CH R2 CO2R 1 On
RNH-
S-»-
CH = CH R2
CO2R 1
Example compound: R = R1 = H; R 2 = NMe 2 ; (n = 1)
300
•
CSI Applications
Intermediate products for cephalosporin
s
r
N
N
CH2:
N N
O
C02Na
Antibiotics
Me
R = H0 2 CH (NH2) CH2 O2 CNH - ^ ^ ~ CH2 CO NH
•
Cephalosporin analogs Useful against staphylococcus aureas.
On
R1 NH
V
J~
•N.
O'
•
"
' CH CHO
Semi - synthetic Cephalosporins
cv
R CH2CONH-
Antibiotics
^~N
CH2R 1 CO2R 2
R = H, MeO; R 1 = OAc, Pyridino, 4- (amino carbonyl) Pyridino •
3-Substd. vinyl cephalosporin derivatives.
N—r- C ( : N R 1 ) C 0 N K
CH = CH R3 R2
Useful as antibacterial against staphlococcus aureas, Escherichia coli, Klebsiella Pneumoniae,
3
301
CSI Applications
Example compound:
"J IN
TV—
H2N-^
V
• CONH-, N
OCONH2
r
OH
Serratia morcescens and Morganella morgani).
336
C02Na
•
Cephalosporin
H2N-^ CCONH
II
o •=?—W
S (CH 2 ) n X
NOCH2 COOH
Oral antibacterial (Inhibits the growth of Escherichia coli. 337
CO2H
(n = 2 ; X = H 2 N C 0 2 ) N a Cephalosporins
Q-
CCONH11
O
NO Me
J
Antibiotics
338
Improved oral cephalosporin type antibiotics
339
CH2O2CNH2
CO2 CH Me OAc
•
(Cefuroxime axetil) Cephalosporin antibiotics
o
H
H
— C-CONH-
(T~
N
\
OMe
CH2 O2 CNH2 CO2 CH RO2 CCR1 R2 OR3
(I)
Example compound: (z) I (R = H; R1 - R 3 = Me)
CSI Applications
302
•
Cephalosporin antibiotics NHOH R1 NH CHROONH
J-y^
R2
CO2H
Antibiotics
340
Antibiotic activity
341
[R = (Un) substd. Ph, cyclohexenyl, CH3~ CH (OH), heterocyclyl etc., R1 = CONR 4 R 5 , etc.; R 4 = H, C,. 4 alkyl; R5 = R 4 , (Un) substd. heterocyclyl etc., R2 = CH 2 OCO Me, CH2~ OCONH 2 , CI, F, OMe etc. Cephems RNH—1
S
N
o^V^
CH2 0 2 CNH2
CO2R 1
Example compound:
H2Nxf
N CH2 O2 CNH2 CO2H
•
Cephem compounds:
R
VS N — ^ (C - C O N H - ^ N NOH
/ - N ^ - C H O
cocr
2
A
(In Vitro) Bactericidal action against Staphylococcus aureus. 342
303
CSI Applications Example compound: H2 N . , / 0 ^ C-CONH-]
f
NOH
>
coo
k^ NHCONH2
Cephem compounds: R5 N—»
R4
C CONH NV^J-CH2N N C02<3
R3
OR2
Example compound: R1 = R4 Protected amino group
Inhibitory action against Escherichia coli.
343
Useful as antibiotics
344
R5 R4 s
'
II N
^N
d'
%
_^LCH2N^
^
.©
CO2
CH3
OMe
•
(Pyrazoliomethyl) Cephemcarboxylates R6
Rl
t5ll S
NOMe
A>CH 2 O
@
N f^
|
N
R3
I
R4 n4
._
X In *
'
CSI Applications
304
Example compound:
N—>
n-r J— N^J^J-CHIVI
R5
C - CONH-,
s'
II
N OMe O
N
I COOH
R4
R1 = R 5 = Protected amino; R 4 = (Protected) hydroxyl (Lower) alkyl •
3 [(Carbamoyloxy) methyl]-7a-methoxy-7 (acylamino)-3- cephem-4-carboxylic acid OMe R2 CH2 CO CONH
(
J
r CH2 0R C02R1
Antibiotics
345
Example compound: Thienyl CH2 CO NH CH2 O CO NH2
o
CO2H
Cephem derivatives R1
X
N
^CONI-U
N—'J—C N
\
0 CH2A
O OR3
COi
Rl = (Un) protected amino; R3 = fluoroalkyl; A + = hetero-cyclyliumyl
Exhibits antibiotic action against Staphlococcus aureus. 346
CSI Applications
305
Beta Lactams OSi R2 R3 R 4
R1 OCH Me
1
\_ O
-NH
//
Antibiotics
347
Antibiotics
348
Inhibitory activity towards staphylococcus aureus.
349
Example compound: Me3 SiOCHMe
OSi Me3 -NH
// O •
N - l Substd. P-lactams RN
R1
\
,K
•R2
-NCONHSO2N
//
N.NHO
O
OH
Example compound: R = Q ; R 1 , R 2 , R 3 = H; A = 0 - CO C = NOC Me2 CO2 H Q=
Nys NH2
•
P-Lactam derivatives S (On) CH2 CH2 NHCR1 = NR2
V -N
//
O
Example compound: Et
#
O
^
, SCH2 CH2 NHCSCH : CH
CSI Applications
306
P-Lactam Compounds R2
I
OSi - R3
Useful as intermediates NH R4 jf in preparing O 1 2 3 4 R = trialkylsilyl; R , R , R , = Cj_ 4 alkyl, P-lactams. Ph, aralkyl MeCH (OR1)-
Penems •
Penem antibiotics (Preparation of intermediate - carbamoyloxy-acetic acid (or Antibiotics its esters) NH 2 - C 0 2 CH 2 COOH
•
1,1 -Disubstituted - pen-2-em-3-carboxylic acids R1
R2
Antibiotics C02H
Example compound:
N0-
•
2,
' COOH
6-Disubstituted Penem Compounds HOCH Me
\
-XR1
-N 'CO2H
Example compound: HOCH Me
V
oJ-
^
. CH2 OCH2 CH NH2
XOOH
Inhibitory action against Staphylococcus aureus.
3
307
CSI Applications •
Penem Compounds R 1
\
/)—N
r
. S . <*
CO2 R 2
cy
Example compound:
//
r
S^ /OH
N
\
x
C02H
(I)
/>-
r
-N —
O
II is claimed to have a minimum inhibitory cone, against staphylococcus aueus A 9573 of 354 lmg/mL.
• CH2 CH2 P (O) (OEt)2
>COOH
(H)
6-Alkyl -2- penems • CH3 O'/r
•
N
C0 2 H
Inhibitory action against Staphylococcus aureus.
355
6-Ethyl -2- penem derivatives Et
0
R /—N-
N
C0 2 H
R = Me, CH 2 OAc, CH 2 CH 2 OAc
Antibacterial activity against Gram-positive bacteria comparable to that of cefoxitin. 356
CSI Applications
308
•
Broad - spectrum Anti-Methicillin Resistant Staphylococcus aureus (MRSA) P-lactam antibiotics.
5, 6-Cis - Penems HCO Me,
%>
R1 N ^ C02Na
Also active against a wide variety of bacteria including P-lactamase producing microorganisms. 357
1
R = Ph.
Penicillins • N-Sulfamylampicillins R COHN SO2 NH HCPh OCHN
, Me >. Me
//
Antibiotics
358
Antibiotics
359
Useful as P-lactamase inhibitor.
360
>C02H
O
R = Alkyl, Aryl, Substd. amino,Nheterocyclic Penicillanic acid and cephalosporanic acid derivatives R NH CH Ph CONH^
^/v
//
, Me •• Me
' CO2 R1
O
Example compound:
R = Me; R1 = H •
2 P-Carbamoyloxy - methyl penicillanic acid sulfone derivatives 02
r
J—N-
O
O2 CNH2 •• Me
CO2H
309
CSI Applications Benzhydryl-3- (carbamoyloxy -methyl), (acylamino) -7- methoxy decephalosporanates and benzyl 6- methoxy -6- (phenyl acetamido) penicillates R1 Me
R CH2 ONH-
Me O
CO2 R2 CO2R 2
Antibiotics
361
Used in drugs.
362
Antibiotic
363
Example compound: OMe Me
Ph CH2 OC NK
i-^^MeF-^
Me
CO2H
CO2H
Thienamycins •
N-acyl derivatives of thienamycin HO CH Me
V /r o •
S CH2 CH2 NH - COEt
CO2H
N- and carboxyl derivatives of thienamycin HO CH Me
„m
S CH2 CH2 NH (Me) - COEt
CO2H
310 •
CSI Applications N-methylene derivative of thienamycin. H
/
HO CH Me
S CH2 CH2 N = C
\
\
NH2
Antibiotic
364
Antibiotic activity
365
Antibiotic activity
366
Antibiotics
367
/^-H O
COOH
o-Derivatives of Thienamycin Alkyl OC CH Me
\ >
•
S CH2 CH2 NH2
C02H
Thienamycin derivatives RO CH Me
S CH2 CH2 NH2
\
J> (R = alkyl.) •
Thienamycin derivatives R20 CH Me
V
J-
S CH2 CH2 NHR
-N CO2R 1
o
Example compound: MeO CH Me /
O
S CH2 CH2 NH Ac
-N C02Me
311
CSI Applications •
o-DerivativesofThienamycin RO CH Me
V #
S CH2 CH2 NH2
Antibiotics
368
COOH
o
R = alkyl, Acyl, Aralkyl, alkenyl, alkynyl Miscellaneous antibiotics •
Aminoacyl adenylate
R2 R1 N,
CONHSO2O—I
I
N=N
Useful as microbial and antiparasitic R3 agents such as I I HO OH multidrug resistant Streptococcus 369 R = amino, alkyl, aryl, cycloalkyl, alkoxy, pyogenes. aryloxy; 0
Mev
R 1 , R 2 = alkyl, aryl, carboalkyloxy, alkylthiocarbonyl, carboxamido, acyl; R 3 = Et,OMe,: n=l,2 •
(Aminoalkyl) - substituted benzoheterocyclic compounds
Antimycotic and antihypercholesteremic activities 370
CSI Applications
312
Dotted line = optional double bond; M = (Un) substd. Heterocyclic atom grouping; Q = (Un) Substd. Cycloalkyl, (Un) Substd. alkenyl, (Un) Substd. alkadienyl, (Un) Substd. H (aminoalkyl) phenyl etc., R = (Un) Substd. aminoalkyl T = H, alkyl, (Un) Substd. NH 2 , CONH 2 , N 0 2 , CF 3 , OH. Carbamoyloxy derivatives of Mutilin
Useful for the treatment of bacterial infections. Example compound: R1 = Et; Y= (Un) substd. Carbamyloxy •
Cyanoacetanilide derivatives HOCMe: C(CN) CONHR R = Substd. Phenyl
•
Analgesic and antiinflammatory 3
Cis - Substituted cyclopentylamine R1
R2
Associated with antimycotic activity. (Useful in the treatment of fungal R 1 , R 2 = H, halogen, Cycloalkyl, (Un) infections). 3 branched (Un) substd. Alkyl; R 3 , R4 = halogen, (Un) substd. alkyl or cycloalkyl;
CSI Applications
313
R5 = H, alkyl: R6 = H, alkyl, phenylalkyl; R7 = (Un) substd. phosphonate, (Un) substd. C02H •
Subtituted -N- (P-alkoxy ethyl) -N- (4phenoxy) dichloroacetamide R1
)^S\- o7 ^ ) -
CH
2 N - CH2 CH2OR CO CH Cl2
Inhibitory activity against Entamoeba histolytica.
374
Amoebicidal activity
375
Example compound: R1 = H 2 N ; R = CH 3 . • Substituted N- (P-alkoxy ethyl) -Nbenzyldichloroacetamides R1 Q - / ( j ) - CH2 N (CH2 CH2 OR2) COCH CI2
(Q= CO, CH 2 Or S). Example compound: R1 = N 0 2 ; R 2 = Et;Q = CO. •
1, 3-Dioxane and - dioxins
Useful as intermediates for the synthesis of carbapenem antibiotics. 376
Imidazo [5, 1-b] thiazole derivatives Intermediates for antibacterial cephems
R7_NH-n— s
N >O
<J
N C -COR6
I
Me
^ \ ^ CH2 R COR5
Inhibits the growth of staphylococcus aureus. 377
314
CSI Applications
Example compound:
®^N _ ^ >
Q=
~
^
R = Q; R5 = O; R6 = OH; R7 = H
•
Isothiazolyl p-lactam
r
R1 NH ^ O
R2
NCO N SO2 NR3 A.
Example compound:
N—r- C - CONHv H2N
A
s
'
H
NO Me
Antibacterial agent, in vitro (Escherichi coli).
378
Quinone antibiotic
379
Me
r
-NCONHS02NK
m
N,
Me
•
(±) Naphthyridinomycin - total synthesis Me
I
*8•
Phosphorathioates
R (R'O) P (R 2 ) SCH 2 C (NR 3 R 4 ) : NS0 2 . Acaricidal and NR5R6 insecticidal Example compound: MeO (MeO) P (O) SCH 2 C (NMe 2 ) : N S 0 2 . NMe 2
380
315
CSI Applications
Pyridone Carboxylate Containing P~ lactam. RHN ,1
M-C-NHSO2N
H
.A.
11
- / . ~ ^V" S - COOH N-NHCO-(v
v_y
M
o
o
As an antibacterial agent.
381
R = COOH derived acyl.
•
l-Aryl- 1, 2, 3- triazolo [4, 5e] pyrimidines Exhibits bactericidal activities against B. substilis and S. aureus. Analogs of Uridinediphosphate hexoses
382
O HN'
O
A
'N
o-
O - C - N H - S - 0 CH2
R10
R1Z
II
O
I -O. N R2Q
Protein glycosilation inhibitors Exhibit antiviral activity; particularly active against several eveloped viruses. 383
OR2
(R ! = PhCH 2 ; Bz; Ac; palmitoyl, R 2 2 = Me 2 C; Z = O; R1 = Ac, R 2 2 =Me 2 C; Z = NH) •
Carboxylsulfamide derivatives
Bacteriostatic activity evaluated
384
CSI Applications
316
5 1 - O- [Hexoyranosyloxy carbonyl) sulfamoyl]- Uridines
Useful as virucides.
R5O
R6
Example Compound:
R1, R2, R 3 = Ph CH 2 , R4 = OCH 2 Ph, OR 5 , R6 = iso-propylidene dioxy
385
317
CSI Applications
II-6
Miscellaneous Applications
General Name & Structure of Compound
Applications
Ref.
Used in neumatic or ferroelectric liquid crystals.
386
1
•
Trans - 2, 2 (1, 4- Cyclohexanedryl) bis (pyrimidine) derivatives /T N / — \ N—\ H17C80—(/ W )--(' V0C 8 H17
•
Oligothiophene - based liquid crystals.
Material useful for optical
Asym. Substd. oligothiophene, 2-cyano properties. -5- octyl quarter thiophene. •
387
Cyclohexyl dioxanes Liquid crystals dielecs. for use in electro-optical display devices. 388
«\K>« (R = Cj_J2 alkyl, alkoxy or alkoxyalkoxy; R1 = CN, F CI or Br) •
Disulfamate diureides RNHCONHCO(X)CONHCONHR
Demonstrated sustained release fertilizer activity. 389
• Merocyanine based spectral sensitising dye for photographic material (R3 CONH S 0 2 NH)n
7 l
Z
0
l
Dye for photographic material
390
CSI Applications
318
(NH SO2 NH COR3) n R2
R5 CONH S02 NH
R4
O
°
1 9
Z " = at group to form 5 or 6 membered N containing heterocycle; R1_6(substd) alkyl; L1"5 substd. C, 3 methine unit; m, n = o,l; m = n^o] Silver Halide recording material for generation of negative images with ultrahigh contrast. Booster (Contrast increasing compound) R1 R2 XSR; R1 R 2 NXSXIN R 3 R 4 and R1 R 2 NSX 2 SX1 NR 3 R4 (R!-4 = Cj_6 alkyl, benzyl, R ' - R 2 and/or R 3 - R 4 may form 5-12 membered ring; x, x 1 , x 2 = divalent connection group, R = alkyl, aralkyl, aryl, S = S 0 2 NR 5 CON R6; S 0 2 NR 7 COO, NR 8 S 0 2 N R 9 ; R5"9 = H, Cj. 6 alkyl, benzyl) Photographic photosensitive units containing azodye-forming compounds
T(ZN R4 ) n Z 1
HO—/ ^—.N = N - ^ X NHSO2 NR3 COZ2 R5
R6
For manufacturin black and white negative images with ultra high contrast.
319
CSI Applications
(Me CH)2 N SO2 HO-^ ^
•
^ - N = N - / ~ ^ - O C H 2 C H 2 0Me ^ ^ S 0 2 N H - / ~ V O C 1 6 H 3 3 -n NHSO2 NH C 0 2 Me \ = < c M e 3
/)-
Pyrrolo [ 1,2-a]-Pyrimidine compound R1
It
R2
N
Gives high quality magenta images with good access time.
392
Provides high density purple to cyan images with improved weatherability, storage, stability and fixability
NH
393
NH; CONHSO 2 NR 3 R 4
•
Radiation - sensitive compn. containing quinonediazide compound for resist Quinonediazosulfonate having substituentXR (X = NH S 0 2 , CONH S 0 2 , NH CONH S 0 2 , NH S 0 2 NH CO; R = alkyl, substd. alkyl, aryl, substd. aryl)
•
394
Cyanobenzoic acid esters R1
CN
"V—C r^
^ — CO2 R Me
Example compound:
(R = Me, R1 = CI, m = 4); (Yield: 80%)
Useful as isoindolinone pigment intermediate.
395
CSI Applications
320
Disperse triazole azodyes /
//
CN •N = N
CH2 I Ph
(C2 H4 OAc)2
NH CO CH2 CH3
Useful for dyeing hydrophobic, high molecular weight polyester fabrics in brilliant yellow shades with good fastness.
High molecular weight aliphatic sulfonamides of alkylene polyamides, and Component of polyalkylene polyamines ashless R CONH S 0 2 NH (CH 2 CH 2 NH) n H lubricating oil
396
397
R = polymeric residue, viz., polyisobutylene. CSI is reacted with a diamine (Dimethylamino propylamine), and Vistalon 4608 (EPDM rubber) •
•
Used as lubricating oil dispersant.
Sulfonic acid As heat sensitive emulsifier in textile finishing Rf (CH 2 ) n O (CH 2 CH 2 O) m CONH S 0 3 and (CH 2 CH 2 0) p H polymerization. Rf = C 6 H 10 perfluoroalkyl; n = 1 -2 m 0-4;p = 4-50
398
Fluorinated urethane N esters.
399
Chlorinated sulphur Compounds containing Intermediate in the nitrogen (like CSI) manufacture of textile assistants, pesticides and pharmaceutical agents. 400
321
CSI Applications Sulfonimines
Chlorosulfonyl deriv. as anaerobic accelerators. R1 R2 N S 0 2 NH CO A (A = OR 3 , OOR 3 , NR 1 R2; R1 = H, org. groups, R 2 R3 = org. groups)
As a bleach catalyst for detergent in clearing of fabric (soiled, for example, with tea stains) or hard surfaces. 401 As catalyst for the curing of anaerobic acrylic compositions. 402
Modified Isoprene and butadiene homo-and As polymers with copolymers better heat resistance and vulcanizates CH2-H2Cwith higher N ^ modulus and / \) lower breaking CI SO2 elongations. 403 R = Me for polyisoprene = H for polybutadiene. The films are endowed Hydrophilic Polyacetylene films with good electric conductivity and mechanical properties. 404 2,5- Dithienyl pyrrole monomers
Semi-conducting oligomers.
405
CSI Applications
322
X = CHO; 0 2 N . C H = CH; Me0 2 CCH = CH; Me0 2 SCH 2 CH(OH); H0 2 C (CH 2 ) 2 CO, Me0 2 C(CH 2 ) 2 CO. etc.) Stable dispersions of polymers in polyfunctional compounds having a plurality of active hydrogens P-Methoxy - acryloyloxyethyl (chlorosulfonyl) carbamate + styrene + (AIBN)
A ^ styrene copolymer
Useful in the manufacture of polyurethane foams.
406
Used as an intermediate for sweeteners.
407
dispersion P-Acyloxycrotonic sulfonahalides ^
acid
amide
N-
o
N - SO2 R
BzO-
Me
(R = C1,F) •
•
CSI modified polymer, based on styrene- Used as isoprene (film) desalination membrane.
408
Sizing of paper with mixtures of an anionic sizing agent and a cationic stabilizer. Octadecanol + Octadecylamine
CSI
Me (CH 2 ) ] 7 C0 2 NH S0 2 NH (CH 2 ) 1? Me (I) [(I) + polyethylenimine] = sizing agent & stabilizer
Used as a sizing agent for paper.
409
Author Index (Part I) Arabic numerals indicate reaction numbers.
Abe, N., 449
Archelas, A., 157
Abdaoui, M , 259, 264
Arnason, T., 517
Abramsk:, W., 299
Arnswald, M., 533, 534
Abt, C D . , 317, 326, 349
Arvanaghi, M., 279
Adams, S.P., 14
Ashe, B.M., 106, 107
Adam, W., 272
Askani, R., 159
Adiwidjaja, G.,313,314
Atkinson, J.G., 350, 435
Adolphi, H., 30
Aue, D.H.,35, 135, 136
Agoh, B., 261, 263, 266, 290 Aida, T., 170
Babad, E., 262
Alarcon, B., 277
Babin, N.A.,328
Albrecht, E., 464
Badawey, E-S. A.M., 465
Alender, J., 260
Bag, A.K., 318, 319, 341, 418, 481
Ali, F.E.,500
Baker, W.R., 352
Allen, (Jr.), G.R.,4, 89
Baldwin, J.E., 215, 216
Allan, R.D., 380
Ball,R.G.,24
Amato, J.S., 424, 425, 429, 431, 434
Balzarini, J., 309
Ammon, H.L., 181
Balzer, H., 148
Anderson, H.J., 440, 442
Barbachyn, M.R., 399
Andreson, M., 289
Barends, R.J.P., 165
Angelov, Kh., 194
Barker, P.L., 107
Anguiar, L., 278
Barnet, G.H., 440
Aouf, N., 254, 255, 257, 259
Barret, A.G.M., 38, 171, 288
Appel, R., 404, 412, 499, 500, 507, 518
Bartisch, H., 97
323
324
Author Index (Part I)
Barton, T.J., 29, 56, 69, 113, 134, 1 228,333,520,523
Borchardt, J.K., 202, 203, 207
Bateson, J.H., 105, 140
Boscacci, A.B., 22
Battistini, C , 271
Botteghi,C.,365,367
Batzer, H., 148
Bousley, R.F.,289
Baum, J., 512
Bovy, P.R., 14
Baxter, A.J.G., 139, 140, 168,400
Boyle, R.W., 441
Begley, M.J., 13
Brackeen, M.F.,438
Behrend, E., 405, 411
Brault, J.F., 292, 295
Bellver,C.,432
Braun, J., 512
Belsky, K.A., 262
Brause, K.A., 106
Belzecki,C.,299
Brems, P., 464
Bennett, G.B., 395 Berezina, V.F., 328
Broadhurst, M.J., 4, 48, 89, 187, 188,215, 217, 220, 222, 223, 229, 231, 232, 233,234
Bergan, T. 269
Brown, D.W., 440,494
Berge, J.M., 67, 156
Brown, F., 371
Berger, H.,408
Brownell, J.,530
Berges, II, D.A., 150
Brunn, E., 87
Bernardinelli, G., 286, 406, 409, 413
Brunsvold, W.R.,221
Bernath, G., 120
Bryan, D.B.,215, 216
Bernstein, P.R., 371
Bryuzgin, A.A., 280
Bentel,P.,30
Borror, A.L., 4, 444
Bertian, H., 31
Buckle, D.R., 300,495
Bestian, H., 53, 191
Bulbenitschek, P.,503
Betts, M.J., 38, 288
Burden, P.M.,380
Beutel, P.,365
Burgess, E.M., 252
Bhadbhade, M.M., 125, 166, 167
Buss, W., 519
Bhushan, V.,272
Butler, B., 24
Biener,H.,53, 175,296,489
Buynak, J.D., 196, 198, 199,200
Black, D.S.C., 22 Black, H.T., 317, 326, 349
Calas, R., 16
Blaschette, A., 503
Calligaris, M., 525
Boettcher, A., 460
Calvo-Flores, F.A.G., 437
Author Index (Part I) Camarasa, M.-J., 309
325
334,360,361,377
Camp, N.P., 177
Cohen, E., 422
Campbell, M.M., 397
Colvin, E.W.,15, 17,59,101, 197
Campion, J.G., 14
Conway, T.T., 46
Camus, P., 401
Cooper, R.D.G., 173
Capmau, M.L., 278
Cossio, F., 126, 193
Capraro, H.G., 385
Coustal, S., 51
Carey, F.A., 114
Coutinho, F.B.,68
Carlsen, P.,269
Crabbe, P., 145
Carrasco, L., 277
Crawford, W.C., 91, 123, 180, 183
Celamerck, G.m.b.H.,414
Criton, M., 256, 257
Chan, G.W., 150
Crombie, L., 10, 13
Chan, W.W.S., 24
Cronk, L.A.,371
Chandler, G.O., 106
Crowley, J., 121
Chandrasekaran, R.Y., 196, 200
Cutler, A., 70, 243
Chang, S.C., 354 Chelucci,G.,365,367
Dahlgren, M.E., 107
Chen, A.F-T., 32, 202, 208, 428
Davlluhn, J.,503
Cheng, K., 24
Damas, C.E., 151,376
Chernega,A.N.,482
Danesi, R., 270
Cherng,Y-J, 152
Daniel, J., 307, 320, 339, 452, 459, 472
Chichetkin, V.I., 328
Datmund, D., 424
Chinoporos, E., 4, 444
Datta, C.P., 490
Chmielewski, M., 19, 57, 84, 204, 299
Datta, S.K., 512
Christensen, B.G., 274
Deak, G., 396
Christl, M. 87
Debaerdemaeker, T., 460, 478
Chu, S.C., 196,200
DeClereq, E., 309
Ciganek, E.,49
De Las Heras, F.G., 277
Ciurdaru, G., 202, 208
Delaunay, B.,263,290
Clardy, J., 113,215,229
Deleris, G., 16,99
Clark, J.D., 352
Dellea,P.S.,106
Clauss, K., 23, 28, 53, 108, 135, 137, 146, 315, 322, 323, 327, 329, 331, 332,
DeMeester, P., 196,200 De Meijere, A., 132, 133
326
Author Index (Part I)
DeOliveira, P.A.M., 72
Dunogues, T., 16
Depres, J-P., 145
Durham, P.J., 273
De Sowsa Gomes, A., 71
Durkheimer, W., 436
Destexhe, R.,470, 497
Durst, T., 170
DeVilliers, O.G., 20, 81,308 Dewynter, G., 254, 255, 256, 257, 259, 263, 264, 266, 267, 290
Eates, G.W.,416
Dhar, D.N., 47, 76, 166, 167, 176, 318, 319, 320, 342, 343, 344, 450, 452, 458, 473, 474, 475, 496,498
Eguchi, S.,42, 44, 45,88, 116
119, 179, 335, 356, 459, 476,
122, 283, 339, 366, 463, 477,
124, 125, 305, 307, 340, 341, 418, 445, 471, 472, 481, 492,
Diaz, M.P., 432 Dickinson, K.H., 139, 168 Diehr, H.J., 142 Dietrich, A., 282 Dilda, P.,256 Diwan, P.V., 293
Effenberger,F., 9, 235,301 Ehntholt, D., 70, 243 Eisenhauer, G , 500 Ejmocki, Z., 420 Ellenberger, S.R.,21, 141 Elloumi,N.,278 Erden, I., 132, 133,221,227,306 Ertas, M., 379, 430 Esch, P.M., 521 Esipenko, A.A., 482 Espie, J.C., 25 Evanics. F., 120
Doherty, J.B., 106 Dolphin, D., 441 Dorn(Jr.), C.P., 106 Dortmund, D., 424, 425, 429, 431, 439 Dosset, D.L., 371 Doyle, T.W., 46 Drach, B.S.,328 Drew, M.G.B., 82 Drogovoz, G.K., 328 DuBois, G.E., 250 Duboudin, J.G., 253 Dugat, D., 170 Duncan, J.A., 251 Dunkelblum, E.,36, 71, 134
Fahey, J.L.,274 Fang, J.M., 152, 153 Fauble, H., 398 Favre, G., 259 Feigen, L.P., 14 Feldman, P.L.,438 Felix, A.S., 277 Felzenstein, A., 39 Fenwick, A., 38, 288 Ferber, P.H.,225,226 Fetyukhim, V.N.,482 Fiandor, J., 277 Figuiredo, A.M., 72
Author Index (Part I) Filosa, M.P.,4, 444
Garner, A. W., 260
Finke, P.E., 106
Gehanne, S., 1 8
Firestone, R.A., 107,274
George, C , 198
Fischer, M.H., 24
Gervasi, G., 270
Fischli, A.,357
Gerwalt, Z., 480
Fish, R.W.,70,243
Giammaruco, M., 18
Fitzpatrick, L.J., 265
Gibbard, A.C., 230
Fletcher, B.S., 106
Giering, W.P., 70, 243
Fliri, A., 77
Giger,R.,417
Floyd, A.J., 440, 494
Gimenez, M., 437
Foster, A., 440, 442
Ginsburg, D.,417
Foucoud, A., 393
Girard,Y.,350,435
Foyos, J., 229
Gleason, J.G., 500
Franceschi, G., 271
Gleiter, R.,9,301
Franck, R.W., 240
Glemser, D., 487
Frappier, F., 51
Goebel, P., 137, 146
Frelak, J., 204
Gomes, A.S., 68, 72
Friedrich, H.J., 52, 315, 322, 323, 327, 329,
Gompper, R., 201, 202, 205
331,332,334,360,361
327
Goodgame, D.M.L., 78
Friedrichsen, W., 460, 478
Gouriou, Y.,393
Fuchs, R., 272
Graboski, G.G., 170
Fukumoto, K., 60,61
Graf, R, 1,2, 23, 33, 72, 98, 126, 131, 248, 281, 284, 297, 298, 311, 315, 323, 363, 365, 391, 433, 435, 489, 493,531
Fulop, F., 117, 120 Furman, B., 19,57,84,204 Furst, G.T., 116
Grandberg, 1.1.,462 Galemmo (Jr,) R.A., 273 Ganschow, S., 310, 368, 374 Garcia, M.V., 484 Garcia - Lopez, M.T., 277 Garcia-Luna, A., 390, 479 Gareth, M., 104 Garland, R.B., 14 Gautun, H., 269
Grant, E., 250 Gream, G.E., 225, 226 Greene, A.E., 145 Grimm, D., 108,377 Groder, J., 299 Gronowitz, S., 515 Groutas, W.C., 258 Gunther, D.,6, 50, 73,391
328
Author Index (Part I) Hetenyi, A., 117
Haas, A., 405, 411
Heydt, A., 488
Hachiken, H., 455
Heyn, H., 53
Hagmann, W.K., 106
Hiemstra, H., 521
Hahn, H., 528
Hill,S.P.W.,78
Haigh, D., 10
Hirai,K.,62, 63,64, 246
Hajri, A.,256
Hirako,Y.,45
Halchak,T., 181
Hirama, M., 65
Hale, J.J., 106
Hodges, M.L., 260
Haley, E., 196, 198,200
Hoechst, A.-G., 330, 421
Hall, C.R., 526
Hofman, J., 110
Hall, R.H., 20, 81,308,358
Hoffmann, H., 142
Hammer, H., 447
Hoft, E.,310, 368, 374
Harcus, R.G., 397
Hogeveen, H., 41, 160
Hard, K.M., 106
Hohenlohe- Oehringen, K., 77
Harnden, M.R., 513
Holland, H.J., 82
Harrison, A.M., 93
Hollywood, F., 109
Harsen, J.F., 172
Holman, R., 289
Harvey, D.M., 177
Homelehle,K.L.,289
Hassner, A., 138, 143, 149, 195, 275, 285 324,325,327
Honda, T., 60, 61
Haug.T., 148
Houk, K, N., 221
Hauser, F.M.,21, 141, 155
Hsiao, C.N., 8
Hayakawa, K., 5,94, 184
Hu,Y.R.,525
Hayase, Y., 387,388, 389
Hugentobler, 362
Hebbel, K.C.,371
Hughton, E., 512
Hedayatullah, M , 287, 292, 295
Hugueny,J.C.,287
Heider, L.,301
Huisman, H.O., 165
Helga, R., 480
Hulen, C , 278
Hendricks, R.T., 251
Hull, R., 109,466,467,490
Hendrickson, J.B., 374
Hummel, C.F., 209, 210, 213, 214, 224
Herchen, S.R.,4,444
Hurst, D.T., 513
Houge-Frydrych, C.S.V., 300, 495
Herczeg, L.J., 262 Iberbia, P.A.,206
Author Index (Part I)
329
Iio, H., 85,302
Kaannich, H.J.,519
Ikeba, M , 455
Kakehi, A., 449
Imajo, S., 66
Kakihana,T., 172
Imanieh, H., 34, 104
Kalita,E.V.,328
Imanishi, T., 118
KaluzaZ., 19,57,84,204,299
Imbach, J.L., 261, 263, 266, 290 Imbert, J-P., 504
Kamal, A., 293, 318, 336, 337, 381, 382, 384,427,446,485
Isaacs, N.S., 31
Kametani, T., 60, 61
Ishiguro, ML, 66
Kampe, K.D., 238
Ito, S., 65
Kanda,Y.,96
Ito,Y.,85
Kaneko, T., 276
Iwahashi, H., 35, 135, 136
Kappe, T., 465
Iwahashi, M., 35
Karady, S., 424, 425, 429, 431, 434, 439
Iwakawa, T., 386, 387, 388, 389
Karnaratne, V.,441
Iwata, C , 118
Katz, T.J., 92
Iwata, H., 66
Kaufmann, D., 133,227
Jacobus, J.O., 260
Kelly,J.F.,3,26, 102, 128, 130, 190, 191, 210,240
Jaffe, I., 374 Jalandoni, C.C., 182 Jandralla, H., 79 Jannitti, N., 270 Jansing, J., 240 Janssen, E., 527 Jasat, A., 441 Jensen, H., 315, 322, 323, 327, 329, 331, 332,334,360,361,391 Jones, C.F., 13 Jones, R.C.F., 10 Jones, P.G., 503 Jordaan, A., 20, 80, 81, 308, 358 Joseph, S.P., 283, 335, 458, 473, 474 Jouany, M., 51 Julian, T.N.,289
Kemp, J.E.G., 66, 156 Keshava Murthy, K.S., 149, 305, 335, 366, 450,498 Kiehs, K., 30 Kim, K-H., 352 Kim, M-H., 453 King,L.W., 14 Kingsbury, W.D., 150 Kinsman, R.G., 440, 494 Kinzig, CM., 150 Kirchgaessner, U., 272 Kirkbride, P.K.,225,226 Kirschner, S.,219 Kishi, Y.,276 Kishida,Y.,62, 63,64, 246 Kissinger, A.L., 106
Author Index (Part I)
330 Kitazume, T., 321
Lachheim, S.,408
Kiuchi, K., 96
Langbeheim, M., 39, 40
Klarberg, B., 422
Lanzendorfer, F., 87
Klein, C.L., 249
Lattrell, R., 86, 291, 403, 415
Klenk, H.,235
Latscha, P.,338
Klot, I.M., 294, 378
Lau, C.J.,4
Knight, W.B., 106
Laumen, K., 79
Ko, T-Y., 152
Lanzendorfer, F., 87
Kobayashi, T., 321
Laziri, N., 278
Kobayashi.Y., 85
Lecea, B, 126, 193
Kobelt, D., 238
Lee, C , 215
Kobrich, G., 245
Lee, C.H., 215, 364,419
Kohenlohe-oehringen, K., 76
Legault, R., 170
Kohn, H.,364, 419
Leitch, L.C.,517
Konkel, M.J., 161
Levkovskaya, G.G., 280
Kousch, E., 504
Levy, S.V., 229
Kraemer, A.D., 351
Lewis, T., 82
Kramarenko, F.G.,482
Leydet, A., 261, 266
Krause, B.R.,289
Lhomme, J., 401
Krebs, B., 486
Lhomme, M.F., 401
Krell, R.D.,500
Lilyefors, S., 515
Krolikiewicz, K., 13, 37, 75, 365, 369,443,
Lincoln, R., 78
510,516
Lindmark, R.J., 14
Krow, G.R., 228
Loader, C.E., 440, 442
Kuang, R.,258
Loewe, W., 353, 355
Kuehlein. K.,316 Kumadaki, S., 96
Lohaus, G., 268, 285, 287, 291, 365, 370, 403,407,415
Kumar, P.R., 158,348
Lohse, F., 148
Kwok, K.L., 262
Lorincz, T., 306
Kwong, K.S.,251
Lourens, G.J., 20, 80, 81, 358 Lysket, R., 204
L'Abbe., G., 464, 470, 491, 497 Lach, D., 201, 202, 205
Macchia, M., 270
Author Index (Part I) MacEachern, A., 517
Merkel, D., 245
Maciejewicz, N.S., 274
Metzanke, N., 353, 355
MacLeod, D., 34, 104
Metzger, K., 148
Maduskuie, (Jr.). J.P.,371
Mews, R., 486, 487, 502, 506, 508
Mahkham, M., 505
Meyers, A.I., 127
Maiti, S.N., 461
Meyer, W.C., 139, 144
Malpass, J.R., 42, 43, 115, 116, 162, 163,
Mickel, S.J., 8
164,211,219
331
Micotich, R.G., 461
Manabe, T., 5, 94, 184
Midenberger, H., 407
Mann, J., 82, 83
Milanese, A., 448
Mansukhani, R., 395
Miller, M.J., 8
Mar, K.E.,441
Minh, D.T., 253
Marchetti, M., 365, 367
Mirskova, A.N., 280
Marquet, A., 51
Miyandera, T., 242
Martin, P., 385
Miyano, M., 14
Martinek, T., 117
Miyano, T., 242
Maruthamuthu, P., 531
Mochizuki, T., 60
Mason, R.B., 395
Moeckel, G., 478
Mathe, S., 373
Moller, M., 313
Mathew, J., 198
Mondeshka, D., 194
Matsuda, H., 62, 63, 64, 246, 449
Monteith, M., 15, 58, 101, 198
Matterstock, K., 98, 391, 531
Montenash, M., 404, 412, 501, 507, 518
Matzanke, N., 353 Matzin, Ab R., 10
Montero, J.L., 254, 255, 256, 257, 258, 259, 261, 263, 264, 266, 267, 290
Maycock, A.L., 106
Moody, C.J., 230, 236, 303, 454
Mayer, H., 357
Morand, P., 517
Mazzocchi, P.H., 74, 90, 93, 181
Moreau, B., 278
McCague, R., 236
Morere, A., 259
McMackins, D.E., 14
Moriconi, E.J.,3,26, 74, 90, 91, 102, 116, 123, 128, 130, 139, 144, 180, 182, 183, 190, 191, 192, 209, 210, 213, 214, 224, 237, 239, 240, 241, 247, 347,365
Mehta, G., 47, 119, 122, 124, 125, 166, 167, 176, 179,340,445 Menendez-Castrillon, P.P., 277 Menendez, J.C., 432, 457, 484 Mengel, R.,410
Morin, C , 157
332
Autho Index (Part I)
Mosebach, R., 528
Oberhaensli,W.,357
Mosher, N.W.,416
Ochal, Z., 420
Mostowicz, D., 299
Ohra, T., 118
Muller,G.W.,250
Olah, G.A.,279,390, 479
Mumford, R.A., 106
Olson, J.T., 317, 326, 349
Mundloss, E., 311
Onan, K.D., 4, 444
Murabayashi, A., 386, 387, 389
Osborne, S., 13
Muschweek, R., 436
Otto, E., 436
Muthu, S., 532
Overton, H, J., 83 Ozmeral, C , 260
Nageswar,Y.V.D.,394 Nagurnaya, N, A., 328
Paddon-Row, M.L.,221
Nakagawa, S., 242
Page, P.C.B.,55, 103,244
Nakata, T., 276
Pajouhesh, H., 505
Nakatsuka, T., 66
Panzerknodle, S.G., 14
Nakayama, A., 60, 61
Paquette, L.A.,4,48,69, 89,95, 172, 185, 186, 187, 188, 202, 208, 215, 217, 218, 219, 220, 222, 223, 228, 229, 231,232,233,234
Nam, N.L.,462 Narasimhan, K., 158 Nardin, G., 525 Narender, A.V., 446 Naser-ud-din, 469 Nativi, C , 54, 57, 100, 178 Natsumi, M., 96 Neergaard, J.R., 114 Neidlein, R.,351,528 Nelson, K.H, 397 Nethercleft, M., 513 Neumann, W.P.,533, 534 Nicholson, N.S., 14 Nicolaou, K.C.,92 Niess, R.,301 Nishida, S.,5,94, 184 Nagurnaya, N.A., 329
Parameswarn, K.N., 294, 378, 383 Parashikov, V., 194 Parson, P.J., 177 Pasto, D.J., 32, 154, 202, 203, 207, 208, 428 Patchatt, A.A., 424, 425, 429, 431, 439 Patel, G.S., 274 Paulus, E.F.,238 Peng, Z., 524 Penton, (Jr.) H.R., 252 Perez-Perez, M.-J., 309 Perrone, E., 271 Perrotta, E., 54, 58, 100, 178 Peter, D., 104 Petersen, C.P., 4, 444
Author Index (Part I) Peterson, E.M., 530
333
Rao, M.N, 196, 198, 199,200
Pfaendler, H.R., 7, 11, 169
Rao, M.V, 293
Philips, J.C., 172
Rashid-baigi,Z.A,289
Picard, J.A.,289
Rasmussen, J.K, 275, 285, 324, 325, 327
Pieron, J., 116
Rassat, A , 25, 373
Pilidis, G.,212
Ray (Jr.), W.J, 249
Pillot, J.P.,99
Rayez, J.C, 99
Pindur, U., 453
Raymond, D.H, 13
Pinto, I.L., 300,495
Reamer, R.A, 424, 425, 429, 431, 434, 439
Pirenhenkov, V.V., 482
Reddy, A.V.N, 461, 485
Pisano, J.M., 107
Rees,C.W,230,236
Pissono, J.M., 24
Regainia, Z , 255,267
Ponsford, P.J.,400
Regitz, M , 402, 488
Potts, K.T., 512
Reich, K , 511
Poutsma, M.L., 206
Reynolds, G.A, 354
Pramod Kumar, 345
Rhee,R.P, 141, 155
Prendergast, K., 24
Ricci, A , 54, 58, 100, 178
Priputina, L.S.,328
Rico, J.G, 14
Proehl, H.H., 503
Rida, S.M, 465
Prossel, G., 108,377
Riddell, F.G, 120 Riegl, 1,469
Quayle, P., 34, 104
Riemenschneider, W , 6
Quinn, A.M., 105
Rihs, G.,385
Quiros, M., 78
Rittersbacher, H , 499 Rivero, R.A, 265
Raduechel, B, 189
Roa, G , 126, 193
Raghu, S., 70,243
Roberson, C , 174, 522
Raghunathan, R., 463, 471, 475, 476,
Roberts, P.M., 140, 168
Rahim, A., 513
Roberts, S.M, 67, 156
Rainer, R., 426
Robles - Diaz, R , 437
Ramasseul, R., 25
Rodakowski, K , 420
Rao, A.B.,288,293
Roehr, A , 314
Rao, K.R., 336, 337, 346, 394, 456, 483
Roesky, H.W, 392,404, 527
334
Author Index (Part I)
Rogers, R.D., 4
Schretzman, L., 14
Rogido, R.J., 29, 56, 69, 113, 134, 135, 333,520,523
Schultz, T.H.,221
Rokach, J.,350, 435
Scott, L.T., 221
Romming, C , 312
Selvi,T.K.,348
Rosenblum, M., 70, 243
Sergeev, S.A., 328
Rosenthal, S., 55, 103,244
Shah, S.K., 106
Roshan, A.Y.,440,494
Shapiro, H.S., 371
Rubenstein, R.,417
Shaviv, A., 71
Rudolf, S., 7
Sheers, E.H., 284
Ruetjes, T., 353, 355
Shellhamer, D.F.,35, 135, 136
Ruppert, I., 507
Shi, G.Y., 294, 378,383
Schwarz, O., 97
Shigemoto, T., 65 Sabat, M., 171
Shimakawa, Y., 237, 240, 241, 247
Salomone, R.A., 3, 26, 102, 130, 240
Shukla, D., 307
Salyers, A.K., 14
Siegfried, B., 362
Samarai, L.I., 482
Simpson, W.R.J.,395
Sampath Kumar, E., 343, 344, 492
Singh, LP., 461
Sano, H.,359
Singh, R., 173
Santoyo, G.F., 437
Siriwardene, U., 198
Sarel, S.,39,40
Skatteboel, L.,312,469
Sasakai,Y.,60
Skuballa,W., 189
Sasaki, T., 5, 42, 44, 45,88,94, 116, 184
Sliskovic, D.R.,289
Sato, T., 386
Smale, T.C., 105, 140, 168,400
Sattur, R.B., 293, 318, 336, 337, 346, 381, 382,394
Smets, G.,491
Sauvage, M., 278 Scarafile, C.,271 Schaumann, E., 313, 314, 504 Schlegel, G., 408 Schmidt, E., 316 Schoen, W.R., 24 Schossler, W., 402
Smith, D.G., 300, 495 Smith, D.J.H., 526 Smith, R.G., 24 Smolders, C.A., 111, 112 Smorada.R.L., 154 Snader, K.M., 500 Snarl, S.,39,40 Snipes, E.R., 150
Author Index (Part I) Soldan, F.,6,50, 73
Taddei,M., 18,54,58, 100, 178
Soliman, F.S.,G.,465
Taite, B.B., 14
Sollhuber, M.M., 432, 457, 484
Takemoto.Y., 118
Soucy-Breau, C , 517
Tamura, H., 387, 388,389
Southgate, P.M., 400
Tanaka, R., 66
Southgate, R., 105, 140, 168
Tanaka, T., 12
Speckamp, W.C.,521
Tanino, H., 276
Speckamp, W.N., 165
Tann, C.H., 262
Sridhara,N.S.,338
Taylor, E.A., 252
Srinivasan, T.N., 346, 394, 456, 483
Taylor, S.J., 171
Sroka,P.,372
Terashima, S., 85
Stacey, A.D., 513
Tesky, F.M., 486, 502, 506, 508
Stanfield, R.L., 289
Thiem, K.W., 245
Steinbeisser, H., 487
Thyagarajan, G., 381
Stephens, R.L., 352
Tiekmk, E.R.T.,226
Stern, C.A., 4,444
Timberlake, J.W., 249, 260, 423
Stevens, E.D., 249
Tjoeng, F.S., 14
Strasser, R., 11, 169
Tokoroyama, T., 302
Strochschein, R.J.,395
Toth, M.V., 14
Sugai, S.,359
Toupet, L., 264
Sugihara, Y., 449
Tripathi, M., 356, 477
Sundermeyer, W., 519
Truestdell, D., 229
Suri, S.C., 47, 119, 122, 124, 125, 166,
Tsai, D.J..S.,262
167, 176, 179,340,342 Suschitzky, H., 66, 109, 156, 466, 467, 468,490 Suwinska, K., 204 Suzuki, K., 242 Swann,E.,303,454 SzaKonyi, Z., 117, 120 Szilagyi, S., 260
Tull, R.J., 424, 425, 429, 431, 439 Tuominen, T.C.,399 Turini, B.L., 154 Tutkunkardes, S.,404 Tweedle,N.J.,42,43, 147, 162, 163, 164 Udupa, M.R., 486 Ueda, Y., 151,376 Ugalde, J.M., 126, 193 Ulivi, P., 18
Tabak, D.,71
335
Ulmschneider, D., 6
336
Author Index (Part I)
Ulrich, H.,31
Wamhoff, H., 379, 430
Underwood, D.J., 106
Wampfler, D.J., 154
Underwood, J.M., 177
Wang, M.H., 152
Urbanczyk-Lipkow ska, Z., 204
Wang,Y.K., 152
Urbanski, R., 299
Wang, Y.W, 152,153
Ushijima, R.,242
Warm, A., 286, 406, 409, 413 Waschman, M.A., 116, 121
Vacek, E.P.,371
Weber, B., 488
Vachta, J.,362
Weber, W., 132,133
Valter, K.,362
Webester, R.A.B., 13
Van Allan, J.A., 354
Wegener, P., 6
Van der Does, L., 110
Weinstock, L.M., 425, 426, 429, 431, 434,
VanderSarel, J.M.,491
439
Van der Velden, P.M., I l l , 112
Weng, W.D., 152
Vankar, Y.D., 279, 366, 390, 479, 498
Weston, H., 106
VanVtteren, T.E.C., 110
Wheeler, C , 180, 183
Vargas Bereguel, A., 437
White, J.G., 116, 121,240
Venkataraman, R., 258
Wiegard.N., 138, 143, 195
Venkataraman, S., 304
Willims, D.J.,78
Venkatesan, K., 125, 166, 167
Williams, K, 14
Vhlenhaut, H.,518
Williams, R.V., 55, 103,244
Villacampa, M., 457, 484
William, W.M., 252
Vince, R., 161,530
Winterfeldt, E., 447
Vinet, V., 151,376
Wipf, P., 304
Vioglio,S.,271
Wittmann, H., 365, 372, 375
Volz, W.E.,69,95, 185, 186,218
Woerpel,K., 174,522,524
Vorbruggen, H., 13, 27, 37, 75, 189, 365, 369,443,510,516
Wojcicki, A., 129,243,525 Wrobel, J., 282 Wyvratt (Jr.), M.J., 24
Walker, D., 262 Walrond, E.R., 466, 467, 468, 490
Xiao, Z., 423
Yagi, S.,455 Yamada, H.,42,44, 88, 116 Yamamoto, T., 321 Yamamoto,Y., 129,243 Yamazaki, T., 321 Yamazaki, Y., 65 Yang,C-C, 153 Yarmenko, V.V., 328 Yasuyoshi, M., 455 Yee,Y.K.,371 Yonetoku,Y., 118 Yovell, J., 39
Zablocki, J.A., 14 Zakonyi, Z., 120 Zamankhan, H., 392 Zara-Kaczian, E., 396 Zenfuku, K., 302 Ziegler, E.,365,372, 375 Zupec, M.E., 14 Zwart, L., 41, 160
This page is intentionally left blank
Author Index (Part II) Arabic numerals indicate reference numbers.
Abdaoui, M., 118
Aouf, N., 118
Abe, T., 38
Arabori, H., 17,29
Acbi, J.,218
Arahira, M., 17, 29
Acker, R.D., 26
Arai, T., 261
Adams C D . , 224
Araki, K., 16
Adams (Jr.), J.B., 47
Arneklev, D.R., 81
Adams, S.P., 144
Asaad, F.M., 98
Addor, R.W.,97
Asari, T., 176
Adolphi, H., 380
Ashe, B.M., 255
Aebi, J.,218, 370
Ashwood, M.S., 137
Aguiar, L., 256
Atsumi, K.,310, 377
Aihara, K.,310, 377
Audiav, F., 232
Ajioka, H., 209
Auel.T., 91
Akiyama, S., 3, 15,20,37,77 Alarcon, B., 108, 114, 222, 223, 383
Bacque, E., 249
Albarella, J.P., 405
Bailey, D.M., 115
Albrecht, H.A., 267, 378
Bailey, E.J., 221
Alessi, T.R., 192
Baker, C , 387
AH, F.E., 148, 149, 151
Baldacci, M., 153
Amano, K., 377
(Baldischa Anilin & Soda) Fabrik A-G., 87
Amedeo, F., 349
Ball, R.G., 230
Anderson, D.J., 397
Balsamo, A., 153
Anderson, M.K., 216, 252
Balzarini, J., 123
Anderson, P.S., 257
Bantjes, A, 171, 175
Andersson, B.R., 203
Bar-Illan, A., 198
Aoki, M., 213
Barash, L., 362
339
340
Author Index (PART II)
Barbachyn, M.R., 348
Bovy, P.R., 189
Barnes, K.D., 96, 102
Brackeen, M.F., 129
Bashiardes, G., 249
Bradshaw, J., 328
Bauer, K., 5, 52, 53, 54, 55, 57, 58, 82
Brady, T.E., 78
Baxter, A.J.G., 247
Braeunlich, G., 143, 146
Beautement, K., 8, 9
Brause, K.A., 255
Bedeschi, A., 356
Brauynes, C.A., 359
Beeby,P.T.,325
Brecht, H., 399
Beecham group Ltd., 290
Breuer, H., 270, 271, 274, 278
Behrend, B., 88
Briggs, B., 143
Bell, R., 221
Bristol-Meyers Co., 354
Bellon, S.,244
Brown, D.G., 97
Bellver, C , 162
Brown, F.J., 239
Bemis, G., 244
Brown, M.F., 136
Berger, H., 6
Brownell, J., 122
Berger, J.,236
Budzinski, J.C., 28, 65
Bernstein, P.R., 239
Buerstell, H.,52, 55, 57, 58, 82
Berredjem, M. 384
Burkholder, T.P.,233
Berthold, R., 207, 208
Buitler, B.,230
Beugeling, T., 171
Buynak, J.D., 281
Beutel, P.,380 Bianchi, A.,219
Cain, P.A.,92
Bickel, H.,358
Cama, L.D., 302, 306, 307, 345, 361
Bieringer, H., 5, 52, 53, 54, 55, 57, 58,
Camaggi, G., 106
Biller, S.A.,379
Camarasa, M.J., 108, 109, 123, 223, 383
Bishop, B.C., 137
Camarasa, Rius, M.J., 385
Bochis, R.J., 225, 227
Campbell, H.F., 238
Boehner, B., 39, 41,43
Capmau, M.L., 256
Bollinger, J.M., 398
Cardozo, M.G., 124
Borrod, G., 27
Carlsson, P.A.E., 203
Boufford, F.A.,306
Carrasco, L., 114,222,223
Bouhaddioui,N„ 211,212
Carter, D.A., 112
Bousley,R.F.,216,252
Carter, D.S., 236
Author Index (Part II) Cartwright, D., 45,46
341
Condon, M.E.,1, 2,78
Caster, K.C., 198
Connor, D.T., 140
Castro, A.C., 144
Conroy.C.W., 198
Cecchi, R.,315
Consonni, P., 298, 309, 315
Chan, W-S., 230
Cook, M.C., 328
Chandler, G.O., 255
Cooper, K., 126,251
Chandrasekaran, R.Y., 281
Cooper, R.D.G., 289
Chandy, T., 172, 181 Chang, M.H., 360
Council of Scientific & Industrial Research, 131
Chavemac, G.,234
Court, J.J., 166, 168
Chen, M-Q., 382
Cozzi, P., 219, 374,375
Chene, A., 27
Crassous, G., 173, 177, 179, 180
Cheng, K., 230
Crawford, T.C., 126, 132
Chin, K., 145
Crespy, S., 211,212
Chiyomaru, I. 104
Crip, H.A., 210, 338
Cho, K., 145
Criton, M., 110
Cho,Y.S.,360
Crowley, P.J., 101, 107
Choi, K.I.,360
Cuervo, J-H., 144
Christensen, B.G., 286, 287, 288, 295, 296, 297, 299, 301, 302, 307, 308, 314, 316 317, 318, 320, 321, 324, 330, 345, 352, 362,363,364,365 Chrystal, E.J.T., 8, 9 Chu, L., 226 Chu, S.C.,281 Chung, B.Y., 360 Ciba- Geigy, A- G., 329, 409 Clark, R., 261 Clauss, K., 407 Clayton, J.C., 210 Cochran, J., 244 Collonges, F.,234 Conception, A., 143
292, 306, 319, 361,
Cullison, D.A., 155 Danesi, R., 153, 154 Darke, P.L., 257 D. Clercq, E., 123 DeCarneri,I.,219, 374, 375 De Crescenzo, G.A., 248 Deguchi,T., 100 Dehmlow, H.,218,370 De Las Heras, F.G., 108, 109, 113, 114, 222,223,383 Delorme, D., 138 Del Tacca, M., 153 De Meester, P., 281 Denzel, T.,278
Author Index (PART II)
342
Depaoli, A., 309, 315
Elebring, S-T., 203
Dereu, N., 249
El-Harfi, A.,211,212
Desai, R.C., 166, 168, 169
Ellingboe, J.W., 192
Devies, P., 117
Elliot, L.G., 210
Devita, R.J., 62, 225, 227
Elloumi,N.,256
Dewynter, G., 118
Emini, E.A., 257
Dhiraj,L.,401
Ennis, M.D., 203
Diaz, M.P., 162
Erdelen, C , 89
Diehl, R.E.,96,97, 102
Ermann, P.H., 274
Dikinson, K.H., 247
Ertel, H., 372
Dilda,P., 110
Es - Sayed, M., 143, 146
Diwan,P.V., 135,190
Eue, L.,85
Djahoudi, A.,384
Eussen, J.H.H., 68
Dodgson, S.P., 165
Euverman, B.J., 175
Dodson, S.A.,238
Evans, D.A., 379
Doherty, J.B., 117, 167
Eyvratt, M.J., 201
DoUinger, M., 14, 19, 33, 34, 67, 75 Dolphin, B., 260
Faarup, P., 214
Dorn(Jr.)CP., 167,255
Fancher, L.E., 95
Doscher, M.E., 90
Fancher, L.W.,44
Drabb(Jr.),T.W.,50, 76
Farge, D., 331, 332, 334
Drewes, M-W., 19,33,34
Favara, D., 298, 309, 315
Driedger, P.E., 121
Favre, G., 118
Drossard, J.M., 274
Fechtig, B., 333, 358
Duccio, C , 349
Feldman.P.L., 129
Duerckheimer, W., 240
Felix, A.S., 114
Duerr, D., 56, 64 Duewel, D., 220
Fernandez- Resa, P., 108, 109, 1 11, 222, 223,383,385
Durham, P.J.,238
Fiandor, J., 113, 114
Dyke, H.J., 264
Filippin, L.A., 236 Filippini, L., 106
Eidenschink, R., 388
Findiensen, K., 14, 19,21
Ejmocki, Z., 93
Finke.P.E., 117, 167,255
Author Index (Part II) Finn, K., 281
Gass, K., 39
Firestone, R.A., 378, 330
Gebelein, C - G . , 183, 185
Fischer. M.H., 62, 226, 227, 229, 230
Georgiev, V.S., 163
Fischer, R., 143, 146
Gerard, M.P.,221
Fisk, T.E.,406
Gervasi, G., 154
Fitzgerald, M., 143
Gesing, E., 12,89
Fkushima, H., 337
Gesing, E.R.F., 14, 19,33,34
Flynn, D.L., 140
Getman, D.P., 248
Foery, W., 39
Ghatlia, N.,401
Franceschi G., 356
Gil - Fernandez, C , 113
Frey, M , 53
Girard, Y., 138
Froyd, J.M., 99
Glaser, D.M., 402
Fugmann, B., 143, 146
Gleason, J.G., 150, 152
Fujita, S., 392
Go, A., 16
Fujiwara, K., 209
Go, E., 145
Fukami, T., 263
Godfrey (Jr.) J.D., 273
Fukuroda, N., 196,263
Goi, M., 127, 128,337
343
Funaki, T., 120
Gomez De Las, H.F., 111,385
Furlenmeier, A., 277
Gough, S.T.D.,27
Furumine, M., 16
Granina, T.E., 59
Fusar, D., 219
Greengrass, C.W., 340
Gabrielsen, B., 112
Groutas, W.C., 147,253
Galemmo (Jr.), R.A., 238
Guare, J.P.,257
Galullo,V.,244
Guerrier, D., 234
Gancedo, A.G., 113
Gusmeroli, M., 106
Gandolfi, C , 356
Guthikonda, R.K., 265, 286, 287, 295, 302
Gregory, G.I., 328
Garavaglia, C., 106 Garcia, L., 385
Ha, Y-J., 360
Garcia - Lopez, M.T., 108, 109, 111, 113
Haadsma, S.R.,203
114,222,223,383
Haas, A., 88
Gardocki, J.F., 165
Hachisu, M., 199
Garland, R.B., 189
Haeflinger, W., 157, 160
344
Author Index (PART II)
Haenssler, G., 85
Heaney, S.P., 101, 107
Hagen, H.,79
Heiba, E.A.,27
Hagiwara, D., 231
Hemelehle, K.L.,216, 252
Hagmann, W.K., 167, 255, 265
Hemmerling, W., 386
Hajri, A., 110
Henmi, K., 188
Hale, J.J., 255
Henning, R., 143, 146
Hall, L.S.,92
Hermann, R.A., 97
Hamada, T., 10, 11, 13,31,32,66,
Hermann, R., 373
Haman, R., 252
Heubach, G., 372
Hamelehle, K.L.,216
Hideaki, N., 74
Hammond, C.E., 144
Hikido, M., 16
Hamprecht, G., 26
Hill, D.T., 152
Hanai, R., 30
Hill, J.M., 369
Haneishi, T., 170
Himber, J.,218,370
Hanessian, S., 83, 105
Hmks, J.D., 371
Hanna, J., 362, 363
Hirai, H., 125
Harada, N., 202
Hishamichi, H., 213
Harada,T., 176,392
Hittich, R., 388
Haramura, M., 170
Hlasta, D.J., 166
Hargrave, K., 124
Hockley, M.H., 262
Harjanto, F., 179, 180, 186
Hoffman, D., 399
Harrington, P.M., 1, 2
Hofheinz, W., 277, 279, 280
Harris, A.E., 201
Hoople, D.W.T.,340
Harutoshi,Y., 24
Hori, T., 120
Hasegawa, M., 127, 128
Hosni, H., 98
Hashiguchi, S.,282
Houghton, P.G., 137
Hattori, K., 300
Howarth, T.T., 340
Hayama, T., 200
Hubschwerlen, C.N., 277, 279, 280
Hayashi. F., 145
Huggins,J.W., 112
Hayashi, K., 235
Hulen, C.,256
Hayashi, S., 100
Humes, J.L., 117
Hayashi, Y., 176
Humphrey, G.R., 137
Hayashibara, T., 351
Hungerbuhler, E., 303
345
Author Index (Part II) Hunt, E., 323, 371
Jensen, H., 407
Hutchinson, A.J., 194
Ji, Y-H.,218,370
Hutchinson. J.H., 138
Jimonet, P., 232
Huth, A., 156, 158, 159
Jinbo.Y., 393 Johannes, K, 359 292, 296, 306,
Iguchi.Y., 174
Johnston, D.B.R., 2 319,330
Illian, G.,386
Jonsen, JR., 19
Imanishi, Y., 174
Joseph, G., 184
Inaba,T., 139,250
Jozefowicz, M., 173, 177, 179
Inamoto, Y.,344
Julian, T.N.,252
Ichinose, I., 29
Inoue, S., 199 Inove, H.,357
Kadin, S.B., 130, 133, 142
Irie, T.,311
Kajitani, M., 209
Isennng, H.P.,277, 279, 280
Kamal, A., 135
Ishida, Y.,35
Kamatu, Y., 336
Ishiguro, M., 357
Kamei, K., 196
Ishihara, E., 104
Kamhi, V.M., 96, 103
Ishii, M., 310
Kamiyama, N., 275, 285
Ishikawa, K., 3, 15, 20, 77, 200
Kampe, K.D., 372
Iso, Y., 311
Kan, K.,276, 285, 304, 350
Ito,Y., 10, 11, 13,32,66,74,76, 174,312, 376
Kanano, K., 199
Itoh, S., 35
Kanda,Y., 17,29,235
Iwaki, T.,311
Kandou, Y., 35
Iwamatsu, K., 310, 326, 379
Kaneko, T., 261
Iwata, M., 213
Kano, J., 377
Iwazawa, Z., 263
Kano, Y., 310
Kanase, K., 94
Kanstrup, A., 214 Jacobine, A.F.,402
Kapadia, S.R., 124
Jakobsen, P.,214
Kariya, A., 94
Jannitti, N., 154
Kashima, S., 199
Jansen, J.R., 12,33, 34, 89
Katada, J., 176
Jaziri, N., 256
Author Index (PART II)
346 Katano, K., 326
Kochler, G.,404
Katano, T., 326
Kocsis, K., 333, 358
Kato, H., 16
Koenig, K., 14, 19,21
Katritzky, A.R., 198
Koga, M., 390
Katsu, K., 336
Koh.H.Y.,360
Kawabata, K., 343, 344
Kondo, M., 282
Kawahara, T., 261
Konig, K., 12
Kayakiri, H., 237
Kondo, S., 326
Kazunari, O., 24
Konzelman, F.M., 267, 378
Kefauver, D.F., 112
Kostlan, C.R., 140
Kehne, H.,4, 5, 54, 55,57, 58
Krause, B.R., 216,252
Kehr,W., 156
Krause, J., 388
Keith, D.D., 267, 378
Krauth, C.A., 112
Kelly, T.A., 124
Krell.R.D., 148
Kempen, H.J.M., 175
Kuang, R.,253
Kern, J.A., 345
Kubota, H., 213
Khare, R., 86
Kudlacz, E.M., 233
Kiehs, K., 380
Kudo, T., 379
Kii, M., 311
Kuhla, D.E.,238
Kim, K.S., 266, 272, 381
Kukel,C.F.,97
Kinoshita, K., 269
Kuroda, A., 237
Kirk, B.E., 221
Kuroda, N.,38
Kirsch, R., 220
Kurumaru, K., 170
Kirsi, J.J., 112
Kusuoka, Y., 10, 11, 13,31,32,66,74
Kirsten, R., 19,89
Kuznetsova, G.V., 18,59
Kishida,Y., 125
Kwiatkowski, P.L., 92
Kishimoto, S., 282
Kwong, CD., 112
Kissinger, A.L., 255 Kityama, I., 120
Lachhein, S., 4, 6
Klotz, M., 187
Landes, A., 79
Kluft, C , 175
Lardy, C , 234
Kluth, J, 14, 19,21
Latha, A., 172, 181
Kobayashi,Y.,312,376
Latif, N., 98
Author Index (Part II)
347
Lawson, K.R., 107
Maerki,H-P.,218, 370
Leanza, W.J., 314, 362, 363, 364, 365
Magerlein, B., 266
Lee, G.H.,27
Maggiori, S., 375
Lee, W-C, 144 Lengsfeld, H.,218, 370
Makino, K., 3. 10, 11, 13, 15,29,32,37, 66,74,77
LeRoy, P.,331,332, 334
Makino, S., 139
Lester, M.G., 221
Manath,T.P, 112
Leudke,E.S., 117
Marc, P.A., 78
Levitt, G., 25,28, 65, 70, 71
Maren, T.H., 198
Liao, Y-S., 144
Marfat, A., 134, 136
Lin,C.H.,200
Maria, T., 223, 385
Lin, K.C., 144
Marteau, J., 403
Lin, N.H.,405
Martel, A., 284, 353
Linker, K-H., 14,21
Maryanoff, B.E., 165
Litieu-Binh, 233
Matassa, V.G., 239
Liftman, B.H., 126, 251
Matsuda, H., 125
Liu, Y., 382
Matsuda, K., 327
Lo,Y.S., 164, 197
Matsumoto, S., 269, 275, 285
Loeher, H.J., 53
Matsuo, M., 231, 282
Loewe, H., 220
Matsushita, T., 393
Loi,N.P.,59
Matzinger, P., 396
Lombardi, P., 355, 356
Maynard, G.D., 233
Lombardo, L.J., 141
Mcdonald, I.,245
Longo, A., 356
McNeil, D.W., 124
Lopes, A., 92
Melikhova, I.N., 59
Lotz, T.J., 395
Menard M., 284, 353
Lowen, G.T., 97
Menchetti,P.,219, 374
Luerssen, K., 7
Mendez, C., 385
Lyle, T.A.,257
Mendez, J.C., 162
Maccha, B., 153 Macchia, M., 153, 154 Maccoss, M., 117, 167
Mendez- Castrillon, P.P., 108, 109, 113, 114,223,383 Mendjel, H., 178, 179, 180, 182, 186, 211,212 Merck and Co, Inc., 293, 294, 366, 367,
Author Index (PART II)
348 368
Mueller, K-H., 14, 19,21,89
Metysova, J., 161
Mueller, R.A., 248, 273
Meyer, F., 186
Muller, K-H., 12,33
Meyer, G., 179, 180
Mullican, M.D., 140
Meyer, W., 39
Mumford, R.A., 117
Mignani, S., 232
Muramoto, K., 261
Mikolajczyk, J., 335
Murata, M., 300, 337
Mildenberger, H., 82
Murphy, D., 183, 185
Mitsui Toatsu Chemicals Inc. 42
Muschaweck, R., 240
Miwa, A., 195
Myake, A., 342, 346, 347
Miyahara, M., 120
Myama, A., 347
Miyai, K., 343, 344 Miyake, N., 231
Naarmann, H., 404
Miyama, A., 268, 269, 275, 285, 304,
Nagai.T., 120
Miyano, M., 189
Nagaki,H., 139
Miyano, T., 202, 205, 206
Nagase, H., 393
Miyazaki, H., 176 Miyazaki, M., 30
Nagaoka, T., 3, 10, 11, 13, 15, 20, 32, 66,77
Miyokan, I., 120
Nagashima, N., 269
Mizukoshi, T., 31
Nageswar,Y.V.D., 190
Moerker, T., 258, 259
Nagura,J., 196,263
Montana, J., 264
Nakabayashi, A., 326
Montero, J.L., 110, 118,384
Nakagawa, S., 205
Moody, C.J., 254
Nakahira, K.,32
Morand, 0 . , 2 1 8 , 370
Nakajimi,T.,300
Moreau, B., 256
Nakamura, A., 351
Moren-Lech, I., 335
Nakamura, T., 336
Morere, A, 118
Nakao, M., 342, 346
Morimoto, K., 37
Nakao,T.,195
Mormile, S., 106
Nakatsuka, T., 357
Motokawa, K., 311
Nami, K.K., 357
Moutonnier, C , 331, 332, 334
Nanjo, K., 94
Mrozik, H., 226, 229
Narukawa, Y., 313
Author Index (Part II) Nasu, T.,357
Olesen, H.P.,214
Nawamaki, T., 3, 10, 11, 13, 15, 20, 32,
Omodei-Sale, A., 298, 309, 315, 349
37,666,74,77
Onodera, A., 337
Negi, S.,336
Onodira, N., 94
Nemecek, C.,249
Onoue, H., 305, 313
Neumann, P., 157, 160
Oohashi, T.,347
Newton, T.W., 22, 36
Oosowa, T., 195
Nielsch, U., 146
Ootsu, S., 30
Nigorikawa, K., 393
Orsetti, A., 211, 212
Niki,T.,3, 10, 11, 13, 15,20,31,32, 66, 74,77
Oszczapowicz, I., 335
Nilz, G., 79
Otto, F., 240
Nishikibe, M., 196,200
Oughton, J.F.,338
Nishimura, T., 341
Outcalt, R.J., 92
Nishitani, Y.,311
Oyama, Y.I.S.,357
Nolan, J.C, 197
Ott, H., 207, 208
Ozaki,F.,261
Nomura, K., 393 Nortey, S.O., 165
Pae, A.N.,360 Paleirac, G., 178, 182,211,212
O' Brien, P.M., 216 Ochal, Z., 93 Ochi,S., 199 Ochiai, M., 282 Ogino, H.,326 Ogiwara, S., 351 Ohashi, T., 268, 269, 275, 276, 285, 304, 350 Ohi, N.,261 Ohkuro, M., 261 Ohno, T., 209 Ohta, K., 35 Ohtani, M., 127, 128 Okazaki, T., 176 Oku, T., 237
Palenschat, D., 156 Paloma, P.,385 Parameswaran, K.N. 187 Paschelke, G., 156 Patchet, A.A., 201 Patel, U.R., 124 Pautrat, R., 403 Pazoles, C.J., 126,251 Perez, C , 113 Perez-Perez, M.J. 123 Perez, S., 113 Peter, H., 258, 259 Petersen, W.C., 63 Peterson, E.M., 122
349
Author Index (PART II)
350 Peyronel, J.F., 331, 332,334
Rodakowski, K., 93
Pham,PT., 116
Roemer, M., 388
Phillipp, V., 89
Roesner, M., 220
Picard, J.A., 216, 217, 241, 242, 243, 2
Rogers, N.H., 322, 323
252
Romero, A-G., 203
Pietro, C.R., 349
Rorer, M.P., 60
Pietsch, H., 407
Rraf, R., 400
Pisano, J.M., 228, 230
Rueger,R.,391
Pobert, P.M., 247
Ruggeri, S.G., 126
Pojouhesh, H.,281
Rusakova, N.I., 59
Prendergast, K., 230
Rye, M., 145
Procopiou, PA., 221 Protiva, M., 161
Sada, I., 268, 276, 304, 347, 350
Proudfoot, J.R., 124
Sadohara, H., 30
Prozd, V.N., 59
Saito, S., 127, 128 Saitoh, Y., 237
Quick, J., 121
Sakaguchi, S., 394 Sakai,J., 100
Rao, A.B., 135, 190
Sakane, K., 343, 344
Rao,K.R., 190
Salituro, F.,244
Rao, M.N.,281
San, F.G.A., 111
Rao, M.V., 135
Sanceau, J-Y., 83, 105
Rashidbaigi, Z.A., 252
San Felix Garcia, A., 385
Ratcliffe, R.W., 286, 287, 295, 314
San Felix, A., 222
Reap, J.J., 23
Santel, H-J., 7, 14, 21, 33, 34, 67, 75, 85
Rebek (Jr.), J , 369
Sarges,R., 191,192
Regainia,Z.,384
Sasaki, T., 310
Rempfler, H.,51,56, 61,64
Sasho, M., 336
Ren, T., 72
Sato, K., 394
Rico, J.G., 189
Sato, T., 17,29,37
Riebel, H-J., 7, 14, 19,21,33,34,67,
Satoh, S.,237
Robert, R., 85
Satoh,Y., 176
Robinson, R.P., 134
Satsudo, K., 300
Author Index (Part II)
351
Sattur, P.B., 135, 190
Shapovalov, A.A., 59
Sauer, G., 158, 159
Sharma, C.P., 172, 181, 184
Sauers, R.F.,47 Sauvage, M., 256
Shell Internationale Research Maatschappij, B.V., 103
Sawada, A., 188
Shi.G.Y., 187
Scartazzini, R., 333
Shih, D.H., 297, 299, 301, 308, 314, 316, 317,318,320,352
Schallner, O., 19 Scher, H.B.,44, 95 Schering, A-G.,215 Schlegel, G., 4, 6 Schlief.W.A., 257 Schmid, G., 218, 283, 370 Schmidt, E., 407 Schmidt, R.R., 7, 21 Schmiechen, R., 156 Schmitt, S.M., 288, 292, 296, 319 Schneider, H.H., 158, 159 Schneider, P.,333 Schneider, S., 143
Shih, D.H-M., 362, 36 Shih, T.L., 229 Shimazaki,N., 188 Shimazaki, Y., 127, 128 Shimizu, S., 29 Shimotori, T., 139 Shimoyama.Y., 199 Shimiziu, S., 29, 204 Shiokawa, S.,310 Shiraishi, H., 38 Shirakawa, K., 394 Shrum, G.P., 140 Shue,Y-K.,369
Schoen, W.R., 62, 225, 226, 227, 228, 229, Sidebottom, P.J.,221 230
Schretzman, L., 189 Schue, F., 178, 179, 180, 182, 186 211, 212,404
Signorini, E., 106 Sikora, A., 335 Singh, J., 144
Sederel, L.C., 171, 175
Singh, H., 86
Sendai, M., 282
Singh, R., 289
Sendo,Y.,311
Sinodis,D.N.,92
Setoi, H., 237
Sinohara, A., 199
Setsu,F.,310
Siokawa, M., 377
Sevensson, K.A.I., 203
Sledz, J., 173, 177, 178, 179, 180, 182, 186,211,212
Shah, S.K., 117, 167,255 Shamblee, D.A., 197 Shank, R.P., 165
Sliskovic, D.R., 216, 241, 242, 243, 246, 252
Author Index (PART II)
352
Smale,T.C.,291
Tachiki, A., 176
Smith, C , 221
Takano, S., 139
Smith, D.B., 99
Takaya, T., 343
Smith, R.G., 230
Takayama, K., 213
Snader, K.M., 148
Takehi,T.,30
Sollhuber, M.M., 162
Takenaka, 0.,261
Sonoda, J., 261
Takeno, R., 139
Sorokin.V.I., 18,59
Takita, K., 104
Sota, K.,337
Takizawa, H., 377
Southgate, R.,247
Takle, A.K.,371
Sperzel, M., 143, 146
Talley, J.J. 248
Sraub, H.,274
Tamaru, M., 30
Srivastava, M., 86
Tamura, A., 310
Stamm, E., 51
Tanaka, H.,237
Stanfield, R.L.,216,252
Tanaka, K., 139
Stenzel, K., 89
Tanaka, L., 390
Stetter, J.S., 85
Tanaka, M., 327
Stevenson, R., 322
Tanaka, R., 357
Stjernlof,N.P.,203
Tanaka, T., 250
Stork, B., 68
Tang, H., 260
Stuborn, G., 146
Taniguchi,Y., 199
Studt, W.L.,238
Tatsuo, N., 24
Sturton, G., 143
Terajima, A., 312, 376
Sudo, K.,32, 66, 77
Tetsunori, K., 393
Suga, K.,268,269,275,347
Theophilou, N., 404
Sugiyama, I., 336
Therien, M., 138
Sun,E.T.,248
Thompson, W.J., 257
Suzuki, H., 3, 10, 11, 13, 15, 20, 31, 32, 66,77
Thummel, R.C.,51,56
Suzuki, K., 3, 15, 20, 37, 202, 205, 206
Thyagrajan, G., 190
Suzuki, M , 127, 128
Timmons, P.R., 92
Swann, E.,254
Timmons, S.F., 387
Thus, J.L.G. 68
Titman, R.B., 262 Tabiie, N., 120
Tjoeng,F.S., 189
Author Index (Part II) Tomimoto, M., 282
Vogt.B.R., 155
353
Tozer, M., 245
Vors,J.P.A. 92
Toyooka, Y.,310
Wachtel, H., 156, 158, 159
Trane, F.,219, 374, 375
Wafilm,B.V.,408
Treuner, U.D., 271, 274, 278
Walsch,D,A.,164
Tristram, E.W., 201
Welter, H., 79
Trueb, W.,40
Watanabe, K., 268, 276, 304, 347, 350
Tsuroka, T., 199,326 Tsushima, M., 377
Watanabe, S.,3, 10,11, 13, 15,20,37,66, 77, 188
Tsushima, S., 341
Watanabe, Y., 337
Tsutsumi, H., 300
Watson, N.S., 221
Tsutsumi, K., 250
Weber. G., 388
Tsybalova, L.A., 59
Weingarten, G.G.,339
Turnbull,J.P.,338
Weinhardt, K.K., 236 Wellinga, K.,68
Ubukawa, Y., 305
Wierenga, W.,217
Ueyama, N., 276, 304
Wijesekera, T., 260
Umemura, E.,. 377
Wikstrom, H.V.,203
Unangst, P.C., 140
Wildfeuer, M.E., 119
Unbametz, J., 220
Wildonger, K.J.,364
Urushibata, I., 100
William, K., 189,265
Ushijima, R.,205
Willms, L., 4, 5, 52, 53, 54, 55, 57, 58, 80, 82
Uwaydah, I.M., 164
Willner,K.D., 126,251 Valenta,V., 161
Wilson, E.M., 210
VanDer,D.,359
Wilson, M.W., 140
Van Der Does, L., 171, 175
Winger, R., 386
VanDuijl, J.F., 171
Wiscount, CM., 257
Van Gemert, B., 48, 49, 69, 73
Woo, E-R., 360
Vazquez, ML., 248
Wright (Jr.), D.P.,97
Venkataraman, R., 253
Wright, M., 338
Vilas, P., 113
Wuerzer, B., 26
Vince.R., 116,122
Wyvratt (Jr.), M.J., 62, 225, 227, 228, 229,230
354
Author Index (PART II) Xie, L.,260 Yamada, S., 209 Yamaji,Y.,30 Yamamori, T., 235 Yamanaka, M., 336 Yamauchi, H., 336 Yammato,N.,209 Yang, R-Y., 83, 105 Yang, S-Y., 382 Yano, M., 200 Yano, S., 209 Yasuo, I., 24 Yokoo,C.,337 Yonekura,N., 100 Yoshida,C, 139 Yoshida, S., 199 Yoshikawa, H.,35, 128 Yoshikawa, K., 127 Yoshimura, T., 100 Youle, D., 101, 107 Yu,G.,369 Yu,K.K.,239
Zablocki, J.A., 189 Zahler, R., 273 Zhang, Z-Y., 382 Ziegler, R., 157, 160 Zimmerman, C.N., 144 Zimmerman, D.F., 65, 84 Zugay, J.A., 257 Zukowski, E., 335 Zupee, M.E., 189 Zydowsky, T.M., 369
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Numerous articles have been published on cholorosulfonyl isocyanate (CSI), but no book compiling research on this versatile reagent has been available up to now. This book fills that gap. It provides an overview of the research on CSI, including information about commercially exploitable patented products involving the use of CSI.
THE CHEMISTRY OF
CHLOROSULFONYL ISOCYANATE The book is divided into two parts. The first part outlines the reactions of CSI with a wide variety of substrates. The second part outlines the applications of CSI in the preparation of useful products. These applications are classified as: herbicides, pesticides, and insecticides; antiviral and anticancer compounds; biologically active compounds; antibiotics; and miscellaneous compounds. The Chemistry of Chlorosulfonyl Isocyanate is an important book that should serve as a one-stop ready reference for researchers interested in the study of CSI.
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