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A Specialist Periodical Report

Organic Compounds of Sulphur,
Selenium, and Tellurium
Volume 4
A Review of the Literature Published between
April 1974 and March 1976

Senior Reporter
D. R. Hogg, Deparfmenf of Chemistry, University of Aberdeen
Reporters

G. C. Barrett, Oxford Polytechnic
R. J. S. Beer, Universify of Liverpool
E. Block, University of Missouri, U.S.A.
D. C. Dittmer, Syracuse University, New York, U.S.A.
G. L. Dunn, Smith Kline and French Laboratories, Pennsylvania, U.S.A.
T. Durst, Universify of Ottawa, Ontario, Canada
U. Eisner, Trent Polytechnic, Nottingham
J. G. Gleason, Smith Kline and French Laboratories, Pennsylvania, U.S.A.
S. Gronowitz, University of Lund, Sweden
M. Haake, lnstifut fur Pharmazeutische Chemie, Marburg, West Germany
B. Iddon, University of Salford
F. Kurzer, Royal Free Hospitai School of Medicine, London
P. A. Lowe, University of Salford

P. Metzner, Universith de Caen, France
G. Prota, Universifa di Napoli, Italy
J. Voss, Universifaf Hamburg, Wesf Germany
W. Walter, Universitat Hamburg, West Germany

I

The Chemical Society
Burlington House, London, W I V OBN


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ISBN :0 85186 289 6

ISSN : 0305-9812

Library of Congress Catalog Card No. 77-23818

Copyright @ 1977
The Chemical Society
All Rights Reserved
No part of this book may be reproduced or transmitted
in any form or by any means -graphic, electronic,
including photocopying, recording, taping or
information storage and retrieval systems - without
written permission from The Chemical Society

Organic formulae composed by Wright's Symbolset method


Printed in Great Britain by John Wright and Sons Ltd. at The Stonebridge Press, Bristol BS4 SNU


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Preface

The general aims of this fourth Volume of ‘Organic Compounds of Sulphur,
Selenium, and Tellurium’ remain those set out in the Preface to Volume 1.
Change of personnel has led to the division of the wide-ranging chapters on
thiocarbonyl compounds and on ylides into more manageable parts. In keeping
with more recent work, the short sections on sulphines and sulphenes have been
confined to the chapter on thiocarbonyl compounds. To avoid possible
inconsistencies, the chemistry of sulphonyl, sulphinyl, and sulphenyl carbanions
has been largely included in the chapter on ylides. The order of the chapters has
been revised so that the chemistry of acyclic sulphur compounds and sulphurcontaining functional groups is covered before cyclic systems.
In general, these Reports cover the period from April 1974 to March 1976
unless otherwise stated. Due to necessary limitations of space, the topics have,
in parts, been treated more summarily than in previous Reports. A review of the
chemistry of thiepins and dithiins, omitted from Volume 3, has been included in
this volume, but accounts of the chemistry of thiazepines and of heterocyclic
compounds of quadricovalent sulphur have been held over to Volume 5 .
As was stated in earlier volumes, constructive criticism, comments, and advice
will be welcomed, particularly if they enable subsequent Reports to be orientated
more exactly with the requirements of research workers.
D. R.H.


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Contents

Chapter 1 Aliphatic Organo-sulphur Compounds, Compounds with
Exocyclic Sulphur Functional Groups, and their Selenium
1
and Tellurium Analogues
By G,C. Barrett
1 Textbooks and Reviews

1

2 Spectroscopic and Other Physical Properties
General Conforinational Studies and Molecular Orbital
Calculations
Ultraviolet Spectra
Infrared, Raman, and Microwave Spectra
Nuclear Magnetic Resonance Spectra
Mass Spectra
Photoelectron Spectra
Electron Diffraction
Dipole-moment and Kerr-effect Studies
Optical Rotatory Dispersion and Circular Dichroism Spectra
Other Physical Properties

2

3 Thiols

Preparation
Heterocyclic ThioIs
Thiols as Nucleophiles
Addition Reactions of Thiols
Further Reactions of Thiols
Protection of Thiols in Synthesis
Generation of Thiyl Radicals and Thiolate-stabilized
Radicals
Thiols in Biochemistry
Thiol-acids and Thiol-esters

4 Sulphides
Preparation
Properties and Reactions of Saturated Sulphides
Preparation of Vinyl Sulphides
Properties of Vinyl and Ally1 Sulphides
Acetylenic Sulphides
Cleavage of Unsaturated Sulphides by Carbenes and
Nitrenes ; Photolysis

2
3
3
4
5
6
6
6
7
7


7
7

9
10
11

12
13
13
13
14

16
16
18
19
21
22
23


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Contents

vi
Rearrangements of Unsaturated Sulphides
Naturally Occurring Sulphides, and Sulphides Related
to Natural Products

Thiocyclopropenium Salts
Heteroaryl Sulphides
Sulphides in Synthesis
Sulphonium Salts
Sulphuranes

23
24
25

25
26
28

30

5 Thioacetals and Related Compounds
Preparation
Reactions

30
30
32

6 Sulphoxides

33
33
35
39

39
40
43

Preparation
Properties and Reactions of Sulphoxides
a-Functional Sulphoxides
IS-Keto-sulphoxides and Related Compounds
Unsaturated Sulphoxides
Elimination Reactions of Aliphatic Sulphoxides
Applications of Dimethyl Sulphoxide and Dimethyl
Selenoxide as Reagents

45

7 Sulphones
Preparation of Sulphones
a-Functional Sulphones
Properties of Sulphones
Uses of Sulphones in Synthesis
Unsaturated Sulphones

46
46

8 Sulphimides and Sulphoximides

50
50


Sulphirnides
Sulphoximides
9 Sulphenic Acids
Preparation
Reactions of Sulphenic Acids
Sulphenates
Sulphenyl Halides
Sulphenamides and Related Compounds

10 Thiocyanates and Isothiocyanates
Preparation of Thiocyanates
Reactions of Thiocyanates
Preparation of Isothiocyanates
Reactions of Isothiocyanates

47

49
49
49

52

53
53
54

54
54
57

58

58
59
59
60


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11 Sulphinic Acids
Preparation
Properties and Reactions of Sulphinic Acids
Sulphinyl Halides
Sulphinate Esters
Sulphinamides and Related Compounds

vii
60
60
61
61
62
63

12 Sulphonic Acids
Preparation
Properties of Sulphonic Acids
Sulphonic Anhydrides
Sulphonyl Peroxides

Sulphonyl Halides
Sulphona tes
Sulphonamides
Sulphonyl Azides

64
64
66
67
67
67
68
69
71

13 Disulphides and Related Compounds

72
72
73

Contents

Preparation of Disulphides and Polysulphides
Properties of Disulphides and Polysulphides
Thiolsulphinates
Thiolsulphonates
a-Disulphones

75


76
76

Chapter 2 Ylides of Sulphur, Selenium, and Tellurium, and Related
Str uctu res

78

I: Ylides and Carbanionic Compounds of Sulphur, Selenium,
and Tellurium

78

By E. Block
1 Introduction

78

2 Sulphonium Ylides

81
81
82

Synthesis and Properties
Reactions
3 Oxosulphonium Ylides
Synthesis and Properties
Reactions


85

4 Alkoxy- and &a-sulphonium and Related Ylides
Alkoxysulphonium Ylides
Aryloxysulphonium Ylides
Azasulphonium Ylides

87
87
88
88

5 Thiocarbonyl Ylides

89

85
86


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viii

Contents

6 Sulphenyl Carbanions
Synthesis and Properties
Reactions
1,3-Dithianyl Anions

Thioallyl and Kelated Anions
Acyclic a-Thiocar bani ons, Thioacet a1 A niotis, and
Trithioformate Anions

90
90
91
91
92

7 Sulphinyl Carbanions
Synthesis and Properties
Reactions

96
96
97

8 Sulphonyl Carbanions
Synthesis and Properties
Reactions

99
99
99

9 Organoselenium and Organotellurium Carbanions and Y l i h

11: Compounds with
By M. Haake


S=N Functional Groups

94

102

105

1 Di-co-ordinate Sulphur
Sulphinylamines and Sulphinylamides
Sulphurdi-imides
Thione-S-imides

105
105
107
109

2 Tri-co-ordinate Sulphur
Sulphonylamines and Sulphurtri-imides
SS-Diorgano-sulphimides and Azasulphonium Salts

110
110
110

3 Tetra-co-ordinate Sulphur
SS-Diorgano-sulphoximides


118
118
121

SS-Diorgano-sulphodi-imides
4 Selenium Analogues

Chapter 3 Thiocarbonyl and Selenocarbonyl Compounds
I: Thioaldehydes, Thioketones, Thioketens, and their
2j++lenium Analogues
By P. Metzner

123

124

124

1 Introduction
Reviews

124
124

2 Thioaldehydes
Synthesis
Reactions

124
124

125


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ix

Contents
3 Thioketones and Selenoketones
Synthesis of Thioketones
Synthesis of Selenoketones
Transient Species
Metal Complexes
Reactions

125
125
129
129
130
131

4 Thioketens and Selenoketens
Synthesis
Reactions

i35
135
136

11: Sulphines and Sulphenes

By D. R. Hogg

136

1 Sulphines

136

2 Sulphenes

139

Ill: Thioureas, Thiosemicarbazides, Thioamides, Thiono- and
Dithio-carboxylic Acids, their Derivatives, and their
Selenium Analogues
141
By W . Walter and J. Voss
1 Reviews

141

2 Thioureas and Selenoureas
Synthesis
Physical Properties
Analytical Properties and Applications
Chemical Reactions
Alkylation
Addition to Multiple Bonds
Oxidation
Hydrolysis and Related Reactions

Cyclization

142
142
145
146
147
147
148
149
149
150

3 Thiosemicarbazides and Selenosemicarbazides
Synthesis
Physical Properties
Reactions

153
153
155
157

4 Thioamides and Selenoamides
Synthesis
Physical Properties
Reactions

159
159

167
171


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X

5 Thiono- and Dithio-carboxylic Acids, their Derivatives, and

their Selenium Analogues
Synthesis of Dithiocarboxylic Acids
Synthesis of Thioacyl Halides
Synthesis of Thiono- and Dithio-esters
Alkylation of Thio- and Dithio-carboxylates
Thiolysis and Thionation of Carboxylic Acid Derivatives
Thioacylation of Alcohols and Thiols
Miscellaneous
Physical Properties
Reactions

Chapter 4 Small Ring Compounds of Sulphur and Selenium
By D. C. Dittmer
1 Thiirans (Episulphides)

Physical Properties and Theoretical Treatments
Formation
Intermediates in Reactions
Reactions


176
176
177
177
177
178
179
180
181
182

186
186
186
187
188
190

2 Thiiranium Ions and Radicals
Theoretical
Formation and Properties
Intermediates in Reactions

192
192
192
193

3 Thiiran 1-Oxides (Episulphoxides)


194

4 Thiiran 1,l-Dioxides (Episulphones)

195

5 Thiiren Derivatives

196

6 Three-membered Rings containing Sulphur and One or Two
0ther Heteroatoms

198

7 Thietans
Physical Properties
Formation
Chemical Properties
8 Thietan 1-Oxides
9 Thietan 1,l-Dioxides

Physical Properties
Formation
Reactions

10 Thiet Derivatives

200

200
201
203

204

204
204
205
205

207


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xi

Contents
11 Four-membered Rings containing One Sulphur Atom and One
or More Heteroatoms
Thiazetidines and Thiazetes
Sultines, Sultones, and Cyclic Sulphates (1,2-0xathietan
2-Oxides, 1,2-Oxathietan 2,2-Dioxides, and 1,3,2-Dioxathietan 2,2-Dioxides)
Silicon

209
209
21 1
212


12 1,3-Dithietans

212

13 1,2-Dithiets

214

14 Selenium Derivatives

215

Chapter 5 Saturated Cyclic Compounds of S u l p h u r and Selenium 217
By T. Durst
1 General Comments

217

2 Thiolans, Thians, Thiepans, Thiocans, and their Oxides and
Dioxides
Synthesis
Properties and Reactions

217
217
223

3 Compounds with Two Sulphur Atoms in the Ring, and their
Oxy-sulphur Analogues
Cycl ic Dis u 1ph ides

1,3-Dithiolans and 1,3-Dithians

230
230
23 1

4 Compounds containing Three or More Sulphur Atoms

236

1,2,3- and 1,2,4-Trithiolans, 1,2,3- and 1,3,5-Trithians,
1,2,4,5Tetrathian, and Larger Rings containing Three
or More Sulphur Atoms
Sulphur-containing Macrocyclic Rings
5 Compounds containing Sulphur and Oxygen
Sultines, Sultones, and Related Systems
1,3-Oxathiolans, 1,3-0xathians, 1,4Oxathians, and Related
Compounds
Cyclic Sulphites and Related Compounds

236
238
239
239
24 1
243

Chapter 6 Thiophets and their Selenium and Tellurium Analogues 244

By S. Gronowitz

1 General

244

2 Monocyclic Thiophens
Synthesis of Thiophens by Ring-closure
Reactions

244

244


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xii

Contents
Syntheses of Thiophens from other Ring Systems
Ultraviolet and Infrared Spectra
Dipole Moments and Conformational Analyses
N.M.R. Spectra
Various Physical Properties
Electrophilic Substitution
Electrophilic Ring-closure Reactions
Radical Reactions
Nucleophilic Substitution
Metal-organic Derivatives
Photochemistry of Thiophens
Electrochemical Reactions
The Structure and Reactions of Hydroxy-, Mercapto-, and

Amino-thiophens
Side-chain Reactivities
‘Benzylic’ Reactivity
Reactions of Thiophen Aldehydes and Ketones
Reactions of Cyano- and Carboxy-thiophens
Various Side-chain Reactions
Bi- and Poly-heterocycles
Macrocyclic Compounds containing Thiophen Rings
Reactions Leading to Destruction of the Thiophen Ring
Naturally Occurring Thiophens
Thiophens of Pharmacological Interest

266
268
269
269
272
272
273
276
277
278
278

3 Thienothiophens, their Benzo-derivatives, and Analogous
Compounds
Synthesis
Reactions
Physical Properties
Non-classical Thienothiophens and Related Systems


280
280
280
28 1
28 1

250
252
253
254
254
255
259
26 1
261
263
265
266

Synthesis of Benzothiophens by Ring-closure Reactions
Electrophilic Substitution
Metallation and Halogen-Metal Exchange
2- and 3-Hydroxybenzo[b]thiophens and Related Systems
Side-chain Reactions
Reaction at Sulphur
Pharmacologically Active Compounds

28 1
28 I

284
285
285
286
287
287

5 Thiophen Analogues of Polycyclic Aromatic Hydrocarbons
Thiophen Analogues of Anthracene and Phenanthrene
Thiophen Analogues of Helicenes
Thiophen Analogues of Indene
Thiophen-fused Tropylium Ions and Related Compounds

288
288
288
289
289

4 Benzothiophens and their Benzo-fused Systems


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xiii

Contents

6 Thiophens Fused to Five-membered Aromatic Heterocyclic
Rings
290

Pyrrole- and Furan-fused Thiophens and Related Compounds 290
Pyrazole-, Thiazole-, and Imidazole-fused Thiophens and
Related Systems
290
7 Thiophens Fused to Six-membered Aromatic Heterocyclic Rings
Thiophen Analogues of Quinoline
Thiophen Analogues of Isoquinoline
Pyrimidine-fused Systems
Miscellaneous Fused Systems

29 1
29 1
292
293
295

8 Selenophens and Tellurophens
Monocyclic Selenophens
Physical Properties
Reactions
Selenophens Fused to other Five-membered Aromatic
Rings
Benzo[b]selenophens and their Benzo-fused Derivatives
Selenophens Fused to Six-membered Heterocyclic Aromatic
Rings
Tellurophens

296
296
296

297

Chapter 7 6a-Thiathiophthens and Related Compounds
By R. J. S. Beer

297
298
298
298

300

1 6a-Thiathiophthens

300

2 Multisulphur Systems

301

3 1,2-Dithiolylidene Aldehydes and Ketones

302

4 1,3-Dithiole Derivatives

303

5 Other Analogues of 6a-Thiathiophthens


304

Chapter 8 1,2- and 1,3-Dithioles
By R. J. S. Beer

308

1 1,2-Dithioles

308

2 1,2-Dithiolium Salts

31 1

3 1,3-Dithiole Derivatives

312

4 1,3-Dithiole-2-thiones and Selenium-containing Analogues

313

5 1,3-Dithiolium Salts

315


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Contents


xiv
6 Dithiafulvene Derivatives

315

7 Tetrathiafulvalenes and Selenium-containing Analogues

316

Chapter 9 Thiopyrans and Related Compounds
By U. Eisner

319

1 Introduction

319

2 Dihydrothiopyrans

319

3 2H-Thiopyrans and Related Compounds

32 1

4 4H-Thiopyrans and Related Compounds

322


5 Thiopyran 1,l-Dioxides

324

6 Thiopyrylium Salts

325

7 Benzothiopyrans and Related Compounds

326

8 Benzothiopyrones

327

9 Thioxanthenes and Thioxanthones

328

10 Complex Thiopyran Derivatives

Chapter 10 Thiepins and Dithiins
By U. Eisner

329
332

1 Thiepins


332

2 Dithiins
1,2-Dithiins
1,3-Dithiins
1,4-Dithiins and Related Compounds
Benzo- and Dibenzo-I ,4-dithiins

335
335
336
336
337

Chapter 11 lsothiazoles and Related Compounds
By F. Kurzer
1 Introduction

339
339

2 Isothiazoles
339
Synthesis
339
From 1,ZDithiolans
339
From /3-Aminocrotonic Esters
340

From j5-Chlorovinylmethine-immonium and Bunte Salts 340
From Sulphenimino-nitriles
340
From Thioxadiazepines
341


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xv

Contents
From Thioacylcyanomethanephosphonate Esters
From Penicillins
Meso-ionic Isothiazoles
Physical Properties
Chemical Properties
Photolytic and Free-radical Reactions
A1kylation
Electrophilic Reactions
Nucleophilic Reactions
Action of Peroxyacetic Acid
Action of Acetylenic Reagents
Biological Aspects

34 1
341
342
343
343

343
344
344
344
345
345
346

3 1,2-Benzisothiazoles
Synthesis
Mass Spectra
Chemical Reactions
Biological Activity

346
346
347
347
348

4 1,2-Benzisothiazole 1,l-Dioxides
Synthesis
Chemical Properties
Saccharin Glucosides
Analytical Procedures
Biological Properties

348
348
348

350
350
35 1

5 1,2-Benzisoselenazoles

35 1

6 2,l-Benzisothiazoles
Synthesis
Chemical Properties

35 1
351
352

7 Other Condensed Ring Systems incorporating Isothiazole
Isothiazolo[5,1-e]isothiazoles [6a-Thia-l,6-diazapentalenes]
Is0thiazolo[5,4-b]pyridine
Is0thiazol o [3,4-d]pyrimidines
Isothiazolo[5,4-d]pyimidines
Isothiazolo[5,4-b]quinoline
Thieno[2’,3’:4, Slpyrimido[1,241[1,2]benzisot hiazoles
1,ZBenzisothiazolo [2,3-a]quinazoline

353

Chapter 12 Thiazoles and Related Compounds
By B. lddon and P. A. Lowe


353
354
354
354
354
354
355
356

1 Introduction

356

2 Synthesis of Thiazoles
Hantzsch’s Synthesis
Other Type A Syntheses

357
357
358


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xvi

Contents
Type B Syntheses
Type C Syntheses
Type D Syntheses
Type F Syntheses

Type K Syntheses
Synthesis of Meso-ionic Thiazoles

358
358
359
359
359
359

3 Physical Properties of Thiazoles

360

4 Chemical Properties of Thiazoles
Electrophilic Substitution
Nucleophilic Substitution
Thiazolyl Radicals and their Reactions
Oxidation and Reduction
Ring Expansion to 1,4-Thiazines
Alkylation
Reactions of Thiazoles with Diiiietliyl Acetylene&
carboxylate
Organometallic Reagents
N-Oxides
Reactions of 2-Amino-thiazoles
Reactions of 2-Hydrazino-thiazoles
Reactions of Thiazolium Salts
Miscellaneous Reactions
Reactions of Meso-ionic Thiazoles


361
361
361
362
363
363
363
364
364
365
365
365
366
366
368

5 Synthesis of A2-Thiazolines
Type A Syntheses
Type B Syntheses
Type C Syntheses
Type E Syntheses
Type K Syntheses

369
369
370
370
370
371


6 Chemical Properties of A2-Thiazolines

371

7 A3-Thiazolines

373

8 Synthesis of A4-Thiazolines

374

9 Physical Properties of A%-Thiazolines

375

10 Chemical Properties of A4-Thiazolines

376

11 Synthesis of Thiazolidines
Type A Syntheses
Type B Syntheses
Type C Syntheses
Type D Syntheses
Type E Syntheses
Type K Syntheses

376

376
377
377
377
378
378


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Contents

xvii
12 Physical Properties of Thiazolidines

379

13 Chemical Reactions of Thiazolidines
Ring-cleavage Reactions
Other Reactions

380
380
380

14 Rhodanines, Isorhodanines, and Thiorhodanines

381

15 Selenazoles


384

Chapter 13 Condensed Ring Systems Incorporating Thiazole
By B. lddon and P. A. Lowe

386

'1 Introduction

386

2 Synthesis of Benzothiazoles
From o-Aminobenzenethiols
Jacobson-Hugershoff Synthesis
Other Type B Syntheses
Type C Syntheses
Type D Syntheses
Synthesis from Thiazoles
Synthesis from 3,5-Bis(arylimino)- 172,4-thiadiazolidines
(Dost's Bases) ; Structure o f Hugershoffs Bases
Synthesis from 1,4-Benzothiazines
Other Syntheses

386
386
387
388
388
388

388
389
389
389

3 Physical Properties of Benzothiazoles

390

4 Chemical Properties of Benzothiazoles
Oxidation and Reduction
Reactions of Benzothiazoles with Singlet Oxygen
Nucleophilic Substitution
Reactions of Benzot hiazoles with Dimethyl Acetylenedicarboxylate
Organometallic Derivatives
Alkylation Reactions
Reactions of Benzothiazoliuni Salts
Reactions of Other Derivatives

39 1
391
392
392
393
393
394
394
395

5 Benzoselenazoles and Naphthoselenazoles


397

6 Structures Comprising Two Five-membered Rings
Thiazolo- [2,3-c]- and - [3,2-b]- [1,2,4]thiadiazoles
Thiazolo-[2,3-c]- and -[3,2-b]-[172,4]triazoles
Thiazolo [2,3-b]t hiazoles
Pyrazolo-[3,4-d]- and -[5,1-b]-thiazoles
Imidazo[2,1 -b]thiazoles
Pyrrolo[2,1-b]t hiazoles
Thieno[2,3-d]thiazoles

398
398
398
399
399
400
402

402


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xviii

Contents
7 Structures Comprising One Five-membered and One Sixmembered Ring
Thiazolo [3,2-a][1,3,5]triazines

Thiazolo[2,3-c][1,2,4]triazines

Thiazolo[3,2-b][1,2,4]triazines
Thiazolo [3,Zblpyridazines
Thiazolo-[4,5-c]- and -[4,5-d]-pyridazines
Thiazolo[5,4-~]pyridazines
Thiazolo [3,2-alpyrirnidines
Thiazolo [3,2-c]pyrimidines
Thiazolo[4,5-d]pyrimidines
Thiazolo [5,4-d]pyrimidines
Thiazolo[3,2-a]pyrimidines
Thiazolo [4,5-b (and -c)]pyridines
Thiazolo [5,4-b]pyridines
Thiopyrano-7H- [2,3-d]thiazoles

402
402
403
403
403
404
404
404
405
405
405
406
407
407
407


8 Structures comprising Two Five-membered Rings and One
Six-membered Ring
[1,2,4]Triazolo-[3,2-b]- and - [3,4-b]-benzothiazoles
Thiazolo [4,5-g]benzisoxazoles
Bis(thiazolo)[4,5-b:5,4-e]thiopyrylium Salts
Thiazolo [2,3-b]benzothiazoles
Thiazolo-[2,3-f]- and -[3,2-e]-purines
Thiazolo-[3,2-a]- and -[3,4-~]-benzimidazoles
Pyrazolo[4,3-g]benzothiazoles
Imidazo [2,1-b]benzothiazoles
Thiazolo-[3,2-a]- and -[3,4-a]-indoles
Thiazolo-[4,5-b]- and -[5,4-b]-indoles
Thiazoloisoindoles
Furo [3,2-e]benzothiazoles
Thiazolo[3,2-a]thieno[2,3-b (and -d)]pyrimidines
lndeno[ 1,2-d]thiazoles

407
407
408
408
408
409
409
409
410
410
410
410

41 1
41 1
41 I

9 Structures Comprising One Five-membered Ring and Two
Six-membered Rings
Pyrimido[2,1-b]thiazolo[4,5-el[1,3,4]thiadiazines
Thiazolo [2,3-c][1,2,4]benzothiadiazines
Benzo[2,1-e]thiazolo[2,3-c][1,2,4]triazines
Pyrido-[2,3-d]- and - [3,2-d]-thiazolo[3,2-b]pyridazines
Pyrido [2,3-d]thiazolo [3,2-a]pyrimidines
Pyrido[ 1,2-a]thiazolo[5,4-e]pyrimidines
Pyrimido[2,l-b]benzothiazoles
Pyrimido[5,4-g]benzothiazoles
Thiazolo [2,3-b]quinazolines
Thiazolo [3,2-a]quinazolines
Pyrido[2,1-b]benzothiazoles

41 1
41 1
41 2
412
412
412
412
412
413
413
41 3
413



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xix

Contents
Thiazolo-12’3-4- and - [3,2-a]-quinolines and -isoquinolines
Thiazolo [5,4-c]isoquinoline
Naphtho[2,l-d]thiazoles

414
414
414

10 Structures Comprising Two Five-membered and Two Sixmembered Rings
Tetrazolo- and [1,2,4]Triazolo-[5,4-b]naphtho[2,l-d]thiazoles
BenzimidazoE2,l-b]benzothiazoles
Imidazot2,l -b]naphtho-[l,2-d]- and - [2,1-d]-thiazoles

415
41 5
41 5

11 Structures Comprising One Five-membered Ring and Three
Six-membered Rings
Thiazolo [4,5-a]phenothiazines
Benzothiazolo-[2,3-b]- and [3,2-c]-quinazolines

41 5

41 5
416

-

Chapter 14 Thiadiazoles and Selenadiazoles
By F. Kurzer

415

417

1 Introduction

417

2 1,2,3-Thiadiazoles
Synthesis
Pechmann’s Synthesis
From Diazo-keto-amides
From Hydrazones
By Oxidation of a-Aryl hydrazono-thioamides
Meso-ionic 1,2,3-Thiadiazoles
Chemical Properties
Photolytic Reactions
Thioketens from 1,2,3-ThiadiazoIes
Biochemical Properties
1,2,3-Benzothiad i azoles

41 7

417
417
41 8
418
418
419
419
419
420
420
421
42 1
422

1,2,3-Thiadiazol0[5,4-b]indoles
1,2,3-Thiadiazolo[3,4-a]isoquinolines
3 1,2,3-Selenadiazoles

422

4 1,2,4-Thiadiazoles
Synthesis
From Perthiocyanic Acid
Type A Syntheses
From 1,2,3,4-thiatriazoles
Type B Syntheses
From amidines
Type C Syntheses
From amidino-thiono-compounds
Oxidation of thioureas


422
422
422
422
422
423
423
423
423
423


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Contents

xx
From dithiazoles
From oxaziridines
From 1,2,4-0xadiazoles
Type D Syntheses
Type F Syntheses
Type G Syntheses
Physical Properties
Chemical Properties
Alkylation
Cycloaddit ion
Biological Activity
5 Condensed 1,2,4-Thiadiazoles


Isoxazolo[3,2-c][1,2,4]thiadiazoles
Thiazolo[2,3-c][1,2,4]thiadiazoles
3H-1,2,4-Thiadiazolo[3,4-b][
1,3,4]oxadiazole
3H-1,2,4-Thiadiazolo[4,3-dI[ 1,2,4]thiadiazole
3H-1,3,4-Thiadiazolo[2,3-c][1,2,4]thiadiazole
lY2,4-Thiadiazolo[2,3-a]pyridines
1,2,4-Thiadiazolo-[4,3-a]and -[4,3-c]-pyrimidines
1,2,4-Thiadiazol0[2,3-b]pyridazines
1,2,4-Thiadiazolo[4,3-c]pyrimidine
1,2,4-Thiadiazol0[2,3-a]pyrazine
6 1,3,4Thiadiazoles

Synthesis
From (Thiojcar bono-hydrazides
From 4-Hydrazino-quinazoline
Physical Properties
Chemical Properties
Alkylation
Ring Fission
Nucleophilic Substitution
Reductive Removal of Mercapto-groups
Dimerization
Formation of Metal Complexes
Polymeric 1,3,4-Thiadiazoles
Analytical
Biochemical Aspects
Biological Activity
Meso-ionic 1,3,4-Thiadiazoles
7 A2-1,3,4-Thiadiazolines

Synthesis
From Hydrazonyl Halides
From Dithizone
Other Syntheses
Properties

424
425
425
426
426
427
427
428
428
428
429
429
429
429
430
430
430
430
430
43 1
43 1
43 1
43 1
43 1

432
433
433
434
434
435
436
436
436
437
437
437
437
437
438
439
439
439

440
440
441


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Contents
8 A3-1,3,4-Thiadiazolines
Formation
Alkene Synthesis


xxi
442
442
442

3 Condensed Ring Systems incorporating 1,3,4-Thiadiazole
Imidazo[2, I -b][1,3,4]thiadiazoles
1,3,4-Thiadiazolo[3,2-n]pyrimidines
1,3,4-Thiadiazolo[3,2-a][ 1,3,5]triazines
1,3,4-Thiadiazolo[3,2-b]isoquinolines

443
443
443
445
445

10 Condensed Ring Systems incorporating 1,3,4-Selenadiazole
1,3,4-Selenadiazolo[3,Z-alpyrimidines

445
445

11 1,2,5-Thiadiazoles
Synthesis
Physical Properties
Chemical Properties

446
446

447
447

12 1,2,5-SeIenadiazoIes

448

13 2,1,3-Benzothiadiazoles and Selenium Analogues

448

14 Condensed Ring Systems incorporating 1,2,5-Thiadiazole
1,2,3-Triazolo[4,5-c][1,2,5]thiadiazoles and Selenaanalogues
1,2,5-Thiadiazolo[3,4-c][
1,2,5]thiadiazoles
1,2,5-Thiadiazol0-[3,4-6]and -[3,4-c]-pyridines
1,2,5-Thiadiazolo[3,4-d]pyridazine
1,2,5-Thiadiazolo[3,4-d]pyrimidines
1,2,5-Thiadiazol0[3,4-b]pyrazines
1,2,5-Thiadiazolo[3,4-b]quinoxaline
Benzo [1,2-c:3,4-c’:5,6-c”]tris [1,2,5]t hiadiazole

450

Chapter 15 Thiazines
By G. Prota

450
450
450

45 1
45 1

45 1
451
452

453

1 Introduction

453

2 1,ZThiazines
Benq-1,Zthiazines

453
453

3 lY3-Thiazines
Simple 1,3-Thiazines
Benzo-l,3-thiazines

454
454

4 lY4-Thiazines
Monocyclic 1,4-Thiazines
Benzo-1,4-thiazines and Related Compounds
Phenothiazines and Related Compounds


458
458
459
463

456


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xxii

Contents

Chapter 16 F-Lactam Antibiotics, other Sulphur-containing Natural
Products, and Related Compounds
466
By J. G. Gieason and G. L. Dunn
1 Introduction

466

2 Fermentation and Biosynthesis

467

3 Modification of the @-LactamRing System
Modification at C-6(7)
Epimerization
Modification at C-7(8)


469
469
47 1
473

4 Modifications in the Thiazine Ring

473

5 Rearrangements of Penicillins and Cephalosporins
1,2-Bond Cleavage
1,5-Bond Cleavage

476
477
48 1

6 Total Synthesis of Penicillins and Cephalosporins

483

7 Structure-Activity Considerations

489

8 Epidithiodioxopiperazines

492


9 Other Sulphur-containing Natural Products

493

Author Index

496


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Abbreviations

The following abbreviations have been used:
ultraviolet
infrared
nuclear magnetic resonance
tristl, 1,1,2,2,3,3 ]heptafluoro-7,7-dimethyl-4,6-octanedionatoeuropium(r1i)
tris[ ],I, 1,2,2,3,3,7,7,8,8,9,9,9]tetradecaAuoroEu(tfn),
4,6-nonanedionato-europium(11~)
optical rotatory dispersion
0.r.d.
circular dichroism
c.d.
electron spin resonance
e.s.r.
3,4dihydroxy-~-phenylalanine
dopa
gas-liquid chromatography
g.1.c.

N-bromosuccinimide
NBS
complete neglect of differential overlap
CNDO
diazabicyclo-octane
DABCO
dicyclohexylcarbodi-imide
DCCI
dimethoxyethane
DME
"-dime t hylformam ide
DMF
dimethyl sulphoxide
DMSO
tetramethylethylenediamine
TMEDA
dimethyl acetylenedicarboxylat e
DMAD
trifluoroacetic acid
TFA
hexamethylphosphoric triarnide
HMPA
tetrahydrofuran
THF
pyridine
PY
VOl. 3, Vol. 2, Reference back to a preceding Volume of this series of
'Specialist Periodical Reports'
VOl. 1
U.V.


i.r.
n.m.r.
Eu(f0d)a