Organic compounds of sulphur, selenium, and tellurium vol 2

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A Specialist Periodical Report

Organic Compounds of Sulphur,
Selenium, and Tellurium
Volume 2

A Review of the Literature Published between
April 1970 and March 1972

Senior Reporter
D
m HI Reid, Department of Chemistry, The University, St. Andrews
Reporters
G. C. Barrett, Oxford Polytechnic
R. J. S. Beer, The University of Liverpool
F. DUUS,Odense University, Denmark
S. Gronowitz, University of Lund, Sweden
A. Wm. Johnson, University of North Dakota, U.S.A.
D. N. Jones, The University, Shefleld
F. Kurzer, Royal Free Hospital School of Medicine, University of London
G. Prota, University of Naples, Italy

@ Copyright 1973

The Chemical Society

Burlington House, London, W I V OBN


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ISBN : 0 85186 269 1
Library of Congress Catalog Card No. 77-23818

Organic formulae composed by Wright's Symbolset method

PRINTED IN GREAT BRITAIN BY JOHN WRIGHT AND SONS LTD., AT THE STONEBRIDGE PRESS, BRISTOL


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Preface

The aims and structure of this second Volume of ‘Organic Compounds of
Sulphur, Selenium, and Tellurium’ remain those set out in the Preface to
Volume 1.
Two changes in the coverage are announced. First, a review of the
Theoretical Aspects of Organosulphur, Organoselenium, and Organotellurium Compounds has been omitted from this volume. A review of the
subject, covering the four-year period beginning April 1970, will appear in
Volume 3. Secondly, an extended chapter on the chemistry of Thiophen
and Related Compounds, which could not be reviewed in time for inclusion
in Volume 1, takes its place in this volume, and covers the three-year
period April 1969 to March 1972. Reviewing of all other material covered
in this volume is for the two-year period April 1970 to March 1972.
D. H. R.

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Contents

Chapter 1 Aliphatic Organo-sulphur Compounds, Compounds
with Exocyciic Sulphur Functional Groups, and
their Selenium and Tellurium Analogues
By G. C.Barreff
1
1 General
1
Text-books and Reviews
2 Thiols
Preparation
Spectroscopic and Related Properties of Thiols
Thiols as Nucleophiles
Reactions of Thiols with Organoboron, Organophosphorus, and Organotin Compounds
Addition of Thiols to Multiple Bonds
Protection of SH Groups in Synthesis
Thiols in Biochemistry

3
3
6

7

8
9
12

12

3 Sulphides
Preparation
Preparation of Sulphides using Organomagnesium,
Organoboron, or Organophosphorus Reagents
Heteroaryl Sulphides
Properties of Sulphides
Reactions of Sulphides
a-Substituted Sulphides
a-Chloro-sulphides
p-Ket o-sulphides
Unsaturated Sulphides
Reactions of Unsaturated Sulphides
Skeletal Rearrangements of Unsaturated Sulphides
Naturally Occurring Organo-sulphur Compounds

27
28
30

4 Thioacetals and Related Compounds
Preparation
Reactions
Tetrathioethylenes and Related Compounds

31
31
31
34

14

14
16
17
18

21
24
25
25
26


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vi

5 Sulphoxides
Preparation
Spectroscopic Properties of Sulphoxides
Resolution and Racemization of Sulphoxides
Reactions of Sulphoxides
StereochemicalFeatures of Reactions of Sulphoxides

Dimethyl Sulphoxide as a Reagent

35
35
37
39
41
45
50

6 Sulphones
Preparation
Properties of Sulphones
Reactions of Sulphones
Addition Reactions of Unsaturated Sulphones
Smiles Rearrangement
Ramberg-Backlund Rearrangement

57
57
59
59
62
64
64

7 Sulphenic Acids and their Derivatives
Sulphenic Acids and Sulphenate Esters
Sulphenamides
Sulphenyl Halides

Sulphenyl Protecting Groups

65
65
67
69
71

8 Thiocyanates and Isothiocyanates
Preparation of Thiocyanates
Preparation of Isothiocyanates
Reactions of Thiocyanates and Isothiocyanates

72
72
73
74

9 Sulphinic acids
Preparation
Reactions of Sulphinic Acids
Sulphinate Esters
Sulphinamides

76
76
77
78
78

10 Sulphonic Acids
Preparation
Sulphonyl Peroxides
Sulphonate Esters
Vinyl Sulphonates
Sulphonyl Halides and Sulphenes
Sulphonyl Cyanides
Sulphonamides and Related Compounds
11 Disulphides, Trisulphides, and their Oxy-sulphur
Analogues
Preparation of Disulphides, Hydrodisulphides, and
Oligosulphides

80
80
82
82
84
85
87
87

90
90


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Contents

Properties of Disulphides
Reactions of Disulphides and Polysulphides
Thiolsulphinates
Thiolsulphonates
Sulphinyl Sulphones and a-Disulphones

Chapter 2 Small Ring Compounds of Sulphur and Selenium
By D. N. Jones
1 Thiirans
Formation
Spectroscopic and Conformational Aspects
Reactions

93
94
97
98
99

100
100
102
103

2 Thiiran 1-Oxides
Format ion
N.M.R. Characteristics
Reactions

104
104
105
105

3 Thiiran 1,l-Dioxides

107

4 Thiiren 1-Oxides and Thiiren 1,l-Dioxides
Formation
Reactions

108
108
1 09

5 Thiiranium and Thiirenium Ions

109

6 Thiaziridines

111

7 Thietans
Formation
By Intramolecular Displacement Reactions
By Cycloadditions involving Thiocarbonyl Compounds
Photolysis

Other Reactions involving Ring Fission
Thietanium Ions

111
111
111

113
114
114
114

8 Thietan 1-Oxides, Thietan 1,l-Dioxides, and Thiet 1,lDioxides
Formation
By Oxidation of Thietans
By Cycloadditions involving Sulphenes
BYCvcloadditions involving Thiet 1.1-Dioxides

116
116
116
116
118


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Contents

Vlll

Reactions
Thermolysis and PhotoIysis of Thietan 1,l-Dioxides
Thermolysis of Thiet 1,l-Dioxides
Reactions of Thietan 1,l-Oxides, Thietan 1,lDioxides, and Thiet 1,l-Dioxides involving
Sulphur-stabilized Carbanions
9 Structure and N.M.R. Properties of Thietan Derivatives

119
120
121

122
124

10 1,3=Dithietansand 1,3-Diselenetans

128

11 1,ZThiazetidines

131

12 1,3-Thiazetidines and 1,2,3-0xathiazetidines

132

13 1,2-Oxathietansand 1,2,3-Dioxathietans

133

Chapter 3 Saturated Cyclic Compounds of Sulphur and
Selenium
By D. N. Jones
1 Thiolans, Thians, Thiepans, Thiocans, their Oxides and
Dioxides, and their Selenium Analogues
Formation
Properties and Reactions
Oxides and Dioxides
Sulphimides and Sulphoximides

2 Compounds with Two Sulphur or Selenium Atoms in the
Ring; their Oxy-sulphur Analogues
Cyclic Disulphides and Cyclic Diselenides
Formation
Properties and Reactions
1,3-Dithiolans, 1,3-Dithians, and their Selenium
Analogues
Formation
Properties and Reactions
1,4-Dithians, 1,4-Diselenans, 1,4-Dithiepans, and
1,5-Dithiocans
Formation
Pronerties and Reactions

135
135
141

149
158

160
160
160
160
163
163
166
173
173
174


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Contents
3 Compounds containing Three or More Sulphur Atoms
1,2,4-Trithiolans
1,3,5-Trithians, 1,2,4-Trithians, and 1,2,4,5-Tetrathians
Macrocyclic Polysulphides

4 Compounds containing Sulphur or Selenium and other
Heteroatoms
Cyclic Sulphonates, Cyclic Sulphinates, and Related
Systems
1,3-0xathiolans, 1,3-0xathians, 1,3-Oxaselenans,

1,4-0xathians, and Related Systems
Cyclic Sulphites, Cyclic Selenites, Cyclic Sulphates,
and Related Systems
Penicillins, Cephalosporins, and Related Compounds

176
176
177
179
180
180

182
187
191

Chapter 4 Thiocarbonyl, Selenocarbonyl, and Tellurocarbonyl

Compounds
By F. Duus
1 Introduction
Reviews
The Thiocarbonyl Group in General
Thioaldehydes and Thioketones
Thioketens
Sulphines
Sulphenes
Thioamides
Derivatives of Thioamides
Thioureas

Thiono- and Dithio-acids and Derivatives
Selenocarbonyl Compounds

200
200
200
200
201
201
201
201
201
201
201
201

2 Thioaldehydes
Synthesis
Transient Species
Metal Complexes

201
202
204

3 Thioketones
Synthesis
Transient Species
The Thio-Claisen Rearrangement
Metal Complexes

Reactions

204
204
209
210
212
214

201


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Contents

X

4 Thioketens

220

5 Thiocarbonyl Ylides

222

6 Sulphines

223

7 Sulphenes

225

8 Thioamides
Synthesis
Reactions

228
228
233

9 Thioureas
Synthesis
Reactions

236
236
239

10 Thiosemicarbazides and Derivatives
Synthesis
Reactions

243
243
246

11 Thionocarboxylic and Dithiocarboxylic Acids and
Derivatives
Synthesis

Reactions

250
250
254

12 Thionocarbonates, Thionodithiocarbonates, and Trithiocarbonates
Synthesis
Reactions

258
258
260

13 Thionocarbamic
Derivatives
Synthesis
Reactions

263
263
267

and

Dithiocarbamic

Acids

and

14 Selenocarbonyl Compounds
Synthesis
Reactions

271
271
271

15 Physical Properties
Structure
Tautomerism
Ring-Chain Isomerism
Polarization Effects and Restricted Rotation
Crystal and Molecular Structures

273
273
273
276
277
279


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xi

Contents
Spectra

Ultraviolet Spectra
Infrared Spectra
N.M.R. Spectra
E.S.R. Spectra
Mass Spectra
0ther Physical Properties
Electrochemistry
Dipole Moments
Acidity and Basicity Measurements

Chapter 5 Ylides of Sulphur, Selenium, Tellurium, and
Related Structures
By A. William Johnson
1 Introduction

279
279
28 1
282
284
285

286
286
286
286

288

2 Sulphonium Ylides

Methods of Synthesis
Physical Properties
Chemical Stability
Reactions of Sulphonium Ylides
Sulphonium Ylides as Reaction Intermediates

289
289
289
29 1
296
306

3 Oxysulphonium Ylides
Synthesis and Properties
Reactions of Oxysulphonium Ylides

307
307

4 Sulphinyl Ylides

312

5 Sulphonyl Ylides

315

6 Sulphenes

317

7 Sulphines

320

8 Sulphur Imines
Iminosulphuranes
Sulphurdi-imines
Imino-oxysulphuranes
Sulphonedi-imines

322
322
328
329
334

9 Sulphonyl- and Sulphinyl-amines

336

10 Ylides of Selenium and Tellurium

339

308


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Contents

Chapter 6 Heterocyclic Compounds of Quadricovalent Sulphur
By D. H. Reid
1 Introduction

341

2 Thiabenzenes

34 1

3 Thiabenzene 1-Oxides

345

4 Azathiabenzenes

347

5 Four- and Five-membered Ring Compounds

349

Chapter 7 Thiophens and their Selenium and Tellurium
Analogues
By S. Gronowitz
1 General

352

2 Monocyclic Thiophens
Syntheses of Thiophens by Ring-closure Reactions
MO Calculations
Electronic Spectra
Molecular Geometry
1.r. Spectra and Dipole Moments
N.M.R. Spectra
E.S.R. Spectra
Mass Spectra
Electrophilic Substitution
Electrophilic Ring-closure Reactions
Radical Reactions
Nucleophilic Substitution
Metallation and Halogen-Metal Exchange
Photochemistry of Thiophens
Application of the Hammett Equation
The Structures and Reactions of Hydroxy- and
Mercapto-thiophens and their Simple Derivatives
Side-chain Reactivities
Rearrangement Reactions
Biheterocyclics
Thiophen Analogues of Porphyrins
Reactions at the Thiophenic Sulphur
Diels-Alder Reactions
Raney-nickel Desulphurization
0t her Ring-opening React ions

353
353
361
362
363
363
365
369
370
371
378
38 1
384
386
392
395
396
401
409
410
414
41 7
417
417
420
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Contents

xi11

Polymers from Thiophen Derivatives
Naturally Occurring Thiophens
Thiophens of Pharmacological Interest
Thiophen Derivatives of Analytical Interest

3 Thienothiophens, their Benzo-derivatives, and Analogous
Compounds
Synthesis
Theoretical Studies and Physical Properties
Substitution Reactions
Non-classical Thienothiophens
4 Benzothiophens and their Benzoannelated Derivatives
Synthesis of Benzothiophens by Ring-closure Reactions
Theoretical Studies and Physical Properties
Electrophilic Substitution
Electrophilic Ring-closure
Radical Substitution
Metallation and Halogen-Metal Exchange
Side-chain Reactions
Photochemistry
The 2- and 3-Hydroxybenzo[b]thiophen Systems and
their Derivatives
Reaction at Sulphur
Pharmacologically Active Compounds

5 Thiophen Analogues of Polycyclic Aromatic Hydrocarbons
Thiophen Analogues of Anthracene
Thiophen Analogues of Phenanthrene
Thiophen Analogues of Helicenes
Thiophen Analogues of Fluorene
Thiophen Analogues of Tropylium Ions and Related
Compounds
Miscellaneous Thiophen Analogues of Polycyclic
Hydrocarbons
6 Thiophen Analogues of Indole, Quinoline, Isoquinoline,
and Similar Systems
Thiophen Analogues of Indole and Related Compounds
Thiophen Analogues of Quinoline and Related Compounds

42 1
422
423
427

428
428
430
430
433
435
435
441
442
445

447
447
449

449
45 1
452
452

455
455
458
460
462

467
470

472
472
473


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xiv

Contents

Thiophen Analogues of Isoquinoline and Related
Compounds

0ther Pyridine-fused Thiophen-cont aining Systerns

475
478

7 Thiophens Fused to Rings containing Two Nitrogens
Pyrazole- and Imidazole-fused Systems
Pyridazine-fused Systems
Pyrimidine-fused Systems
Miscellaneous Rings containing Several Nitrogens

480
480
480
483
485

8 Miscellaneous Fused Systems
Thiazole-fused Systems
Pyrylium-fused Systems
Thiapyrylium-fused Systems
Other Fused Systems

487
487
487
488
489

9 Selenophens and Tellurophens

Monocyclic Selenophens
Benzo[blselenophens
Miscellaneous Fused Selenophens
Tellurophens

490
490
49 1
495
495

Chapter 8 6a-Thiathiophthens and Related Compounds
By R. J. S. Beer
1 Introduction

497

2 Structural and Theoretical Studies

497

3 Synthesis, Properties, and Reactions of 6a-Thiathiophthens

500

4 Compounds Structurally Related to 6a-Thiathiophthen

505

Chapter 9 1,2- and 1,3-Dithioles

By R. J. S. Beer
1 Introduction

51 1

2 1,2-Dithioles and Related Compounds
Synthesis
Reactions

51 1
51 1
512


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xv

Contents

3 1,ZDithiolium Salts

515

4 1,3-Dithioles and Related Systems

519

Chapter 10 Thiopyrans and Related Compounds
By R. J. S. Beer

1 Introduction

526

2 Dihydrothiopyrans

526

3 2H-Thiopyrans and Related Compounds

529

4 4H-Thiopyran Derivatives

530

5 Thiopyrylium Salts

532

6 Thiochromans and Related Compounds

535

7 Thio- and Seleno-coumarins

537

8 2-Thioisocoumarins, Dithioisocoumarins, and Related
Compounds

538

9 Thioxanthones, Selenoxanthones, and Related Compounds

541

10 Peri-Fused Naphthothiopyrans

542

11 Complex Thiopyran and Selenopyran Derivatives

543

Chapter 11 Thiepins and Dithiins
By D. H. Reid
1 Thiepins

545

2 Dithiins
1,ZDithiins
1,4-Dithiins and 1,4-Diselenins
Benzo- and Dibenzo-l,4-dithiins

551
55 1
552

554


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Contents

Chapter 12 lsothiazoles
By F. Kurzer
1 Introduction

556

2 Synthesis
From a-Amino-ketones or fl-Cyano-enamines and
Sulphur Chlorides (Type A)

556

From Oxathiazolones (Type B)
From Chlorosulphonyl Isothiocyanates and Olefins
(Type B)
From 3,3’-Dithiodipropionamides (Type C)
From Phenylcysteine (Type C)
From Vilsmeier Salts (Type C)
From 1,2-Dithiolans (Type C)
From Thiazoles

558

556

559
560
560
561
563
563

3 Physical Properties

564

4 Chemical Properties
Free-radical and Photolytic Reactions
Nitration and Halogenation
Diazo tization
Conversion into 1,2,3-Thiadiazoles
Metallation
Miscellaneous Substitution Reactions (mostly
Nucleophilic)
Nucleophilic Ring Cleavage
Base-catalysed Dimerization
S-Oxides and -Dioxides
Complexes
Some Biological Properties

567
567

567
568
569
569

5 Condensed Ring Systems
2,l -Benzisothiazoles
Synthesis
Electrophilic Substitution
1,ZBenzisothiazoles
Synthesis
Mass Spectra
Chemical Properties
Nucleophilic Substitution and Ring Fission
Complexing
Isothiazolo[5, 1-e]isothiazoles
Isothiazolo[2,3-b]quinazolines

576
576
576
577
577
577
579
579
582

570
574

574
575
575
576

585

585
585


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xvii

Contents

Chapter 13 Thiazoles
By F. Kurzer
587

1 Introduction

2 Synthesis
Hantzsch’s Synthesis (Type A, S-C-N
C-C)
Other Type A (S-C-N
C-C) Syntheses
+ C) Synthesis
Type E (N-C-C-S
Type F (C-N-C-S

+ C) Synthesis
Type G (N-C-S-C-C)
Synthesis
Fission of Thiamine

587
587
589
590
59 1
591
592

3 Physical Properties

594

4 Chemical Properties
Deuterium and Tritium Exchange
Free-radical Reactions
Alkylation
Electrophilic Substitution
Miscellaneous Substitutions
Reactions of Aminothiazoles
Ring Cleavage
Ring Expansion to 1,4-Thiazines
Dimerization
Azines and Dyes
Metal Complexes

595
595
596
597
598
599
600
603
605
606
607
609

5 Biochemical Aspects
Thiamine (Vitamin B,)
Miscellaneous Biochemical Contributions
Biological Activity
Mesionic Thiazoles
Formation from Mesionic Oxazoles

610
610
612
613
614
614

6 2-Thiazolines
Synthesis
From (Thio)carbamoyl Isothiocyanates

From Thioamides and Acetylenedicarboxylic
Acid
Further Syntheses from Thioamides (Linear and
Cyclic)
From Aziridines
2-Thiazoline Pept ides
Physical Properties

616
616
616

+

+

617
618
620
622
624


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xviii
Chemical Properties
Alkylation
Acylat ion

Action of Isocyanate Esters
Hydrolysis and Aminolysis
Conversion into Triazoles

625
625
625
627
628
629

7 4-Thiazolines
Synthesis
Properties

630
630
632

8 Thiazolidines
Synthesis
Hantzsch’s Synthesis and Related Cyclizations
From 2-Aminoethanethiol and Related Compounds
From Aziridines
From Thiirans
From 1,4-Thiazines by Ring Contraction
From Thiocarbonylamino-acid Silyl Esters
From Enamines and Mercaptocarboxylic Acids
From Keten, Carbodi-imide, and Sulphur Dioxide
Physical Properties

Chemical Properties
Thiazolidines in Peptide Synthesis
Rhodanines

632
632
632
634
636
639
640

640
641
641
642
642
645
648

Chapter 14 Condensed Ring Systems incorporating Thiazole
By F. Kurzer
1 Benzothiazole
Synthesis
Synthesis from o-Aminothiophenols
Synthesis from Thioamides and Related Compounds
Synthesis from Quinones and Thioureas
Synthesis from Benzothiazines
Physical Properties
X-Ray Analysis

Chemical Properties
Oxidation
Benzothiazolin-Zone Hydrazones
Benzothiazole 3-Oxides

653
653
653
656
658
658
659
664
664
665
665
665


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xix
Diazotization
Alkylation and Related Reactions
Aminomethylation
Michael Reaction
Azidobenzothiazoles
Acylation
Alkylation and Acylation by Free-radical Reactions

Alkylation and Arylation
Acylation
Heterocyclic Carbenes
Nucleophilic Substitution
Silylbenzothiazoles
Polymethine Dyes
Polymers
Metal Complexes
Biochemical Aspects
Physiological Activity
Benzoselenazoles
Condensed Ring Systems

670
670
67 1
67 1
67 1
672
673
676
677
679
680
680
68 1

2 Structures Comprising Two Five-membered Rings (5,5)
Thiazolo[2,3-c or 3,2-b]-s-triazoles
Thiazolo [2,3-b]t hiazoles

Thiazolo [5,4-d]thiazoles
Pyrrolo[2,1-b]thiazole

682
682
683
683
684

3 Structures Comprising One Five-membered and One
Six-membered Ring (5,6)
Thiazolo [3,Za]-s-triazines
Thiazolo[3,2-b]- and Thiazolo[2,3-c]-ns-triazines

Thiazolo[4,5-d]pyridazines
Thiazolo[3,2-a]pyrimidines
Synthesis from 2-Mercapt opyrimidines
Synthesis from 2-Aminothiazoles
Thiazolo[3,2-c]pyrimidines
Thiazolo[4,5-d]pyrimidines
Thiazolo [3,2-a]pyrazines
Thiazolo [3,2-a]pyridines
Synthesis from L-Cysteine
Synthesis from Penicillamine
Synthesis from Substituted 2-Mercaptopyridines
Thiazolo[3,2-a]pyridinium 3-Oxides
Thiazolo [5,4-b(and c)]pyridines

667
668

668
669
669
669

684
684
685
686
688
688
689
692
694
695
695
696
697
697
699
700


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Contents

4 Structures Comprising One Five-membered and One
Seven-membered Ring ( 5 7 )

Thiazolo[5,4-f]- 1,4-diazepines
Thiazolo [5,4-c]azepines

700
700
70 1

5 Structures Comprising Two Five-membered and One
Six-membered Ring (5,5,6)
Bisthiazolo[3,2-a; 4’,5’-d]pyrimidines
Thiazolo [2,3-b]benzothiazoles
Thiazolo[3,2-f]xanthine
Thiazolo [3,2-a]benzimidazoles
Thiazolo [3,4-a]benzimidazole
Thiazolo[4,3-b] benzot hiazoles
Thiazolo [3,2-a]pyrrolo[2,3-d]pyrimidines

701
70 1
702
703
703
706
707
707

6 Structures Comprising One Five-membered and Two
Six-membered Rings (5,6,6)
[ 1,3]Thiazino [2,3-b]benzo thiazoles
Pyrimido [2,1-b]benzot hiazoles

Thiazolo [3,2-a]quinazolines
Thiazolo[4,5-b]quinoxalines
Thiazolo [2,3-a]isoquinolines
Thiazolo[ 3,2-b]isoquinolines
Pyrano [3,2-g]benzothiazoles
Thiazolo [5,4-~]benzo(thio)pyrans
Naphtho[ 1,2-d]thiazoles
Selenazolo [5,4-f]quinolines

707
707
707
708
709
709
710
710
710
71 1
71 1

7 Structures Comprising One Five-membered, One Sixmembered, and One Seven-membered Ring (5,6,7)
Thiazolo [3,2-b][2,4]benzodiazepines

712
712

8 Structures Comprising Two Five-membered and Two
Six-membered Rings (5,5,6,6)
Thiazolo [3’,4’- 1,2]pyrazino[7,8-a]benzimidazoles

Benzimidazo [2,1-b]benzothiazole
Naphth[ 1,2-d]imidazo[3,2-b]thiazole
Thiazolo [S ,4-a]carbazoles
Isoindolo[1,2-b]benzothiazoles

712
712
712
713
713
71 3

9 Structures Comprising Two Five-membered, One Sixmembered, and One Seven-membered Ring (5,5,6,7)
Thiazolo [3’,4’-1,2] [1,4]diazepin0[8,9-a]benzimidazoles

714
714


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Contents

xxi

10 Structures Comprising One Five-membered and Three
Six-membered Rings (5,6,6,7)
Thiazolo[5,4-b]- and Thiazol0[4,5-~]-phenothiazine
Thiazolo [4,5-c]acridines
Isoquinolino[3,2-b]benzothiazole
11 Structures Comprising One Five-membered and Four

Six-membered Rings (5,6,6,6,6)
Quinoxalino [2’,3’-4,5]t hiazolo [3,2-a(and b)]quinazolines

714
714
716
716

716
716

Chapter 15 Thiadiazoles and Selenadiazoles
By F. Kurzer
1 Introduction

71 7

2 1,2,3-ThiadiazoIes
Synthesis
Pechmann’s Synthesis
Synthesis from Sulphonyl Azides
0ther React ions
Properties
1,2,3-SeIenadiazoles
Benzo-1,2,3-t hiadiazoles

717
717
717
718

718
718
719
72 1

3 1,2,4-Thiadiazoles
Synthesis
Chemical Properties

72 1
72 1
723
724

1,2,4-ThiadiazoIo[4,3-a]pyridines
4 1,3,4-Thiadiazoles
Synthesis
From Thiosemicarbazides
Cyclization of Acylthiosemicarbazides
From Aminoguanidines and Diaminoguanidines
From Carbonohydrazide
From Thiocarbonohydrazide
From Thiosemicarbazides and (Thio)phosgene
Oxidation of Thiosemicarbazones
Syntheses from Dithiocarbazates
Synthesis from Acylhydrazines
Synthesis from 1-Thiocyanato-2,3-diazabuta1,3dienes

725
725

725
725
725
727
727
730

731
732
733
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xxii

Contents
Synthesis from 1,2-Dithiole-3-thiones
Synthesis from Oxadiazolium Salts
Chemical Properties
Ring Expansion to Thiazines
Miscellaneous Reactions
Biological Properties
Mesionic 1,3,4-Thiadiazoles
Synthesis
Properties
Condensed Ring Systems
1,3,4-Thiadiazoio[3,2-a]pyridines
1,3,4-Thiadiazolo[3,Za]pyrimidines
1,3,4-Thiadiazol0[2,3-c]-1,2,4-triazines

1,3,4-Thiadiazolo[2,3-c]quinazolines

734
734
736
741
741
743
745
745
746
749
749
749
749
749

5 1,3,4-Selenadiazoles

751

6 1,2,5-Thiadiazoles
Condensed Systems incorporating 1,2,SThiadiazole
Benz0-2,1,3-thiadiazoles
1,2,5-Thiadiazolo[3,4-b(and c)]pyridines
1,2,5-Thiadiazolo[3,4-d]pyridazines

752
753
753

755
756

7 1,2,5-Selenadiazoleand Condensed Ring Systems
1,2,5-SeIenadiazolo[3,4,-b(and c)]pyridines
Naph tho [2,3-d]-2,1,3-selenadiazole

756
756
757

Chapter 16 Thiazines
By G. Profa
1 1,2-Thiazines
Simple 1,2-Thiazines
Benzo-l,2-thiazines

758
758
759

2 1,3-Thiazines
Simple 1,3-Thiazines
Benzo-l,3-thiazines

760
760
765

3 1,4-Thiazines

Monocyclic 1,4-Thiazines
Benzo- 1,4-thiazines and Related Compounds
Phenothiazines (Dibenzo- 1,4-thiazines) and Related
Compounds

769
769
77 1
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xxiii

Contents

Chapter 17 Thiazepines and Thiadiazepines
By D. H. Reid
1 1,4-Thiazepines

785

2 Benzothiazepines

788

3 Dibenzothiazepines

793

4 Thiadiazepines

795

Errata

797

Author Index

798