Sulfur Chemistry

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Con ents

Chapter 1 Aliphatic Organosulphur CompoundsCompounds wi th Exocyclic Sulphur Functional Groups,

B y G. C. Barrettand their Selenium and Tellurium Analogues 1

1 Textbooks and Reviews 1

2Spectroscopic and Other Physical Properties

ofOrganosulphur,Organoseleniurn, and Organotelluriurn Compounds 2

Molecular Orbital Calculations and Con formational Analysis

Ultraviolet Spectra, Circular Dichroism, and Optical

Infrared, Raman, and Microwave Spectra

Nuclear Magnetic Resonance Spectra 4

Mass Spectra 6Photoelectron Spectra 7Electron Diffraction 7

Dipole Moments and Studies of the Kerr Effect

X-Ray Crystal Analysis 8Electron Spin Resonance Spectra 8

3 Thiols, Selenols, and TellurolsPreparation 8Reactions 10Thiyl and Related Selenium Radicals

Preparation 13Reactions of Thiolacids and Thiolesters, Selenolesters, and

2

Rotatory Dispersion 33

7

8

134 Thiolesters, Selenolesters, and Telluro lesters 13

Tellurolesters 145 Sulphides, Selenides, and Tellurides 15

Preparation from Thiols, Selenols, and Tellurols

Preparation from Sulphenyl and Selenenyl Halides

Preparation from Disulphides, Diselenides, and Ditellurides

Preparation from Thiocyanates, Selenocyanates, and

Preparation using Other Sulphenyiation, Selenenylation, and

15

1720

Tellurocyanates 2 1

Tellurenylation Reagents 22


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...Vll l Organic Compounds of Sulphur, Selenium, and Tellurium

Preparation using the Elements Themselves, or Other Inorganic

Miscellaneous M ethodsof Preparation 23Reactions of Sulphides: Simple Reactions and Fundam ental

Properties 24Reactions of Sulphides, Selenides, and Tellurides: Rearrange-

ments, an d C- s, C-Se, and C-Te Bond Cleavage Reac tionsReactions of Sulphides, Selenides, and Tellurides: Effects

of Neighbouring Functional Grou ps 27Uses of Saturated Sulphides, Selenides, and Tellurides

in Synthesis 28Vinyl Sulphides, Selenides, and Tellurides

Allenic Sulphides 36Ally1 Sulph ides and Selenides 37Acetylenic Sulphides 38

Sulphur, Selenium, and Tellurium C om pounds 23

25

3 1

6 Naturally Occurring Organosulphur Com poun ds7 Sulphonium Salts 39

Trialkyl- and Triaryl-sulphonium, -selenonium,and -telluronium Salts 39

Halogeno-sulphonium Salts 41

Amino-sulphonium Salts 42Alkoxy-sulphonium Salts 42Alkylthio-sulphonium Salts 43

Analogues 44Saturated Thioacetals and Selenoacetals 44Keten Dithioacetals 46

39

8 Thioacetals [ 1-(Alkylthio)alkyl Sulphides] and their Selenium

9 Trithio-orthoesters [ 1,l-Bis(a1kylthio)alky l Sulphides] 4710 Sulphuranes and Hypervalent Sulphur, Selenium, and Tellurium

1 1 Sulphoxides, Selenoxides, and TelluroxidesCompounds 48

Preparation 49Deoxygenation of Sulphoxides, Selenoxides, and TelluroxidesReactions of Saturated Sulphoxides and SelenoxidesReactions of Unsaturated Sulphoxides and SelenoxidesPhysical Properties and Stereochemistryof Sulphoxides

Preparation of Saturated Sulphones 57Reactions of Saturated Sulphones 58Unsaturated Sulphones 59Sulphones Used in Synthesis 60

Sulphenic and Selenenic Acids

49

5 15 1

5 55 7

12 Sulphones 57

13 Sulphenic and Selenenic Acids, and their Derivatives 6 16 1


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X Organic Compounds of Sulphur, Selenium, and Tellurium

4 Oxy- and Aza-sulphonium Ylides 8 5Oxysulphonium Ylides 85Azasulphonium Ylides 87

5 Thiocarbonyl Ylides 87

6 Sulphenyl Carbanions 89Synthesis and Properties 89

Reactions 90

1,3-Dithianyl Anions 90

Acyclic Thioacetal and Orthothioformate Anions

Thioallyl and Related Anions 97

tr-Thiovinyl Anions 98

Miscellaneous rr-Thiocarbanions 100

94

7 Sulphinyl an d Sulphiliminyl Carbanions 102Synthesis and Properties 102

Reactions 103

Synthesis and Properties 106

Reactions 106

8 Sulphonyl and Sulphonimidoyl Carbanions 106

Par t It Ylides a nd Ca rban ion ic Com pound s of Se len iumand Te l lu r iumB y D. L. J . Clive

Reviews 112I Ylides 1122 Selenium-stabilized Carbanions 1 12

Methods of Preparation 1 12Deprotonation of Aryl Alkyl SelenidesDeprotonation of Selenoketals and Seleno-

Deprotonation of Benzyl SelenidesDeprotonation of Vinyl SelenidesDeprotonation of Allylic, Propargylic,

and Allenic Selenides 115

Deprotonation of Selenides that have anAdditional Anion-stabilizing Group 1 16

Formation by Michael Addition 116

Based on C-Se Bond Cleavage in Selenoketals

Based on Deprotonation of Selenides that have

1 13

orthoesters 1141 1 5

115

Applications of Selenium-stabilized Carbanions 118

and Seleno-orthoesters 118

an Additional Anion-stabilizing Group 12 1

112


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Con ents xi

Based on Deprotonationof Selenoketalsand Seleno-orthoesters 124

Based on Deprotonation of Vinyl SelenidesBased on Deprotonationof Benzyl Selenides

Based on M ichael Addition t o Phenyl Vinyl SelenideBased on a-Lithio-selenoxides 125

Miscellaneous Studies on Selenium-stabilized Carba nions

124124

124

126

Part I l l Compounds wi th S=N Functional GroupsBy S. O ae and N. Furukawa

Introduction 126

Sulphinyl-amines and -amides 127Structure 127Preparation and Reactions 127

Preparation and propertiesof (SN),Tetrasulphur Tetranitride 131Preparation of Other Sulphur Di-imides

Reactions 132Structure 133

Thione S-Im ides 133

Sulphonylamines and Sulphur Tri-imidesSulphimides and Azasulphonium Salts 134

Preparation and Structureof SulphimidesReactions of Sulphimides and Azasulphon ium Salts

Sulphonamidines 140Preparation of Azasulphonium Salts

3 Tetra-co-ordinate Sulphur 143

1 Di-co-ordinate Sulphur 127

Sulphur Di-imides 130130

13 1

2 Tri-co-ord inate Sulphur 13313 3

134136

14 1

Sulphoximides 143Sulphodi-imides 147

4 Selenium and Tellurium Analogues 147

Chapter 3 Thiocarbonyl and Selenocarbonyl CompoundsBy 0. . Hogg, J. K. Landquist, andA. Ohno

Part I Thioaldehydes, Thioketones, Thioketens, andtheir Selenium Analogues

B y A. Ohno

Reviews 148

126

148

148


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x i i Organic Compou nds of Sulphur, Selenium,and Tellurium

1 Thioaldehydes and Selenoaldehydes 148Synthesis 148Tran sient Species 148M ass Spectrometry 150

Mo lecular Or bital Calculations 1502 Thioketones 150

Synthesis 150Reactions I52Spectroscopy 157

Synthesis 158Reactions 159

Spectroscopy 160

3 Thioketens and Selenoketens 158

Part It S u l p h in e s a n d S u l p h e n e sBy D. R. Hogg

160

1 Sulphines 1602 Sulphenes 163

Part I Thioureas , T hiosemicarbazides, Thio am ides , Thiono-and Dithio-carboxylic Acids, and their S elen ium An alog ues

By J . K . Landquist

165

Reviews 165

Synthesis 165Physical Properties 168Reactions I69

1

Thioureas and Selenoureas 165

Oxidation 169Alkylation 169Acyl Derivatives 17 0Additions to Multiple Bonds 170Formation of Thiazoles 172Miscellaneous Rea ctions 17 3

2 Thiosemicarbazides, Dithiocarbazates, andThiocarbohydrazides 174Synthesis 174Physical Properties 174Reactions 175


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Con en s...

Xll l

3 Thioamides and Selenoamides 177Synthesis 177Physical Properties 180Reactions 182

Hydrolysis 182Oxidation 182Alkylation and Arylation 183Nucleophilic Reactionsof the a-C arbo n AtomDiels-Alder an d Similar Reactions 184Additions to a@-U nsaturated Thioamides 185Displacement of Sulphur 185Synthesis of Thiazole Derivatives 186

Synthesis of Other Heterocyclic Com pound sMiscellaneous 189

184

188

4 Thiono- and Dithio-carboxylic Acids, their Derivatives,and their Selenium Analogues 189Synthesis of Derivatives of Thionocarboxylic AcidsSynthesis of Dithiocarboxylic Acids and their D erivativesPhysical Properties 194Reactions 194

Synthesis 197Physical Properties 199Reactions 199

Preparation 203Physical Properties 204Reactions 204

189

19 I

5 Thio- and Dithio-carbamates 197

6 Xanthates and Trithiocarbonates 203

Chapter 4 Small-ring Compounds of Sulphur and Selenium 207B y C. G. Venier

1 Thiirans (Episulphides) 207Reviews 207Formation 207Reactions 2 10

2 Thiiran Oxides (Episulphoxides and Episulphones)3 Thiiranium Ions (Episulphonium Ions)4 Thiirens and Thiiren Oxides 2 165 Three-membered Rings with More than One Heteroatam6 Thietans 219

2 152 15

218

Formation 2 19Reactions 220


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xiv Organic Compounds of Sulphur, Selenium,and Tellurium

7 Thietan Oxides and Imides 222Formation 222Reactions 222

Formation 223Reactions 224

1,2-Dithietans 2241,2-Dithiets 224Formation of 1,3-Dithietans 225Reactions of 1,3-Dithietans 226Selenium Derivatives 226

8 Thiet and its Derivatives 22 3

9 Dithietans, Dithiets, an d their Derivatives 224

10 Four-mem bered Rings containing Sulphur and Oxygen1 1 Four-m em bered Rings containing S ulphu r an d Nitrogen

226

and/or Phosphorus 2271,2-Thiazetidines and their Derivatives 22 71,3-Thiazetidines and their Derivatives 228Othe r Four-membered Rings containing Sulph ur and Nitrog en

1,3,2,4-Dithiadiphosphetans 229Four-mem bered Rings containing Sulphur, Nitrogen,

and Phosphorus 230Selenium Derivatives 23 1

or Germanium 23 1

228

12 Four-membered Ring s containing S ulphu r and Silicon

13 Thiadiazaboretidines 23 114 Bibliography 232

Chapter 5 Saturated Cyclic Compounds of Sulphur,Selenium, and TelluriumBy P. K. Claus

233

I Introduction 2332 Thiolans, Thians, Thiepans, Thiocans, and

their Oxides, Dioxides, a nd ImidesSynthesis 233Properties 242Reactions 247

233

3 Com poun ds containing Tw oor More Sulphur Atomsin the Ring 253Di- and Poly-sulphides 2531,3-Dithiolans, 1,3-Dithians, 1,4-Dithians, an d 1,3,5-TrithiansMedium -sized Dithiacycloalkanes 26 1

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Contents xv

4 Sulphur- and Oxygen-containing RingsSultenes, Sultines, and Sultones 2631,3-Oxathiolans and 1,3- and 1,4-OxathiansCyclic Sulphites and Sulphates 266

Selenium- and Tellurium-containing Rings 268

263

264

Chapter 6 Heteroaromatic Compounds of Sulphur,Selenium, and TelluriumBy M . Davis

27 I

I Introduction 2712 Theoretical and Spectroscopic Studies

Molecular Orbital Calculations 271Nuclear Magnetic Resonance 272

General 273Ring Synthesis and Destruction 273Reactions and Reactivity 276

Rate D ata , Substitutent Effects, and Hamm ettRelationships 277Synthetic Uses of Thiophen Derivatives 277N aphthothiophens, especially Thiapseudop henalenonesThiophen Rings Fused to other Heteroaromatic Systems

27 1

3 Thiophens, Selenophens, and Tellurophens 273

2 78

tha t do not containS, Se, or TeThieno- and Selenolo-pyrroles 278Thienopyridines 278

Polythiophens and Related Systems 279Non-classical Thiophens 28 1Selenophens and Tellurophens 281

4 Thiopyrylium and Selenopyrylium Salts5 Thiazoles and Selenazoles 283

278

282

General 283Mass Spectrometry 283Synthesis and Reactions 273Fused Systems containing Thiazole 284Selenazoles 285

Synthesis 286Reactions 288Isothiazoles Fused to other Nitrogen-containing Heterocycles1,2-Benzisoselenazole nd 1,2-Benzisotellurazole 290

6 Isothiazoles, Isoselenazoles, and Isotellurazoles 286

289


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xvi Organic Compounds of Sulphur, Selenium , and Tellurium

7 Oxathiolium and Dithiolium Salts 290General 290Synthesis 291Physical and Chemical Properties

292Synthesis of Thiadiazoles 292The First S"-N Bond in a Natural Product?Synthesis of Selenadiazoles 293Photolysis and Thermolysisof Thiadiazoles and

29 18 Thiadiazoles and Related Compounds

293

Selenadiazoles 2949 Benzodithiazolium Salts and their Selenium An alogues 295

10 Com pounds with Two Fused Aromatic Rings, each

containing Sulphur or Selenium Atom sThienothiophens and their Selenium AnaloguesThienothiazoles and Selenolothiazoles 296Thienoisothiazoles 297Meso-ionic Thiazolo[2,3-blthiazoles 299

Synthesis 299Structural and Spectroscopic Studies 300

'Bond Switch' at x-Hypervalent Sulphur

296296

11 1,6-Dihetera-6a A4-thiapentalenes and Related Systems 299

301

Author Index 303

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Sulfur Chemistry