Science of Synthesis: Houben-Weyl Methods of Molecular Transformations Vol. 40b (eBook)

Science of Synthesis – Volume 40b: Amine N-Oxides, Haloamines, Hydroxylaminesand Sulfur Analogues, and Hydrazines 1
Title page 3
Imprint 5
Preface 6
Volume Editor's Preface 8
Overview 10
Table of Contents 12
40.2 Product Class 2: Nitroxyl Radicals (Nitroxides) 26
40.2.1 Synthesis of Product Class 2 27
40.2.1.1 Method 1: Oxidation of Amines 27
40.2.1.2 Method 2: Oxidation of Hydroxylamines 28
40.2.1.2.1 Variation 1: From Hydroxylamines 28
40.2.1.2.2 Variation 2: From Nitrones 29
40.2.1.3 Methods 3: Other Methods 29
40.2.2 Applications of Product Class 2 in Organic Synthesis 30
40.2.2.1 Method 1: Alcohol Oxidation 30
40.2.2.2 Method 2: Controlled Radical Polymerization 31
40.2.2.3 Method 3: Radical Carboaminoxylations 32
40.3 Product Class 3: Amine N-Oxides 36
40.3.1 Synthesis of Product Class 3 41
40.3.1.1 Method 1: Reaction of Hydroxylamines with Alkylating Agents 41
40.3.1.2 Method 2: Oxidation of Tertiary Amines 42
40.3.1.2.1 Variation 1: Using Hydrogen Peroxide 43
40.3.1.2.2 Variation 2: Using Alkyl Hydroperoxides 46
40.3.1.2.3 Variation 3: Using Peracids 49
40.3.1.2.4 Variation 4: Using Molecular Oxygen 53
40.3.1.2.5 Variation 5: Using Ozone 53
40.3.1.2.6 Variation 6: Using Oxaziridines 54
40.3.1.2.7 Variation 7: Using Dimethyldioxirane 55
40.3.1.2.8 Variation 8: Using Magnesium Monoperoxyphthalate 56
40.3.1.2.9 Variation 9: Using Hypofluorous Acid--Acetonitrile Complex 56
40.3.1.2.10 Variation 10: Using Biomimetic Hydroperoxides 56
40.3.1.2.11 Variation 11: Using Enzymatic Transformations 58
40.3.1.3 Method 3: Reverse Cope Cyclization 59
40.3.1.4 Method 4: Synthesis of Enamine N-Oxides 66
40.4 Product Class 4: N-Haloamines 74
40.4.1 Product Subclass 1: N-Fluoroamines 75
40.4.1.1 Synthesis of Product Subclass 1 75
40.4.1.1.1 Method 1: Synthesis of N-Fluoroalkanamines 75
40.4.1.1.1.1 Variation 1: From Imines 75
40.4.1.1.1.2 Variation 2: From Amides 76
40.4.1.1.1.3 Variation 3: From Amines 77
40.4.1.1.2 Method 2: Synthesis of Acyclic N-Fluorodialkylamines 78
40.4.1.1.2.1 Variation 1: From Imines 78
40.4.1.1.2.2 Variation 2: From Secondary Amines 78
40.4.1.1.3 Method 3: Synthesis of 1-Fluoroaziridines 79
40.4.1.1.4 Method 4: Synthesis of Higher N-Fluoroazacyclanes 82
40.4.2 Product Subclass 2: N-Chloroamines 82
40.4.2.1 Synthesis of Product Subclass 2 82
40.4.2.1.1 Method 1: Synthesis of N_Chloroalkanamines 82
40.4.2.1.1.1 Variation 1: From Primary Amines Using Chlorine 82
40.4.2.1.1.2 Variation 2: From Primary Amines Using a Metal Hypochlorite 83
40.4.2.1.1.3 Variation 3: From Primary Amines Using tert-Butyl Hypochlorite 84
40.4.2.1.1.4 Variation 4: From Primary Amines Using N-Chlorosuccinimide 84
40.4.2.1.1.5 Variation 5: From N-(Trimethylsilyl)ethanamine 85
40.4.2.1.2 Method 2: Synthesis of Acyclic N-Chlorodialkylamines 85
40.4.2.1.2.1 Variation 1: From Secondary Amines Using Metal Hypochlorites 85
40.4.2.1.2.2 Variation 2: From Secondary Amines Using tert-Butyl Hypochlorite 88
40.4.2.1.2.3 Variation 3: From Secondary Amines Using N-Chloroamides 88
40.4.2.1.2.4 Variation 4: From (Trialkylsilyl)amines 89
40.4.2.1.2.5 Variation 5: From Imines and Alkenes 90
40.4.2.1.2.6 Variation 6: From Aziridines 91
40.4.2.1.3 Method 3: Synthesis of 1-Chloroaziridines 91
40.4.2.1.3.1 Variation 1: Using Chlorine 92
40.4.2.1.3.2 Variation 2: Using a Metal Hypochlorite 92
40.4.2.1.3.3 Variation 3: Using tert-Butyl Hypochlorite 93
40.4.2.1.3.4 Variation 4: Using N-Chlorosuccinimide 96
40.4.2.1.4 Method 4: Synthesis of 1-Chloroazetidines 96
40.4.2.1.5 Method 5: Synthesis of Higher N-Chloroazacyclanes 97
40.4.2.1.5.1 Variation 1: From Azacyclanes Using Chlorine 97
40.4.2.1.5.2 Variation 2: From Azacyclanes Using Hypochlorites 98
40.4.2.1.5.3 Variation 3: From Azacyclanes Using N-Chlorosuccinimide 99
40.4.2.1.5.4 Variation 4: From Cyclic Imines 100
40.4.3 Product Subclass 3: N-Bromoamines 101
40.4.3.1 Synthesis of Product Subclass 3 101
40.4.3.1.1 Method 1: Synthesis of N-Bromoalkanamines 101
40.4.3.1.1.1 Variation 1: Using Bromine 101
40.4.3.1.1.2 Variation 2: Using Sodium Hypobromite 102
40.4.3.1.2 Method 2: Synthesis of Acyclic N-Bromodialkylamines 102
40.4.3.1.2.1 Variation 1: From Secondary Amines 103
40.4.3.1.2.2 Variation 2: From N-Silylamines 103
40.4.3.1.2.3 Variation 3: From Imines 104
40.4.3.1.3 Method 3: Synthesis of 1-Bromoaziridines 104
40.4.3.1.3.1 Variation 1: Using Bromine 104
40.4.3.1.3.2 Variation 2: Using N-Bromosuccinimide 105
40.4.3.1.4 Method 4: Synthesis of 1-Bromoazetidines 106
40.4.3.1.5 Method 5: Synthesis of Higher N-Bromoazacyclanes 106
40.4.3.1.5.1 Variation 1: From Azacyclanes Using Bromine 106
40.4.3.1.5.2 Variation 2: From Azacyclanes Using Hypobromite 106
40.4.3.1.5.3 Variation 3: From Azacyclanes Using N-Bromosuccinimide 107
40.4.3.1.5.4 Variation 4: From Cyclic Imines 107
40.4.3.1.5.5 Variation 5: From Tertiary Cyclic Amines 108
40.4.4 Product Subclass 4: N-Iodoamines 109
40.4.4.1 Synthesis of Product Subclass 4 109
40.4.4.1.1 Method 1: Synthesis of N-Iodoalkanamines 109
40.4.4.1.2 Method 2: Synthesis of Acyclic N-Iododialkylamines 109
40.4.4.1.2.1 Variation 1: From Secondary Amines 109
40.4.4.1.2.2 Variation 2: From N-(Trimethylsilyl)amines 110
40.4.4.1.3 Method 3: Synthesis of Higher N-Iodoazacyclanes 111
40.4.4.1.3.1 Variation 1: From Cyclic Amines 111
40.4.4.1.3.2 Variation 2: From Cyclic Imines 111
40.5 Product Class 5: Hydroxylamines 118
40.5.1 Product Subclass 1: Acyclic N-Alkylhydroxylamines, N,N-Dialkylhydroxylamines, and Alkoxyammonium Salts 118
40.5.1.1 Synthesis of Product Subclass 1 118
40.5.1.1.1 Acyclic N-Alkylhydroxylamines 118
40.5.1.1.1.1 Method 1: Alkylation of Hydroxylamines 118
40.5.1.1.1.1.1 Variation 1: Direct Alkylation of Hydroxylamine 118
40.5.1.1.1.1.2 Variation 2: Alkylation of O,N-Diprotected Hydroxylamines 120
40.5.1.1.1.1.3 Variation 3: Alkylation of N-(Benzyloxy)-4-toluenesulfonamide 122
40.5.1.1.1.1.4 Variation 4: Addition to Multiple Bonds 123
40.5.1.1.1.1.5 Variation 5: Alkylation of Ethyl 3-Methyl-5-oxo-2,5-dihydroisoxazole-4-carboxylate 123
40.5.1.1.1.2 Method 2: Reduction of Oximes 124
40.5.1.1.1.2.1 Variation 1: Using Borohydride or Cyanoborohydride 124
40.5.1.1.1.2.2 Variation 2: Using Pyridine--Borane 129
40.5.1.1.1.2.3 Variation 3: Using Diborane 131
40.5.1.1.1.2.4 Variation 4: Using Borane--Trialkylamines 131
40.5.1.1.1.3 Method 3: Reaction of Organometallic Reagents with Oximes 132
40.5.1.1.1.3.1 Variation 1: Addition of Organolithium Reagents to Oximes 132
40.5.1.1.1.3.2 Variation 2: Addition of Organomagnesium Reagents to Oximes 132
40.5.1.1.1.3.3 Variation 3: Reaction of O-Trimethylsilyl Oxime Ethers with Ketene Acetals 133
40.5.1.1.1.3.4 Variation 4: Addition of Allylboronates to Oximes 134
40.5.1.1.1.4 Method 4: Synthesis from Nitrones and Organometallic Reagents 134
40.5.1.1.1.5 Method 5: Alkylation of Oximes 136
40.5.1.1.1.6 Method 6: Synthesis from O-Benzylhydroxylamines 137
40.5.1.1.1.7 Method 7: Synthesis from a-Chloro-a-nitroso Compounds 137
40.5.1.1.1.8 Method 8: Reduction of Nitroalkanes 140
40.5.1.1.1.8.1 Variation 1: By Catalytic Hydrogenation 140
40.5.1.1.1.8.2 Variation 2: Using Diborane or Borohydrides 140
40.5.1.1.1.8.3 Variation 3: Using Aluminum Amalgam 141
40.5.1.1.1.8.4 Variation 4: Using Zinc 142
40.5.1.1.1.8.5 Variation 5: Using Tin(II) Compounds 142
40.5.1.1.1.8.6 Variation 6: Using Samarium(II) Iodide 143
40.5.1.1.1.8.7 Variation 7: Using Sodium Dithionite 143
40.5.1.1.1.8.8 Variation 8: By Electrochemical Reduction 144
40.5.1.1.1.8.9 Variation 9: By Palladium-Catalyzed Hydrogenation with Triethylsilane 145
40.5.1.1.1.9 Method 9: Synthesis from Nitroso Compounds 145
40.5.1.1.1.10 Method 10: Oxidation of Primary Amines 146
40.5.1.1.1.10.1 Variation 1: Using Peroxy Acids or Peroxy Acid Anhydrides 146
40.5.1.1.1.10.2 Variation 2: Using Hydrogen Peroxide and Sodium Tungstate 147
40.5.1.1.1.10.3 Variation 3: Using Oxone/Silica Gel 148
40.5.1.1.1.10.4 Variation 4: Using Dimethyldioxirane 149
40.5.1.1.1.11 Method 11: Hydrolysis of Oxaziridines 149
40.5.1.1.2 N,N-Dialkylhydroxylamines 150
40.5.1.1.2.1 Method 1: Alkylation of Hydroxylamines 151
40.5.1.1.2.1.1 Variation 1: Using Alkyl Halides 151
40.5.1.1.2.1.2 Variation 2: By Alkylation--Hydrogenolysis of N-Alkyl-O-benzylhydroxylamines 151
40.5.1.1.2.1.3 Variation 3: Using Organosulfonic Acid Esters 152
40.5.1.1.2.1.4 Variation 4: By Addition of N-Alkylhydroxylamines to Activated Double Bonds 153
40.5.1.1.2.1.5 Variation 5: By Reaction of N-Alkylhydroxylamines with Epoxides 155
40.5.1.1.2.1.6 Variation 6: By Reaction of N,N-Bis(benzotriazol-1-ylmethyl)hydroxylamine with Organometallic Reagents 156
40.5.1.1.2.1.7 Variation 7: By Palladium(0)-Catalyzed Hydroxyamination of Allyl Esters 156
40.5.1.1.2.1.8 Variation 8: By Cyclic Alkylation of N-(Pent-4-enyl)hydroxylamines 157
40.5.1.1.2.1.9 Variation 9: From N-Substituted Hydroxylamines and Sugar Derivatives 157
40.5.1.1.2.2 Method 2: Reduction of N-Hydroxyimides and N-Hydroxylactams 159
40.5.1.1.2.3 Method 3: Reductive Alkylation of Oximes with Carboxylic Acids 159
40.5.1.1.2.4 Method 4: Reduction of Nitrones 160
40.5.1.1.2.4.1 Variation 1: Using Complex Metal Hydrides 160
40.5.1.1.2.4.2 Variation 2: Using Trichlorosilane 161
40.5.1.1.2.4.3 Variation 3: By Asymmetric Hydrogenation Using Iridium Catalysts 161
40.5.1.1.2.4.4 Variation 4: By Asymmetric Hydrosilylation with a Ruthenium(II)--Phosphine Complex Catalyst 162
40.5.1.1.2.5 Method 5: Synthesis from Nitrones and Organometallic Reagents 162
40.5.1.1.2.6 Method 6: Synthesis from Nitrones Using Vinylboronic Esters and Dimethylzinc 171
40.5.1.1.2.7 Method 7: Addition of Organometallic Reagents to Organic Nitro Compounds 171
40.5.1.1.2.8 Method 8: Pyrolysis of Tertiary Amine Oxides 172
40.5.1.1.2.9 Method 9: Rearrangement of O-Allyl-N-benzylhydroxylamines 175
40.5.1.1.2.10 Method 10: Oxidation of Secondary Amines 176
40.5.1.1.2.10.1 Variation 1: Using Dibenzoyl Peroxide 176
40.5.1.1.2.10.2 Variation 2: By Catalytic Oxidation with Hydrogen Peroxide 177
40.5.1.1.2.10.3 Variation 3: Using Dimethyldioxirane 177
40.5.1.1.2.10.4 Variation 4: Using Oxone 178
40.5.1.1.2.11 Method 11: Samarium(II) Iodide Induced Reductive Cross Coupling of Nitrones with Aldehydes and Ketones 178
40.5.1.1.3 N-Alkoxyammonium Salts 179
40.5.1.1.3.1 Method 1: Alkylation of Tertiary Amine Oxides with Haloalkanes 179
40.5.1.1.3.2 Method 2: Alkylation of Tertiary Amine Oxides with Sultones or Glycolo Sulfites 180
40.5.1.1.3.3 Method 3: Alkylation of O,N,N-Trisubstituted Hydroxylamines with Haloalkanes 181
40.5.1.1.3.4 Method 4: Alkylation of O,N,N-Trisubstituted Hydroxylamines with Methyl Trifluoromethanesulfonate 182
40.5.1.1.3.5 Method 5: Exhaustive Methylation of O-Alkylhydroxylamines 183
40.5.1.1.3.6 Method 6: Synthesis from 3-(Bromomethyl)-3-phenyl-1,2-dioxetane and Tertiary Amines 183
40.5.2 Product Subclass 2: Acyclic O-Alkyl-, O,N-Dialkyl-, and Trialkylhydroxylamines 184
40.5.2.1 Synthesis of Product Subclass 2 184
40.5.2.1.1 Acyclic O-Alkylhydroxylamines 184
40.5.2.1.1.1 Method 1: Synthesis from O-Alkyloximes 184
40.5.2.1.1.2 Method 2: Synthesis from O-Alkyl Hydroxamates 187
40.5.2.1.1.3 Method 3: Synthesis from Cyclic N-Hydroxyimides by Alkylation with Organic Halides 188
40.5.2.1.1.4 Method 4: Synthesis from Cyclic N-Hydroxyimides by Alkylation with Alcohols 199
40.5.2.1.1.5 Method 5: Synthesis from N-Hydroxycarbamates 208
40.5.2.1.1.6 Method 6: Synthesis from Ethyl N-Hydroxyimidates 211
40.5.2.1.1.7 Method 7: Electrophilic Amination of Alkoxides 213
40.5.2.1.1.8 Method 8: Synthesis from Hydroxylamine-N,N-disulfonic Acid 215
40.5.2.1.2 Acyclic O,N-Dialkylhydroxylamines 216
40.5.2.1.2.1 Method 1: Alkylation of Hydroxylamine 217
40.5.2.1.2.2 Method 2: Alkylation of O-Alkylhydroxylamines 217
40.5.2.1.2.3 Method 3: Alkylation of N-Alkoxycarbamates 219
40.5.2.1.2.4 Method 4: Alkylation of Hydroxamic Acids 222
40.5.2.1.2.5 Method 5: Alkylation of N-Alkoxyureas 223
40.5.2.1.2.6 Method 6: Alkylation of O-Benzyl-N-(diethoxyphosphoryl)hydroxylamine 223
40.5.2.1.2.7 Method 7: Synthesis from Quaternized Oximes 224
40.5.2.1.2.8 Method 8: Reduction of Oxime Ethers 225
40.5.2.1.2.9 Method 9: Carbon Radical Addition to Aldoxime Ethers 229
40.5.2.1.2.10 Method 10: Addition of Organometallic Reagents to Oxime Ethers 230
40.5.2.1.2.11 Method 11: Oxidation of Tertiary Alkyl Lithium Amides with tert-Butyl Peroxybenzoate 233
40.5.2.1.2.12 Method 12: Electroreductive Coupling of Ketones with Oxime Ethers 233
40.5.2.1.3 O,N,N-Trialkylhydroxylamines 234
40.5.2.1.3.1 Method 1: Alkylation of O-Alkylhydroxylamines 234
40.5.2.1.3.2 Method 2: Alkylation of O,N-Dialkylhydroxylamines 235
40.5.2.1.3.3 Method 3: Alkylation of N,N-Dialkylhydroxylamines 236
40.5.2.1.3.4 Method 4: Reductive Alkylation of O,N-Dialkylhydroxylamines with Ketones or Aldehydes 237
40.5.2.1.3.5 Method 5: Addition of Carbon Radicals to Nitroxides 239
40.5.2.1.3.6 Method 6: Synthesis from Tertiary Amine Oxides by Meisenheimer Rearrangement 241
40.5.2.1.3.7 Method 7: Synthesis from 2,2-Disubstituted Isoxazolidinium Salts 244
40.5.2.1.3.8 Method 8: Synthesis from Acyclic Oxyiminium Ions 244
40.5.2.1.3.9 Method 9: Reduction of Weinreb Amides 245
40.5.2.1.3.10 Method 10: Direct Amination of Alkenes 246
40.6 Product Class 6: 1-Oxa-2-azacycloalkanes 264
40.6.1 Synthesis of Product Class 6 264
40.6.1.1 Method 1: Synthesis from Hydroxylamine and 2,4-Dibromo-2,4-dimethylpentan-3-one 264
40.6.1.2 Method 2: Intramolecular Cyclization of N-Alkylhydroxylamines 264
40.6.1.3 Method 3: Synthesis from Phorone with Hydroxylamine 265
40.6.1.4 Method 4: Alkylation of Alkyl N-Hydroxycarbamates 265
40.6.1.5 Method 5: Synthesis from N-Hydroxyphthalimide 267
40.6.1.6 Method 6: Synthesis from Benzohydroxamic Acid 269
40.6.1.7 Method 7: Synthesis from N-Allylhydroxylamines 270
40.6.1.8 Method 8: Synthesis from N-Homoallylic Hydroxylamines 270
40.6.1.9 Method 9: Synthesis from O-Allylic Hydroxylamines 271
40.6.1.10 Method 10: Synthesis from O-Homoallylic Hydroxylamines 272
40.6.1.11 Method 11: Synthesis from N-Alka-2,3-dienylhydroxylamines 273
40.6.1.12 Method 12: Synthesis from O-Allyloximes by Selenocyclization 274
40.6.1.13 Method 13: Ring-Closing Metathesis of N,O-Dialkenyl-Substituted Hydroxylamines 275
40.6.1.14 Method 14: Reduction of 5,6-Dihydro-4H-1,2-oxazines 278
40.6.1.15 Method 15: Reduction of 4,5-Dihydroisoxazolium Tetrafluoroborates 279
40.6.1.16 Method 16: Boron Trifluoride Assisted Alkylation of 4,5-Dihydroisoxazoles 279
40.6.1.17 Method 17: Synthesis from 5,6-Dihydro-4H-oxazinium Salts 280
40.6.1.18 Method 18: Allylation of Isoxazolidin-5-ols 281
40.6.1.19 Method 19: Synthesis from Organonitroso Compounds by Cycloaddition 281
40.6.1.19.1 Variation 1: Synthesis from Perfluoronitrosoalkanes 281
40.6.1.19.2 Variation 2: Synthesis from Acylnitroso Compounds 282
40.6.1.19.3 Variation 3: Synthesis from a-Chloronitroso Compounds 286
40.6.1.20 Method 20: Rearrangement of Cyclic N-Oxides (Meisenheimer Rearrangement) 288
40.6.1.21 Method 21: Synthesis from Nitrones by 1,3-Dipolar Cycloaddition 292
40.6.1.21.1 Variation 1: Synthesis from Achiral Nitrones 292
40.6.1.21.2 Variation 2: Synthesis from Chiral Nitrones 300
40.6.1.21.3 Variation 3: Addition of Lithiated Methoxyallene to Chiral Nitrones 302
40.6.1.21.4 Variation 4: In Situ Conversion of Oximes into Nitrones Followed by 1,3-Cycloaddition 303
40.6.1.21.5 Variation 5: Palladium-Catalyzed Allene Insertion Coupled with Nitrone 1,3-Dipolar Cycloaddition 305
40.6.1.21.6 Variation 6: Synthesis from Nitrones via [3 + 3] Dipolar Cycloaddition with Cyclopropane-1,1-dicarboxylates 305
40.6.1.22 Method 22: Synthesis from Nitrones and a-Lithiated Aryloxiranes 307
40.6.1.23 Method 23: Synthesis from Nitrones and Lithiated 2-(1-Chloroethyl)-4,5-dihydrooxazoles 308
40.6.1.24 Method 24: Synthesis from Oxaziridines and Alkenes 309
40.7 Product Class 7: Hydrazines and Hydrazinium Salts 314
40.7.1 Product Subclass 1: Acyclic Alkylhydrazines 314
40.7.1.1 Synthesis of Product Subclass 1 316
40.7.1.1.1 Method 1: Direct Substitution (Alkylation) of Free Hydrazine and Alkylhydrazines 316
40.7.1.1.1.1 Variation 1: Using Alkyl Halides 317
40.7.1.1.1.2 Variation 2: Using Alcohols 318
40.7.1.1.1.3 Variation 3: Using Cyclic Carboxylates (Lactones) 318
40.7.1.1.1.4 Variation 4: Using Alkyl Sulfonates 319
40.7.1.1.1.5 Variation 5: Using Sultones 320
40.7.1.1.1.6 Variation 6: Using Dialkyl Sulfates 320
40.7.1.1.1.7 Variation 7: Using Oxiranes 321
40.7.1.1.1.8 Variation 8: Using Thiiranes 322
40.7.1.1.1.9 Variation 9: Using Aziridines 322
40.7.1.1.1.10 Variation 10: Using Sulfones 323
40.7.1.1.1.11 Variation 11: Using Alkylamines 324
40.7.1.1.1.12 Variation 12: Using Diazenolates 325
40.7.1.1.2 Method 2: Substitution of Protected Hydrazines 325
40.7.1.1.2.1 Variation 1: Alkylation of Hydrazones 326
40.7.1.1.2.2 Variation 2: Alkylation of Hydrazides 326
40.7.1.1.2.3 Variation 3: Reductive Alkylation of Hydrazides 328
40.7.1.1.2.4 Variation 4: Alkylation of Azines 328
40.7.1.1.2.5 Variation 5: Alkylation of tert-Butyl Isopropylidenehydrazinecarboxylate 329
40.7.1.1.2.6 Variation 6: Alkylation of P,P-Diphenylphosphinic Hydrazide 331
40.7.1.1.2.7 Variation 7: Alkylation of Di-tert-butyl Hydrazine-1,2-dicarboxylate 332
40.7.1.1.2.8 Variation 8: Alkylation of Tri-tert-butyl Hydrazine-1,1,2-tricarboxylate 334
40.7.1.1.2.9 Variation 9: Alkylation of Orthogonally Triprotected Hydrazines 335
40.7.1.1.3 Method 3: Addition of Hydrazines to Activated Alkenes 336
40.7.1.1.4 Method 4: Reduction of Hydrazones 339
40.7.1.1.4.1 Variation 1: Catalytic Hydrogenation 339
40.7.1.1.4.2 Variation 2: Using Complex Hydrides 340
40.7.1.1.5 Method 5: Reduction of Azines 342
40.7.1.1.5.1 Variation 1: Catalytic Hydrogenation 342
40.7.1.1.5.2 Variation 2: Using Metals 343
40.7.1.1.5.3 Variation 3: Using Complex Hydrides 343
40.7.1.1.6 Method 6: Reduction of Hydrazides 344
40.7.1.1.7 Method 7: Addition of Organometallic Compounds to Hydrazones (C-Alkylation) 346
40.7.1.1.7.1 Variation 1: Using Grignard Reagents 346
40.7.1.1.7.2 Variation 2: Using Aryllithium Reagents 347
40.7.1.1.7.3 Variation 3: Stereoselective Addition of Organometallic Compounds 347
40.7.1.1.7.4 Variation 4: Stereoselective Addition of Radicals 349
40.7.1.1.8 Method 8: Reductive Coupling of Phenylhydrazones 349
40.7.1.1.9 Method 9: Amination of Amines 350
40.7.1.1.9.1 Variation 1: Using N-Chloro(alkyl)amines with Amines and Metalated Amines 350
40.7.1.1.9.2 Variation 2: Using Hydroxylamine-O-sulfonic Acids 352
40.7.1.1.9.3 Variation 3: Using Oxaziridines 352
40.7.1.1.10 Method 10: Amination of Amines via Diaziridines 353
40.7.1.1.10.1 Variation 1: Using Hydroxylamine-O-sulfonic Acid 353
40.7.1.1.10.2 Variation 2: Using Hypochlorite 354
40.7.1.1.11 Method 11: Synthesis from Ureas 355
40.7.1.1.12 Method 12: Synthesis from N-Alkylsulfamides 356
40.7.1.1.13 Method 13: Synthesis from Phosphonic Acid Diamides 357
40.7.1.1.14 Method 14: Tetraalkylhydrazines by Anodic Oxidation of Secondary Amine Anions 357
40.7.1.1.15 Method 15: Hydrolysis of Nitrogen Heterocycles 357
40.7.1.1.15.1 Variation 1: Of Dihydropyrazolium Compounds 358
40.7.1.1.15.2 Variation 2: Of Pyrazolidin-3-ones 358
40.7.1.1.15.3 Variation 3: Of Diaziridines 359
40.7.1.1.15.4 Variation 4: Of Diaziridinones 360
40.7.1.1.15.5 Variation 5: Of Sydnones 361
40.7.1.1.16 Method 16: Hydrolysis of Alkylhydrazones 361
40.7.1.1.17 Method 17: Hydrolysis of Acylated Alkylhydrazines 362
40.7.1.1.18 Method 18: 1,1-Dialkylhydrazines by Reduction of Dialkylnitrosamines 362
40.7.1.1.18.1 Variation 1: Using Catalytic Hydrogenation 362
40.7.1.1.18.2 Variation 2: Using Metals 363
40.7.1.1.18.3 Variation 3: Using Complex Hydrides 364
40.7.1.1.18.4 Variation 4: Using Metal Salts 365
40.7.1.1.18.5 Variation 5: Using Sodium Bisulfite 365
40.7.1.1.18.6 Variation 6: Electrochemical Reduction 365
40.7.1.1.19 Method 19: Monoalkylhydrazines by Reduction of N-Alkyl-N-nitrosoureas 366
40.7.1.1.20 Method 20: Monoalkylhydrazines by Reduction of N-Nitrosoamides 366
40.7.1.1.21 Method 21: Monoalkylhydrazines by Reduction of N-Alkyl-N-nitrosohydroxylamines 367
40.7.1.1.22 Method 22: 1,2-Dialkylhydrazines by Reduction of Dialkyldiazenes 368
40.7.1.1.23 Method 23: Trialkylhydrazines from 1,1,1-Trialkylhydrazinium Salts 368
40.7.1.1.24 Method 24: Tetraalkylhydrazines by Thermolysis of Tetraaz-2-enes 369
40.7.1.1.25 Method 25: Addition of Organometallic Compounds to Azodicarboxylic Esters (N-Alkylation) 370
40.7.1.1.26 Method 26: Synthesis from Dialkylnitrosamines and Grignard Reagents 370
40.7.1.1.27 Method 27: Synthesis from N-Phthalimidoaziridines 370
40.7.1.1.28 Method 28: Addition to Azodicarboxylic Esters 371
40.7.1.1.29 Method 29: Synthesis from 1-Aminoaziridines 372
40.7.1.1.30 Method 30: Oxidative Coupling of Amines 373
40.7.1.2 Applications of Product Subclass 1 in Organic Synthesis 373
40.7.2 Product Subclass 2: Hydrazinium Salts 374
40.7.2.1 Synthesis of Product Subclass 2 374
40.7.2.1.1 Method 1: Alkylation of Hydrazines and Alkylhydrazines 374
40.7.2.1.1.1 Variation 1: Using Alkyl Halides 374
40.7.2.1.1.2 Variation 2: Using Dialkyl Sulfates or Alkyl Sulfonates 375
40.7.2.1.2 Method 2: Amination of Tertiary Amines 376
40.7.2.1.2.1 Variation 1: Using N-Chloro(alkyl)amines 376
40.7.2.1.2.2 Variation 2: Using Hydroxylamine-O-sulfonic Acids 377
40.7.2.1.3 Method 3: Dicationic Hydrazinium Compounds by Protonation of Hydrazinium Compounds 378
40.7.2.1.4 Method 4: Dicationic Hydrazinium Compounds by Alkylation of Hydrazinium Compounds 379
40.7.2.1.5 Method 5: Ammoniumimines by Deprotonation of Hydrazinium Compounds 379
40.7.2.1.6 Method 6: (Ammonium)acylimines from 1,1-Dialkylhydrazines 380
40.7.2.1.6.1 Variation 1: Using Oxiranes and Carboxylic Acid Esters 380
40.7.2.1.6.2 Variation 2: Using Acyl Halides and Alkyl Halides 380
40.7.2.1.7 Method 7: (Ammonium)acylimines from 1,1,1-Trialkylhydrazinium Compounds 382
40.7.2.1.7.1 Variation 1: Using Acyl Halides 382
40.7.2.1.7.2 Variation 2: Acylation of (Trialkylammonium)imines--Bis(tert-butyl alcohol) Adducts 383
40.7.2.1.8 Method 8: (Ammonium)cyanoimines from Trialkylamines 384
40.7.2.1.9 Method 9: Synthesis of Hydrazinium C,N-Betaines 384
40.7.2.2 Applications of Product Subclass 2 in Organic Synthesis 385
40.8 Product Class 8: 1,2-Diazacycloalkanes 392
40.8.1 Synthesis of Product Class 8 393
40.8.1.1 Method 1: Alkylation of Hydrazines 393
40.8.1.1.1 Variation 1: Alkylation with Haloalkanes 393
40.8.1.1.2 Variation 2: Alkylation with Alkanesulfonates 396
40.8.1.1.3 Variation 3: Alkylation with Epoxides 397
40.8.1.2 Method 2: Cyclization of N-Chloroalkanamines 399
40.8.1.3 Method 3: Reduction of N==N Bonds 399
40.8.1.4 Method 4: Reduction of C==N and C==O Bonds 400
40.8.1.4.1 Variation 1: Reduction of Hydrazones and Azines 400
40.8.1.4.2 Variation 2: Reduction of N-Acylhydrazines and N-Acylhydrazones 401
40.8.1.4.3 Variation 3: Reductive Amination 405
40.8.1.5 Method 5: Reductive Alkylation of Azo Compounds 405
40.8.1.6 Method 6: Reductive a-Aminoalkylation 405
40.8.1.7 Method 7: Reduction of Dialkyl Nitrosamines 410
40.8.1.8 Method 8: Synthesis by Cycloaddition 411
40.8.1.8.1 Variation 1: [4 + 2] Cycloadditions of Azo Compounds 411
40.8.1.8.2 Variation 2: [3 + 2] Cycloadditions 415
40.8.1.8.3 Variation 3: Criss-Cross [3 + 2] Cycloadditions 422
40.8.1.9 Method 9: Addition of Organometallic Reagents to N==N Bonds 424
40.8.1.10 Method 10: Addition of Organometallic Reagents to C==N Bonds 425
40.8.1.11 Method 11: Addition of Hydrazines to Activated Alkenes 426
40.8.1.12 Method 12: Diazenium Cyclization 426
40.8.1.13 Method 13: Alkene Metathesis 427
40.9 Product Class 9: Triazanes and Tetrazanes 434
40.9.1 Synthesis of Product Class 9 434
40.9.1.1 Method 1: Synthesis of Triazanes by Addition of Amines to Azo Compounds 434
40.9.1.2 Method 2: Synthesis of Triazanes by Ring Opening of Oxaziridines with Hydrazines 435
40.9.1.3 Method 3: Synthesis of Triaziridines and Heteroatom Analogues 436
40.9.1.4 Method 4: Synthesis of Tetrazanes 437
40.10 Product Class 10: Amido Derivatives of Sulfanediol 440
40.10.1 Product Subclass 1: Alkylaminesulfenyl Halides 440
40.10.1.1 Synthesis of Product Subclass 1 440
40.10.1.1.1 Method 1: Synthesis of Alkylaminesulfenyl Fluorides by Halide Exchange 440
40.10.1.1.2 Method 2: Synthesis of Alkylaminesulfenyl Chlorides 441
40.10.1.1.2.1 Variation 1: Using Sulfur Dichloride 441
40.10.1.1.2.2 Variation 2: By Chlorination of the Corresponding Diamino Disulfides 441
40.10.1.1.3 Method 3: Synthesis of Alkylaminesulfenyl Bromides and Alkylaminesulfenyl Iodides 442
40.10.1.1.3.1 Variation 1: By Bromination of Bis(dialkylamino) Disulfides 442
40.10.1.1.3.2 Variation 2: By Halide Exchange 443
40.10.1.2 Applications of Product Subclass 1 in Organic Synthesis 443
40.10.2 Product Subclass 2: Bis(alkylamino) Disulfides and Polysulfides 444
40.10.2.1 Synthesis of Product Subclass 2 444
40.10.2.1.1 Method 1: Synthesis of Bis(alkylamino) Disulfides 444
40.10.2.1.2 Method 2: Synthesis of Bis(alkylamino) Trisulfides 445
40.10.3 Product Subclass 3: Bis[(alkylamino)sulfanyl]amines 446
40.10.3.1 Synthesis of Product Subclass 3 446
40.10.4 Product Subclass 4: Bis(alkylamino) Sulfides 446
40.10.4.1 Synthesis of Product Subclass 4 447
40.10.4.1.1 Method 1: Synthesis of Bis(alkylamino) Sulfides from N-Alkylaminesulfenyl Chlorides 447
40.11 Product Class 11: Amido Derivatives of Sulfurous Acid 450
40.11.1 Product Subclass 1: (Alkylamino)sulfinyl Halides, (Alkylamino)sulfur Trifluorides, and Bis(alkylamino)sulfur Difluorides 450
40.11.1.1 Synthesis of Product Subclass 1 450
40.11.1.1.1 Method 1: Synthesis of (Alkylamino)sulfinyl Fluorides from Thionyl Fluoride 450
40.11.1.1.2 Method 2: Synthesis of (Alkylamino)sulfinyl Chlorides from Thionyl Chloride 451
40.11.1.1.3 Method 3: Synthesis of (Alkylamino)sulfinyl Bromides from Thionyl Bromide 452
40.11.1.1.4 Method 4: Synthesis of (Alkylamino)sulfur Trifluorides from Sulfur Tetrafluoride 452
40.11.1.1.5 Method 5: Synthesis of Bis(dialkylamino)sulfur Difluorides from (Alkylamino)sulfur Trifluorides 453
40.11.1.2 Applications of Product Subclass 1 in Organic Synthesis 453
40.11.2 Product Subclass 2: N-Alkylamidosulfurous Acids 455
40.11.2.1 Synthesis of Product Subclass 2 455
40.11.3 Product Subclass 3: N,N'-Sulfinyldiamines (N,N'-Dialkylsulfurous Diamides) 455
40.11.3.1 Synthesis of Product Subclass 3 455
40.11.3.1.1 Method 1: Synthesis by Reaction of Amines with Thionyl Chloride 455
40.11.4 Product Subclass 4: N-Sulfinylalkanamines 456
40.11.4.1 Synthesis of Product Subclass 4 456
40.11.4.1.1 Method 1: Synthesis from Thionyl Chloride 456
40.11.4.2 Applications of Product Subclass 4 in Organic Synthesis 458
40.11.5 Product Subclass 5: N-Thiosulfinylalkanamines 459
40.11.5.1 Synthesis of Product Subclass 5 459
40.11.5.1.1 Method 1: Synthesis via Reaction of Anilines with Disulfur Dichloride 459
40.11.6 Product Subclass 6: N,N'-Dialkylsulfur Diimides 460
40.11.6.1 Synthesis of Product Subclass 6 460
40.11.6.1.1 Method 1: Synthesis of N,N'-Bis(methoxycarbonyl)sulfur Diimide 460
40.11.6.1.2 Method 2: Synthesis of N,N'-Dialkylsulfur Diimides from Sulfur Tetrafluoride 461
40.11.6.1.3 Method 3: Synthesis of N,N'-Diarylsulfur Diimides via Amidosulfur Dichlorides 462
40.11.6.2 Applications of Product Subclass 6 in Organic Synthesis 462
40.12 Product Class 12: N-Alkylsulfamic Acids and Derivatives 466
40.12.1 Product Subclass 1: N-Alkylsulfamoyl Halides 466
40.12.1.1 Synthesis of Product Subclass 1 466
40.12.1.1.1 Method 1: Synthesis of N-Alkylsulfamoyl Fluorides 466
40.12.1.1.1.1 Variation 1: From Amines and Sulfuryl Fluoride 466
40.12.1.1.1.2 Variation 2: From Amines and Sulfuryl Chloride Fluoride 467
40.12.1.1.1.3 Variation 3: From N-Alkylsulfamoyl Chlorides 467
40.12.1.1.2 Method 2: Synthesis of N-Alkylsulfamoyl Chlorides 468
40.12.1.1.2.1 Variation 1: From N-Alkylsulfamic Acids and Phosphorus Pentachloride 468
40.12.1.1.2.2 Variation 2: From Amines and Sulfuryl Chloride 468
40.12.1.1.3 Method 3: Synthesis of N-Alkylsulfamoyl Bromides 469
40.12.2 Product Subclass 2: N-Alkylsulfamic Acids 470
40.12.2.1 Synthesis of Product Subclass 2 470
40.12.2.1.1 Method 1: Synthesis from Amines and Chlorosulfonic Acid 470
40.12.2.1.2 Method 2: Synthesis by Aminolysis of Amine--Sulfur Trioxide Complexes 471
40.12.2.1.3 Method 3: Synthesis from Isocyanates and Sulfuric Acid 471
40.12.2.1.4 Method 4: Synthesis by Hydrolysis of Aryl Sulfamates 472
40.12.2.1.5 Method 5: Synthesis from N-Alkylsulfamoyl Chlorides 473
40.12.2.1.6 Method 6: Synthesis by Hydrolysis of Sulfamoyl Azides 473
40.12.3 Product Subclass 3: N-Alkylsulfamides 473
40.12.3.1 Synthesis of Product Subclass 3 474
40.12.3.1.1 Method 1: Synthesis of Linear Sulfamides 474
40.12.3.1.1.1 Variation 1: From N-Alkylsulfamoyl Chlorides 474
40.12.3.1.1.2 Variation 2: From N-Alkylsulfamic Acid Esters 474
40.12.3.1.1.3 Variation 3: From Chlorosulfonyl Isocyanate 475
40.12.3.1.1.4 Variation 4: From N-Sulfamoyloxazolidinone Derivatives 476
40.12.3.1.1.5 Variation 5: From Sulfamide and Amines 478
40.12.3.1.2 Method 2: Synthesis of Cyclic Sulfamides 478
40.12.3.1.2.1 Variation 1: From Amino Alcohols with Burgess-Type Reagents 478
40.12.3.1.2.2 Variation 2: From Linear Sulfamides and Alkenes 480
40.12.3.1.2.3 Variation 3: From N,N-Dimethylsulfamoylaziridines and Amines 482
40.12.3.1.2.4 Variation 4: From a-Amino Acid Esters and Sulfamide 483
40.13 Product Class 13: Ammoniumsulfonates, Thiohydroxylamines, and Aminosulfonium Salts 486
Keyword Index 490
Author Index 520
Abbreviations 552