Science of Synthesis: Houben-Weyl Methods of Molecular Transformations Vol. 41 (eBook)

Science of Synthesis – Volume 41: Nitro, Nitroso, Azo, Azoxy, and Diazonium Compounds, Azides, Triazenes, and Tetrazenes 1
Title page 3
Imprint 5
Preface 6
Volume Editor’s Preface 8
Overview 10
Table of Contents 12
Introduction 32
41.1 Product Class 1: Nitroalkanes 40
41.1.1 Synthesis of Product Class 1 40
41.1.1.1 Synthesis by Substitution 40
41.1.1.1.1 Method 1: Substitution of Hydrogen Using Nitric Acid 40
41.1.1.1.1.1 Variation 1: Using Dilute Nitric Acid 40
41.1.1.1.1.2 Variation 2: Using Concentrated or Fuming Nitric Acid 41
41.1.1.1.1.3 Variation 3: Using Nitric Acid with Sulfuric Acid 43
41.1.1.1.1.4 Variation 4: Using Nitric Acid with Acetic Acid 44
41.1.1.1.1.5 Variation 5: Using Nitric Acid in Ionic Liquids 44
41.1.1.1.1.6 Variation 6: Using Nitric Acid in the Gas Phase 44
41.1.1.1.1.7 Variation 7: Using Nitric Acid with Oxygen and Halogens in the Gas Phase 45
41.1.1.1.2 Method 2: Substitution of Hydrogen Using Metal Nitrates 46
41.1.1.1.2.1 Variation 1: Using Copper(II) or Manganese(II) Nitrates 46
41.1.1.1.2.2 Variation 2: Using Aluminum Trinitrate 46
41.1.1.1.3 Method 3: Substitution of Hydrogen Using Sulfuric Acid and Ammonium Nitrate 46
41.1.1.1.4 Method 4: Substitution of Hydrogen Using Nitrogen Dioxide 46
41.1.1.1.4.1 Variation 1: Without Additional Reagents 46
41.1.1.1.4.2 Variation 2: With Oxygen 47
41.1.1.1.4.3 Variation 3: With Hydrogen Peroxide 48
41.1.1.1.5 Method 5: Substitution of Hydrogen Using Sodium Nitrite and Silver(I) Nitrate 48
41.1.1.1.6 Method 6: Substitution of Hydrogen Using Alkyl Nitrites 48
41.1.1.1.6.1 Variation 1: Without Additional Reagents 48
41.1.1.1.6.2 Variation 2: With 3-Methylbutyl Nitrite and Butyllithium 49
41.1.1.1.7 Method 7: Substitution of Hydrogen Using Alkyl Nitrates with a Base 49
41.1.1.1.8 Method 8: Substitution of Hydrogen Using 2,4,6-Trichloro-N-nitroaniline 51
41.1.1.1.9 Method 9: Substitution of Lithium 51
41.1.1.1.10 Method 10: Substitution of Potassium 51
41.1.1.1.11 Method 11: Substitution of Magnesium 51
41.1.1.1.12 Method 12: Substitution of Mercury 52
41.1.1.1.13 Method 13: Substitution of a Carboxy Group 52
41.1.1.1.14 Method 14: Substitution of a Cyano Group 53
41.1.1.1.15 Method 15: Substitution of Chlorine Using Sodium Nitrite 53
41.1.1.1.15.1 Variation 1: Without Additional Reagents 54
41.1.1.1.15.2 Variation 2: With Urea 54
41.1.1.1.15.3 Variation 3: With Benzene-1,3,5-triol 55
41.1.1.1.16 Method 16: Substitution of Chlorine Using Potassium Nitrite 55
41.1.1.1.16.1 Variation 1: In the Presence of a Base 55
41.1.1.1.16.2 Variation 2: With Crown Ethers 56
41.1.1.1.17 Method 17: Substitution of Chlorine Using Silver(I) Nitrite 56
41.1.1.1.17.1 Variation 1: Without Additional Reagents 56
41.1.1.1.17.2 Variation 2: With Urea 57
41.1.1.1.18 Method 18: Substitution of Chlorine Using Mercury(I) Nitrite 58
41.1.1.1.19 Method 19: Substitution of Chlorine Using Polymer-Supported Nitrite 58
41.1.1.1.20 Method 20: Substitution of Bromine Using Sodium Nitrite 58
41.1.1.1.20.1 Variation 1: Without Additional Reagents 58
41.1.1.1.20.2 Variation 2: With Benzene-1,2-diol 60
41.1.1.1.20.3 Variation 3: With Benzene-1,3,5-triol 60
41.1.1.1.20.4 Variation 4: With Urea 62
41.1.1.1.20.5 Variation 5: With Urea and Benzene-1,3,5-triol 63
41.1.1.1.20.6 Variation 6: With a Phase-Transfer Catalyst 65
41.1.1.1.20.7 Variation 7: With an Ionic Liquid 65
41.1.1.1.21 Method 21: Substitution of Bromine Using Potassium Nitrite 65
41.1.1.1.22 Method 22: Substitution of Bromine Using Silver(I) Nitrite 66
41.1.1.1.23 Method 23: Substitution of Bromine Using Ammonium Nitrites 69
41.1.1.1.24 Method 24: Substitution of Bromine Using Polymer-Supported Nitrite 70
41.1.1.1.25 Method 25: Substitution of Iodine Using Sodium Nitrite 70
41.1.1.1.25.1 Variation 1: Without Additional Reagents 71
41.1.1.1.25.2 Variation 2: With Benzene-1,3,5-triol 72
41.1.1.1.25.3 Variation 3: With Urea 72
41.1.1.1.25.4 Variation 4: With Urea and Benzene-1,3,5-triol 73
41.1.1.1.26 Method 26: Substitution of Iodine Using Silver(I) Nitrite 74
41.1.1.1.27 Method 27: Substitution of Iodine Using Ammonium Nitrites 77
41.1.1.1.28 Method 28: Substitution of Iodine Using Polymer-Supported Nitrite 77
41.1.1.1.29 Method 29: Substitution of Sulfates 77
41.1.1.1.30 Method 30: Substitution of Sulfonates 78
41.1.1.1.31 Method 31: Substitution of Oxonium Tetrafluoroborates 79
41.1.1.1.32 Method 32: Substitution of Nitrogen in Azo Compounds 79
41.1.1.2 Synthesis by Oxidation Reactions 80
41.1.1.2.1 Method 1: Oxidation of a Primary Amino Group Using Caro's Acid 80
41.1.1.2.2 Method 2: Oxidation of a Primary Amino Group Using Hypofluorous Acid 80
41.1.1.2.3 Method 3: Oxidation of a Primary Amino Group Using Organic Peroxides 81
41.1.1.2.3.1 Variation 1: Using Dimethyldioxirane 81
41.1.1.2.3.2 Variation 2: Using tert-Butyl Hydroperoxide and Chromium Silicalite 83
41.1.1.2.3.3 Variation 3: Using tert-Butyl Hydroperoxide and Zirconium(IV) tert-Butoxide 83
41.1.1.2.3.4 Variation 4: Using Oxaziridinium Salts 84
41.1.1.2.4 Method 4: Oxidation of a Primary Amino Group Using Organic Peroxy Acids 84
41.1.1.2.4.1 Variation 1: Using Peracetic Acid 84
41.1.1.2.4.2 Variation 2: Using 3-Chloroperoxybenzoic Acid 85
41.1.1.2.5 Method 5: Oxidation of a Primary Amino Group Using Ozone 86
41.1.1.2.6 Method 6: Oxidation of an Azido Group Using Hypofluorous Acid 87
41.1.1.2.7 Method 7: Oxidation of an Azido Group Using Ozone and a Phosphine 88
41.1.1.2.8 Method 8: Oxidation of a Hydroxyamino Group Using Nitric Acid 88
41.1.1.2.8.1 Variation 1: Without Additional Reagents 88
41.1.1.2.8.2 Variation 2: With Ammonium Nitrate 89
41.1.1.2.9 Method 9: Oxidation of a Hydroxyamino Group Using Potassium Permanganate in Sulfuric Acid 89
41.1.1.2.10 Method 10: Oxidation of a Nitroso Group Using Nitric Acid 90
41.1.1.2.10.1 Variation 1: With Ammonium Nitrate 90
41.1.1.2.10.2 Variation 2: With Acetic Acid 90
41.1.1.2.11 Method 11: Oxidation of a Nitroso Group Using Hydrogen Peroxide 90
41.1.1.2.11.1 Variation 1: Without Additional Reagents 90
41.1.1.2.11.2 Variation 2: With Sulfuric Acid 90
41.1.1.2.12 Method 12: Oxidation of a Nitroso Group Using Manganese(VII) 91
41.1.1.2.12.1 Variation 1: Using Potassium Permanganate in Acetone 91
41.1.1.2.12.2 Variation 2: Using Manganese(VII) Oxide 91
41.1.1.2.13 Method 13: Oxidation of a Nitroso Group Using Chromium(VI) 91
41.1.1.2.13.1 Variation 1: Using Chromium(VI) Oxide Alone 91
41.1.1.2.13.2 Variation 2: Using Chromium(VI) Oxide and Acetic Acid 91
41.1.1.2.13.3 Variation 3: Using Chromium(VI) Oxide with Acetic and Sulfuric Acids 92
41.1.1.2.14 Method 14: Oxidation of a Nitroso Group Using Lead(IV) Oxide 93
41.1.1.2.15 Method 15: Oxidation of a Nitroso Group Using Oxidizing Gases 93
41.1.1.2.15.1 Variation 1: Using Air 93
41.1.1.2.15.2 Variation 2: Using Oxygen 93
41.1.1.2.15.3 Variation 3: Using Nitrogen Dioxide/Dinitrogen Tetroxide 93
41.1.1.2.16 Method 16: Oxidation of a Nitroso Group Using Organic Peroxy Acids 94
41.1.1.2.16.1 Variation 1: Using Trifluoroperoxyacetic Acid 94
41.1.1.2.16.2 Variation 2: Using 3-Chloroperoxybenzoic Acid 94
41.1.1.2.17 Method 17: Photochemical Oxidation of a Nitroso Group 95
41.1.1.2.18 Method 18: Oxidation of a Nitroso Group Using Iodosylbenzene 95
41.1.1.2.19 Method 19: Oxidation of an Oxime Group Using Nitric Acid 95
41.1.1.2.19.1 Variation 1: Without Other Reagents 95
41.1.1.2.19.2 Variation 2: With Sulfuric Acid 95
41.1.1.2.20 Method 20: Oxidation of an Oxime Group Using Peroxysulfates 96
41.1.1.2.20.1 Variation 1: Using Caro's Acid 96
41.1.1.2.20.2 Variation 2: Using Oxone 96
41.1.1.2.21 Method 21: Oxidation of an Oxime Group Using Hydrogen Peroxide with Urea and Methyltrioxorhenium(VII) Catalyst 97
41.1.1.2.22 Method 22: Oxidation of an Oxime Group Using Lead(IV) Acetate 97
41.1.1.2.23 Method 23: Oxidation of an Oxime Group with Potassium Permanganate 97
41.1.1.2.24 Method 24: Oxidation of an Oxime Group with Sodium Perborate 98
41.1.1.2.25 Method 25: Oxidation of an Oxime Group Using Organic Peroxy Acids 98
41.1.1.2.25.1 Variation 1: Using Trifluoroperoxyacetic Acid 98
41.1.1.2.25.2 Variation 2: Using 3-Chloroperoxybenzoic Acid 101
41.1.1.2.26 Method 26: Oxidation of an Oxime Group Using Dinitrogen Tetroxide 102
41.1.1.2.27 Method 27: Enzymatic Oxidation of an Oxime Group 102
41.1.1.3 Synthesis by Addition Reactions 102
41.1.1.3.1 Method 1: Oxidative Nitrosation of an Oxime Group 103
41.1.1.3.2 Method 2: Oxidative Nitration of an Oxime Using Nitric Acid 103
41.1.1.3.2.1 Variation 1: Without Additional Reagents 103
41.1.1.3.2.2 Variation 2: Followed by Hydrogen Peroxide 104
41.1.1.3.2.3 Variation 3: With Acetic Acid, Followed by Hydrogen Peroxide 104
41.1.1.3.3 Method 3: Oxidative Nitration of an Oxime Using Nitrogen Oxides 105
41.1.1.3.3.1 Variation 1: Using Nitrogen Dioxide/Dinitrogen Tetroxide 105
41.1.1.3.3.2 Variation 2: Using Nitrogen Dioxide and Magnesium Sulfate 105
41.1.1.3.3.3 Variation 3: Using Dinitrogen Pentoxide 106
41.1.1.3.4 Method 4: Oxidative Chlorination of an Oxime Using Chlorine 107
41.1.1.3.4.1 Variation 1: Using Chlorine Followed by Ozone 107
41.1.1.3.4.2 Variation 2: Using Chlorine with Hydrochloric, Nitric, and Acetic Acids 108
41.1.1.3.5 Method 5: Oxidative Chlorination of an Oxime Using Sodium Hypochlorite 108
41.1.1.3.6 Method 6: Oxidative Chlorination of an Oxime Using Sodium Chloride, Oxone, and Alumina 108
41.1.1.3.7 Method 7: Oxidative Chlorination of an Oxime Using Hydrochloric Acid and Hydrogen Peroxide 109
41.1.1.3.8 Method 8: Oxidative Bromination of an Oxime Using Sodium Hypobromite Followed by Nitric Acid 109
41.1.1.3.9 Method 9: Oxidative Bromination of an Oxime Using N-Bromoacetamide 110
41.1.1.3.10 Method 10: Oxidative Bromination of an Oxime Using N-Bromosuccinimide and Potassium Carbonate 111
41.1.1.3.11 Method 11: Oxidative Bromination of an Oxime Using Sodium Bromide, Oxone, and Alumina 112
41.1.1.3.12 Method 12: Oxidative Acetoxylation of an Oxime Using Lead(IV) Acetate, Hydrogen Peroxide, and Sodium Nitrite 112
41.1.1.3.13 Method 13: Addition of Nitrous Acid to an Alkene 113
41.1.1.3.13.1 Variation 1: Using Sodium Nitrite and Acetic Acid 113
41.1.1.3.13.2 Variation 2: Using Sodium Nitrite and Hydrochloric Acid 113
41.1.1.3.14 Method 14: Addition of Tetranitromethane to an Alkene 114
41.1.1.3.15 Method 15: Nitrofluorination of an Alkene 115
41.1.1.3.15.1 Variation 1: Using Nitric and Hydrofluoric Acids 115
41.1.1.3.15.2 Variation 2: Using Nitryl Fluoride 116
41.1.1.3.15.3 Variation 3: Using Nitronium Tetrafluoroborate and Pyridinium Fluoride 116
41.1.1.3.16 Method 16: Nitrochlorination of an Alkene 117
41.1.1.3.16.1 Variation 1: Using Nitrosyl Chloride 117
41.1.1.3.16.2 Variation 2: Using Nitrosyl Chloride, Nitrogen Dioxide, and Oxygen 118
41.1.1.3.16.3 Variation 3: Using Nitryl Chloride 119
41.1.1.3.16.4 Variation 4: Using Nitrogen Dioxide and Boron Trifluoride 120
41.1.1.3.16.5 Variation 5: Using Nitrogen Dioxide and Chlorine 120
41.1.1.3.16.6 Variation 6: Using Nitrogen Dioxide, Phosphorus Trichloride, and Oxygen 121
41.1.1.3.17 Method 17: Nitrobromination of an Alkene 121
41.1.1.3.17.1 Variation 1: Using Sodium Nitrite, Mercury(II) Chloride, and Bromine 121
41.1.1.3.17.2 Variation 2: Using Nitrosyl Bromide 122
41.1.1.3.17.3 Variation 3: Using Nitrogen Dioxide and Bromine 123
41.1.1.3.17.4 Variation 4: Using Nitrogen Dioxide, Phosphorus Tribromide, and Oxygen 123
41.1.1.3.18 Method 18: Nitroiodination of an Alkene 123
41.1.1.3.18.1 Variation 1: Using Silver(I) Nitrite and Iodine 123
41.1.1.3.18.2 Variation 2: Using Nitrogen Dioxide and Iodine 124
41.1.1.3.19 Method 19: Nitroacetamidation of an Alkene 125
41.1.1.3.20 Method 20: Nitronitrosation of an Alkene (Synthesis of .-Nitrosites) 125
41.1.1.3.20.1 Variation 1: Using Sodium Nitrite and Sulfuric Acid 126
41.1.1.3.20.2 Variation 2: Using Sodium Nitrite and Hydrochloric Acid 127
41.1.1.3.20.3 Variation 3: Using Sodium Nitrite and Acetic Acid 127
41.1.1.3.20.4 Variation 4: Using Sodium Nitrite and Phosphoric Acid 128
41.1.1.3.20.5 Variation 5: Using Nitric Oxide with Catalysts 128
41.1.1.3.20.6 Variation 6: Using Nitric Oxide with Air 129
41.1.1.3.21 Method 21: 1,2-Dinitration of an Alkene 130
41.1.1.3.21.1 Variation 1: Using Pentyl Nitrite and Acetic Acid 130
41.1.1.3.21.2 Variation 2: Using Nitrogen Dioxide 130
41.1.1.3.21.3 Variation 3: Using Nitrogen Dioxide and Oxygen 132
41.1.1.3.22 Method 22: Nitrohydroxylation of an Alkene 132
41.1.1.3.22.1 Variation 1: Using Nitric Acid 132
41.1.1.3.22.2 Variation 2: Using Nitric and Sulfuric Acids 133
41.1.1.3.22.3 Variation 3: Using Sodium Nitrite and Ammonium Cerium(IV) Nitrate 133
41.1.1.3.22.4 Variation 4: Using Dinitrogen Trioxide 134
41.1.1.3.22.5 Variation 5: Using Nitrogen Dioxide 134
41.1.1.3.22.6 Variation 6: Using Organic Nitrating Agents 135
41.1.1.3.23 Method 23: Nitromethoxylation of an Alkene Using Tetranitromethane and Methanol 136
41.1.1.3.24 Method 24: Addition of a Nitro Group and a Nitrate Group to an Alkene 136
41.1.1.3.24.1 Variation 1: Using Nitric Acid 136
41.1.1.3.24.2 Variation 2: Using Nitrogen Dioxide and Oxygen 136
41.1.1.3.24.3 Variation 3: Using Dinitrogen Pentoxide 137
41.1.1.3.25 Method 25: Nitroacetoxylation of an Alkene 139
41.1.1.3.25.1 Variation 1: Using Acetyl Nitrate 139
41.1.1.3.25.2 Variation 2: Using Nitric and Sulfuric Acids Followed by Acetic Anhydride 140
41.1.1.3.26 Method 26: Addition of a Nitro Group and a Perchlorate Group to an Alkene 140
41.1.1.3.27 Method 27: Addition of a Nitro Group and an Ethyl Sulfate Group to an Alkene 141
41.1.1.3.28 Method 28: Conversion of Alkenes into a-Nitro Ketones 141
41.1.1.3.28.1 Variation 1: Using Nitrogen Dioxide and Oxygen in Dimethyl Sulfoxide 141
41.1.1.3.28.2 Variation 2: Using Chlorotrimethylsilane, Silver(I) Nitrate, and Chromium(VI) Oxide 142
41.1.1.3.28.3 Variation 3: Using Chlorotrimethylsilane, Silver(I) Nitrate, and Dimethyl Sulfoxide 143
41.1.1.3.29 Method 29: Nitration of Silyl Enol Ethers 143
41.1.1.3.29.1 Variation 1: Using Tetranitromethane 143
41.1.1.3.29.2 Variation 2: Using Nitronium Ethyl Sulfate 144
41.1.1.3.30 Method 30: Destructive Nitration 144
41.1.1.4 Synthesis by Rearrangement or Disproportionation 146
41.1.1.4.1 Method 1: Rearrangement of Alkyl Nitrates 146
41.1.1.4.2 Method 2: Disproportionation Reactions 147
41.1.1.5 Synthesis with Retention of the Nitro Group 147
41.1.1.5.1 Method 1: Alkylation of Nitroalkanes with Alkyl Halides 148
41.1.1.5.1.1 Variation 1: With Fluoroalkanes 148
41.1.1.5.1.2 Variation 2: With Chloroalkanes 148
41.1.1.5.1.3 Variation 3: With Bromoalkanes 150
41.1.1.5.1.4 Variation 4: With Iodoalkanes 152
41.1.1.5.2 Method 2: Alkylation of Nitroalkanes with Alkylammonium Salts 153
41.1.1.5.3 Method 3: Alkylation of Nitroalkanes with Alkyl(phenyl)iodonium Reagents 153
41.1.1.5.4 Method 4: Alkylation of Nitroalkanes with Alkyl Arenesulfonates 154
41.1.1.5.5 Method 5: Alkylation of Nitroalkanes with Alkyl Aryl Sulfones 155
41.1.1.5.6 Method 6: Alkylation of Nitroalkanes with Hydrates or Hemiacetals of Aldehydes 156
41.1.1.5.7 Method 7: Alkylation of Nitroalkanes with Alkyl Azides 157
41.1.1.5.8 Method 8: Alkylation of Nitroalkanes with an Alkyl Difluoromethyl Nitrite 157
41.1.1.5.9 Method 9: Vinylation of Nitroalkanes 157
41.1.1.5.10 Method 10: Arylation of Nitroalkanes 158
41.1.1.5.11 Method 11: Allylation of Nitroalkanes 160
41.1.1.5.11.1 Variation 1: Nucleophilic Substitution 160
41.1.1.5.11.2 Variation 2: Palladium-Catalyzed Allylation 162
41.1.1.5.12 Method 12: Reaction of Nitroalkyl Anions with Aldehydes and Ketones (Henry Reaction) 164
41.1.1.5.13 Method 13: Aza-Henry Reaction 168
41.1.1.5.14 Method 14: Reaction of Nitroalkyl Anions with Carboxylic and Carbonic Acid Derivatives 170
41.1.1.5.14.1 Variation 1: With Acid Halides 170
41.1.1.5.14.2 Variation 2: With Esters 171
41.1.1.5.14.3 Variation 3: With Anhydrides 171
41.1.1.5.14.4 Variation 4: With Carbonates 172
41.1.1.5.14.5 Variation 5: With Carbamoyl Chlorides 172
41.1.1.5.14.6 Variation 6: With Isatoic Anhydride 173
41.1.1.5.14.7 Variation 7: With Benzotriazole Derivatives 173
41.1.1.5.15 Method 15: Reaction of Nitroalkyl Anions with Reactive Alkenes Not Conjugated to a Carbonyl Group 174
41.1.1.5.16 Method 16: Reaction of Nitroalkyl Anions with Alkylmercury Compounds 175
41.1.1.5.17 Method 17: Substitution of Chlorine in a-Chloronitroalkanes by a Carbanion Prepared from a Ketone 175
41.1.1.5.18 Method 18: Substitution of Chlorine in a-Chloronitroalkanes by a Carbanion Prepared from a Nitroalkane 176
41.1.1.5.19 Method 19: Substitution of Chlorine in a-Chloronitroalkanes by a Carbanion Prepared from a Malonate 177
41.1.1.5.20 Method 20: Substitution of Chlorine in a-Chloronitroalkanes by a Carbanion Prepared from a 3-Oxo Ester 178
41.1.1.5.21 Method 21: Substitution of Chlorine in a-Chloronitroalkanes by a Carbanion Prepared from a 1,3-Diketone 179
41.1.1.5.22 Method 22: Substitution of Chlorine in a-Chloronitroalkanes by a Carbanion Prepared from a Nitrile 180
41.1.1.5.23 Method 23: Substitution of Chlorine in a-Chloronitroalkanes by a Carbanion Prepared from an (Alkoxycarbonyl)methyl Aryl Sulfone 180
41.1.1.5.24 Method 24: Substitution of Chlorine in a-Chloronitroalkanes by an Alkynyllithium Reagent 180
41.1.1.5.25 Method 25: Substitution of Chlorine in a-Chloronitroalkanes by an Organotin(IV) Reagent 181
41.1.1.5.26 Method 26: Substitution of Bromine in a-Bromonitroalkanes by a Carbanion Prepared from a Nitroalkane 181
41.1.1.5.27 Method 27: Substitution of Bromine in a-Bromonitroalkanes by a Carbanion Prepared from a Malonate 182
41.1.1.5.28 Method 28: Substitution of Bromine in a-Bromonitroalkanes by a Carbanion Prepared from a Nitrile 182
41.1.1.5.29 Method 29: Substitution of Bromine in a-Bromonitroalkanes by a Carbanion Prepared from a 3-Oxo Nitrile 183
41.1.1.5.30 Method 30: Substitution of Bromine in a-Bromonitroalkanes by a Carbanion Prepared from a 2-Cyano Ester 183
41.1.1.5.31 Method 31: Substitution of Bromine in a-Bromonitroalkanes by a Carbanion Prepared from an a-Cyanoalkyl Sulfone 184
41.1.1.5.32 Method 32: Substitution of Bromine in a-Bromonitroalkanes by a Carbanion Prepared from a Malononitrile 184
41.1.1.5.33 Method 33: Substitution of Bromine in a-Bromonitroalkanes by an Organotin(IV) Reagent 184
41.1.1.5.34 Method 34: Substitution of Iodine in a-Iodonitroalkanes by a Carbanion Prepared from a Nitroalkane 185
41.1.1.5.35 Method 35: Substitution of an Arylsulfonyl Group or Arylsulfanyl Group in Nitroalkanes by Carbon Nucleophiles 185
41.1.1.5.36 Method 36: Substitution of a Nitro Group in Geminal Dinitroalkanes by Carbon Nucleophiles 186
41.1.1.5.37 Method 37: Dimerization of Nitroalkanes 188
41.1.1.5.37.1 Variation 1: Starting from Nitroalkanes 188
41.1.1.5.37.2 Variation 2: Starting from Halonitroalkanes 189
41.1.1.5.38 Method 38: Decarboxylation of 2-Nitro Acids 191
41.1.1.5.39 Method 39: Dehalogenation of a-Halonitroalkanes 192
41.1.1.5.39.1 Variation 1: Using Potassium Hydroxide 192
41.1.1.5.39.2 Variation 2: Using Sodium Borohydride 193
41.1.1.5.39.3 Variation 3: Using Catalytic Hydrogenation 193
41.1.1.5.39.4 Variation 4: Using Tributyltin Hydride 194
41.1.1.5.40 Method 40: Desulfonylation of Nitro Sulfones 195
41.1.1.5.41 Method 41: Catalytic Reduction of Nitroalkenes 195
41.1.1.5.42 Method 42: Borohydride Reduction of Nitroalkenes 197
41.1.1.5.42.1 Variation 1: Using Sodium Borohydride 197
41.1.1.5.42.2 Variation 2: Using Lithium Borohydride 198
41.1.1.5.42.3 Variation 3: Using Zinc Borohydride 198
41.1.1.5.42.4 Variation 4: Using Sodium Trimethoxyborohydride 199
41.1.1.5.43 Method 43: Reduction of Nitroalkenes with Lithium Aluminum Hydride 199
41.1.1.5.44 Method 44: Enantioselective Reduction of Nitroalkenes with Silanes 200
41.1.1.5.45 Method 45: Reduction of Nitroalkenes Using Biological and Biomimetic Reducing Agents 200
41.1.1.5.46 Method 46: Hydrocyanation of a Nitroalkene Using Hydrogen Cyanide 201
41.1.1.5.47 Method 47: Hydrocyanation of a Nitroalkene Using Potassium Cyanide 202
41.1.1.5.48 Method 48: Addition to a Nitroalkene by Electrophilic Aromatic Substitution 203
41.1.1.5.49 Method 49: Addition to a Nitroalkene Using a Carbanion Prepared from an Aldehyde 205
41.1.1.5.50 Method 50: Addition to a Nitroalkene Using a Carbanion Prepared from a Ketone 207
41.1.1.5.51 Method 51: Addition to a Nitroalkene Using a Carbanion Prepared from an Ester 210
41.1.1.5.52 Method 52: Addition to a Nitroalkene Using a Carbanion Prepared from a Nitrile 212
41.1.1.5.53 Method 53: Addition to a Nitroalkene Using a Carbanion Prepared from an Amide 213
41.1.1.5.54 Method 54: Addition to a Nitroalkene Using a Carbanion Prepared from a 1,3-Diester 215
41.1.1.5.55 Method 55: Addition to a Nitroalkene Using a Carbanion Prepared from a 1,3-Diketone 220
41.1.1.5.56 Method 56: Addition to a Nitroalkene Using a Carbanion Prepared from a 3-Oxo Ester 222
41.1.1.5.57 Method 57: Addition to a Nitroalkene Using a Carbanion Prepared from a 2-Cyano Ester 225
41.1.1.5.58 Method 58: Addition to a Nitroalkene Using a Carbanion Prepared from a Dinitrile 226
41.1.1.5.59 Method 59: Addition to a Nitroalkene Using a Carbanion Prepared from a Thioester 226
41.1.1.5.60 Method 60: Addition to a Nitroalkene Using a Carbanion Prepared from a (2,2,6,6-Tetramethylpiperidin-1-yloxycarbonyl)alkane 227
41.1.1.5.61 Method 61: Addition to a Nitroalkene Using a Carbanion Prepared from a 1,3-Oxazine 227
41.1.1.5.62 Method 62: Addition to a Nitroalkene Using a Silyl Enol Ether 228
41.1.1.5.63 Method 63: Addition to a Nitroalkene Using Enamino Compounds 230
41.1.1.5.63.1 Variation 1: Using Enamines 230
41.1.1.5.63.2 Variation 2: Using Enamino Esters 232
41.1.1.5.63.3 Variation 3: Using Enamino Ketones 233
41.1.1.5.63.4 Variation 4: Using Enaminonitriles 234
41.1.1.5.64 Method 64: Addition to a Nitroalkene Using Organosulfur Reagents 234
41.1.1.5.64.1 Variation 1: Using Sulfones 234
41.1.1.5.64.2 Variation 2: Using 1,3-Dithianes 235
41.1.1.5.64.3 Variation 3: Using Sulfur Ylides 236
41.1.1.5.65 Method 65: Addition to a Nitroalkene Using a Carbanion Prepared from an Isocyanide 236
41.1.1.5.66 Method 66: Addition to a Nitroalkene Using a Carbanion Prepared from a Nitroalkane 237
41.1.1.5.67 Method 67: Addition to a Nitroalkene Using a Carbanion Prepared from a 2-Nitro Ester 238
41.1.1.5.68 Method 68: Addition to a Nitroalkene Using a Carbanion Prepared from an a-Cyano-a-nitro Ester 239
41.1.1.5.69 Method 69: Addition to a Nitroalkene Using Organophosphorus Reagents 239
41.1.1.5.69.1 Variation 1: Using Phosphonoacetate Esters 239
41.1.1.5.69.2 Variation 2: Using Phosphorus Ylides 240
41.1.1.5.70 Method 70: Addition to a Nitroalkene Using an Organolithium Reagent 241
41.1.1.5.71 Method 71: Addition to a Nitroalkene Using an Organomagnesium Reagent 242
41.1.1.5.71.1 Variation 1: Using Alkylmagnesium Chlorides 242
41.1.1.5.71.2 Variation 2: Using Alkylmagnesium Bromides 243
41.1.1.5.71.3 Variation 3: Using Alkylmagnesium Iodides 244
41.1.1.5.72 Method 72: Addition to a Nitroalkene Using an Alkylsamarium(II) Bromide 245
41.1.1.5.73 Method 73: Addition to a Nitroalkene Using an Alkylmanganese(II) Chloride 245
41.1.1.5.74 Method 74: Addition to a Nitroalkene Using an Alkylcopper Reagent 246
41.1.1.5.74.1 Variation 1: Using Alkylcoppers 246
41.1.1.5.74.2 Variation 2: Using Halozinc Alkylcyanocuprates 246
41.1.1.5.74.3 Variation 3: Using Alkylzinc Alkylcyanocuprates 247
41.1.1.5.75 Method 75: Addition to a Nitroalkene Using an Organozinc Reagent 248
41.1.1.5.75.1 Variation 1: Using Alkylzinc Chlorides 248
41.1.1.5.75.2 Variation 2: Using Alkylzinc Bromides 249
41.1.1.5.75.3 Variation 3: Using Dialkylzincs 249
41.1.1.5.76 Method 76: Addition to a Nitroalkene Using an Arylboronic Acid 252
41.1.1.5.77 Method 77: Addition to a Nitroalkene Using an Alkylaluminum Reagent 253
41.1.1.5.77.1 Variation 1: Using Trialkylaluminums 253
41.1.1.5.77.2 Variation 2: Using Tetraalkylaluminates 255
41.1.1.5.78 Method 78: Addition to a Nitroalkene Using a Lithium Tetraalkylgallate 256
41.1.1.5.79 Method 79: Addition to a Nitroalkene Using Triethoxy(phenyl)silane 256
41.1.1.5.80 Method 80: Addition to a Nitroalkene Using a Tetraalkylstannane 257
41.1.1.5.81 Method 81: Addition to a Nitroalkene Using Dialkyl Phosphites 257
41.1.1.5.82 Method 82: [2 + 2]-Cycloaddition Reactions of Nitroalkenes 258
41.1.1.5.82.1 Variation 1: With Another Nitroalkene 258
41.1.1.5.82.2 Variation 2: With Enamines 259
41.1.1.5.82.3 Variation 3: With Tetramethoxyethene 260
41.1.1.5.83 Method 83: [3 + 2]-Cycloaddition Reactions of Nitroalkenes 260
41.1.1.5.83.1 Variation 1: With Diazo Compounds 260
41.1.1.5.83.2 Variation 2: With Methylenecyclopropanes 261
41.1.1.5.83.3 Variation 3: With Azides 262
41.1.1.5.83.4 Variation 4: With Azomethine Ylides 262
41.1.1.5.83.5 Variation 5: With Enamino Ketones 262
41.1.1.5.83.6 Variation 6: With Nitrones 263
41.1.1.5.84 Method 84: [2 + 4]-Cycloaddition Reactions of Nitroalkenes with Dienes 263
41.1.1.5.85 Method 85: Rearrangements in the Synthesis of Nitroalkanes from Other Nitro Compounds 269
41.1.1.5.85.1 Variation 1: Baylis--Hillman Reaction 269
41.1.1.5.85.2 Variation 2: Disproportionation 269
41.1.1.5.85.3 Variation 3: Thio-Claisen Rearrangement 270
41.1.1.5.85.4 Variation 4: Cope Rearrangement 270
41.2 Product Class 2: Nitrosoalkanes and Nitroso Acetals (N,N-Dialkoxyamines) 290
41.2.1 Synthesis of Product Class 2 290
41.2.1.1 Method 1: Substitution Reactions 290
41.2.1.1.1 Variation 1: Substitution of a Hydrogen Atom in Nonactivated Compounds 291
41.2.1.1.2 Variation 2: Substitution of a Hydrogen Atom in Halogenated Compounds 291
41.2.1.1.3 Variation 3: Substitution of a Hydrogen Atom in Acceptor-Substituted Compounds 292
41.2.1.1.4 Variation 4: Substitution of Other Functional Groups 294
41.2.1.1.5 Variation 5: Substitution of Metals 295
41.2.1.2 Method 2: Addition Reactions 296
41.2.1.2.1 Variation 1: Addition to Alkenes 296
41.2.1.2.2 Variation 2: Addition to Electron-Rich Aromatic Compounds 300
41.2.1.3 Method 3: Elimination Reactions and Pyrolysis 300
41.2.1.4 Method 4: Oxidation Reactions 303
41.2.1.4.1 Variation 1: Oxidation of Amines 303
41.2.1.4.2 Variation 2: Oxidation of Hydroxylamines 306
41.2.1.4.3 Variation 3: Oxidation of Cyclic Nitrogen Compounds 307
41.2.1.5 Method 5: Reduction of Nitroalkanes 311
41.2.1.6 Method 6: Photochemical Reactions 311
41.2.1.7 Method 7: Rearrangements 315
41.2.1.8 Method 8: Conversions of Oximes 316
41.2.1.9 Method 9: Derivatization of Stable Nitrosoalkanes 327
41.2.1.10 Method 10: Synthesis of Metal-Coordinated Nitrosoalkanes 330
41.2.1.11 Method 11: Synthesis of Nitroso Acetals 333
41.2.2 Applications of Product Class 2 in Organic Synthesis 339
41.2.2.1 Method 1: Oxidation to Nitroalkanes 339
41.2.2.2 Method 2: Reduction to Amines 342
41.2.2.3 Method 3: Formation of Oximes and Derivatives 347
41.2.2.3.1 Variation 1: Formation of Oximes 347
41.2.2.3.2 Variation 2: Formation of Oxime Ethers and Phosphates 354
41.2.2.3.3 Variation 3: Formation of Hydroxamic Acid Derivatives 356
41.2.2.4 Method 4: Synthesis of Compounds with an N==X Functionality (X = C, N, P) 358
41.2.2.4.1 Variation 1: Synthesis of Nitrones 358
41.2.2.4.2 Variation 2: Synthesis of Azoxy Compounds 358
41.2.2.4.3 Variation 3: Synthesis of Other N==X Compounds (Imines and Azo Compounds) 360
41.2.2.4.4 Variation 4: Synthesis of N==P Compounds 361
41.2.2.5 Method 5: Conversion into Nitrosoalkenes 362
41.2.2.6 Method 6: Synthesis of Heterocycles 363
41.2.2.6.1 Variation 1: Synthesis of Four-Membered Heterocycles 363
41.2.2.6.2 Variation 2: Synthesis of Five-Membered Heterocycles 365
41.2.2.6.3 Variation 3: Synthesis of Six-Membered Heterocycles 369
41.2.2.7 Method 7: Synthesis of a-Carbonyl Hydroxylamines and N-Allyl Hydroxylamines 378
41.2.2.8 Method 8: Reactions of Nitroso Acetals 383
41.3Product Class 3: N-Nitroamines 402
41.3.1 Product Subclass 1: N-Alkyl-N-nitroamines 404
41.3.1.1 Synthesis of Product Subclass 1 404
41.3.1.1.1 Method 1: Nitration of Amines with Cyanohydrin Nitrates 404
41.3.1.1.2 Method 2: Nitration of Lithium Amides 405
41.3.1.1.3 Method 3: Deacylation of N-Acyl-N-nitroamines and Related Reactions 405
41.3.1.1.3.1 Variation 1: Of N-Nitrocarbamates 405
41.3.1.1.3.2 Variation 2: Of N-Nitroureas 408
41.3.1.1.3.3 Variation 3: Of N-Nitroguanidines 410
41.3.1.1.3.4 Variation 4: Of N-Nitro Amides 412
41.3.1.1.3.5 Variation 5: Of N-Nitro Sulfonamides 413
41.3.1.1.4 Method 4: Substitution of N,N-Dichloroamines 414
41.3.1.1.5 Method 5: Reduction of N-Nitroimines 415
41.3.1.1.6 Method 6: Cleavage of Alkyl Groups in N,N-Dialkyl-N-nitroamines 417
41.3.2 Product Subclass 2: N-Aryl-N-nitroamines 418
41.3.2.1 Synthesis of Product Subclass 2 419
41.3.2.1.1 Method 1: Nitration of Anilines 419
41.3.2.1.2 Method 2: Nitration of Metal Anilides 426
41.3.2.1.3 Method 3: Deacylation of N-Acyl-N-nitroanilines 426
41.3.2.1.4 Method 4: Oxidation of (E)-Diazenolates 427
41.3.3 Product Subclass 3: N-Nitro-N-vinylamines 428
41.3.3.1 Synthesis of Product Subclass 3 428
41.3.3.1.1 Method 1: Isomerization of N-Nitroimines 428
41.3.4 Product Subclass 4: N,N-Dialkyl-N-nitroamines 430
41.3.4.1 Synthesis of Product Subclass 4 430
41.3.4.1.1 Method 1: Nitration of Amines 430
41.3.4.1.1.1 Variation 1: Using Nitric Acid 430
41.3.4.1.1.2 Variation 2: Using Dinitrogen Pentoxide or Dinitrogen Tetroxide 434
41.3.4.1.1.3 Variation 3: Using Cyanohydrin Nitrates 435
41.3.4.1.1.4 Variation 4: Using Mesitylcarbonyl Nitrate 436
41.3.4.1.1.5 Variation 5: Using Nitronium Salts 436
41.3.4.1.1.6 Variation 6: Using N-Methyl-N,N-dinitroamine 437
41.3.4.1.2 Method 2: Nitrolysis of Amides 437
41.3.4.1.2.1 Variation 1: Using Nitric Acid 437
41.3.4.1.2.2 Variation 2: Using Dinitrogen Pentoxide 439
41.3.4.1.2.3 Variation 3: Using Nitronium Salts 439
41.3.4.1.3 Method 3: Nitration of Sulfamates 440
41.3.4.1.4 Method 4: Substitution of tert-Butylamines 440
41.3.4.1.5 Method 5: Nitroso Group Exchange by Nitration 441
41.3.4.1.6 Method 6: Alkylation of N-Alkyl-N-nitroamines 442
41.3.4.1.6.1 Variation 1: Using Alkyl, Allyl, and Benzyl Halides, Dimethyl Sulfate, Activated Alcohols, or Activated Amines 442
41.3.4.1.6.2 Variation 2: Using Diazoalkanes 446
41.3.4.1.7 Method 7: Radical Cyclizations of N-Alkyl-N-nitroamines 447
41.3.5 Product Subclass 5: N-Alkyl-N-aryl-N-nitroamines 448
41.3.5.1 Synthesis of Product Subclass 5 448
41.3.5.1.1 Method 1: Nitration of N-Alkylanilines 448
41.3.5.1.2 Method 2: Nitration of N,N-Dialkylanilines 453
41.4 Product Class 4: N-Nitrosoamines 468
41.4.1 Synthesis of Product Class 4 469
41.4.1.1 Formation of the N--N Bond 469
41.4.1.1.1 Method 1: Nitrosation with Sodium Nitrite and Acids 469
41.4.1.1.1.1 Variation 1: Nitrosation with Sodium Nitrite and Aqueous Acids 469
41.4.1.1.1.2 Variation 2: Nitrosation with Sodium Nitrite and Solid Acids 470
41.4.1.1.2 Method 2: Nitrosation with Nitrogen Oxides 470
41.4.1.1.3 Method 3: Nitrosation with Nitrosyl Chloride 471
41.4.1.1.4 Method 4: Nitrosation with Nitrosonium Tetrafluoroborate 472
41.4.1.1.5 Method 5: Nitrosation with Alkyl Nitrites 473
41.4.1.1.6 Method 6: Dealkylating Nitrosation of Tertiary Amines 474
41.4.1.2 Formation of C--C Bonds 474
41.4.1.2.1 Method 1: a-Alkylation of N-Nitrosoamines 474
41.4.1.2.2 Method 2: Alkylation of Diazenolates 476
41.4.1.3 Formation and Cleavage of N--O Bonds 477
41.4.1.3.1 Method 1: Reduction of N-Nitroamines 477
41.4.1.3.2 Method 2: Oxidation of 1,1-Disubstituted Hydrazines 477
41.5 Product Class 5: Aliphatic Azoxy Compounds (Aliphatic Diazene Oxides) 480
41.5.1 Synthesis of Product Class 5 481
41.5.1.1 Formation or Cleavage of N--O Bonds 481
41.5.1.1.1 Method 1: Oxidation of Diazenes 481
41.5.1.1.2 Method 2: Oxidation of Hydrazones 482
41.5.1.1.3 Method 3: Oxidation of Hydrazines 483
41.5.1.1.4 Method 4: Reduction of Dimeric Nitroso Compounds 483
41.5.1.2 Formation of the N==N Bond 483
41.5.1.2.1 Method 1: Condensation of Hydroxylamines with Dimeric Nitroso Compounds 483
41.5.1.2.2 Method 2: Condensation of N,N-Dihaloamines with Nitroso Compounds 485
41.5.1.2.3 Method 3: Oxidation of Hydroxylamines 486
41.5.1.3 Formation of the C--N Bond 486
41.5.1.3.1 Method 1: Alkylation of Diazenolates 486
41.6 Product Class 6: Aliphatic Azo Compounds 490
41.6.1 Synthesis by Formation of the N==N Bond 491
41.6.1.1 Method 1: Oxidative Coupling of Primary Amines 491
41.6.1.2 Method 2: Condensation of Nitrosoalkanes with Alkylamines 493
41.6.1.3 Method 3: Rearrangement of N,N'-Dialkylsulfamides 495
41.6.1.3.1 Variation 1: Rearrangement of N,N'-Dialkylureas 499
41.6.2 Synthesis from Compounds Containing an N--N Bond 500
41.6.2.1 Method 1: Oxidation of 1,2-Dialkylhydrazines 500
41.6.2.1.1 Variation 1: From Corresponding Ketazines 508
41.6.2.2 Method 2: 1,4-Elimination of a-Substituted Alkylhydrazones 509
41.6.2.3 Method 3: Reduction of Azoxy Compounds 512
41.6.2.4 Method 4: Oxidation of Alkylhydrazones 514
41.6.2.4.1 Variation 1: Oxidation with Lead(IV) Acetate 514
41.6.2.4.2 Variation 2: Oxidation with Peracetic Acid 515
41.6.2.4.3 Variation 3: Oxidation with (Diacetoxyiodo)benzene 516
41.6.2.4.4 Variation 4: Oxidation of Ketazines with Lead(IV) Acetate 517
41.6.2.5 Method 5: Alkylation of Alkylhydrazones 518
41.6.2.6 Method 6: Isomerization of Alkylhydrazones 522
41.6.2.7 Method 7: Hydrogenation of Ketazines 523
41.6.2.8 Method 8: Chlorination of Ketazines 523
41.6.2.9 Method 9: Ring Opening of Heterocycles 528
41.6.2.10 Method 10: [2,3]-Sigmatropic Rearrangement of 1-Alkyl-1-allyldiazenes and 1-Alkyl-1-propargyldiazenes 531
41.6.2.11 Method 11: Reactions of 2-Diazo 1,3-Diketones with CH-Acidic Compounds 532
41.6.3 Synthesis by Other Methods 533
41.7 Product Class 7: Diazonium Compounds 538
41.7.1 Product Subclass 1: Alkanediazonium Compounds 538
41.7.1.1 Synthesis of Product Subclass 1 540
41.7.1.1.1 Method 1: Synthesis from Primary Amines 540
41.7.1.1.1.1 Variation 1: With Nitrous Acid 540
41.7.1.1.1.2 Variation 2: With Disodium Pentacyanonitrosylferrate(III) 541
41.7.1.1.1.3 Variation 3: With Alkyl Nitrites 541
41.7.1.1.1.4 Variation 4: With Nitrosyl Chloride 542
41.7.1.1.1.5 Variation 5: With Dinitrogen Tetroxide 542
41.7.1.1.2 Method 2: Synthesis from Triazenes 542
41.7.1.1.3 Method 3: Synthesis from N-Nitrosoamides 543
41.7.1.1.3.1 Variation 1: By Thermolysis 543
41.7.1.1.3.2 Variation 2: By Alkali Cleavage 544
41.7.1.1.4 Method 4: Synthesis from Diazoalkanes 545
41.7.1.1.5 Method 5: Miscellaneous Methods 545
41.7.2 Product Subclass 2: Alkenediazonium Compounds 545
41.7.2.1 Synthesis of Product Subclass 2 548
41.7.2.1.1 Method 1: Synthesis from Diazoalkanes 548
41.7.2.1.2 Method 2: Synthesis from 2-Diazocarbonyl Compounds 548
41.7.2.1.2.1 Variation 1: By O-Alkylation 549
41.7.2.1.2.2 Variation 2: By O-Sulfonylation or O-Benzoylation 551
41.7.2.1.3 Method 3: Synthesis from Hydrazones 552
41.7.2.1.3.1 Variation 1: From Aldehyde Hydrazones 553
41.7.2.1.3.2 Variation 2: From Ketone Hydrazones 555
41.7.2.1.4 Method 4: Synthesis from Alk-1-enyl Derivatives 556
41.7.2.1.4.1 Variation 1: From Enamines 556
41.7.2.1.4.2 Variation 2: From Alk-1-enyl Isocyanates 558
41.7.2.1.4.3 Variation 3: From Alk-1-enyltriazenes 559
41.7.2.1.4.4 Variation 4: From 1-(Tosylazo)alk-1-enes 560
41.7.2.1.5 Method 5: Synthesis from N-Nitrosooxazolidin-2-ones 560
41.7.2.1.6 Method 6: Synthesis from Other Alkenediazonium Compounds 562
41.7.2.2 Applications of Product Subclass 2 in Organic Synthesis 565
41.7.2.2.1 Method 1: Synthesis of Pyrazoles 565
41.7.2.2.2 Method 2: Synthesis of 1H-1,2,3-Triazoles 566
41.7.2.2.3 Method 3: Synthesis of 6H-1,3,4-Oxadiazines and 1,3,4-Oxadiazoles 567
41.7.2.2.4 Method 4: Synthesis of 2-Diazoimines 567
41.8 Product Class 8: Azidoalkanes 574
41.8.1 Synthesis of Product Class 8 574
41.8.1.1 Method 1: Synthesis from Benzyl Ethers or Related Compounds by Radical Substitution (C--H Activation) 574
41.8.1.2 Method 2: Synthesis from Carboxylic Acids by Azidative Decarboxylation 575
41.8.1.3 Method 3: Synthesis from Alkyl Halides by Radical Substitution 576
41.8.1.4 Method 4: Synthesis by Nucleophilic Substitution of Alkyl Halides 576
41.8.1.4.1 Variation 1: Classical Synthesis 576
41.8.1.4.2 Variation 2: Asymmetric Synthesis 579
41.8.1.4.3 Variation 3: 1,3-Substitution in Allyl Halides 581
41.8.1.5 Method 5: Synthesis by Nucleophilic Substitution of Alkyl Esters and Related Compounds 582
41.8.1.5.1 Variation 1: Classical Synthesis 582
41.8.1.5.2 Variation 2: Asymmetric Synthesis 585
41.8.1.6 Method 6: Synthesis by Nucleophilic Substitution of Alkanols and Related Compounds 587
41.8.1.6.1 Variation 1: Classical Synthesis 587
41.8.1.6.2 Variation 2: Asymmetric Synthesis 591
41.8.1.7 Method 7: Synthesis from Acetals 597
41.8.1.8 Method 8: Synthesis by Ring Opening of Epoxides, Aziridines, and Related Compounds 598
41.8.1.8.1 Variation 1: Classical Synthesis 598
41.8.1.8.2 Variation 2: Asymmetric Synthesis 608
41.8.1.9 Method 9: Electrophilic Azidation 609
41.8.1.10 Method 10: Synthesis by Addition to C==C Bonds 611
41.8.1.10.1 Variation 1: Nucleophilic Hydroazidation of C==C Bonds 611
41.8.1.10.2 Variation 2: Electrophilic Hydroazidation of C==C Bonds 612
41.8.1.10.3 Variation 3: Radical Hydroazidation of C==C Bonds 615
41.8.1.10.4 Variation 4: Carboazidation of C==C Bonds 616
41.8.1.10.5 Variation 5: Haloazidation of C==C Bonds 616
41.8.1.10.6 Variation 6: Azidoselanylation of C==C Bonds 621
41.8.1.11 Method 11: Synthesis by Addition to C==X Bonds 621
41.8.1.12 Method 12: Synthesis from Amines by Nitrogen Transfer 621
41.8.1.13 Method 13: Synthesis with Retention of Azide Functionality 622
41.8.2 Applications of Product Class 8 in Organic Synthesis 625
41.8.2.1 Method 1: Reactions with All-Carbon Functional Groups 625
41.8.2.1.1 Variation 1: [3 + 2]-Cycloaddition Reactions 625
41.8.2.2 Method 2: Hydrogenation and Reactions with Heteroatom-Containing Groups 626
41.8.2.2.1 Variation 1: Reduction to Amines 626
41.8.2.2.2 Variation 2: Schmidt and Boyer Reactions 629
41.8.2.2.3 Variation 3: Staudinger Reductions 631
41.8.2.2.4 Variation 4: Staudinger Ligations 633
41.8.2.2.5 Variation 5: Aza-Wittig Reactions 634
41.8.2.2.6 Variation 6: Miscellaneous Reactions 636
41.9 Product Class 9: Alkyltriazenes 644
41.9.1 Synthesis of Product Class 9 645
41.9.1.1 Method 1: Alkylation of Alkyl Azides 645
41.9.1.1.1 Variation 1: By Grignard Reagents 645
41.9.1.1.2 Variation 2: By Lithium Reagents 646
41.9.1.2 Method 2: Alkylation or Acylation of Aryl- or Alkyltriazenes 647
41.9.1.2.1 Variation 1: Alkylation 647
41.9.1.2.2 Variation 2: Acylation 647
41.9.1.3 Method 3: Reaction of Arenediazonium Salts with Primary Amines 648
41.9.1.4 Method 4: Reaction of Diazonium Salts with Secondary Amines 650
41.9.1.4.1 Variation 1: Diazotization of Arylamines and Reaction with Secondary Amines 650
41.9.1.4.2 Variation 2: Preparation of Bistriazenes of Secondary Amines 654
41.9.1.4.3 Variation 3: Formation on Solid Supports 655
41.9.1.4.4 Variation 4: Preparation of Imidazolyltriazenes 656
41.9.1.4.5 Variation 5: Preparation of Indol-3-yltriazenes 656
41.9.1.4.6 Variation 6: Preparation of Pyrrol-3-yltriazenes 657
41.9.1.4.7 Variation 7: Preparation of Pyridyltriazenes 658
41.9.1.4.8 Variation 8: Preparation of Pyrazolyltriazenes/Indazolyltriazenes 658
41.9.1.4.9 Variation 9: Preparation of Acyl(alkyl)triazenes 659
41.9.1.5 Method 5: Synthesis from N'-Alkyl-N-aryl-N-nitrosoureas 660
41.9.1.5.1 Variation 1: With Primary Amines/Secondary Amines 660
41.9.1.5.2 Variation 2: By Decomposition 660
41.9.1.6 Method 6: Synthesis from Nitroso-Containing Compounds with Alkylhydrazines 661
41.9.1.7 Method 7: Reaction of Arenediazonium Salts with Primary Amines and Formaldehyde 662
41.9.1.8 Method 8: Reaction of Arenediazonium Salts with Diamines and Formaldehyde 663
41.9.1.9 Method 9: Synthesis by Ring Opening of Cyclic Compounds 664
41.9.1.9.1 Variation 1: Ring Opening of Triaziridines 664
41.9.1.9.2 Variation 2: Ring Opening to 3-Alkyl-1-aryltriazenes 664
41.9.1.9.3 Variation 3: Ring Opening of Spirocyclic Triazoles 665
41.9.1.9.4 Variation 4: Ring Opening of Benzotriazoles 665
41.9.2 Applications of Product Class 9 in Organic Synthesis 666
41.10 Product Class 10: Alkyltetrazenes 672
41.10.1 Product Subclass 1: Tetraz-1-enes 672
41.10.1.1 Synthesis of Product Subclass 1 672
41.10.1.1.1 Method 1: Reaction of 1,1-Dialkylhydrazines with Diazonium Chlorides 672
41.10.2 Product Subclass 2: Tetraz-2-enes 673
41.10.2.1 Synthesis of Product Subclass 2 673
41.10.2.1.1 Method 1: Symmetrical Oxidative Dimerization of Hydrazines 673
41.10.2.1.2 Method 2: Tetrazenes from N-Nitrosoamines 676
41.10.2.1.3 Method 3: Dimerization of Diazenes Generated from Amines 676
41.10.2.1.4 Method 4: Dimerization of Diazenes Generated from Hydrazones 677
41.10.2.1.5 Method 5: Synthesis of Unsymmetrical Tetrazenes 677
41.10.2.1.6 Method 6: Synthesis of Tetrazenes from Cyclic Precursors 678
41.10.2.1.7 Method 7: Synthesis of Vinyltetrazenes 679
41.11 Product Class 11: N,N-Dihaloamines 682
41.11.1 Product Subclass 1: N,N-Difluoroamines 682
41.11.1.1 Synthesis of Product Subclass 1 684
41.11.1.1.1 Method 1: Direct Fluorination of Amines and Related Reactions 684
41.11.1.1.2 Method 2: Difluoroamination of Carbon Skeletons 686
41.11.1.1.2.1 Variation 1: With Tetrafluorohydrazine 686
41.11.1.1.2.2 Variation 2: With Difluoroamine and Related Reagents 690
41.11.1.1.3 Method 3: Other Methods 693
41.11.2 Product Subclass 2: N,N-Dichloroamines 694
41.11.2.1 Synthesis of Product Subclass 2 696
41.11.2.1.1 Method 1: Direct Chlorination of Amines 696
41.11.2.1.2 Method 2: Chlorination of Nitriles and Related Reactions 697
41.11.2.1.3 Method 3: Dichloroamination of Carbon Skeletons 699
41.11.2.1.4 Method 4: Other Methods 700
41.11.3 Product Subclass 3: N,N-Dibromoamines 700
41.11.3.1 Synthesis of Product Subclass 3 701
41.11.3.1.1 Method 1: Direct Bromination of Amines 701
41.11.3.1.2 Method 2: Halide Metathesis of N,N-Dichloroamines 701
41.11.3.1.3 Method 3: Other Methods 703
41.11.4 Product Subclass 4: N,N-Diiodoamines 703
41.11.4.1 Synthesis of Product Subclass 4 703
41.11.5 Product Subclass 5: N-Chloro-N-fluoroamines 704
41.11.5.1 Synthesis of Product Subclass 5 704
41.11.5.1.1 Method 1: Chlorofluorination of Nitriles 704
41.11.5.1.2 Method 2: Chlorofluorination of N-Fluoroimines 705
41.11.5.1.3 Method 3: Fluorination of N-Chloroaziridines 706
41.11.6 Product Subclass 6: N-Bromo-N-fluoroamines 706
41.11.6.1 Synthesis of Product Subclass 6 706
41.11.7 Product Subclass 7: N-Bromo-N-chloroamines 706
41.11.7.1 Synthesis of Product Subclass 7 707
Keyword Index 712
Author Index 752
Abbreviations 796