Nitrosation Reactions and the Chemistry of Nitric Oxide (eBook)

Front Cover 1
Nitrosation Reactions and The Chemistry of Nitric Oxide 4
Copyright Page 5
CONTENTS 6
INTRODUCTION 12
Chapter 1. Reagents effecting nitrosation 14
1.1. Nitrous acid 14
1.2. Nitrosyl halides HalNO 25
1.3. Nitrosonium salts NO+X- 27
1.4. Alkyl nitrites RONO 29
1.5. N-Nitrososulfonamides RSO2N(NO)R' 35
1.6. Nitrogen oxides 36
1.7. Miscellaneous reagents 40
Chapter 2. Nitrosation at nitrogen centres 48
2.1. Primary aromatic amines 48
2.2. Primary aliphatic amines 53
2.3. Secondary amines 56
2.4. Tertiary amines 58
2.5. Amides and related compounds 60
2.6. Other nitrogen-containing compounds 64
Chapter 3. The reactions of N-nitrosamines and related compounds 70
3.1. Rearrangement of aromatic N-nitrosamines Ar(R)NNO (the Fischer-Hepp rearrangement) 70
3.2. Denitrosation of nitrosamines R(R')NNO 78
3.3. Denitrosation of nitrosamides RCON(NO)R' 85
3.4. Denitrosation of nitrososulfonamides ArSO2N(NO)R 86
3.5. Carcinogenic properties of N-nitroso compounds 87
Chapter 4. Aliphatic and alicyclic C-nitrosation 92
4.1. Nitrosation of ketones 92
4.2. Nitrosation of other carbonyl compounds 96
4.3. Nitrosation of nitroalkanes 99
4.4. Nitrosation of carbanions 100
4.5. Addition to alkenes 102
Chapter 5. Aromatic C-nitrosation 106
5.1. Products of the reactions 106
5.2. Reaction mechanisms 110
5.3 Nitrous acid-catalysed nitration reactions 115
Chapter 6. O-Nitrosation 118
6.1. Nitrosation of alcohols 118
6.2. Nitrosation of hydrogen peroxide 122
6.3. Nitrosation of ascorbic acid 125
6.4. Other O-nitrosation reactions 127
Chapter 7. S-Nitrosation 130
7.1. Nitrosation of thiols 130
7.2. Nitrosation of thiocarbonyls 134
7.3. Nitrosation of organic sulfides 141
7.4. Nitrosation of sulfmic acids 143
7.5. Nitrosation of thiocyanate ion 144
7.6. Nitrosation of sulfite/bisulfite 145
7.7. Nitrosation of thiosulfate ion 146
7.8. Nitrosation of inorganic sulfide 147
Chapter 8. Synthesis, properties and reactions of S-nitrosothiols 150
8.1. Synthesis 150
8.2. Physical properties 150
8.3. Thermal and photochemical decomposition 152
8.4. Decomposition in aqueous solution 154
8.5. Reaction with nucleophiles 163
8.6. Detection and quantitative determination of S-nitrosothiols 169
Chapter 9. Nitrosation involving metal-nitrosyl complexes 174
9.1. Sodium nitroprusside (pentacyanonitrosylferrate II) 174
9.2. Other metal nitrosyls 177
9.3. Iron-sulfur cluster nitrosyls 179
9.4. Nitrosation of nucleophiles co-ordinated to metals 180
Chapter 10. The biological chemistry of nitric oxide 184
10.1. Background 184
10.2. Reactions of nitric oxide with oxygen and superoxide 185
10.3. Reactions of nitric oxide with haem proteins 188
10.4. Reactions of nitric oxide with thiolate ion 191
10.5. Analytical methods for the determination of nitric oxide 192
Chapter 11. Nitric oxide in biological systems 200
11.1. Biological properties of nitric oxide 200
11.2. Biosynthesis of nitric oxide 205
11.3. NO synthase enzymes 207
11.4. Nitric oxide in the treatment of foods 210
Chapter 12. Nitric oxide-releasing compounds (NO donors) 212
12.1. Organic nitrates 212
12.2. Organic nitrites 214
12.3. S-Nitrosothiols 215
12.4. Inorganic nitrosyl complexes 221
12.5. NONOates (Diazeniumdiolates) 224
12.6. Sydnonimines 226
12.7. Furoxans (oxadiazoles) 227
12.8. Hydroxyurea 228
12.9. Other NO-donors 229
Chapter 13. Nitroxyl (HNO) and the nitroxyl anion (NO-) 234
13.1. Generation of HNO/NO- 234
13.2. Physical and chemical properties of HNO/NO" 236
13.3. Determination of HNO/NO- 240
13.4. Biological implications 241
Appendix 244
References 248
Index 270