The Pyrazines, Volume 58, Supplement 1
Published on 16. January 2002
Book
Hardback
576 pages
978-0-471-40382-1 (ISBN)
Description
This book serves as a supplement to The Pyrazines, Volume 41 of the Chemistry of Heterocyclic Compounds series. It covers the literature published between 1979 and 2000, and-together with Volume 41-provides a complete, up-to-date reference for heterocyclic chemists. It emphasizes practical approaches to pyrazine chemistry, offers a full appendix of all simple pyrazines up to 2000, and features detailed coverage of the following topics:
Systematic descriptions of all primary synthetic routes to pyrazines
Other preparative routes to alkylpyrazines and their reactions
Halogenopyrazines and their synthetic uses
Oxypyrazines and trivial names for pharmaceutical or agrochemical pyrazines
Thiopyrazines
Amino-, nitro-, and other similar pyrazines and their reactions
Pyrazinecarboxylic acids and their derivatives
The supplement features extensive cross-references to the original volume and uses chemical nomenclature as per current IUPAC recommendations
Systematic descriptions of all primary synthetic routes to pyrazines
Other preparative routes to alkylpyrazines and their reactions
Halogenopyrazines and their synthetic uses
Oxypyrazines and trivial names for pharmaceutical or agrochemical pyrazines
Thiopyrazines
Amino-, nitro-, and other similar pyrazines and their reactions
Pyrazinecarboxylic acids and their derivatives
The supplement features extensive cross-references to the original volume and uses chemical nomenclature as per current IUPAC recommendations
Reviews / Votes
"...embraces a mass of important historical material as well as a modern systematic treatment of pyrazine chemistry." (SciTech Book News, Vol. 26, No. 2, June 2002)More details
Series
Edition
Volume 58 edition
Language
English
Place of publication
United States
Publishing group
John Wiley & Sons Inc
Target group
College/higher education
Professional and scholarly
Product notice
sewn/stitched
Dimensions
Height: 241 mm
Width: 175 mm
Thickness: 31 mm
Weight
916 gr
ISBN-13
978-0-471-40382-1 (9780471403821)
Copyright in bibliographic data and cover images is held by Nielsen Book Services Limited or by the publishers or by their respective licensors: all rights reserved.
Schweitzer Classification
Other editions
Additional editions
Person
Desmond J. Brown is Professor of Chemistry at The Australian National University.
Content
Chapter 1 Primary Syntheses From Aliphatic Or Carbocyclic Synthons 1
1.1 From a Single Six-Atom Synthon 1
1.1.1 By Completion of the N-C2 Bond 1
1.1.1.1 From Appropriate ?-Unsaturated Azaalkylamines 1
1.1.1.2 From Appropriate ?-Halogeno(azaalkylamines) 2
1.1.1.3 From Appropriate ?,?-Diamino(azaalkanes) 2
1.1.1.4 From Appropriate ?-Amino(azaalkanols) 3
1.1.1.5 From Appropriate ?-Amino(azaalkanals) 3
1.1.1.6 From Appropriate ?-Amino(azaalkanones) 4
1.1.1.7 From Appropriate ?-Amino(azaalkanoic Acids) 6
1.1.1.8 From Appropriate ?-Amino(azaalkanoic Esters) 6
1.1.1.9 From Appropriate ?-Amino(azaalkanamides) 8
1.1.1.10 From Appropriate ?-Amino(azaalkanamides) 8
1.1.2 By Completion of the C2-C3 Bond 9
1.2 From Two Synthons 10
1.2.1 By Using a One-Atom and a Five-Atom Synthon 11
1.2.1.1 Where the One-Atom Synthon Supplies N1 11
1.2.1.2 Where the One-Atom Synthon Supplies C2 14
1.2.2 By Using a Two-Atom and a Four-Atom Synthon 15
1.2.2.1 Where the Two-Atom Synthon Supplies N1 + C2 15
1.2.2.2 Where the Two-Atom Synthon Supplies C2 + C3 16
1.2.3 By Using Two Three-Atom Synthons 29
1.2.3.1Where Identical Synthons Provide N1 + C2 + C3 and N4 + C5 + C6 29
1.2.3.2 Where Different Synthons Provide N1 + C2 + C3 and N4 + C5 + C6 34
1.2.3.3 Where the Synthons Provide N1 + C2 + C6 and C3 + N4 + C5 37
1.3 From Three Synthons 39
1.4 From Four or More Synthons 39
1.4.1 Where Synthons Provide N1, C2 + C3, N4 + C5 + C6 40
1.4.2 Where Synthons Provide N1 + C2, C3 + N4, C5, C6 41
1.4.3 Where Synthons Provide N1 + C2 + C3, N4 + C5, C6 42
1.5 Appendix: Glance Index to Typical Pyrazine Derivatives Available from Aliphatic or Carbocyclic Synthons 42
Chapter 2 Primary Syntheses From Other Heterocyclic Systems 47
2.1 Pyrazines from Other Heteromonocyclic Systems 47
2.1.1 Azepines as Substrates 47
2.1.2 Azetes as Substrates 48
2.1.3 Azirines as Substrates 48
2.1.4 Azocines as Substrates 51
2.1.5 1,2-Diazepines as Substrates 52
2.1.6 1,4-Diazepines as Substrates 52
2.17 Furans as Substrates 52
2.1.8 Imidazoles as Substrates 53
2.1.9 Isoxazoles as Substrates 55
2.1.10 Oxazoles as Substrates 56
2.1.11 Oxirenes as Substrates 56
2.1.12 Pyridazines as Substrates 57
2.1.13 Pyridines as Substrates 57
2.1.14 Pyrroles as Substrates 58
2.1.15 l,2,5-Selenadiazoles as Substrates 58
2.1.16 1,2,5-Thiadiazoles as Substrates 59
2.1.17 Thiirenes as Substrates 59
2.2 Pyrazines from Heterobicyclic Systems 59
2.2.1 1, 2-Diazabicyclo[2.2.0]hexanes as Substrates 60
2.2.2 2, 4,-Diazabicyclo[3.l.0}hexanes as Substrates 60
22.3 2, 3-Dioxa-5,7-diazabicyclo[2.2.2} octanes as Substrates 60
2.2.4 Furo[2, 3-b]pyrazines as Substrates 60
2.2.5 Imidazo[l, 2-a]pyrazines as Substrates 61
2.2.6 Indoles as Substrates 61
2.2.7 Isoxazolo[2,3-a]pyrazines as Substrates 62
2.2.8 Isoxazolo[4,5-b]pyrazines as Substrates 63
2.2.9 Pteridines as Substrates 63
22.10 Pyrazino[2,3-d][1,3]oxazincs as Substrates 66
2.2.11 Pyrazino[2,3-e][l,3,4]thiadiazines as Substrates 66
2.2.12 Quinoxalines as Substrates 66
2.2.13 4-Thia-l-azabicyclo[3.2.0]heptanes as Substrates 67
2.2.14 [1,2,5]Thiadiazolo[3,4-b)pyrazines as Substrates 68
2.2.15 Thiazolo[3,2-a]pyrazines as Substrates 68
2.2.16 Thiazolo[3,4-a]pyrazines as Substrates 69
2.3 Pyrazines from Heterotricyclic Systems 69
2.4 Pyrazines from Spiro Heterocycles 70
2.5 Appendix: Glance Index to Typical Pyrazine Derivatives Available from Other Heterocyclic Systems 71
Chapter 3 Pyrazine, Alkylpyrazlnes, And Arylpyrazines 75
3.1 Pyrazine 76
3.1.1 Preparation of Pyrazine 76
3.1.2 Properties of Pyrazine 76
3.1.3 Reactions of Pyrazine 77
3.2 C-Alkyl- and C-Arylpyrazines 79
3.2.1 Preparation of C-Alkyl- and C-Arylpyrazines 80
3.2.1.1 By Direct C-Alkylation 80
3.2.1.1.1 General Procedures for C-Alkylation 80
3.2.1.1.2 C-Alkylation in the Scboellkopf Synthesis 86
3.2.1.2 By Replacement of Halogeno Substituents 93
3.2.1.3 By Replacement of Alkoxy, Cyano, Nitro, or Oxo Substituents 100
3.2.1.4 By Interconversion of Simple Alkyl Substituents 101
3.2.1.5 By Elimination of Functionality from Existing Substituents. 102
3.2.1.6 By Ipso-Substitution of Trimethylsiloxycarbonyl Substituents 105
3.2.2 Preparation of N-Alkyl- and N-Arylpiperazines 105
3.2.2.l By N-Alkylation Processes 106
3.2.2.2 By Reduction of N-Acyl or N-Alkoxycarbonylpiperazines 112
3.2.2.3 By Miscellaneous Routes 113
3.2.3 Properties of Alkyl- and Arylpyrazines 114
3.2.4 Reactions of Alkyl- and Arylpyrazines 117
3.2.4.1 Oxidative Reactions 117
3.2.4.2 Reductive Reactions 119
3.2.4.3 Extranuclear Halogenation 120
3.2.4.4 Extranuclear Alkylation 122
3.2.4-.5 Extranuclear Alkylidenation 123
3.2.4.6 Extranuclear Acylation or Carboxylation 125
3.2.4.7 Cyclization 126
3.24.8 "Ammoxidation" of Methyl to Cyano Groups 128
3.2.4.9 Addition Reactions at Alkenyl or Alkynyl Substituents 128
3.2.4.10 Miscellaneous Reactions 130
3.3 N Alkylpyrazinium Salts and Related Ylides 1313.3.1 Preparation of N-Alkylpyrazinium Salts 131
3.3.2 Reactions of N-Alkylpyrazinium Salts 132
Chapter 4 Halogenopyrazines 137
4.1 Preparation of Nuclear Halogenopyrazin137
4.1.1 Nuclear Halogenopyrazines from Pyrazinones 137
4.1.2 Nuclear Halogenopyrazines by Direct Halogenation 141
4.1.3 Nuclear Halogenopyrazines by Deoxidative Halogenation of Pyrazine N-Oxides 145
4.1.4 Nuclear Halogenopyrazines from Pyrazinamines 146
4.1.5 Nuclear Halogenopyrazines by Transhalogenation 148
4.1.6 Nuclear Halogenopyrazines via Trimethylsiloxypyrazines 149
4.2 Reactions of Nuclear Halogenopyrazines 150
4.2.1 Aminolysis of Nuclear Halogenopyrazines 158
4.2.2 Hydrolysis of Nuclear Halogenopyrazines 164
4.2.3 Alcoholysis or Phenolysis of Nuclear Halogenopyrazines 159
4.2.4 Thiolysis of Nuclear Halogenopyrazines 164
4.2.5 Alkanethiolysis or Arenerhiolysis of Nuclear Halogenopyrazines 166
4.2.6 Azidolysis of Nuclear Halogenopyrazines 170
4.2.7 Hydrogenolysis of Nuclear Halogenopyrazines 171
4.2.8 Cyanolysis of Nuclear Halogenopyrazines 173
4.2.9 Miscellancous Displacement Reactions of Nuclear Halogenopyrazines 174
4.2.10 Fission, Rearrangement, or Cyclocondensation of Nuclear Halogenopyrazines 176
4.3 Preparation of Extranuclear Halogenopyrazines 178
4.3.1 Extranuclear Halogenopyrazines from Corresponding Hydroxypyrazines 178
4.3.2 Extranuclear Halogenopyrazines by Minor Procedures 180
4.4 Reactions of Extranuclear Halogenopyrazines
Chapter 5 Oxypyrazines 191
5.1 Tautomeric Pyrazinones 191
5.1.1 Preparation of Tautomeric Pyrazinones 191
5.1.2 Reactions of Tautomeric Pyrazinones 191
5.1.2.1 Conversion into Pyrazinethiones
5.1.2.2 Conversion into O- and/or N-Alkylated Derivatives 198
5.1.2.3 Conversion into O- and/or N-Alkylated Derivatives 198
5.1.2.4 Miscellaneous Reactions 205
5.2 Extranuclear Hydroxypyrazines 208
5.2.1 Preparation of Extranuclear Hydroxypyrazines 208
5.2.2 Reactions of Extranuclear Hydroxypyrazines 202
5.3 Nuclear and Extranuclear Alkoxy- or Aryloxypyrazines 217
5.3.1 Preparation of Alkoxy- or Aryloxypyrazines 217
5.3.2 Reactions of Alkoxy- or Aryloxypyrazines 219
5.4 Nontautomeric Pyrazinones_and N-Alkylpyraziniumolates 221
5.4.1 Preparation of Nontautomeric Pyrazinones 221
5.4.2 Reactions of Nontautomeric Pyrazinones 222
5.5Pyrazine N-Oxides 225
5.5.1 Preparation of Pyrazine N-Oxides 226
5.5.1.1 From N-Alkoxypyrazinones 226
5.5.1.2 By Direct, N-Oxidation 226
5.5.2 Reactions of Pyrazine N-Oxides 230
5.5.2.1 Deoxygenation 231
5.5.2.2 O-Alkylation or O-Acylation 233
5.5.2.3 Conversion into C-Acyloxypyrazines 234
5.5.2.4 Conversion into C-Amino-, C-Azido-, C-Cyano-, or C-Alkylthiopyrazines 237
5.5.2.5 Miscellaneous Reactions 238
5.6 Appendix: Trivial Names for Pyrazine Derivatives 240
Chapter 6 Thiopyrazines 245
6.1 Pyrazinethiones and Pyraz1nethiols 245
6.1.1 Preparation of Pyrazinethiones and Pyrazinethiols 245
6.1.2 Reactions of Pyrazinethiones and Pyrazinethiols 248
6.2 Alkylthiopyrazines and Dipyrazinyl Sulfides 251
6.2.1 Preparation of Alkylthiopyrazines 251
6.2.2 Reactions of Alkylthiopyrazines 252
6.2.2.1 Oxidation to Sulfoxides or Sulfones 252
6.2.2 2 Miscellaneous Reactions 254
6.3 Dipyrazinyl Disulfides and Pyrazinesulfonic Acid Derivatives 255
6.4 Pyrazine Sulfoxides and Sulfones 255
Chapter 7 Nitro- Amino-, And Related Pyrazies 259
7.1 Nitropyrazines 259
7.1.1 Preparation of Nitropyrazines 259
7.1.2 Reactions of Nitropyrazines 261
7.2 Nitrosopyrazines 262
7.2.1 C-Nitrosopyrazines 262
7.2.2 N-Nitrosopipcrazines and Related Compounds 262
7.3 Regular Aminopyrazines 265
7.3.1 Preparation of Regular Aminopyrazines 265
7.3.2 Reactions of Regular Aminopyrazines 273
7.3.2.1 N-Acylation of Aminopyrazines and Subsequent Cyclizations 273
7.3.2.2 N-Alkylidenation of Aminopyrazines and Subsequent Cyclizations 277
7.3.2.3 N-Alkylation of Aminopyrazines and Subsequent Cyclizations 280
7.3.2.4 Conversion into Ureidopyrazines or Related Products 282
7.3.2.5 Conversion into Trialkylsilylamino-, Triphenylphosphoranylideneamino-, or Dimethylsulfitnidopyrazines 285
7.3.2.6 Miscellaneous Minor Reactions 287
7.4 Preparation and Reactions of Hydrazinopyrazines 290
7.5 Preparation, Structure, and Reactions of Azidopyrazines 294
7.6 Nontautomeric Iminopyrazines 297
7.7 Arylazopyrazines 298
Chapter 8 Pyrazecarboxylic Acids And Related Derivatives 299
8.1 Pyrazinecarboxylic Acids 299
8.1.1 Preparation of Pyrazinecarboxylic Acids 299
8.1.2 Reactions of Pyrazinecarboxylic Acids 302
8.2 Pyrazinecarboxylic Esters 308
8.2.1 Preparation of Pyrazinecarboxylic Esters 308
8.2.2 Reactions of Pyrazinecarboxylic Esters 311
8.3 Pyrazinecarbonyl Halides 317
8.3.1 Preparation of Pyrazinecarbonyl Halides 317
8.3.2 Reactions of Pyra:dnecarbonyl Halides 318
8.4 Pyrazinecarboxamides, Pyrazinecarboxamidines, and Related Derivatives 321
8.4.1 Preparation of Pyrazinecarboxamides and the Like 321
8.4.2 Reactions of Pyrazinecarboxamides and the Like 324
8.5 Pyrazinecarbohydrazides and Pyrazinecarbonyl Azides 328
8.6 Pyrazinecarbonitriles 330
86.1 Preparation of Pyrazinecarbonitriles 330
8.6.2 Reactions of Pyrazinecarbonitriles 340
8.7 Pyrazinecarbaldehydes 336
8.7.1 Preparation of Pyrazinecarbaldehydes 336
8.7.2 Reactions of Pyrazinecarbaldehydes 338
8.8 Pyrazine Ketones 340
8.8.1 Preparation of Pyrazine Ketones 341
8.8.2 Reactions of Pyrazine Ketones 343
8.9 Pyrazine Cyanates, Isocyanates, Thiocyanates, Isothiocyanates, and Carbonitrile Oxides 349
Appendix: Table Of Simple Pyrazines 349
References 461
Index 515
1.1 From a Single Six-Atom Synthon 1
1.1.1 By Completion of the N-C2 Bond 1
1.1.1.1 From Appropriate ?-Unsaturated Azaalkylamines 1
1.1.1.2 From Appropriate ?-Halogeno(azaalkylamines) 2
1.1.1.3 From Appropriate ?,?-Diamino(azaalkanes) 2
1.1.1.4 From Appropriate ?-Amino(azaalkanols) 3
1.1.1.5 From Appropriate ?-Amino(azaalkanals) 3
1.1.1.6 From Appropriate ?-Amino(azaalkanones) 4
1.1.1.7 From Appropriate ?-Amino(azaalkanoic Acids) 6
1.1.1.8 From Appropriate ?-Amino(azaalkanoic Esters) 6
1.1.1.9 From Appropriate ?-Amino(azaalkanamides) 8
1.1.1.10 From Appropriate ?-Amino(azaalkanamides) 8
1.1.2 By Completion of the C2-C3 Bond 9
1.2 From Two Synthons 10
1.2.1 By Using a One-Atom and a Five-Atom Synthon 11
1.2.1.1 Where the One-Atom Synthon Supplies N1 11
1.2.1.2 Where the One-Atom Synthon Supplies C2 14
1.2.2 By Using a Two-Atom and a Four-Atom Synthon 15
1.2.2.1 Where the Two-Atom Synthon Supplies N1 + C2 15
1.2.2.2 Where the Two-Atom Synthon Supplies C2 + C3 16
1.2.3 By Using Two Three-Atom Synthons 29
1.2.3.1Where Identical Synthons Provide N1 + C2 + C3 and N4 + C5 + C6 29
1.2.3.2 Where Different Synthons Provide N1 + C2 + C3 and N4 + C5 + C6 34
1.2.3.3 Where the Synthons Provide N1 + C2 + C6 and C3 + N4 + C5 37
1.3 From Three Synthons 39
1.4 From Four or More Synthons 39
1.4.1 Where Synthons Provide N1, C2 + C3, N4 + C5 + C6 40
1.4.2 Where Synthons Provide N1 + C2, C3 + N4, C5, C6 41
1.4.3 Where Synthons Provide N1 + C2 + C3, N4 + C5, C6 42
1.5 Appendix: Glance Index to Typical Pyrazine Derivatives Available from Aliphatic or Carbocyclic Synthons 42
Chapter 2 Primary Syntheses From Other Heterocyclic Systems 47
2.1 Pyrazines from Other Heteromonocyclic Systems 47
2.1.1 Azepines as Substrates 47
2.1.2 Azetes as Substrates 48
2.1.3 Azirines as Substrates 48
2.1.4 Azocines as Substrates 51
2.1.5 1,2-Diazepines as Substrates 52
2.1.6 1,4-Diazepines as Substrates 52
2.17 Furans as Substrates 52
2.1.8 Imidazoles as Substrates 53
2.1.9 Isoxazoles as Substrates 55
2.1.10 Oxazoles as Substrates 56
2.1.11 Oxirenes as Substrates 56
2.1.12 Pyridazines as Substrates 57
2.1.13 Pyridines as Substrates 57
2.1.14 Pyrroles as Substrates 58
2.1.15 l,2,5-Selenadiazoles as Substrates 58
2.1.16 1,2,5-Thiadiazoles as Substrates 59
2.1.17 Thiirenes as Substrates 59
2.2 Pyrazines from Heterobicyclic Systems 59
2.2.1 1, 2-Diazabicyclo[2.2.0]hexanes as Substrates 60
2.2.2 2, 4,-Diazabicyclo[3.l.0}hexanes as Substrates 60
22.3 2, 3-Dioxa-5,7-diazabicyclo[2.2.2} octanes as Substrates 60
2.2.4 Furo[2, 3-b]pyrazines as Substrates 60
2.2.5 Imidazo[l, 2-a]pyrazines as Substrates 61
2.2.6 Indoles as Substrates 61
2.2.7 Isoxazolo[2,3-a]pyrazines as Substrates 62
2.2.8 Isoxazolo[4,5-b]pyrazines as Substrates 63
2.2.9 Pteridines as Substrates 63
22.10 Pyrazino[2,3-d][1,3]oxazincs as Substrates 66
2.2.11 Pyrazino[2,3-e][l,3,4]thiadiazines as Substrates 66
2.2.12 Quinoxalines as Substrates 66
2.2.13 4-Thia-l-azabicyclo[3.2.0]heptanes as Substrates 67
2.2.14 [1,2,5]Thiadiazolo[3,4-b)pyrazines as Substrates 68
2.2.15 Thiazolo[3,2-a]pyrazines as Substrates 68
2.2.16 Thiazolo[3,4-a]pyrazines as Substrates 69
2.3 Pyrazines from Heterotricyclic Systems 69
2.4 Pyrazines from Spiro Heterocycles 70
2.5 Appendix: Glance Index to Typical Pyrazine Derivatives Available from Other Heterocyclic Systems 71
Chapter 3 Pyrazine, Alkylpyrazlnes, And Arylpyrazines 75
3.1 Pyrazine 76
3.1.1 Preparation of Pyrazine 76
3.1.2 Properties of Pyrazine 76
3.1.3 Reactions of Pyrazine 77
3.2 C-Alkyl- and C-Arylpyrazines 79
3.2.1 Preparation of C-Alkyl- and C-Arylpyrazines 80
3.2.1.1 By Direct C-Alkylation 80
3.2.1.1.1 General Procedures for C-Alkylation 80
3.2.1.1.2 C-Alkylation in the Scboellkopf Synthesis 86
3.2.1.2 By Replacement of Halogeno Substituents 93
3.2.1.3 By Replacement of Alkoxy, Cyano, Nitro, or Oxo Substituents 100
3.2.1.4 By Interconversion of Simple Alkyl Substituents 101
3.2.1.5 By Elimination of Functionality from Existing Substituents. 102
3.2.1.6 By Ipso-Substitution of Trimethylsiloxycarbonyl Substituents 105
3.2.2 Preparation of N-Alkyl- and N-Arylpiperazines 105
3.2.2.l By N-Alkylation Processes 106
3.2.2.2 By Reduction of N-Acyl or N-Alkoxycarbonylpiperazines 112
3.2.2.3 By Miscellaneous Routes 113
3.2.3 Properties of Alkyl- and Arylpyrazines 114
3.2.4 Reactions of Alkyl- and Arylpyrazines 117
3.2.4.1 Oxidative Reactions 117
3.2.4.2 Reductive Reactions 119
3.2.4.3 Extranuclear Halogenation 120
3.2.4.4 Extranuclear Alkylation 122
3.2.4-.5 Extranuclear Alkylidenation 123
3.2.4.6 Extranuclear Acylation or Carboxylation 125
3.2.4.7 Cyclization 126
3.24.8 "Ammoxidation" of Methyl to Cyano Groups 128
3.2.4.9 Addition Reactions at Alkenyl or Alkynyl Substituents 128
3.2.4.10 Miscellaneous Reactions 130
3.3 N Alkylpyrazinium Salts and Related Ylides 1313.3.1 Preparation of N-Alkylpyrazinium Salts 131
3.3.2 Reactions of N-Alkylpyrazinium Salts 132
Chapter 4 Halogenopyrazines 137
4.1 Preparation of Nuclear Halogenopyrazin137
4.1.1 Nuclear Halogenopyrazines from Pyrazinones 137
4.1.2 Nuclear Halogenopyrazines by Direct Halogenation 141
4.1.3 Nuclear Halogenopyrazines by Deoxidative Halogenation of Pyrazine N-Oxides 145
4.1.4 Nuclear Halogenopyrazines from Pyrazinamines 146
4.1.5 Nuclear Halogenopyrazines by Transhalogenation 148
4.1.6 Nuclear Halogenopyrazines via Trimethylsiloxypyrazines 149
4.2 Reactions of Nuclear Halogenopyrazines 150
4.2.1 Aminolysis of Nuclear Halogenopyrazines 158
4.2.2 Hydrolysis of Nuclear Halogenopyrazines 164
4.2.3 Alcoholysis or Phenolysis of Nuclear Halogenopyrazines 159
4.2.4 Thiolysis of Nuclear Halogenopyrazines 164
4.2.5 Alkanethiolysis or Arenerhiolysis of Nuclear Halogenopyrazines 166
4.2.6 Azidolysis of Nuclear Halogenopyrazines 170
4.2.7 Hydrogenolysis of Nuclear Halogenopyrazines 171
4.2.8 Cyanolysis of Nuclear Halogenopyrazines 173
4.2.9 Miscellancous Displacement Reactions of Nuclear Halogenopyrazines 174
4.2.10 Fission, Rearrangement, or Cyclocondensation of Nuclear Halogenopyrazines 176
4.3 Preparation of Extranuclear Halogenopyrazines 178
4.3.1 Extranuclear Halogenopyrazines from Corresponding Hydroxypyrazines 178
4.3.2 Extranuclear Halogenopyrazines by Minor Procedures 180
4.4 Reactions of Extranuclear Halogenopyrazines
Chapter 5 Oxypyrazines 191
5.1 Tautomeric Pyrazinones 191
5.1.1 Preparation of Tautomeric Pyrazinones 191
5.1.2 Reactions of Tautomeric Pyrazinones 191
5.1.2.1 Conversion into Pyrazinethiones
5.1.2.2 Conversion into O- and/or N-Alkylated Derivatives 198
5.1.2.3 Conversion into O- and/or N-Alkylated Derivatives 198
5.1.2.4 Miscellaneous Reactions 205
5.2 Extranuclear Hydroxypyrazines 208
5.2.1 Preparation of Extranuclear Hydroxypyrazines 208
5.2.2 Reactions of Extranuclear Hydroxypyrazines 202
5.3 Nuclear and Extranuclear Alkoxy- or Aryloxypyrazines 217
5.3.1 Preparation of Alkoxy- or Aryloxypyrazines 217
5.3.2 Reactions of Alkoxy- or Aryloxypyrazines 219
5.4 Nontautomeric Pyrazinones_and N-Alkylpyraziniumolates 221
5.4.1 Preparation of Nontautomeric Pyrazinones 221
5.4.2 Reactions of Nontautomeric Pyrazinones 222
5.5Pyrazine N-Oxides 225
5.5.1 Preparation of Pyrazine N-Oxides 226
5.5.1.1 From N-Alkoxypyrazinones 226
5.5.1.2 By Direct, N-Oxidation 226
5.5.2 Reactions of Pyrazine N-Oxides 230
5.5.2.1 Deoxygenation 231
5.5.2.2 O-Alkylation or O-Acylation 233
5.5.2.3 Conversion into C-Acyloxypyrazines 234
5.5.2.4 Conversion into C-Amino-, C-Azido-, C-Cyano-, or C-Alkylthiopyrazines 237
5.5.2.5 Miscellaneous Reactions 238
5.6 Appendix: Trivial Names for Pyrazine Derivatives 240
Chapter 6 Thiopyrazines 245
6.1 Pyrazinethiones and Pyraz1nethiols 245
6.1.1 Preparation of Pyrazinethiones and Pyrazinethiols 245
6.1.2 Reactions of Pyrazinethiones and Pyrazinethiols 248
6.2 Alkylthiopyrazines and Dipyrazinyl Sulfides 251
6.2.1 Preparation of Alkylthiopyrazines 251
6.2.2 Reactions of Alkylthiopyrazines 252
6.2.2.1 Oxidation to Sulfoxides or Sulfones 252
6.2.2 2 Miscellaneous Reactions 254
6.3 Dipyrazinyl Disulfides and Pyrazinesulfonic Acid Derivatives 255
6.4 Pyrazine Sulfoxides and Sulfones 255
Chapter 7 Nitro- Amino-, And Related Pyrazies 259
7.1 Nitropyrazines 259
7.1.1 Preparation of Nitropyrazines 259
7.1.2 Reactions of Nitropyrazines 261
7.2 Nitrosopyrazines 262
7.2.1 C-Nitrosopyrazines 262
7.2.2 N-Nitrosopipcrazines and Related Compounds 262
7.3 Regular Aminopyrazines 265
7.3.1 Preparation of Regular Aminopyrazines 265
7.3.2 Reactions of Regular Aminopyrazines 273
7.3.2.1 N-Acylation of Aminopyrazines and Subsequent Cyclizations 273
7.3.2.2 N-Alkylidenation of Aminopyrazines and Subsequent Cyclizations 277
7.3.2.3 N-Alkylation of Aminopyrazines and Subsequent Cyclizations 280
7.3.2.4 Conversion into Ureidopyrazines or Related Products 282
7.3.2.5 Conversion into Trialkylsilylamino-, Triphenylphosphoranylideneamino-, or Dimethylsulfitnidopyrazines 285
7.3.2.6 Miscellaneous Minor Reactions 287
7.4 Preparation and Reactions of Hydrazinopyrazines 290
7.5 Preparation, Structure, and Reactions of Azidopyrazines 294
7.6 Nontautomeric Iminopyrazines 297
7.7 Arylazopyrazines 298
Chapter 8 Pyrazecarboxylic Acids And Related Derivatives 299
8.1 Pyrazinecarboxylic Acids 299
8.1.1 Preparation of Pyrazinecarboxylic Acids 299
8.1.2 Reactions of Pyrazinecarboxylic Acids 302
8.2 Pyrazinecarboxylic Esters 308
8.2.1 Preparation of Pyrazinecarboxylic Esters 308
8.2.2 Reactions of Pyrazinecarboxylic Esters 311
8.3 Pyrazinecarbonyl Halides 317
8.3.1 Preparation of Pyrazinecarbonyl Halides 317
8.3.2 Reactions of Pyra:dnecarbonyl Halides 318
8.4 Pyrazinecarboxamides, Pyrazinecarboxamidines, and Related Derivatives 321
8.4.1 Preparation of Pyrazinecarboxamides and the Like 321
8.4.2 Reactions of Pyrazinecarboxamides and the Like 324
8.5 Pyrazinecarbohydrazides and Pyrazinecarbonyl Azides 328
8.6 Pyrazinecarbonitriles 330
86.1 Preparation of Pyrazinecarbonitriles 330
8.6.2 Reactions of Pyrazinecarbonitriles 340
8.7 Pyrazinecarbaldehydes 336
8.7.1 Preparation of Pyrazinecarbaldehydes 336
8.7.2 Reactions of Pyrazinecarbaldehydes 338
8.8 Pyrazine Ketones 340
8.8.1 Preparation of Pyrazine Ketones 341
8.8.2 Reactions of Pyrazine Ketones 343
8.9 Pyrazine Cyanates, Isocyanates, Thiocyanates, Isothiocyanates, and Carbonitrile Oxides 349
Appendix: Table Of Simple Pyrazines 349
References 461
Index 515