Quinoxalines, Volume 61, Spplement 2

Desmond J. Brown is Professor of Chemistry at The Australian National University.

"This book updates Volumes 5 and 35 of this series on quinoxalines and covers the literature on quinoxalines from approximately 1976-2002." (Journal of the American Chemical Society, June 9, 2004)

• Chapter 1 Primary Syntheses 11.1 From a Single Benzene Substrate 11.1.1 By Formation of the N1,C8a Bond 11.1.2 By Formation of the N1,C2 Bond 41.1.2.1 Cyclization of o-(Ethylamino)aniline Derivatives 41.1.2.2 Direct Cyclization of o-(Ethylamino)nitrobenzene Derivatives 61.1.2.3 Reductive Cyclization of o-(Ethylamino)nitrobenzene Derivatives 81.1.3 By Formation of the C2,C3 Bond 121.2 From a Benzene Substrate with an Ancillary Synthon 131.2.1 When the Synthon Supplies N1 of the Quinoxaline 131.2.2 When the Synthon Supplies C2 of the Quinoxaline 141.2.3 When the Synthon Supplies C2 + C3 of the Quinoxaline 161.2.3.1 Using a Dialdehyde (Glyoxal) or Related Synthon 161.2.3.2 Using an Aldehydo Ketone or Related Synthon 181.2.3.3 Using an Aldehydo Acid or Related Synthon 221.2.3.4 Using an Aldehydo Ester or Related Synthon 231.2.3.5 Using an Aldehydo Amide, Nitrile, Acyl Halide, or Related Synthon 241.2.3.6 Using a Diketone or Related Synthon 241.2.3.7 Using a Keto Acid or Related Synthon 301.2.3.8 Using a Keto Ester or Related Synthon 311.2.3.9 Using a Keto Amide, Nitrile, Acyl Halide, or Related Synthon 341.2.3.10 Using a Diacid (Oxalic Acid) as Synthon 351.2.3.11 Using a Diester (a Dialkyl Oxalate) or Related Synthon 361.2.3.12 Using an Estero Amide, Nitrile, Acyl Halide, or Related Synthon 381.2.3.13 Using a Diamide (Oxamide), Amido Nitrile, or Related Synthon 401.2.3.14 Using a Diacyl Dihalide (Oxalyl Halide) or Related Synthon 401.2.4 When the Synthon Supplies N1 + C2 + C3 of the Quinoxaline 421.2.5 When the Synthon Supplies N1 + C2 + C3 + N4 of the Quinoxaline 421.3 From a Benzene Substrate with Two or More Synthons 44     1.4 From a Pyrazine Substrate with or without Synthon(s) 451.5 From Other Heteromonocyclic Substrates/Synthons 461.5.1 Azirines as Substrates/Synthons 471.5.2 1,2,3-Dithiazol-1-iums as Substrates/Synthons 471.5.3 Furans as Substrates/Synthons 481.5.4 Isothiazoles as Substrates/Synthons 491.5.5 Isoxazoles as Substrates/Synthons 501.5.6 Oxazoles as Substrates/Synthons 511.5.7 Oxirenes as Substrates/Synthons 511.5.8 Pyrans as Substrates/Synthons 531.5.9 Pyridazines as Substrates/Synthons 531.5.10 Pyridines as Substrates/Synthons 541.5.11 Pyrimidines as Substrates/Synthons 541.5.12 Pyrroles as Substrates/Synthons 551.5.13 Thiophenes as Substrates/Synthons 551.5.14 1,2,4-Triazines as Substrates/Synthons 561.5.15 1,2,3-Triazoles as Substrates/Synthons 561.6 From Heterobicyclic Substrates/Synthons 571.6.1 7-Azabicyclo[4.1.0]heptanes as Substrates/Synthons 571.6.2 Benzimidazoles as Substrates/Synthons 571.6.3 1,4-Benzodiazepines as Substrates/Synthons 591.6.4 1,5-Benzodiazepines as Substrates/Synthons 591.6.5 1-Benzopyrans (Chromenes) as Substrates/Synthons 611.6.6 2,1,3-Benzoselena(or thia)diazoles as Substrates/Synthons 611.6.7 2,1,3-Benzoxadiazoles as Substrates/Synthons 621.6.8 Cycloheptapyrazines as Substrates/Synthons 681.6.9 Indoles as Substrates/Synthons 681.6.10 Pyrrolo[3,4-b]pyrazines as Substrates/Synthons 691.7 From Heteropolycyclic Substrates/Synthons 701.7.1 Azeto- or Azirino[1,2-a]quinoxalines as Substrates/Synthons 701.7.2 Benz[g]indoles as Substrates/Synthons 711.7.3 Benzo[3,4]cyclobuta[1,2-b]quinoxalines as Substrates/Synthons 711.7.4 Benzo[g]pteridines as Substrates/Synthons 711.7.5 [1]Benzopyrano[2,3-b]quinoxalines as Substrates/Synthons 731.7.6 [1]Benzothiopyrano[4,3-b]pyrroles as Substrates/Synthons 731.7.7 Cyclobuta[b]quinoxalines as Substrates/Synthons 731.7.8 1,3-Dithiolo[4,5-b]quinoxalines as Substrates/Synthons 741.7.9 1,4-Ethanoquinoxalines as Substrates/Synthons 741.7.10 Furo[2,3-b]quinoxalines as Substrates/Synthons 751.7.11 Furo[3,4-b]quinoxalines as Substrates/Synthons 761.7.12 Indeno[1,2-b]pyrroles as Substrates/Synthons 761.7.13 Isoxazolo[2,3-d][1,4]benzodiazepines as Substrates/Synthons 771.7.14 Isoxazolo[2,3-a]quinoxalines as Substrates/Synthons 771.7.15 [1,3,4]Oxadiazino[5,6-b]quinoxalines as Substrates/Synthons 781.7.16 [1,2,4]Oxadiazolo[2,3-a]quinoxalines as Substrates/Synthons 781.7.17 [1,2,5]Oxadiazolo[3,4-f]quinoxalines as Substrates/Synthons 791.7.18 Phenazines as Substrates/Synthons 791.7.19 Pyrazolo[3,4-b]quinoxalines as Substrates/Synthons 791.7.20 Pyridazino[4,5-b]quinoxalines as Substrates/Synthons 801.7.21 Pyrrolo[3,4-b]quinoxalines as Substrates/Synthons 811.7.22 Quinoxalino[2,3-b]quinoxalines as Substrates/Synthons 821.7.23 Thiazolo[2,3-b]benzothiazoliums as Substrates/Synthons 821.7.24 Thiazolo[3,2-a]quinoxaliniums as Substrates/Synthons 821.8 From Spiro Heterocyclic Substrates 831.9 Glance Index to Typical Quinoxaline Derivatives Available by Primary Syntheses 84Chapter 2 Quinoxaline, Alkylquinoxalines, And Arylquinoxalines 932.1 Quinoxaline 932.1.1 Preparation of Quinoxaline 932.1.2 Properties of Quinoxaline 942.1.3 Reactions of Quinoxaline 952.2 Alkyl- and Arylquinoxalines 1002.2.1 Preparation of C-Alkyl- and C-Arylquinoxalines 1012.2.1.1 By Direct Alkylation or Arylation 1012.2.1.2 By Alkanelysis or Arenelysis of Halogenoquinoxalines 1022.2.1.3 From C-Formyl-, C-Aroyl-, C-Cyano-, or Oxoquinoxalines 1062.2.1.4 By Interconversion of Alkyl or Aryl Substituents 1082.2.1.5 By Elimination of Functionality from Substituted-Alkyl Substituents 1132.2.2 Preparation of N-Alkyl or N-Aryl Derivatives of Hydroquinoxalines 1142.2.3 Properties of Alkyl- and Arylquinoxalines 1152.2.4 Reactions of Alkyl- and Arylquinoxalines 1172.3 N-Alkylquinoxalinium Salts 1292.3.1 Preparation of N-Alkylquinoxalinium Salts 1292.3.2 Reactions of N-Alkylquinoxalinium Salts 131Chapter 3 Halogenoquinoxalines 1333.1 Preparation of Nuclear Halogenoquinoxalines 1333.1.1 Nuclear Halogenoquinoxalines from Quinoxalinones 1333.1.2 Nuclear Halogenoquinoxalines by Direct Halogenation 1393.1.3 Nuclear Halogenoquinoxalines from Quinoxalinamines 1413.1.4 Nuclear Halogenoquinoxalines by Transhalogenation 1423.1.5 Nuclear Halogenoquinoxalines from Miscellaneous Substrates 1443.2 Reactions of Nuclear Halogenoquinoxalines 1463.2.1 Aminolysis of Nuclear Halogenoquinoxalines 1463.2.2 Hydrolysis, Alcoholysis, or Phenolysis of Nuclear Halogenoquinoxalines 1563.2.3 Thiolysis, Alkanethiolysis, Arenethiolysis, or Arenesulfinolysis of Nuclear Halogenoquinoxalines 1613.2.4 Azidolysis of Nuclear Halogenoquinoxalines 1643.2.5 Cyanolysis of Nuclear Halogenoquinoxalines 1663.2.6 Hydrogenolysis of Nuclear Halogenoquinoxalines 1673.2.7 Other Displacement Reactions of Nuclear Halogenoquinoxalines 1683.2.8 Cyclization Reactions of Nuclear Halogenoquinoxalines 1703.3 Preparation of Extranuclear Halogenoquinoxalines 1743.4 Reactions of Extranuclear Halogenoquinoxalines 1753.4.1 Aminolysis of Extranuclear Halogenoquinoxalines 1753.4.2 Hydrolysis, Alcoholysis, or Phenolysis of Extranuclear Halogenoquinoxalines 1793.4.3 Acyloxy Derivatives from Extranuclear Halogenoquinoxalines 1813.4.4 Thiolysis, Alkanethiolysis, Arenethiolysis, or Arenesulfinolysis of Extranuclear Halogenoquinoxalines 1833.4.5 Other Displacement Reactions of Extranuclear Halogenoquinoxalines 1843.4.6 Cyclization Reactions of Extranuclear Halogenoquinoxalines 186Chapter 4 Oxyquinoxalines 1894.1 Tautomeric Quinoxalinones 1894.1.1 Preparation of Tautomeric Quinoxalinones 1904.1.2 Reactions of Tautomeric Quinoxalinones 1944.1.2.1 Conversion into Quinoxalinethiones 1954.1.2.2 Conversion into O- and/or N-Alkylated Derivatives 1954.1.2.3 Miscellaneous Reactions 2004.2 Quinoxalinequinones 2064.2.1 Preparation of Quinoxalinequinones 2064.2.2 Reactions of Quinoxalinequinones 2084.3 Extranuclear Hydroxyquinoxalines 2114.3.1 Preparation of Extranuclear Hydroxyquinoxalines 2124.3.2 Reactions of Extranuclear Hydroxyquinoxalines 2154.4 Alkoxy- and Aryloxyquinoxalines 2194.4.1 Preparation of Alkoxy- and Aryloxyquinoxalines 2194.4.2 Reactions of Alkoxy- and Aryloxyquinoxalines 2214.5 Nontautomeric Quinoxalinones 2234.5.1 Preparation of Nontautomeric Quinoxalinones 2234.5.2 Reactions of Nontautomeric Quinoxalinones 2244.6 Quinoxaline N-Oxides 2254.6.1 Preparation of Quinoxaline N-Oxides 2264.6.2 Reactions of Quinoxaline N-Oxides 2304.6.2.1 Deoxygenation 2304.6.2.2 Deoxidative C-Substitutions 2354.6.2.3 Other Reactions 237Chapter 5 Thioquinoxalines 2415.1 Quinoxalinethiones and Quinoxalinethiols 2415.1.1 Preparation of Quinoxalinethiones and Quinoxalinethiols 2415.1.2 Reactions of Quinoxalinethiones and Quinoxalinethiols 2425.2 Alkylthioquinoxalines and Diquinoxalinyl Sulfides 2465.2.1 Preparation of Alkylthioquinoxalines 2465.2.2 Reactions of Alkylthioquinoxalines 2485.3 Diquinoxalinyl Disulfides and Quinoxalinesulfonic Acid Derivatives 2505.4 Quinoxaline Sulfoxides and Sulfones 251Chapter 6 Nitro-, Amino-, and Related Quinoxalines 2556.1 Nitroquinoxalines 2556.1.1 Preparation of Nitroquinoxalines 2556.1.1.1 By Direct Nitration 2556.1.1.2 From Dimethylsulfimidoquinoxalines 2606.1.2 Reactions of Nitroquinoxalines 2606.1.2.1 Reduction to Quinoxalinamines 2606.1.2.2 Displacement Reactions 2656.2 Nitrosoquinoxalines 2676.3 Regular Aminoquinoxalines 2696.3.1 Preparation of Regular Aminoquinoxalines 2696.3.2 Reactions of Regular Aminoquinoxalines 2786.3.2.1 N-Acylation of Aminoquinoxalines or Reduced Quinoxalines 2796.3.2.2 N-Alkylation or Alkylidenation of Aminoquinoxalines 2836.3.2.3 Reactions Involving Initial Diazotization of Aminoquinoxalines 2866.3.2.4 Miscellaneous Transformations of Aminoquinoxalines 2886.3.2.5 Cyclization of Aminoquinoxalines 2916.4 Hydrazino- and Hydrazonoquinoxalines 2966.4.1 Preparation of Hydrazino- and Hydrazonoquinoxalines 2976.4.2 Reactions of Hydrazino- and Hydrazonoquinoxalines 2996.4.2.1 Noncyclization Reactions 3006.4.2.2 Cyclization Reactions 3056.5 Azidoquinoxalines 3126.6 Arylazoquinoxalines 314Chapter 7 Quinoxalinecarboxylic Acids And Related Derivatives 3177.1 Quinoxalinecarboxylic Acids and Anhydrides 3177.1.1 Preparation of Quinoxalinecarboxylic Acids 3177.1.2 Reactions of Quinoxalinecarboxylic Acids 3227.2 Quinoxalinecarboxylic Esters 3277.2.1 Preparation of Quinoxalinecarboxylic Esters 3277.2.2 Reactions of Quinoxalinecarboxylic Esters 3297.3 Quinoxalinecarbonyl Halides 3337.4 Quinoxalinecarboxamides and Related Derivatives 3347.4.1 Preparation of Quinoxalinecarboxamides and the Like 3357.4.2 Reactions of Quinoxalinecarboxamides and the Like 3377.5 Quinoxalinecarbonitriles 3427.5.1 Preparation of Quinoxalinecarbonitriles 3427.5.2 Reactions of Quinoxalinecarbonitriles 3437.6 Quinoxalinecarbaldehydes 3457.6.1 Preparation of Quinoxalinecarbaldehydes 3467.6.2 Reactions of Quinoxalinecarbaldehydes 3487.7 Quinoxaline Ketones 3527.7.1 Preparation of Quinoxaline Ketones 3527.7.2 Reactions of Quinoxaline Ketones 3537.8 Quinoxaline Cyanates, Isocyanates, Thiocyanates, Isothiocyanates, and Nitrones 356Appendix: Table of Simple Quinoxalines 359References 437Index 471