Nitrogen with Four Rings, Volume 2

Introduction 1

I. Azanaphthacencs 3
By Eleanor R. Webster

1. Monoazanaphthacenes 3

A. 1-Azanaphthacenc 3

B. 2-Azanaphthacene 7

C. 5-Azanaphthacene 8

2. Diazanaphthacenes 21

A. 1,3-Diazanaphthacene 21

B. 1,4-Diazanaphthacene 24

C. 1,11-Diazanaphthacene 26

D. 2,3-Diazanaphthacene 26

E. 5,6-Diazanaphthacene 27

F. 5,11-Diazanaphthacene 34

G. 5,12-Diazanaphthacene 37

3. Triazanaphthacenes 43

A. 1,6,11 -Triazanaphthacene 43

B. 5,6,11-Triazanaphthacene 45

4. Tetrazanaphthacenes 45

A. 1,3,5,12-Tetrazanaphthacene 45

B. 1,4,6,11-Tetrazanaphthacene 47

C. 5,6,11,12-Tetrazanaphthacene 50

II. Azabenz[a]anthracenes 57
By Jean V. Crawjard and Eleanor K. Webster

1. Monoazabenz [a]anthracenes 57

A. 1-Azabenz [a]anthracene 57

B. 4-Azabenz[a]anthracene 61

(1) Alkyl Derivatives 65

(2) Oxidation Products 66

(3) Halogen Derivatives 67

(4) Nitro Derivatives 68

(5) Sulfonated and Hydroxylated Derivatives 68

(6) Physical Properties 73

(7) Amino Compounds 75

C. 5-Azabenz[a]anthracene 83

D. 8-Azabenz[a]anthracene 85

E. 10-Azabenz[a]anthracene 88

F. 11-Azabcnz [a]anthracene 89

2. Diazabenz [a]anthracenes 91

A. 1,3-Diazabenz[a]anthracene 91

B. 1,4-Diazabenz [a]anthracene 93

C. 1,7-Diazabenz [a]anthracene 96

D. 1,12-Diazabenz [a]anthracene 96

E. 2,4-Diazabenz [a]anthracene 98

F. 4,7-Diazabenz [a]anthracene 99

G. 4,12-Diazabcnz [a]anthracene 100

H. 5,7-Diazabenz [a]anthracene 101

(1) Ciba Yellow 3G 102

(2) Hochst Yellow U 107

13) Hochst Yellow R 109

I. 5,12-Diazabenz [a]anthracene 114

J. 6,7-Diazabenz [a]anthracene 117

K. 6,12-Diazabenz [a]anthracene 120

3. Triazabenz [a]anthraccnes 121

A. 4,7,12-Triazabenz[a]anthracene 121

B. 6,7,12-Triazabenz[a]anthracene 122

4. Tetrazabenzjajanthracenes 123

A. 7,8,10,12-Tetrazabenz [a]anthracene 124

B. 7,9,11,12-Tetrazabenz [a]anthracene 124

5. Pentazabenz [a Janthraccnes 127

A. 4,7,9,11,12-Pentazabenz[a]anthracene 127

B. 4,7,8,10,12-Pentazabenz[a]anthracene 127

III. Azabenzojc Jphenanthrenes 133
By Eleanor K. Webster

1. Monoazabenzo [c]phenanthrenes 133

A. 1-Azabenzo[c]phenanthrenc 133

B. 2-Azabenzo[c]phenanthrenc 134

C. 4-Azabenzo[c]phenanthrenc 134

D. 6-Azabenzo[c]phenanthrenc  139

2. Diazabenzo[c]phenanthrenes 141

A. 1,3-Diazabenzo[c]phenanthrcne 141

B. 5,8-Diazabenzo[c]phenanthrenc 142

IV. Azachrysenes 151
By Jean V. Crawford

1. Monoazachrysenes 151

A. 1-Azachrysene 151

B. 2-Azachrysene 154

C. 3-Azachrysene 154

D. 4-Azachrysene 155

E. 5-Azachrysene 157

(1) Chelidonine 160

(2) Sanguinarine 166

(3) α-Homochelidoninc 168

(4) Chelerythrine 169

F. 6-Azachrysene 174

2. Diazachrysenes 174

A. 1,10-Diazachrysene 174

B. 2,4-Diazachrysene 175

C. 4,10-Diazachrysenc 175

V. Azatriphenylenes 185
By Jean K Crawford

1. Monoazatriphcnylcncs 185

A. 1-Azatriphenylene 185

B. 2-Azatriphenylene 186

2. Diazatriphenylenes 188

A. 1,2-Diazatriphenylene 188

B. 1,4-Diazatri phenylene 188

C. 1,8-Diazatriphenylene 191

D. 2,3-Diazatriphcnylene 192

3. Triazatriphenylenes 192

A. 1,2,4-Triazatriphenylene 193

B. 1,5,9-TriazatriphenyIene 198

VI. Azabensanthrenes 201
By C. F. H. Allen, D. M. Burners, and F. W. Spangler

Introduction 201

A. Historical 201

B. Nomenclature 202

(1) Numbering 202

(2) 3-Azabenzanthrones (Anthrapyridines, Anthrapyridones) 202

(3) 1,3-Diazabenzanthrones (Anthrapyrimidines) 203

1. Monoazabenzanthrenes 204

A. 7H,1-Azabenzanthrene 204
By D. M. Burners

(1) Preparation 204

(2) Reactions 205

(3) Properties 205

B. 2-Azabenzanthrenes 207
By D. M. Burners 207

(1) Preparation 207

(2) Reactions 208

(3) Properties 209

C. 3-Azabenzanthrenes 209
By C. F. H. Allen

(1) Monoketo Derivatives: 3-Azabenzanthroncs (Anthrapyridines) 209

(2) Diketo Derivatives: 2-Keto-3-azabenzanthrones (Anthrapyridines) 213

(a) Ring Closure, from 1-Aminoanthraquinone 214

(b) Ring Closure. Seka’s Method 216

(c) Formation of Substituted 2-Keto-3-azabenzanthrones 217

(1) In the 1-Position 217

(2) In the 3-Position 219

(3) In the 4-Position 219

(4) In the 6-Position 219

(5) In the 8- and 11-Positions 220

(6) Miscellaneous 221

(d) Products of Uncertain Structures 222

(e) “Dianthrapyridones” 223

(3) Color 223

D. 5-Azabenzanthrenes 228
By D. M. Burness 228

E. 6-Azabenzanthrenes 228
By D. M. Burness 228

(1) Introduction 229

(2) Historical 229

(3) Nomenclature 230

(4) Stereochemistry 231

(5) Preparation 231

(6) Reactions 235

(7) Properties 237

(8) Source, Properties, and Physiological Action of the Natural Alkaloids 238

(a) Apomorphine 238

(b) Apocodeine 239

(c) Roemerine 239

(d) Anolobine 239

(e) Morphothebaine 239

(f) Tuduranine 240

(g) Isothebaine 240

(h) Pukateine 240

(i) Laureline 241

(j) Laurotetanine 241

(k) Actinodaphnine 241

(l) Boldine 242

(m) Corytuberine 242

(n) Laurepukine 243

(o) N-Methyllaurotetanine 243

(p) d-Corydine 243

(q) Isocorydine 244

(r) Domesticine 244

(s) Isodomesticine 244

(t) Bulbocapnine 245

(u) Glaucine 245

(v) Epidicentrine 246

(w) Dicentrine 246

(x) Glaucidine 246

F. 7H,8-Azabenzanthrene 254
By D. M. Burness

G. 7H,11-Azabenzanthrene 254
By D. M. Burness

(1) Preparation 254

(2) Reactions 256

(3) Properties 257

H. x-Azabenzanthrenes 257
By D. M. Burness

2. Diazabenzanthrenes 260

A. 1,2-Diazabenzanthrones (Pyridazinoanthrones) 260
By F. W. Spangler

(1) Historical 261

(2) 3-Substituted 1,2-Diazabenz an thrones 262

(a) Preparation 262

(b) Properties 262

(c) Uses 263

(3) 3-Keto-1,2-diazabcnzanthrones 263

(a) Preparation 263

(b) Properties 265

(c) Uses 265

B. 1,3-Diazabenzanthrones 267
By C. F. H. Allen

(1) Monoketo-1,3-diazabenzanthrenes (Anthrapyrimidines) 267

(a) Ring Closure 267

(b) Replacement Reactions 272

(1) Amines 272

12) Halogenated Derivatives 273

(3) Sulfonic Adds 273

(4) Hydroxy Derivatives 274

(5) Miscellaneous Derivatives 274

(a) Acylamino-1,3-diazabenzanthrones 274

(b) Arylamino-1,3-diazabenzanthrones 275

(c) Haloamino-1,3-diazabenzanthrones 275

(d) N-Alkylsulfonic Acids 275

(e) Nitriles 275

(f) Carboxylic Adds 276

(g) Oxy, Thio, and Seleno Derivatives 276

(2) Diketo-1,3-diazabenzanthrenes (Anthrapyrimidones) 277

(3) Products of Uncertain Structure 279

(4) Physical Properties 280

(5) Uses 281

VII. Azapyrenes 295
By Eleanor R. Webster

1. Monoazapyrenes 295

A. 2-Azapyrene 295

B. 4-Azapyrene 296

2. Diazapyrenes 298

A. 2,7-Diazapyrene 298

B. 4,9-Diazapyrene 302

3. Tetrazapyrenes 305

1,3,6,8-Tetrazapyrene 305

Azsbenzanthrenes: Addendum 311
By C. P. Wilson

1. 2-Keto-3-methyl-3-azabenzanthrones 311

2. 1,3-Diazabenzanthrones 312

A. Aryl Group in the 4-Position 312

B. Sulfobenzoylation 312

Index 315