Chemistry of Heterocyclic Compounds. Volume 2. Six-Membered Heterocyclic Nitrogen Compounds With Four Condensed Rings

352 Pages·6.98 MB·english

by  Allen C.F.H.

SIX-MEMBERED HETEROCYCLIC
NITROGEN COMPOUNDS
WITH FOUR CONDENSED
RINGS
This is :he second wlume published in :he sr*icr
THE CHEMISTRY OF HETEROCYCLIC COMPOUNDS
THE CHEMISTRY OF HETEROCYLIC COMPOUNDS
A SERIES MONOGRAPHS
OF
ARNOLD Consulting Editor
WEISSBERGER,
SIX-MEMBERED HETEROCYCLIC
NITROGEN COMPOUNDS
WITH FOUR CONDENSED RINGS
H.
C. F. ALLEN
Eastman Kodak Company, Rochester, N. Y.
collaboration with
In
BUHNESS, EAN V. CRAWFORD,
D. M.
F. ELLNOR
W. SPANGLERd . WILSORN. WEBSTER,a nd
V.
1951
INTERSCIENCE PUBLISHERS, INC., NEW YORK
INTERSCIENCE PUBLISHERS LONDON
LTD.,
Cnpyright, 1951, Interscirnce Publishers, Inc.
ALL RIGHTS RESERVED. This book or any part thereof must not be reproduced
without permission of the publisher in writing. This applies specifically to photontat
and microfilm reproductions.
INTERSCIENCE PUBLISHERS, INC., 250 Fifth Ave., New York I, N. Y.
Fm Great Britain and Northern Ireland:
Intrmcience Publishers Ltd., 2a Southampton Row, W. C. 1
London
INTHODUCTION TO THE
SERIES
The Chemistry of Heterocyclic
Compounds
The chemistry of heterocyclic compounds is one the most complex
of
branches of organic chemistry. It is equally interesting for its theoretical
implications, for the diversity of its synthetic procedures, and for the
physiological and industrial significance heterocyclic compounds.
of
A field of such importance and intrinsic difficulty should be made
as
readily accessible possible, and the lack a modern detailed and
as of
comprehensive presentation of heterocyclic chemistry is therefore keenly
felt. It is the intention of the present series to fill this gap by expert
presentations of the various branches of heterocyclic chemistry. The
subdivisions have been designed to cover the field in its entirety by
monographs reflect the importance and the interrelations of the
which
various compounds, and accommodate the specific interests of the authors.
Research Loboratories ARNOLD WElSSBERGER
fistman K& Company
Rochester, New York
V
The polynuclear heterocyclic compounds containing nitrogrn and four
fused six-membered rings are not only of considerable interest to the
drug and dye industries, but are also of great theoretical interest and
historical importance. In several instances the proof of structure was
unexpectedly difficult, requiring many years, to which well-known
chemists devoted much of their scientific lives. The similarities and
significant differences shown by the various members of the larger hetero-
cyclic condensed systems are lost in the usual treatment given them in
the literature. It is hoped that the arrangement and discussion of the
closely related classes included in this volume will arouse a greater interest
in and impart a new viewpoint to the chemistry of the individual sub-
stance. The literature has been covered through 1950.
The varied nomenclature was most confusing, each group of investi-
gators applying names that gave little clue as to structures. Even the
indexing journals were not consistent. Both names and numbering
differed markedly for strictly analogous types of compounds. In a
monograph such as this, uniformity is essential, particularly for locating
different series of compounds for comparison. For these reasons, the
system of nomenclature has been adopted, and every substance
“a”
named accordingly. In the index, all individual chemical substances
are listed under the names in the text. The name of the parent
used
ring system, as listed in the Ring Index and used in Chemical Abstracts, is
also indexed. Thus, anyone unfamiliar with the “a” nomenclature can
find the “a” name of the corresponding ring system by its Chemical Abstracts
name, and then up the individual substance under the “a” name of
look
the parent ring system.
The publishers have cooperated in every way to make the volume of
the greatest possible use and have been most liberal in the allowance of
space for structural formulas and an extensive index. The authors are
very grateful to A. H. Talbot for typing, proofreading, and general
Mrs.
editorial assistance.
Eastman Kodak Companp C. F. AILEN
H.
Rochester, New York
March 15, 1951
vii
Contents
Preface ............................................................... vii
Introduction .......................................................... 1
. . .
I Armaphthcencr EIconorR Wabster ............................... 3
By
1. Monoazanaphthacenes . .................................... 3
A. 1-~anaphthaccn.c. ......................................... 3
. 2-Azanaphthaccne ........................................... 7
B
C. 5-Azanaphthaccne ...... ........... 8
.
2 IXazanaphthacenu ........
A . 1,3-Diazanaphthacene ........................................ 21
. 1,4Diazanaphthacene ........................................ 24
B
C. 1, 1I -Diazanaphthacenc ....................................... 26
. 2,3-Diazanaphthaccne ...... ..................... 26
1). 5,CDiazanaphthacenc ........................................ 27
E. 5,ll-Diazanaphthacene ....................................... 34
F .
G 5.1 2.Diazanaphthacenc ....................................... 37
3. Triazanaphthacenes. ............................................ 43
A. ..............................
. 51,,66, ,111l- -TTrriaizaaznanaapphhththaacceennce . .............................
B
4 . Tetrazanaphthacenol ............................................ 45
A. ....... .............. 45
. 11.,43.6,,5 ,1112- T-Tcetrtarzaaznaanapphhththaacceennce ................................... 47
CB . ............................... 50
5,6,11,12.Tetrazanaphthacene
. .
I1 Az1a. b eMnzo(nuo]aaznatbhernrzc[ueJaacnrt hrBayc eJneacns. .1..' .C rawjord a dE lrunor K . W'bsh... ............ 57
57
A . ...
. l-Azabenz[aJanthracenc.,. ................................... 61
B 4-.4zal~enz[aJanthracene.,
(1) Derivatives .......................... .....
Alkyl 65
(2) Oxidation Products ....................................... 66
(3) Halogen Derivatives. .................. ................. 67
(4) Nitro Derivatives ..................... ................. 68
(5) Sulfonatcd and Hydroxylated Derivatives .................... 68
(6) Physical Properties ......
(7) Amino Compounds ......
C. 5-Azabenz[o]anthracene ...................................... 83
1). 8-Azabenz [aI anthracenc ...................................... 85
E. lO-Azabenz[o]anthracenc ..................................... 88
P . 1I -Azabcnz[o]anthraccnc ..... ........ ........... 89
ix
X Contents
.
11 Azabenz[a]anthtocener (continued)
. ........................................
2 Diazabenz[a]anthracenes 91
A . ... ..............
. 1,3-Diazabenz[alanthracene ... ............... 9913
BC . 11 ,,74 --DDiiaazzaabbeennzz[[ aa]l aanntthhrraacceennec ................................... 96
. . . ............
D. 1,12-Diazabenz[a]anthrace.n.e. ............ 96
E. 2,4-Diazabenz[o]anthracene. .. 98
F . 4,7-Diazabenz[a]anthracene
G ..................................
. 4,1ZDiazabenz[ajanthracen.e. . ............ 100
H 5,7-Diazabcnz[a]anthracenc 101
.........................................
(1) Ciba Yellow 3C 102
H&ht ....................................
(2) Yellow U 107
(3) ......... .......... ....
Htichst Yellow R 109
. . . .......................
I. 5,12-Diazabenz[a]anthracene 114
J ..................................
. 6,7-Diazabenz[o]anthracene 117
.................... ....
. K 6,12-Diazabenz[a]anthracene 120
. ................................
3 Tr.i azabenz[a]anthracenes 121
A 4,7,12-Triazabenz[a]anthracenc ............................... 121
. .............................
. B 6,7,12-Tr[ iazabenz[a]an.t.h.r.a.c.e.n.c. ........ .................. 122
4 Te.t razabenz a ]anthracenes 123
.......................
A . 7,8,10,12-Tetrazabenz[a)anthraccnc 124
............................
. B 7,9,11,12-Tctrazabenz[o]anthracrne 124
.....................................
5 Pe.n tatabenz[a]anthracene s 127
..........................
A . 4,7,9,11,12-Pentazabenz[o]anthracene 127
................
B 4,7,8,1O,1 ZPentazabenz [aJ anthracenr 127
. . .
IXX A.a obcnrto[cjphenlnthrener By Eltanor H W'rbstn., ................. 133
1 Monoazabenzo[c]phenanthrenes. ....... ......................... 133
A. . l.Azabenzo[c]phenanthrenc .......... ........................ 133
........... ........................
B . 2.Azabenzo[c]phenanthrenr: 134
.......... ........................
C . bAzabenzo[c]phcnanthrenc 134
D ......... .......................
. 6-Azabenzo[c]phenanthrenc 133
2 Diazabenzo[c]phenanthrenes. ......... . . . . . . . . . . . . . . 141
A. . 1 ,Z Diazabenzo[cj phenanthrcnr ........ ..................... 141
B 5,8.Diazabenzo[c]phenanthrrnr ....... ...................... 142
. . .
1V A.z achrysencr ByJean V CroccJord ........................... 151
1 Mo.n oazachrysenc l ............................................ 151
................................ ..........
A 1-Azachrysenc 151
B .. 2-Azachrysene. ....... .................................. 154
..............................................
C 3-Azachrysene .. 154
. . . . . . . . . . . . . . . . . . . . . . . . . .
155
E. 5-Azachryscnc. ............... . . . . ........... 157
............ . . . . . . . . . . . . . . . . . . . . . .
(1) Chelidonine 160
.....................................
166
.....................................
(3) a-Homochelidonine 168
........................................
. (4) Chelerythrine 169
.............................................
F 6-Azachryscne 174
Contents xi
.
IV 2A .z aDciharzyarcehnryesre n(ccosn .t.i.nu.e.d.). ....... ....... .................... 174
A . 1.lO.Diazachrysene ....... ............................... 174
B. 2.rl- Diazachryscne ........................................... 175
C. 4.1O.Diazachrysenc ..................... ................ 175
. .
Axrtriphenylener ByJcun V. Crowford .......................
V .
1 Monoazatriphcnylcnes ...................................
A . 1- Azatriphenylcne ............. ........................... 185
B. 2-Azatriphenylene ............. ........................... 186
2 . Diazatriphenylenes ................ ........................... 188
A . 1..2 .Diazatriphenylene ........................................ 188
B. 1 4-Diazatriphenylene .... ................ 188
.
C 1.8-Diazatriphcnylene ........................................ 191
D. 2,f-Diazatriphenylcne .. ........... ... ... 192
. Triazatriphenylencs .................. ... ... 192
3 A . 1.2.CTriazatriphenylcne ...... ........................ 193
B. 1.5.9-Triazatriphenylene. ..... ........................ 198
. hbenaanthrener . By C. F. H . Allen. D . M . Burness. and F. W .S panglcr . . 201
VI
Introduction ...................................................... 201
A . Historical ................................................
B. Nomenclature ...... ......... ........................ 202
(1) Numbering ................................................. 202
(2) Zhabenzanthrones (Anthrapyridines. Anthrapyridoncs) ......... 202
(3) 1, 3-Diazabcnzanthrones (Anthrapyrimidincs) ................... 203
1. Monoazabenzanthrenes .......................................... 204
A . 7H.l.Azabenzanthrenc . By D . M . Burncss ...................... 204
(1) Preparation ............................................. 204
(2) Reaaiona ................................ 205
( 3.)it .. ............................................... 205
B. 2-Atabenzanthrur~. ~ By D . M . BUWWS.S. ................. 207
(I) Preparation ............. ......... .......... 207
(2) Reactionr ............................................... 208
(3) Propertia ..................................... 209
C . 3-Azabenzanthrcncs . By C. F. H . Allm ......................... 209
(1) Monokcto Derivatives: 3-Azabenzanthmna (Anthrapyridines) . 209
(2) Diketo Mvativcs: 2-Keto-3-azabenzanthmna (Anthrapyri-
dona) ............................................... 213
(a) Ring from 1-Aminoanthraquinone ........ .. 214
CClloossuurree,. Method ...... ............. 216
(b) Ring seka’s
(c) Formation Substituted 2-Kcto-3-az nthrones ...... 217
of
(1) In the 1-Position .................................. 217
(2) In the 3-Pdtion ......... ...................... 219
(3) In the CPOeition ............................ 219
(4) In the &Position .................................. 219
(5) the 8- and 11-Positions. ......................... 220
(6) MIn tecllaneous. .................................. 221
xii Contentr
.
Anbenunthrener (COrJinurd)
VI
(d) Products Uncertain Structures ....................... 222
of
(e) Wianthrapyridoncs” .................................. 223
DE. . C5(3-A)A zzcaaobbleoenrnz .za.an.n.tth.h.rr.ee.nn.e.es.s ... ..BB..yy. .DD... . . MM.. .... BB..uw.m wtssss .. ....................... 222222388
(1) Introduction ................................... 229
(2) Hittotical ............................................... 229
(3) Nomenclature ........................................... 230
(4) Sterrochdtry. ......................................... 231
(5) prepatation. ............................................ 231
(6) Reactionr ........................... ................ 235
(7) pmpertia ........................... ................ 237
(8) Source, Roputieq and Physiological Action of the Natural
................. ....................... 238
Alkaloid8
(a) Apomorphine ........................................ 238
(b) Apocodeinc .............. ........... 239
(c) Rounaine .......................................... 239
(d) Anolobime ............................................ 239
(e) Morphothebaine ..................................... 239
..........................................
(f) Tuduranine 240
..........................................
(g) Iaothebaine
240
(h) Pukatcine ........................................... 240
(i) Laurcline .................................... .. 241
(j) Laurotetanine ........................................ 241
Actinodaphnine ....................................... 241
(k)
(I) Boldine. ............................................ 242
(m)Corytuberinc ........................................ 242
Laurepukine ............ ..... ... 243
(n)
(0) N-Mcthyllaurotetanine ................................ 243
(p) d-Corydine. ......................................... 243
Isocorydinc. .......... 244
(q)
(r) Domesticine ......................................... 244
Isodomaticine 244
(s)
(t) Bulbocapninc ...................... .............. 245
(u) Glaucinc ............................................ 245
(v) Epidicentrinc . . ........... 246
(w)Diccntrine ........................................... 246
. 7H,8(x-A) zGablaeunzJadnin ther .e.n.e.. . .B..y. .D.. . .M. ... B..u.n.u.s.s ..... ........................... ... 225446
GF . 7H,ll-Azabenzanthrcne. By D . M . Burness ..................... 254
(1) Preparation ... .............................. .. 254
(2) Reactions .............................. ............. 256
(3) Properties. .............................................. 257
. x-Azabcnzanthrenes. By D. M . Burness ........................ 257
. H
2 Diazabenzanthrena ............................................. 260
A. 1, 2-Diazabenzanthrones (Pyridazinoanthroncs). By F . I+‘. Spongltr . 260
(1) Historical. .............................................. 261