Chemistry of Heterocyclic Compounds. Volume 7. Compounds with Condensed Thiophene Rings

526 Pages·34.9 MB·english

by  Hartough H.D.

WITH
COMPOUNDS
CONDENSED THIOPHENE RINGS
This is the amenih volume published in the series
THE CHEMISTRY HETEROCYCLIC COMPOUNDS
OF
~
THE CHEMISTRY OF HETEROCYCLIC
COMPOUNDS
h MONOGRAPHS
SERIES OF
ARNOLD WEISSBERGER, CmuZting Editor
COMPOUNDS WITH
CONDENSED
THIOPHENE RINGS
D. HARTOUGH
H.
Formerly , Somy-V acuum Idmatorie8
and
S. L. MEISEL
Sowng-Vacuum hboraton’es, Padsboro, Neev Jersey
1 9 5 4
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The Chemistry of Heterocyclic Compounds
The chemistry of hetmocyclic compounds is one of the most complex
braricherr of organic chemistry. It is equally interesting for its theoretical
implications, for the diversity of its synthetic procedures, arid for the
physiological and industrial silpliscmce of heterocyclic compounds.
A field of such importance and intrinsic difficulty should be made as
readily accemible as possible, and the lack of a modern detailed and com-
prehensive presentation of heterocyclic chemistry therefore keenly felt.
is
It is the intention of the present series to fill this gap by expert presenta-
tions of thc various branches of heterocyclic chemistry. The subdivisions
have been designed to cover the field in its entirety by monographs which
reflect the importance and the interrelations of the various compounds,
and accommodate the specific interests of the authors.
Reseurch Laborafories ARNOLDW EISSBEKQER
Eastmun K& Company
Rocheetm, h'ew York
V
Preface
The chemistry of compounds containing the condensed thiophene nu-
cleus was originally scheduled to he included the volnme, Thiophene rand
in
Its DerivcStiws. However, since the material collected on the.several hun-
dred condensed systems containing a thiophene nucleus so voluminous
was
and diverse, it, seemed advisahle t.0 treat thiR mbject in a separate volume.
The two volumes have been designed to cover critically all pbes of the
chemistry of the thiophene systems. Thus, whenever it has been possible,
physical constants, reaction conditions, yields, and other pertinent data
have included. An exception made in the case of the thioindigo
been was
dyes, which are so numerous that to lkt them with their physical constants
and colors would have required several hundred additional pages. For
that reason, the existing data are summarized in a separate chapter, which,
while it does not constitute a thorough review of the thioindigo dyes, will,
we hope, fill a gap the chemical literature. The remaining chapters con-
in
tain a critical review of the literature and a complete list of references
to all condensed ring systems containing the thiophene nucleus and their
respective derivatives. We shall be grateful for any omissions which
are brought to our attention.
Various nmnencldure systems have been used in the naming of condensed
thiophene compounds. In the past few years, two new nomenclature sys-
tems have heen proposed. One is the “ox&-aza-thiLtfsl ystem which sys-
tematically names osygon, nitrogen, and sulfur heterocycles. The other
system, which pertains only to sulfur heterocycles, uses the term “thio-
phene” the basic root of all names. Both of these systems differ from
as
that currently used by Chemical Ab8tl.racls.
In view of this confused state, both the A. C. S. OrganoSulfur and the
A. C. S. Heterocyclic Komenclature subcommittees were consulted. There
appeared to be a of agreement between these committees. For ex-
lack
ample, one committee suggested that 1-thiaindene be substituted for the
common name, thianaphthene, while the other proposed the name, benzo-
[blthiophene. Since neither of these new sy&ems had official sanction, it
iv&s decided to use ChemicaE Abstmct8 nomenclature, although the alter-
native names that have been used for each system are also listed. It
should be pointed out h t c ommon names such as thianaphthene and
thiophanthrene form the roots of many of the names of the complex ring
of Chapters V to WII, and changing the Chemical Abstracts nomen-
systems
vii
viii rwfm
clature would have required the changing of all of these names without any
wurance that the system we chose would eventually receive official a p
proval. We are of the opinion that the systematic names, benzo [bI thio-
phene and 1-thiaindene, have some over the common name,
advantages
thianaphthene. However, we feel that one nomenclature system must be
officially approved before the names now in use should be changed.
We thank the Socony-Vacuum Oil Company for permission to write this
and for the use of their library facilities. Dr. W. P. Hawthorne, by
book
his painstakhg proofreading and critiml reviewing of this volume, has
improved immeasurably its quality and organization. We are grateful to
Dr. R. Dobres and Dr. C. hf. Fontans of Socony-Vacuum Oil Company
M.
and to Dr. E. M. Crane of Eastman Kodak Company for their critical
comments, and to Dr. R. 0. Offenhauer and Mr. J. J. Dickert, Jr., for their
help in the reading of proof. Hercules Powder Company furnished library
facilities during the latter phases of the writing of this and steno-
book
graphic help in the typing of the manuscript.
Originally we had hoped to pemade someone familiar with thioindigo
dyes to write Chapter 111. This w~ not possible, but Mr. A. J. Johnson of
E. 1. du Pont de Nemours & Company reviewed this chapter and
kindly
us during the writing period. Mr. Johnson also provided the
advised
patent bibliography at the end of Chapter 111 and compiled Table I which
deals with commercially available thioindigo dyes.
The writing of this book WBB facilitated by private communications from
friends in this country and abroad. Sincere thanks for such help are due
to Prof. F. G. Bordwell of Northwestern University, Prof. E. V. Brown of
Fordham University, Prof. Frederick Challenger, The University, Led,
England, Prof. 0. Dam of the University of Erlangen, Germany, Prof. H.
Gilman of Iowa State University, Prof. W. Hera of the University of Flor-
ida, and Prof. P. A. S. Smith of the Tinivemity of Michigan.
The original draft of the book waa completed in May, 1951; therefore,
references 701 to 770 which appeared between that date and 15,1952,
May
mere inserted the completed manuscript. Since it was not always pos-
into
sible to incorporate these references into the text, in some instances only a
tabulation of the compounds and their physical constants has been given.
With the exception of article13 and patents that we may have overlooked,
all references are included up to May 15, 1952.
HOWARDD. HART~UGH
Hercules Ezpcrimml slahbn
Hrrnrles Poloder Company, Wiimington, Delaware
SEYMOULR. M EISEL
Sowny-Vacuwn oil Company, Pauidwo, New Jersey
CONTENTS
1 . Factors Influencing Chemical Reactivity and Substitution of Thio-
.....................................................
pheneSyetems 1
1. Introduction ................................................. 1
I1. Electrophilic Substitution of Furan. Thiophene and Selenophene ... 2
.
I11 Electrophilic Substitution of Benzofursn. Ttiiansphthene. Seleno-
naphthene and the Thienothiophenaq ............................ 4
IV. Electrophilic Subetitutjon of Dibeneofuran. IXbenzothiophttne and
Dihenzodenophene ........................................... 10
V. Metalation of Thiopheiio Systems ............................... 14
.
VI Reactivity of tho Sulfur Atom in Thiophcne Systems .............. 15
Thianaphthene and Other Thiophene Compounds Containing One
XI Carbocyclic Fused Ring ............................................ 17
1nt.roduction. ......................... ......................... l?
A . Thianaphthene and Derivatives ................................... 17
Ite
Nomenclature ................ .................... 18
Occurrence of Thianaphthene Nat.urc. ............................. 18
I . Preparation of Thianaphthcne and Its Hornologu .... 20
A . Thimaphthcne .......................................... 20
.
XJ Monoalkylthianaphthenes ................................. 22
C. Dialkylthianaphthcnes .................................... 24
.
D Trial kylthianaphtheries ..................... ...... 25
E . Arylthianaphthenes ............ 26
11 . hfiwe~~aneou&sa ctions and Propertie8 ........................ 29
111 . The Hydrothianaphthencs ......... 34
.
.4 2,:Z-Dihydrot.hinnaphphtherlea nd Its Derivatives. .............. 34
. 6,i-Dihvdrothianaphthene. ........................
IC3 . and Denvativen. . 36
IV. Hal4o,.g5t,i8 ,D7-eTreitv,artsilvieysd r.(.,.t.hi.R.n.n.l.r.h.th.c.n.c.!. ....I.t.s. .................. 3457
V . NA i.t rNoigtemnt ,Dliiexrnivaapth.itv.leier.n .e..'.l... ....... ............................................................ 4488
R . Arninothianapht henw ......... .. ......... 51
C. neriv~tiverw ith NitroKen in a Side Chain .................. 5a
. Hydrox?ll.hianapht,heries( Thianxpht.heno1~or Thioindoxyla) ...... 63
VL
. Tttutomeriem of 2- and 3-€€\.droxq-thianapht.henes... ......... 04
Bh . Preparation of Hydroxythianaphthenea ..................... 86
1 . 2FIydroxpthiannphthenes .............................. 66
. ;3-I.fydrox.~hianaphthenes.. ............................ 87
2
ix
X Contanta
.
I1 Thianaphthene Thfophene Compounds Containing One
and Other
oprbocyclic Fused Ring (continuad)
.
4-Hydroxytlhmphthenes ..............................
3. 73
6Hydmxythianaphthenehenee. .............................
45 . &Hydroxythkmphthenee. ............................. 80
. 7-Hydroxythianaphthenes ............ 81
6. a2
7 Di- and Trihydroxythianaphthenee ......................
C. Resotions of Hydroxythiaphthenes. . 8842
.
1 of the Enol ............................
. Reactions Form a4
VII . Thi2a nRspehsotthioemqu ohf otnhee aK. .e.to. .F.o.r.m. ..................................................... .... 8968
................................
A.. 2,3-Thisnsphthenequinonea 95
B B.e menoid “hianaphthenequinonea ......................... 102
1 .................... ..... 102
. 4,6-Thianaphthenequinonea
2 6,7-Thianaphthenequhonee .................... ..... 104
. .............................
. 3 4,7-Tbianaphthenequinonm 104
VIII Derivatives Containing Hydroxyl Group in a Side Chain .........
. ........................................ 107
IX Carbonyl Derivetivea 109
A . ............................ 109
. B . TKheitaon aDpehrtihveantievceaar bofo xTahiidaenhaypdhenth ene ........................ 114
X TAh .i aMnoapnhotchaerbnoecxayrlbico Axcyildics h..i.d..e.. ......................................... .......... 124
B. . 2, &Thianaphthenedi&xylic Acid and .It.e. .D.e.r.iv..at.i.v.e.s. ............ 112344
C 3-Amin+!&thisnrrphtxylic Acid 137
D. Acid .................. 1%.
. 3-Hydroxy-%thianaphthenecsrboxylic
Thianaphthenecarboxylic Acida with the Carboxyl Group in the
E
Sidechain .............................................. 141
........
XI. Thisnaphtheneeulfonic and Thianaphthene Sulfide6 153
. ..A.c.i.d.s. ................................
XII Darivativee 154
XI11. TMehricaunrayp hthene 1-Oxide8 (Sulfoxides) ......................... 155
.
XIV Thianaphthene l-Eoxides (Sulfones) .......................... 156
A. Preparation ..................................... 156
. Reactions ...............................................
. IsothianBa phthene and Ita Derivatives. ............................... 115697
B
I . Th.e Hydroisothianaphthenee. ................................ 167
A 1, 3-Dihydroisothianaphthsne (o-XyIylene Sulfide). ........: ..
167
B. 6,7-Dihyd1v- and ........ 168
I1. Derivatives of Ieothia4n,faip,h6t,h7e-Tneet. r.&.y.d.r.o.i.s.o.t.h.i.a.n.a.p.h.t.h.e.n.e.e. ...... 168
.
C Miecellaneoua System., ............................................
. Cyclopents[b Jthbphene. .......................... 117722
I1I. Cyclohepta[b]thiophene. ..........................
111 . ............................... 173
4,7-Endovinylenethianaphthene 173
111. Thioindigo and Related Dyes .......................................
175
Introduction ...................................................
. Nomenclature .................................................. 175
T . Friedliinder’e Commercial Thioindigo Synthasie ..................... 178
IT 181
Contente
xi
.
III Thioindigo and Related (continued)
Dyes
III . Symmetrical Thioindigo Dyes ..................................... 181
A . 2,2'-Bisthioindigo~. .......................................... 181
B. 2,s '-Bithioindigoa (Thioindirubins). .......................... 187
C . 3,3' -Bisthioindigo (Ieothioindigo) .............................. 188
IV. Asymmetrical Thioindigos ........................................ 189
A . .............................. 189
h~ymmetrica12,2'-Thioindigoi&
I3 . ksymmetrical Thioindirubina ................................. 189
C . Miscellaneous Thioindigoids and Related Materials .............. 190
D . Condensation with Phenanthroquinones. ....................... 192
. Thioindogenidcs and Anils Thioindoxyls ......................... 194
V . Leucothioindigos (Thioindigofo Whites) .............................. 195
VI.
1'11 Reactions of the Thioindigo Dyes ................................. 197
VIII . Factors Meeting the Colors of Thioindigo Dyes .................... 199
TX . Indophenine and Related Dyes ................................... ... 206
Scheme of Reactions Proving the Presence of the Dithienyl Nucleus 212
Index of References Pertaining to the Thioindigo Dyes Not in Text .... 215
Index of Reference8 Perbining to Naphthioindigoe and Thioindigos
Having More Complex Ring System Not Included in Preceding Index
......................................................
or Text 215
United Patents Pertaining Thioindigoe., .................. 216
States to
German Putenta Pertaining to Thioindigos ......................... 218
British Patenta Pertaining to Thioindigos .......................... 221
French Patents Pertaining to Thioindigos .......................... 223
.
and Its Dedvativea ............................... 225
IV Dibenzothiophene
.
I IntrcHiuction .................................................... 225
.
Dibenzothiophene. .............................................. 226
I1 A . Nomenclature ......................................... 226
B. Occurrence in Nature ........................................ 220
.
C Preparation ................................................. 227
1. Historic .............. .............................. 227
2 . CyclkataiIo n of Biphenyls ................................... 227
3 . Cyclization of Sulfur Compounde ........................... 228
4 . Reduction of Oxides and Dioxides .......................... 230
5 . hli~cellaneousM ethods ............... ................. 231
232
233
1. Physical Properties ....................................... 233
2 . Toxicological Properties ............... ................ 234
3. Miscellaneous Properties ................................... 235
235
IV. Sulfoxides and Sdfones. ..
237
241
A . Chlorodibenmthiophenes ..................................... 241
B . Bromodibenzothiophenes ..................................... 242
.
C Iododibenzothiophenes ....................................... 247