Chemistry of Heterocyclic Compounds. Volume 23. Furopyrans and Furopyrones

386 Pages·26.84 MB·english

by  Mustafa A.

FUROPYRONES
FUROPYRANS AND
TSa is tlrc twenty-thiM &me. in the aerh
THE OF HETEROCYCLIC
CHEMISTRY COMPOUNDS
THE CHEMISTRY OF HETEROCYCLIC
COMPOUNDS
A OF MONOBRAPHB
SERIES
ARNOLD WEISSBERGER, Editor
FUROPYRANS and FUROPYRONES
1967
INTERSCIENCE PUBLISHERS
a division John Wiley & Sons
of
- -
London New York Sydney
Copyright @ 1967 Wiles and Som, Ltd.
by John
All Rights Reserved
Library of Congrese Catalog Card Number: 67-16130
The Chemistry Heterocyclic Compounds
of
The chemistry of heterocyclic compounds is one of the most complex
branches of organic chemistry. It is equally interesting for its theoretical
implications, for the diversity of its synthetic prooedures, for the
and
physiological and industrid significance of heterocyclic compounds.
A field of such importance and intrinsic difficulty should be made
L~S
readily accessible possible, the lack of modern detailed and
as and a
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
8ubdiViaiona have been designed cover the field in its entirety by
to
monographs which reflect the importance and the interrelations of the
various compounds and accommodate the specific interests of the
&uthors.
Research I.abomtories ARNOLDW EISSBEWER
Eaatmn K&k Cmpany
Rachim%w,N ew Ywk
Preface
The furopyram, and -pyrones occupy a prominent position among the
plant phenols, and comprise a body of organic substances of extm
ordinary variety and interest. The use of certain planta 88 an aid in
catching fish; the increasing of derris products, including rotenone
use
itself, insecticides; the recognition of the active principles of Kellah
aa
plant (Ammi visnaga L.) by Egyptians centuries ago, a home remedy
aa
against leucoderma, in relieving the pain of renal colic and uretral
spms, and in facilitating the passing of uretral stones ; the production
of antifungal compounds by host plants following the fungal infection,
phytoalexins; and the isolation of metabolites from the mycelium of
variant strains of mould, all present a rich field of scientific inquiry from
which have come many interesting and important findings.
Them compounds occupy a close structural and chemical
inter-
relationship that appears to reflect a similarly close relationship in the
processes by which they are formed in plants.
v&ed nomenclature was most confusing. It is not u n dto find
The
many names attached to each of the widespread natural products,
more
and two or three for each of the many plants. In general, the name given
here is that apparently used most aften ;t he of trivial names has been
u88
adopted with the more complex ring systems in order to avoid unwieldy
and cumbersome Sgstematicn ames. In all instances, however, alternative
nomenclature and numbering have been indicated so that no confusion
should result. The can be found in the Kowtetitution
synonyms usually
und Vorkommen den Orgcsnischen Pfkcnzenstoffe, compiled by
W.
Karrer, which also givea the important references to historical matters
details of isolation. A good of analytical data is Moderns
and source
Hethoden der PJEanwmw&se, edited by K. Pach and Traoey,
M. V.
and the Merck Idea:i s as convenient source any for references to the
a as
medical and clinical aapecta of many of the compounds to be dealt with.
The Chemhty of FhuonoS Crnpound.9, edited by T. A.
Finally,
Geissman, Natumlly Owwring Oxygen Ring Cmppounda, compiled by
F. M. Dew, the chapter on ‘Naturlich vorkommende Chromone’ by
vii
viii Preface
Schmid in F0rtsChritt-e der Chmde wganiwher Natur8k$e, edited by
N.
Zechmeister, and on ‘Compounds Containing Two Hetero-Oxygen
L.
Atoms in Different Rings ’ by B. WhaHey in €ZeterocycE%C’co nzpound~,
W.
edited by R. C. Eldefield, discuss not only chemical matters, but also
a
variety of related subjects of economic
importance.
effort has been made to include in the manuscript, papers
Every
indexed by Amerhn ChmkaZ Abstracts, up and including, 1964, and
to
subsequent papers in the more important Journals up to Deoember 1965.
Chemkal Ab&wts reference is listed in addition to the primary
The
reference for any article not consulted in the original. Steroid
sapogenins
(spiroshns), compounds, having a fused five-membered lactonic ring
with a pyran nucleus, and those chmacterized spiro rather than
by fused
ring systems are outside the of this
scope book.
It is aim of this contribution to bring together the knowledge of
an
these compounds that hm 80 far been gained, iand to present a systematic
and bibliography of the present position which further
survey h m
progress c&n be made. Present day studies on the eyntheeis, stereo-
chemistry, physioiogical activity, and biosynthesis of furoppnes
mntinue to add new information.
It hoped that the arrangement and discussion of the closely related
is
chases, included in the volume, will greater inte& impart a
arouse and
new viewpoint to the chemistry of the individual substanm.
Finally, I wish to acknowledge the underahding of wife,
my
Professor Dr. W. Asker, who not only suffered patiently all the problems
of writing a book, but helped me to eolve so many of them, by proof-
reading and indexing,
Department of C&m&trg A. MUSTAFA
Faculty of Science
Cairo University
Contents
.
I. Fumpyrans and -pyronea . 1
I. Naturally Occurring Furopyrms . . 2
.
1. Plumericin . 2
2. . 9
Anhydrotetrahydroaucubigenin .
Synthetic Furopyrans and -pyrones 11
II. .
ReferenMs. 13
III.
. .
purocoumorina 14
II. . .
I. Isolation 15
PhysicalPropertiRs . . 32
II. . .
36
Iu. NNoamteunrcalllayt Ourcecu rring Furocoumarh . 35
IV. .
1. Structure and Chemicd Properties 35
A. Angelicin . . 36
. .
B. Psoralen 38
. .
C. Bergapten 41
D. Bergaptol . . 44
. .
E. Isobergapten. 44
. .
F. Bergamuttin. 46
G. Xanthotoxin . . 46
H. Xanthotoxol . . 52
.
I. Isoimperetorin . 52
J. Oxypeucedanin . . 52
K. ostruthol .. .. 6 3
L. Imperstorin 56
. .
M. Alloimperatorin 66
. .
N. Herdenin
66
0. Isopimpinellin . , 56
.
P. Phellopterin , . 68
Q. Byekangelicol , 69
. .
R. Byakangelicin 61
. .
S. Pimpinellin 61
. .
T. Sphondin 62
.
U. Halfordin and Isohalfordm 62
.
V. Nodakenetin. 66
w. Peucedanin . . 09
. .
X. Athamantin 70
. 1
Y. Discophoridin. *. 72
2. Edultin
73
1* ix
X contents
.
kA.Peulustrin
73
Columbiansdin and Columbisnin .
BB. 76
Archangelicin
cc. 77
DD. Archangelin.
78
Ppwmmcin.
EE. . 78
F'F.
4,5',8-Trimethylpralen.. 79
Affstoxh Bmd G.
W. - . 79
Configuretion
2. . 80
Biosynthesia
3. 82
A. a@'-Hydroxypropyl)dihydrofurans and a-Lsopropenyl-
dihydrofuranB.
83
B. Relations.
a-hpmpyl-fi-.h ydroxyfimamnsd 84
C. SimpleFurans
85
4. Phyaiologiwl Activity .
87
References.
V. 90
.
Furochromonari
III. . 102
I. Isolation
102
PhysicelPraperties .
II. . 103
III. Nomenclature
. 104
Naturally Occurring Furochromonea
IV. . 104
ChemioalF'ropertiee
1. . 104
A.Khellin
. 104
wrellin
(1) synthesis of 107
(2) Synthesis of khellin analogs .
. 112
Reactions
(3) 112
B. Visnagin.
. 133
synthesis of vismgin
(1) 134
(2) Synthe.e is of visnagin analogs and related transforma-
tions
. 136
Rerrctions
(3) 138
Khellinol.
c. 143
D.Khellinin .
. 144
Khellol
E. . 145
-01
F. . 147
Q. Vieaanminol
. 148
8.
ColorReactiona . 150
PhysiologicelA ctivity
v. 3. 161
R0f-m.
153
.
IV.Fpraxanthoner
160
I. Naturallp Ocourn'slg Furoxmthones .
. 160
1.sterigmetacystin . 180
11. SynthetioFuroxanthonee 189
Referenme.
ICII. 174
v,Ehroflrvonsll ,
. 175
I. Iaol~tion
176
II. PhyaimlPropertiw , 176
Contents
xi
.
Naturdy Occurring Furo&svonee. 183
III.
1. chemw&l Pmpertiee 183
.
A. B;ersnjin 183
.
B. LanoeohtinB 186
c. .
Pongapin 186
.
D. Kenjone. 186
E. Pongaglabrone.. , 188
F.Atamwin. 190
(3. Gamatin. 190
191
H. pinrrcltin. .
Synthetiohfbvones 192
IV. .
1. LineaE-type 192
.
2. 196
v. Angular-type
Referencee. 198
.
vI.Fllro~~noiaB 201
.
I. Introduction 201
.
Furoisoflavanonee 201
Ix. .
1. Naturally Ocourring Furoisofiavenonea 201
.
A. Nepseudin 201
.
B. Neotenone 218
.
2. SyntheticMoaoflamonm 220
.
A. AngularFuroisoflavonea 220
(1) Introduction of furan into hflavone
a nucleus . an
skeleton (T&’s method) 220
.
(2) Ethyl orthoformate (VenkstsMunan) 224
method .
B. Ljnw h ( 3 ’ , 2ff-6,7)mfhvonea 228
.
In. CQum~oahromSns. 227
.
1. 227
Introduction .
2. Naturally Oacurring Coumaranoahromans 228
.
A. Homopterocarpin 228
.
B. Pteroasrpin 230
c.&aOu .
233
D. Pisatin. 234
.
E. Neodulin 238
.
F.PhslPeollin 237
.
cOUmSronOfl8VSn-4-0h 238
Iv. .
1. Na.twalIy &curring Coumamnofiavan -4-01s 238
.
A. Gyanomaolurin 238
.
2. Synthetic l~-benzofuro(3,2-b)-l-benzopyran-ll-onee 242
.
V,&-nocoumh 243
1. Naturally Occurring Coumaronocoumarins . 243
.
A. Coumestrol 243
WeddoIrtatone . 246
B. .
Triioliol 261
C. .
D.Mediosgol 263
.
E. Psoralidin 254
VI. 3-ArylfuroCO~~hS. 268