Encyclopedia of the Alkaloids: Volume 2 (I-Z)

693 Pages·1975·18.24 MB·English

by  John S. Glasby (auth.)

ENCYCLOPEDIA OF
THE ALKALOIDS
Volume 2 (1-Z)
ENCYCLOPEDIA OF
THE ALKALOIDS
Volume 2 (I-Z)
John S. Glasby
leI (Organics Division) Ltd.
Ayrshire, Scotland
PLENUM PRESS • NEW YORK AND LONDON
Library of Congress Cataloging in Publication Data
Glasby, John Stephen.
Encyclopedia of the alkaloids.
Includes bibliographical references.
I. Alkaloids - Dictionaries. l. Title.
QD42l.G54 547'.72'03 75-17753
ISBN-13: 978-1-4615-8731-6 e-ISBN-13: 978-1-4615-8729-3
DOl: 10.1007/978-1-4615-8729-3
Softcover reprint of hardcover 1st edition 1975
Contents
Volume 1 K. 801
L. 820
A. 1 M. 886
B. 192 N. 983
c. 233 o. 1031
D. 389 P . 1060
E. 499 Q. 1150
F . 567 R. 1156
G. 604 S . 1195
H. 650 T. 1282
U. 1353
V. 1363
w.
Volume 2 1412
x. 1416
I 735 Y 1418
J 790 z. 1421
I
IBOGAINE
C2oH260N2
M.p. 152°C Et
'H
This indole alkaloid occurs in the root of Tabernanthe iboga Baill. It was first
examined in detail by Raymond-Hamet who assigned to it the empirical formula
C19H24(26)ON2, now altered to that given above. The base forms colourless
crystals from EtOH and is laevorotatory with [Q1D - 53° (EtOH). It is insoluble
in Et20, slightly so in Me2CO or CHC13 but dissolves freely in MeOH, EtOH or
H20. The alkaloid yields a hydrochloride, m.p. 299°C (dec.); lQlhs - 67°
(MeOH) or - 37.3° (H20). It contains one methoxyl group and gives the typical
indole reactions. On distillation with Zn dust or soda-lime it furnishes products
which are indole derivatives with the ~-position free.
In a manner similar to that of cocaine, the alkaloid potentiates the pressor
action of adrenaline and abolishes the sino-carotid reflexes. Unlike cocaine,
however, it also augments the action of tyramine and that of dl-ephedrine to a
slight extent. Vincent and Sero have reported that it inhibits the action of serum
cholinesterase.
Raymond-Hamet., Bull. Soc. Chirn. Fr., 9,620 (1942)
Delourme-Houde., Chern. Abstr., 41, 1390 (1947)
Bartlett, Dickel, Taylor.,J. Arner. Chern. Soc., 80, 126 (1958)
Arai, Coppola, Jeffery., Acta Cryst., 13, 553 (1960)
Shamma, Soyster., Experientia, 20,36 (1964)
Synthesis:
Buchi et ai., f. Arner. Chern. Soc., 88,3099 (1966)
Pharmacology:
Raymond-Hamet, Rothlin., C.R. Soc. Bioi., 127,592 (1938)
Raymond-Hamet, Rothlin., Arch. inst. Pharrnacodyn., 63, 27 (1939)
Raymond-Hamet., Cornpt. rend., 201,285 (1940)
Raymond-Hamet., C.R. Soc. Bioi., 135, 176 (1941)
Raymond-Hamet, Perrot., Bull. Acad. Med., 24,423 (1941)
Vincent, Sero., C.R. Soc. Bioi., 136,612 (1942)
IBOGAMINE
A further alkaloid obtained from Tabernanthe iboga Baill. This base forms
colourless needles and has [Qlh8 - 54.7° (EtOH). The ultraviolet spectrum
exhibits two absorption maxima at 230 and 285 m{J.. The structure has been
735
confirmed by the total synthesis of the alkaloid in the (±)-form. The synthetic
base has m.p. 128.5-130.5°C.
Burckhardt et aI., Helv. Chim. Acta, 35,642 (1952)
Bartlett, Dickel, Taylor.,J. Amer. Chem. Soc., 80, 126 (1958)
Crystal structure:
Arai, Coppola, Jeffery., Acta Cryst., 13, 553 (1960)
Synthesis:
Biichi et al., 1. Amer. Chem. Soc., 87,2073 (1965)
Biichi et al., ibid, 88, 3099 (1966)
Sallay., ibid, 89,6762 (1967)
Nagata et al., ibid, 90, 1650 (1968)
Hirai, Kawata, Nagata., Chem. Commun., 1016 (1968)
IBOLUTEINE
C2oH2602N2
M.p. 142°C
This indole base also occurs in Tabernanthe iboga BailI. and has subsequently
been discovered in Rejoua aurantica Gaud. It yields colourless crystals from
MeOH and is laevorotatory with [a1bS - 114° (CHC13). A crystalline oxime has
been prepared with m.p. 293-4°C. The structure has been determined from the
infrared, NMR and mass spectra.
Goutarel, Janot., Ann. Pharm. Fr., 11,272 (1953)
Goutarel et al., Helv. Chim. Acta., 39,742 (1956)
DickeletaI.,l. Amer. Chem. Soc., 80, 123 (1958)
Guise et al., Austral. 1. Chem., 18,927 (1965)
Spectrum:
Goutarel et al., Helv. Chim. Acta., 39,742 (1956)
IBOXYGAINE
C2oH2602N2
M.p. 234°C
Present in several Iboga species, this base is slightly laevorotatory, having [alD -
5° (CHC13). It contains one methoxyl group, an imino group and a secondary
hydroxyl group. It forms a crystalline p-toluenesulphonyl derivative, m.p. 267-
8°C. On catalytic reduction, the base furnishes ibogaine (q.v.). The structure has
been determined from chemical and spectroscopic evidence to be decarbo
methoxyvoacangarine.
Goutarel, Percheron, Janot., Compt. rend., 246,279 (1958)
Stauffacher, Seebeck., Helv. Chim. Acta., 41, 169 (1958)
Renner, Prins., Experientia, 15,456 (1959)
Biemann, Friedmann-Spiteller., Tetrahedron Lett., 68 (1961)
736
IBOXYGAINE HYDROXYINDOLENINE
C20H2603N2
Isolated from Peschiera lundii (D.C.) Miers, this indole alkaloid is dextrorotatory
with [alfis + III ° (c 0.026, CHCI3) and gives an ultraviolet spectrum in ethanol
which has absorption maxima at 227, 265,285 and 313 mil. It contains a
methoxyl group and two hydroxyl groups, one secondary and the other tertiary.
Whang et al., J. Org. Chern., 34,412 (1969)
ICAJINE
C22H2403N2
M.p. 271-2°C (dec.).
A strychnine type alkaloid, this base is found in the leaves of Strychnos icaja
Baill. It may be crystallized from MeOH when it yields colourless prisms. The
alkaloid has [aID - 10° (c 1.0, CHCI3) and the ultraviolet spectrum in EtOH
shows absorption maxima at 254 and 291 mil. The structure has been established
as that of N-methyl-sec-pseudostrychnine.
Bisset., Cornpt. rend., 261,5237 (1965)
IFFLAIAMINE
o
C1SH1702N ® .
M.p. Indefinite
3
This furanoquinoline alkaloid has been obtained from the bark of the Australian
tree Flindersia ifflaiana. It is obtained in the form of a colourless gum which
cannot be crystallized. The alkaloid is laevorotatory with [al~~9 - 0.6° or
[al~~o - 3.6° (c 8.0, MeOH). From aqueous solvents, a crystalline hydrate is
formed, m.p. 62-3°C. The ultraviolet spectrum in MeOH shows absorption
maxima at 215, 236, 309 and 320 mil with a shoulder at 251 and an inflexion at
298 mil. A yellow crystalline picrate is known, m.p. 207-9°C. The probable
structure obtained from infrared and NMR spectra, and dependent upon analogy
737
with other alkaloids of this type, has been confirmed by the total synthesis of
the (±)-form, m.p. 128-9°C.
Bosson et al., Austral. 1. Chem., 16, 480 (1963)
Total syn thesis:
Chamberlain, Grundon., Tetrahedron Lett., 3547 (1967)
IGNAVINE
C27H3106N OH
M.p. 226-8°C
This aconitine alkaloid is present in several A conitum species indigenous to
Japan, e.g. Aconitum calliantum Koidzumi, A. grossedentatum, Nakai, A.
hakusanense Nakai, A. kamtschaticum Willd. et Reichb., A. lucidusculum Nakai,
A. senanense Nakai, A. subcuneatum Nakai, A. tortuosum Willd. and A. Zuccarini
Nakai. It yields clusters of colourless needles when crystallized from Me2CO
MeOH and gives a form, m.p. 172-4 °c in addition to the one having the above
melting point. It is dextrorotatory with [al~} + 85.27° (MeOH), or [a1b4 +
92.98°. Crystalline salts of the alkaloid have been prepared, e.g. the hydro
chloride, m.p. 245-6°C (dec.); hydrobromide, m.p. 260-2°C (dec.) and the
nitrate which crystallizes as the monohydrate, m.p. 220-2°C (dec. dry). Alkaline
hydrolysis furnishes benzoic acid and hydroignavinol, C20H2S04N, m.p. 302°C.
Ochiai et al., J. Pharm. Soc., Japan, 72, 816 (1952)
Ochiai et al., ibid, 76, 550 (1956)
Ochiai", Okamoto, Sasaki., ibid, 75,545 (1955)
Ochiai et al., Chem. Pharm. Bull., 6,327 (1958)
Ochiai et al., ibid, 8, 976 (1960)
Pelletier., Tetrahedron, 14,103 (1961)
ILLUDININE
C16H1703N OCH3
~
2
A sesquiterpenoid alkaloid found as a metabolite of Clitocybe illudens. On
decarboxylation, the methoxyl group is simultaneously cleaved to yield 7: 7-
dimethyl-9-hydroxy-6: 7 -dihydro-8H-cyclopenta [g l-isoq uinoline.
Nair et al., J. Org. Chem., 34, 240 (1969)
738
IMENINE
C2oH'70SN
M.p. 206-7°C
An oxodibenzoquinoline alkaloid found in the stem extract of Abuta irnene, this
base contains four methoxyl groups in the molecule and gives an ultraviolet
spectrum in EtOH solution with absorption maxima at 240,275,345 and
438 mj1. The structure, established from spectroscopic data, is 1:2:3:4-
tetramethoxy-7-oxodibenzo [de,g] quinoline.
Glick et al., Chern. Cornrnun., 1217 (1969)
IMPERIALINE
C27H4303N
M.p. 254°C (dec.).
o
A steroidal alkaloid isolated from the bulbs of Fritillaria irnperialis L. and
Petiliurn eduardi, the base crystallizes in short, colourless needles and has
[alo - 35.4° (CHCI3). It yields crystalline salts and with sucrose gives a
sequence of characteristic colours on addition of dilute H2S04 from yellow
green, through pale green, pink, cherry red, to dark violet. The structure has been
determined from mass spectrometry and the NMR spectrum, the latter proving
the presence of tertiary hydroxyl and methyl groups at C-20.
Fragner., Ber., 28,3284 (1888)
Structure:
Nuriddinov, Shakirov, Yunusov., Khirn. Prir. Soedin., 3,316 (1967)
INANDENINE
C23H4S02N3
~
N~
a
H H
2
739
The leaves of Oncinotis inandensis yield a base which consists of two inseparable
isomers. The structure have been shown to be 1-( 4-aminobutyl)-1 : 5-diazacyc1o
heneicosane-l 2: 2l-dione (Inandenine A) and the corresponding 13: 2l-dione
(Inandenine B).
Veith, Hesse, Schmid., Helv. Chirn. Acta, 53, 1355 (1970)
INDACONITINE
C34H4701ON
M.p. 202-3°C
An aconitine alkaloid obtained from A coniturn chasrnanthurn Stapf. by Dunstan
and Andrews, the base crystallizes from EtOH as hexagonal prisms or rosettes of
fine needles. It has [ado + IS.3° (EtOH) and gives a series of crystalline salts,
e.g. the hydrobromide as hexagonal prisms from H20, m.p. lS3-7°C; [edo -
17.3° or as crystals from EtOH or Et20, m.p. 217 -SoC and the aurichloride,
yellow needles, m.p. 147 -152°C with sintering at 142°C. Indaconitine resembles
Aconitine (q. v.) in giving a crystalline precipitate with KMn04 but in this case
the crystals are markedly smaller. Four methoxyl groups are present and when
the SUlphate is heated in aqueous solution in a sealed tube it furnishes acetic acid
and benzoylpseudaconine (Indbenzaconine), as a colourless glass, m.p. 130-3°C;
[alo + 33.6° (EtOH), also giving crystalline salts: hydrochloride, m.p. 242-4°C;
[alo - S.Oo (H20); hydrobromide as the dihydrate, m.p. 247°C (dry) and the
aurichloride, rosettes of orange needles, m.p. ISO-2°C.
Alkaline hydrolysis gives acetic and benzoic acids and pseudaconine,
C2sH4108N. On pyrolysis, the alkaloid loses one mole of acetic acid with the
formation of a-pyroindaconitine which is amorphous, m.p. 130-2°C; [a1o +
91.9° (EtOH), giving a crystalline hydro bromide, m.p. 194-SoC. When inda
conitine hydrochloride is subjected to the same treatment it yields the isomeric
~-pyroindaconitine, also amorphous, but furnishing a crystalline hydrobromide,
m.p. 24S-250°C; [alo + 27.6°.
Dunstan, Andrews, J. Chern. Soc., 87, 1620 (1905)
See also:
Bauer, Radjhan., Pharrn. Zent., 72,145 (1931)
INDICAINE
ClOHllON
This liquid alkaloid occurs in Plantago indica and has been characterized as the
crystalline picrate, m.p. 151-3°C.
Danilova, Konovalova., J. Gen. Chern., USSR, 22,2237 (1952)
INDICAININE
C H 0N+
12 16
740