-CHAPTER 6-

ALKALOIDS UNCLASSIFIED AND OF UNKNOWN

STRUCTURE
R. H. I?. MANSKE
University of Waterloo, Waterloo, Ontario, Canada

I. Introduction ........................................................ 263

11. Plants and Their Contained Alkaloids .................................. 263
References .......................................................... 300

I. Introduction

Much of the data collected in the following chapter was gleaned

from Chemical Abstracts and is so indicated by listing a CA reference
although such a reference is often included for the convenience of
readers even where the original was available. Most of the alkaloids are
of structural types not treated in recent chapters of earlier volumes.
This chapter is supplementary to Volume XIV, Chapter 12, p. 507.

11. Plants and their Contained Alkaloids

1. Abuta imene Eichl, and A . rufescens Griseb. (Menispermaceae)

(XIII, 397)*
Two azafluoranthine alkaloids, a new type of alkaloid structure,
were isolated. Imeluteine (1) and rufescine (2) were isolated from the
stems of the plant and their structures were assigned on spectra1
evidence.
These structures were confirmed by syntheses. The amide 3 prepared
from known compounds was reacted with phosphorus oxychloride in
acetonitrile to generate a dihydroisoquinoline which on reduction,
diazotization, and treatment with activated copper gave dihydro-
imeluteine. Dehydrogenation to the natural alkaloid was effected by
* The Roman numeral followed by a n Arabic number refers t o volume number and
page where the subject of the heading has been treated in previous volumes.
264 R. H. F. MANSKE

heating in p-cymene with palladium/charcoal. Rufescine was syn-

thesized by a parallel series of reactions from the amide 4 (I).

2. Adalia bipunctata L. (Coleoptera; Coccinelidae)

The above-named insects have a chemical defense and an extract
of them has yielded the alkaloid adaline ( C,,H,,ON; amorphous;
[aID - 13') ( 5 ) .It was shown to have a carbonyl and an NH group, and
NMR spectroscopy indicated certain features which were confirmed
by an X ray study of adaline hydrochloride crystals (mp 204-205').
Adalia quadrimaculata Scopoli and A. pantherina L. also yielded
adaline (2).

3. Alchornea jloribunda Muell. Arg. (Euphorbiaceae) (VIII, 696; XI,

25)
Alchorneine (C,,H,,ON,; mp 43";[.ID - 105') was isolated from the
above-named plant as well as from A . hirtella Benth. Its structure (6),
largely determined by spectral methods including an X-ray examination
of its methiodide, was confirmed by chemical degradation to recognizable

Me0 ,

\ /
OMe
OMe
1 R-OMe 8 R=OMe
2 R = H 4 R = H

8 1-8
 6. ALKALOIDS UNCLASSIFIED AND OF UNKNOWN STRUCTURE 265

fragments. Isoalchorneine (C12H190N3;liquid; [a]= 5 0) (7)and al-

chorneinone (C12H2,0,N,; liquid) (8) were minor constituents of A .
jioribunda. Their structures were also largely based on spectral studies
and confirmed in whole and in part by chemical transformations ( 3 ) .

4. Ammodendron argenteum Kuntze (A. sieversii DC.) (Leguminosae)

(VII, 255)
Argentine (9) and argentamine (10) are two new alkaloids whose
structures were determined by spectral methods ( 4 ) .

5. Ancistrocladus heyeanus Wall. (Ancistrocladaceae; Dipterocarpaceae)

( x r v , 509)
The new alkaloid, ancistrocladisine (C26H,g0,N; mp 178-1 80';
[a]=- 16.13') was given structure 11 on the basis of a spectral study,

e2
a Hofmann degradation, and further chemical manipulation ( 5 ) .

N+

M e O OMe
e Me
M e

Me0
0
10 Me0 ' 11

13
266 R. H. F. MANSKE

6. Anona glabra L. (Anonaceae) (XIV, 228)

The first natural occurrence of N-methylactinodaphnine is reported.
Reticuline was also isolated ( 6 ) .
7. Anona squamosa L. (IV, 8 6 )
The following aporphine alkaloids were isolated : anonaine, roemerine,
norcorydine, corydine, norisocorydine, isocorydine, and glaucine (7').

8. Anopterus macleyanus F. Muell. and A . glandulosus Labill. (Escal-

loniaceae)
Anopterine (C,,H,,O,N; mp 222-223"; [.ID - 12") is an 0,O-ditigloyl
ester with two secondary and one tertiary hydroxyls. Hydrolysis with
alkali afforded tiglic acid and the pentahydroxy base, anopteryl
alcohol (C,,H,,O,N; mp 258-261"; [a],,+ 4"). Acetic anhydride reaction
served to generate a tetraacetyl anopteryl alcohol (C29H,gOgN;mp
156-158'; [.ID oJ,88'). X-ray examination of a derivative of the latter
showed that it has structure 12 (R = CH,CO) and therefore anopteryl
alcohol is 12 (R = H). Spectral evidence indicates that anopterine is
12 in which the two radicals R on the right-hand side of the given
formula are tigloyl (8).

9. Argemone fruticosa Thurber and Gray and A . echinata G. B. Ownb.

(Papaveraceae) (XII, 335)
The main alkaloid in A. fruticosa is hunnemanine along with allo-
cryptopine; A. echinata contains mostly cryptopine and berberine (9).

10. Argemone mzlnita Dur. and Hilg. (XII, 335; XIII, 398; XIV, 512)
2,9-Dimethoxy-3-hydroxypavinane(13) (C,,H,,O,N; mp 197-198";
[a];'- 254") was isolated from this plant. Its structure was confirmed
by a total synthesis involving the penultimate 1,2-dihydroisoquinoline
and its cyclization with formic and phosphoric acids (10).

11. Argemone spp. (XIII, 397)

+
Argemone turnerae A. M. Powell yielded mostly ( )-armepavine and
( - )-tetrahydropalmatine neither of which had been reported as
occurring in Argemone species. Argemone brevicornuta G. B. Ownbey
gave mostly norargemonine with traces of berberine. Argemone
albi$ora Hornem. gave sanguinarine, protopine, and allocryptopine
along with small amounts of berberine and coptisine (11).
 6. ALKALOIDS UNCLASSIFIED AND O F UNKNOWN STRUCTURE 267

12. Argemone subfusiformis Ownb. (XIII, 397)

Berberine, protopine, allocryptopine, chelerythrine, sanguinarine,
and three unidentified bases (12).

13. Argyreia spp. (Convolvulaceae) (XIV, 512)

Fourteen species of Argyreia and two plants of closely related genera
were shown to contain ergoline type of alkaloids twenty-one of which
were identified. Argyreia nervosa Boj. previously investigated had
already yielded most of these (13).

14. Atalantia ceylonica Oliver (Rutaceae) (XII, 500; XIV, 513)

Two new alkaloids, atalanine (C3,H3,0gN2; mp 216-217") (14) and
ataline (C3,H,,0gN2; mp 209-210") (15)were obtained. They represent
a new type of acridone base in which two acridone rings are joined by
an ether bridge. Mass spectral data supplemented by other physical
measurements and by analogy with other natural acridones served to
provide the given structures (14).
Further examination yielded alkaloid A (CI9Hl7O4N;mp 252-254O) as
red needles in 0.0470 from the bark of this plant. It was shown to have
structure 16 complete methylation of which gave the 0,O-dimethyl
ether (mp 97-98'). Alkaloid B (C,,H,,O,N; mp 190-191"), also obtained
in red needles in only 0.003% yield, was given structure 17. It reacted
with diazomethane to yield the ll-O-monomethyl ether (mp 126').
All structures were dependent upon spectral studies (15).

15. Atalantia monophylla Correa (XII, 500)

An earlier report disclosed the presence of atalaphylline (C23H2504N;
mp 246") (18) and of its N-methyl derivative (mp 192") in this plant
(16).The presence of the cyclized derivative of the latter, namely,
N-methylbicycloatalaphylline (Cz4NZ,O4N;mp 185") (19) has now
been reported (17).

16. Banisteriopsis inebrians Morton (Malpighiaceae) (X, 495; XI, 12)

I n addition to the known harmine this plant yielded harmaline,
tetrahyldroharmine, and harmol (18).

17. Bellendine (XIV, 514)

A synthesis of racemic bellendine (19a) has been announced. Tro-
pinone was condensed with 3-methoxymethacrylyl chloride in the
268 R. H. F. MANSKE

$
p--Q
0 -- OH Me OMe

\ \
OH 0
14

0 OH

OH 0
15

16 17

OH

18 19

19a
 6. ALKALOIDS UNCLASSIFIED AND OF UNKNOWN STRUCTURE 269

presence of sodium hydride. The product (mp 128') had UV, IR, NMR,
and mass spectra identical with those of bellendine (mp 162') (18a).
18. Camptothecine (XII, 464, XIV, 515)
The potent antileukemic and antitumor activity of this alkaloid
served to inspire other syntheses of it. The keto acid 20 (19) was
reduced with sodium borohydride to 21 and the latter on an a-methyl-
ene lactam rearrangement in acetic anhydride generated 22 as a
mixture of isomers. Oxidation of the latter with selenium dioxide in
acetic acid gave 23. Hydrolysis of 23 gave 24 and this on heating with
excess trimethyl orthobutyrate in the presence of a trace of propionic
acid gave a mixture which was hydrolyzed to 25. Oxidation of 25 to
the corresponding ketone (26) was achieved by means of dicyclo-
hexylcarbodiimide in DMSO. The latter, when condensed with N -
(2-aminobenzylidine)-p-toluidineunder the Friedliinder conditions
gave 27. The subsequent reactions to achieve the synthesis involved
aromatization of the pyridine ring and the formation of the a-hydroxyl-
actone. This was achieved by selenium dioxide oxidation in acetic
acid, and the resulting deoxycomptothecine (28) on further oxidation
(CuC1,-DMF-0,) was converted into camptothecine (29) (20).
In another synthesis of this alkaloid the tricyclic lactone 30 was
prepared by a series of reactions in which most of the steps gave
satisfactory yields. Hydrolysis with aqueous oxalic acid and con-
densation with anthraniladehyde generated compound 31 which had
already been converted into camptothecine (21). It should be added
that the early promise of this alkaloid as a therapeutic agent in cancer
therapy has not been confirmed in clinical trials (22).
Still another synthesis has been announced. Compound 33 was
obtained by heating 32 with diethyl acetonedicarboxylate and then
converted to 34 by heating with piperidine in acetonitrile. The latter
was hydrolyzed and decarboxylated by heating with concentrated
hydrochloric acid a t 150" to 35 which was methylated to 36 with
dimethyl sulfate and alkali, and this in turn converted to the aldehyde
37 by the Vilsmeier reaction. Reduction of 37 gave 38, formylation of
which gave 39 and then 40 by another Vilsmeier reaction and the latter
in turn was condensed with di-t-butyl malonate to 41, reduction of
which with sodium borohydride generated 42. Lactone formation and
deformylation of 42 by treatment with hydrochloric acid gave 43,
and this on dehydrogenation with dicyanodichloroquinone (DDQ)
afforded 44. Finally, ethylation of 44 with ethyl iodide and sodium
hydride gave 28 convertible into dl-camptothecine (29) by oxidation
(2323).
270 R. H. F. MANSKE

Continued interest in camptothecine stimulated yet another syn-

thesis. This involved the synthesis of the penultimate material 45
which is readily convertible into the alkaloid. The key intermediate 46
was prepared by a series of six synthetic operations from furfuraldehyde
dimethylacetal although the actual number of reactions was twice that
number. While there were no entirely new reactions involved the
experimental skill was evidently of a high order (24).

20 X + Y = O 22 23 X = H , Y = CH3.CO2, R = CH3.CO
21 X = H, Y = OH 24 X = H, Y = OH, R = H

25 X = H , Y =OH 27 28 R = H 0
26 X + Y = O 29 R = O H

0 0
30 31

AR- N

b
38 R = H
33 R = -CO.CHZ.CO.CH2.CO2Et
R'
34 R = -COzEt, R' = OH, R2 = H
35 R = R2 = H, R' = OH
36 R = R2 = H, R' = OMe
37 R. = H, R' = OMe, R2 = -CHO
 6. ALKALOIDS UNCLASSIFIED AND O F UNKNOWN STRUCTURE 271

R H /

TT %
R'
38 R = RZ = H, R' = OMe

0 OMe
\'0
,c=o

c'
44
45 0
0

46

19. Cassia carnaval Speg. (Leguminosae) (XI, 492)

Prosopinone (C,,H,,O,N) from this plant has structure 47 and
alkaloid D is probably represented by 48 (25).

20. Cephalotaxine (X, 552)

The structure of cephalotaxine (49) has been determined by X-ray
crystallographic studies supplemented by chemical methods (26). A
synthesis of the racemic form has now been reported (27).Condensation
of prolinol with 3,4-methylenedioxyphenylacetylchloride gave the
alcohol 50 (R = CHOH) which upon oxidation to the aldehyde 50
(R = CHO) and condensation generated 51 (R = H; X = 0).Reduc-
tion of this with LAH gave 51 (R = H; X = H,). Condensation of the
latter with 2-acetoxypropinyl chloride gave 51 (R = COCH(0AC)Me;
X = H2). This on hydrolysis and oxidation gave the diketone 51
(R = CO.CO.Me; X = H,) which ultimately on condensation with
magnesium methoxide gave 52. Methylation of 52 with 2,2-dimethoxy-
propane in the presence of p-toluenesulfonic acid gave the O-methyl
ether 53 whose reduction with sodium borohydride proceeded stcreo-
rpeciiczdy to meemie eephalotuike (49).
272 R. H. F. MANSKE

HO * CHZ (CH,),. CH(0H).(CH2)Io.CH(OH)Me

H H

(:at-$
47 48

H'
OMe
49 50 51

(o \ O -3
q

H'
0 OMe 0
52 5a 54

R'
RQ

MeO"
55 R + R' = O.CHZ.0 57 R + R' = O.CHa.0
56 R = R 1= OMe 58 R = OMe, R' ::OH
I9 R = R ' = OMe

21. Cephalotaxusfortunei Hook. (Taxaceae) (X, 552; XIII, 400)

Cephalotaxinone (C1,H,,O,N; mp 200'; [a]g4 - 155') (53) is identical
with alkaloid B previously isolated from C. hrringtonia (28).Alkaloid
C (mp 141-143') from the above source proved to be acetylcepha-
lotaxine; alkaloid D (mp 109'; [a]i5- 110') proved to be O-demethyl-
cephalotaxine (54) obtainable by mild hydrolysis of the O-methyl base;
alkaloid E (mp 136-137'; - 150) was shown to be epicephalotaxine
(29).

22. Cephalotaxus harringtonia C. Koch ( C . pedunculata Sieb. & Zucc.)

(X, 552; XIII, 400)
Five new homoerythrina alkaloids have been isolated from this
plant in addition to others which were known. Their properties and
 6. ALKALOIDS UNCLASSIFIED AND OF UNKNOWN STRUCTURE 273

structures are as follows: alkaloid 11, [.ID + 76" (55); 111, [.ID + 118"
(56); IV, [a],,+123" (57); V, mp 150-152", [a],,+115" (58); VI,
[.ID +122" (59) (30).

23. Chaenorhinum origanifolium (L.) Willk. et Lge. (Scrophulariaceae)

Thealkaloid chaenorhine (C,,H4,0,N4; mp 263-268" dec. ;[aID+ 46.7')
proved to be macrocyclic containing a spermine moiety. The entire
gamut of spectral studies was involved to determine its structure (60).
Of special interest is the observation that the hydrogenolysis of the
alkaloid with sodium in liquid ammonia occurred at the ether linkage
and generated 61 with concomitant reduction of the cyclic double bond.
Hydrolysis, some chemical degradation, and further spectral studies
served to elucidate the entire structure (31).

81

24. Cinnamomum laubatii F. Muell. (C. tamala T. Nees & Eberm.)

(Lauraceae) (X, 419; XIV, 518)
The chief alkaloid proved to be ( +)-reticdine (32).

25. Clausena heptaphylla Wt. & Am. (Rutaceae) (XIII, 467)

The alkaloid heptaphylline (CI3H,,O3N) was shown to have structure
62 by means of spectral methods and confirmation by a synthesis.
Girinimbine was also present in this plant (33).

26. Coccinella septempunctata L. (XIV, 518)

The base, coccinellin (C,,H,,ON; mp 235' dec.) from this Coleoptera
was shown to have structure 63 by means of an X-ray analysis. It is
the N-oxide of precoccinellin. It had been shown to protect the insect
from attack by predators, especially ants (34).
274 R. H.F. MANSKE

27. Cocculine and cocculidine (VI,443; XII,468)

NMR and mass spectral studies as well as a Hofmann degradation
call for a revision of the assigned structures. The new structures are
64 and 65, respectively, for cocculine and cocculidine (35).

CHa*CH:CH,
62
Me
63 Me0 /
64 R = H
65 R = M e

28. Convolvulus erinacius Ledeb. & 6. subhirsutus Regel & Schmalh.

(Convolvulaceae)(X,554)
The roots of these plants yielded cuscohygrine and convolvine,
respectively (36).

29. Coryphunthu macromeris (Engelm.) Lem. (Cactaceae) (XII, 468,

505)
The following were isolated largely by chromatography and identified
by spectral properties and by comparison with known bases: N -
formylnormacromerine, metanephrine, N-methylmetanephrine, syne-
phrine, N-methyltyramine, N-methyl-4-methoxy-/3-phenethylamine,
N-methyl-3,4-dimethoxy-/3-phenethylamine,tyramine, hordenine,
macromerine, and normacromerine (37).

30. Coryphntha ramillosa Cutak (XII,468)

The following bases were isolated as their hydrochlorides: N-methyl-
4-methoxy-/3-phenethylamine, hordenine, N-methyltyramine, syne-
phrine, and O-methylsynephrine (38).

31. Crotalaaria albida Heyne (Leguminosae) (XII,

253)
The alkaloid croalbine (66)(mp 208-209') was shown to be the
cyclic diester of croalbinecine and trichodesmic acid (39).
 6. ALKALOIDS UNCLASSIFIED AND OF UNKNOWN STRUCTURE 275

(F
66 67

Me Me Me
H I I
I
O y 7 (N]
Ro\
\ CH, C H 'H
0L O I
I
H I H
Ph Ph
68 69 70 R = H
71 R = P h * C O .

32. Crotalaria barbata R. Grah. (XII, 247)

The structure 67 of the new alkaloid, crobarbatine (mp 142"), is
based on spectral evidence and hydrolysis to retronecine and to
crobartic acid (C,H,,O,; mp 177-178") (40).
33. Crotalaria madurensis Wight (XII, 247)
Crispatine (mp 134"; [a]E3+39.5") was the major alkaloid accom-
panied by fulvine (mp 212-213"; [a]hg- l.6"),a diastereoisomer of the
former (41).

34. Cryptoearya odorata (Panch. et Seb.) Guillaum. (Lauraceae) (XI,

453; XII, 471)
Reticuline, laurotetanine, N-methyllaurotetanine, isocorydine, and
a new alkaloid, cryptodorine (C18H1504N;[a]hg + 61"; sulfate, mp
219-221") were isolated. The latter on N-methylation generated
neolitsine; hence, it has structure 68 (42).

35. Cynometra ananta Hutchinson & Dalziel (Leguminosae)

Three imidazole alkaloids have been isolated from this plant. Their
structures were ascertained largely by spectral methods and con-
firmed wholly or partly by limited chemical reactions: anantine
(C,,H,,ON,; mp 204"; [.ID - 549; N-acetyl, mp 99") (69);cynometrine
276 R. H. F. MANSKE

(CI6Hl9O2N3;mp 213'; [a]= - 30") (70); and cynodine (C,,H,,O,N,;

mp 155"; [aID + 15') (71) which is the benzoyl ester of cynometrine (43).
36. Cyphomandra betaceae Sendtn. (Solanaceae) (X, 1 7 )
In addition to the known solamine, tropinone, cuscohygrine, hyos-
cyamine, tropine, +tropine, and tigloidine there was isolated solaca-
proine (C,,H,,ON,; dipicrate, mp 149') whose structure proved to be
[Me,N (CH2)4]2N .CO(CH,),Me. Hydrolysis generated solamine and
caproic acid and recombination of these fragments gave the natural
base ( 4 4 ) .
37. Cytisus hirsutus I,. and related spp. (Leguminosae) (VII, 255)
Cytisus hirsutus gave 1-sparteine, D-lupanine, 13-hydroxylupanine,
and a new alkaloid, 7-hydroxysparteine. The main alkaloid from C.
supinus (Auth.) was D-lupanine. Cytisus nigricans L. was almost
devoid of alkaloids. Genista sessilifolia DC. gave chiefly retamine and
anagyrine. Lotus aegeus Boiss. gave chiefly lupanine (45).
38. Daphniphyllidine (XII, 471)
This alkaloid (C,,H,,O,N; mp 204") is an isomer of deacetyldaphni-
phylline and the latter was converted to daphniphylline (72)by heating
with sodium methylate in methanol (46).
0

72

OAQ

71 R = O
74 R = H, OH
 6. ALKALOIDS UNCLASSIFIED AND OF UNKNOWN STRUCTURE 277

75 H 76

39. Daphniphyllum macropodum Miq. (Euphorbiaceae) (X, 556; XII,

472)
In addition to the eight new alkaloids previously reported upon,
this plant has yielded the new daphmacropodine (C,,H,,O,N; mp
214";[a],,+ 4.9").Spectral studies indicated the essential features of its
structure (74).Mild alkaline hydrolysis afforded the deacetyl derivative
and Jones oxidation converted it into a lactone which proved to be
identical with daphmacrine (73)of known structure ( 4 7 ) .

40. Dendrobates histrionicus and D. purnilio

A general review of the toxins elaborated by the Columbian frogs
of the genus Dendrobates. The structures of two of the more important
toxins, pumiliotoxin (75)and histrionicotoxiii (76),are reproduced
(48, 49). A later communication describes dihydrohistrioCnicotoxin
which proved to be a powerful anticholinergic agent and which differs
from 76 only in that the side of the piperidine ring of the latter chain
is altered to -CH,. CH, .CH=C=CH,. The structure is based upon an
X-ray study of the hydrochloride (50).

41. Dendrobine (X, 558; XII, 475; XIV, 525)

The enol acetate 77 of 3,4-dihydro-7-methoxy-5-methyl-l-(2H)-
naphthalenone was converted to the acid 78 by ozonolysis and hydroly-
sis and this by a Wittig reaction with a-methoxyethyltriphenyl-
phosphonium chloride gave 79.Compound 79 was converted into 80 by
a series of reactions, five in number, which in turn was converted into
81 by reaction with potassium in t-butanol. The methyl ester of com-
pound 81, one isomer of which was recognized as that having the
correct stereo structure, was converted to 82 by heating with acetic
anhydride and 1 O-camphorsulfonic acid. Subsequent steps involved
ozonization, reaction with N,N'-carbonyldiimidazole, lactam forma-
tion, reaction with pyridinium bromide perbromide, reaction with
sodium hydride, and a further series in which ( t- )-oxodendrobine (83)
was ultimately obtained. Reduction of the latter to ( -I )-dendrobine
278 R. H. F. MANSKE

(84) was achieved by reacting it first with triethyloxonium fluoroborate

in methylene chloride and then reducing with sodium borohydride in
diglyme (52).

Me Me Me

OAC
77 78 R = COzH 80
79 R = -CH,.CO.Me

81 82 81 R = O
84 R = H,

Ho& 0 ".H
 6. ALKALOIDS UNCLASSIFIED AND OF UNKNOWN STRUCTURE 279

42. Dendrobium primulinum Lindl. (Orchidaceae) (XIV, 525)

Dendroprimine (oil; [a],, -38"; methiodide, mp 263") (52) (85) was
converted to ( + )-4-methylnonane by a series of Hofmann degradations
(53).
43. Dendrobium wardianum Wr. (XIV, 525)
Spectral studies indicated that the new quaternary base dendro-
wardine (C,,H,,O,N.Cl; mp 168-172"; [a]g5 - 28") isolated from this
plant has structure 85a. When treated with lithium hydride in DMF
there was generated 85b which on hydrogenolysis (PtO,) gave
dihydronobilinone (8512) (53a).

44. Desmodium tiliaefolium G . Don (Leguminosae) (XIII, 406)

Tyramine, hordenine, 3,4-dimethoxy-P-phenethylamine, N-methyl-
3,4-dimethoxy-P-hydroxyphenethylamine(86; amorphous; a new
natural base), salsoline, salsolidine, tryptamine, abrine, and hypa-
phorine ( 5 4 ) .

45. Dictamnus albus L. (Rutaceae) (IX, 229)

Two new bases have been isolated from this much investigated plant:
isomaculosidine (C14H,,0,N; mp 170-172") (87), identical with a
known degradation product of maculosidine ; and preskimmianine
(C,,H,,O,N; mp 151-152"), whose proposed structure (88) was con-
firmed by a synthesis (55, 56).

46. Dictamnus caucasicus (Boiss.) Fisch. (IX, 229)

Dictamnine, y-fagarine, skimmianine, 6,8-dimethoxydictamnine
(maculosidine), 6-methoxydictamnine, robustine, and isodictamnine.
Dictamnus caucasicus appears to be a variety of D . fraxinella Pers.,
which in turn has been regarded as synonymous with D . albus L. (57).
280 R. H. F. MANSKE

47. Dipsacus azureus Schrenk (Dipsaceae) (VI, 133)

The alkaloid (CllH1303N;mp 130-131") from the seeds was shown
to be identical with cantaleine (58).
48. Elaeagnus umbellata Thunb. (Elaeagnaceae) (XI, 10; XII, 481)
Seratonin was shown to be present in the leaves, stems, and cotyle-
dons of this plant (59).
49. Emilia flammea Cass. (Compositae)
The alkaloid emiline (89) is given the structure shown on the evidence
of spectral data. Strong hydrogen bonding of the hydroxyl to the
nitrogen is indicated. The basic moiety is otonecine (60).

50. Euonymus alatus Thunb. (Celastraceae) (X, 561; XI, 489)

This plant has yielded the known evonine, evonymine, wilfordine,
and a new alkaloid alatamine (C,,H,,018N; mp 185-193"; + 44").
Its structure (91)was indicated by an examination of its various
spectra and a series of chemical transformations gave credence to that
structure. It was finally converted into wilfordine (90) by reduction
(NaBH, - DMF) and acetylation in which the C-7 epimer was also
generated (61).

51. Euonymus europaeus L. (X, 561; XI, 489)

The new 4-deoxyevonine (92) was isolated from this plant. Evonine
(93) and neoevonine (94) were also reported (62).In another report the
+
isolation of evonine and isoevonine (amorphous; [aID 30.5") was
described. The structure of the latter differed from the former only in
the nature of the pyridine moiety. Methanolysis afforded methyl
2-(3-(methoxycarbonyI)propyl)nicotinate (63, 64).
52. Euonymus sieboldiana Blume (X, 561; XI, 489)
Two new alkaloids, evonimine (C2,H3,012N; mp 184") (95) and
evonine (96) have been isolated. Spectral studies, interconversions,
and critical chemical reactions prove the given structures (65).Further
extensive chemical and spectral studies confirmed these assignments
(66, 67').Earlier assignments of structures gave 97 to evonine and 95
to evonoline (68).
53. Festuca arundinaceae Vill. (Gramineae) (X, 562; XII, 322)
The presence of three new alkaloids from the seeds of this plant was
demonstrated. A combination of adsorption and gas chromatography
 6. ALKALOIDS UNCLASSIFIED AND O F UNKNOWN STRUCTURE 281

I
Me
89 OAc
90 x=(
‘H
91 x=o

o@ AcO Ac

---Me

0
N-
Me
96 X=O,R=OH
Me OAc
92 R = H, R1 = AC 96 X = ( ,R=OH
98 R = OH, R’ = AC ‘H
94 R = O H , R ’ = H 97 X = O , R = H

served to identify N-formylloline, N-acetylloline, and demethy1-N-

acetylloline identified by spectral methods (69).

54. Ficus septica Forst. f. ( 2) (Urticaceae)

The major alkaloid was antofine. Bases of the phenanthroindolizidine
type appeared to be present but were not identified (70).

55. Gebeline (IX, 213)

The structure of gebeline which had been proposed (71, 72) was
282 R. H. F. MANSKE

revised to 98 on the basis largely of its mass spectrum. It had been

isolated from Sophora pachycarpa Schrenk. (mp 231"; [.ID - 12.9")and
yielded a dihydro derivative (mp 207"; picrate, mp 192') (73).

56. Genista tinctoria L. (Leguminosae) (IX, 188;XIII, 408)

On the basis of spectral studies the new alkaloid tinctorine has
structure 99. Its hydrogenation product was enantiomeric with that
similarly obtained from N-methylangustifoline (74).

57. Gentiana olivieri Griseb. (G. decumbens L.) (Gentianaceae) (X,

563; XI, 487)
This plant yielded gentioflavine, gentianaine, and oliveramine whose
structure, based on spectral study, was given as 100. It was not indica-
ted whether or not these bases are artifacts generated during isolation
(75).
58. Glycozolidine (XIII, 279)
On the basis of NMR and other data this base has been reformulated
as 2,6-dimethoxy-3-methylcarbazole (76).

59. Gymnema sylvestre R.Br. (Asclepiadaceae)

Gymnamine (C,,H2,0,N2; amorphous; picrate, mp 260") has
structure 101 as determined by spectral methods. Hydrolysis followed
by Wolff-Kishner reduction converted it into lycodine (102) (77).

0
98 99

0
\
100 101 102
 6. ALKALOIDS UNCLASSIFIED AND O F UNKNOWN STRUCTURE 283

60. Gymnocalycium schickendantzii Britton & Rose and Cereus aethiops

Haw. (C. caerulescens Salm-Dyck) (Cactaceae)
The former yielded hordenine and candicine while the latter yielded
these as well as tyramine (78).

61. Halfordia kendack Guillaumin (Rutaceae) (XI, 498)

The structure of halfordamine (C12N1304N; mp 240-244") (103)
(78a)was confirmed by a synthesis (79). Another synthesis involved the
condensation of malonic acid with 2,4-dimethoxyaniline followed by
heating with polyphosphoric acid a t 105". The resulting quinoline
(104) on treatment with diazomethane generated halfordamine (80).

62. Haplophyllum acutifolium G. Don (Ruta acutifolium DC.) (Rutaceae)

(X, 565; XII, 480; XIII, 408)
Acutine (C,,H,,ON; mp 122-123") from this plant was given
structure 105 on the basis of spectral studies. Hydrogenation generated

0
OM0
108 R = Me 101
104 R = H

108

1078 108
284 R. 3.F. MANSKE

a dihydrobase which was also prepared by acid-catalyzed condensation

of Me(CH,), .CO .CH,CO,Me with aniline and subsequent ring closure
in boiling diphenyl ether (81, 82).

63. Haplophyllum foliosum Vved. (XIV, 534)

Folimidine (C,,H,,O,N) has been given structure 106 on the basis of
a spectral study (83).

64. Haplophyllum hispanicum Spach ( 2 ) (IX, 225)

Evoxin and its secondary monoacetate (mp 169") were isolated (84).

65. Huplophyllum pedicellatum Bge. (X, 565; XII, 480)

The above plant yielded haplopine and robustine; H . obtusifolium
Ldb. yielded skimmianine and evoxine; and H . bucharicum Litv.
yielded dictamnine, skimmianine, y-fagarine, robustine, haplopine,
bucharine, benzamide, and a new alkaloid, bucharamine. Of several
possible structures for the latter the more probable is 107 (85).

6 6. Helmint hosporium sativum

A base, first isolated from H . victoriae (86),and named victoxinine
(oil, [a]g5 -78"; hydrochloride, mp 172"; O-acetyl, oil, [a]g5 -56") has
been obtained from the above fungus. Its structure (107a) was largely
deduced from spectral data and chemically confirmed by its prepara-
tion from prehelminthosporal (108) of known structure (87).

67. Hernandia ovigera L. (Hernandiaceae) (IX, 30)

In addition to the known alkaloids from this plant the trunk bark
yielded the new hernandonine (C,,H,O,N; mp > 280") whose structure
(109) was determined largely by spectral methods and confirmed by its
synthesis from N-methylhernovine by known reactions (88).

68. Hippodamia convergens (Coleoptera) (XIV, 518)

The American ladybug was shown to elaborate two alkaloids:
hippodamin (CI3H,,N), which gives a mass spectrum almost identical
with that of precoccinellin (110) (89), and convergin (C,,H,,ON)
(111 or 112), which on reduction of its carbonyl generates a base
regarded as hydroxyhippodamin; it is therefore 3-methyl-13-aza-
bicyclo[7.3.lltrideca n-&one (111) or 1l-methyl-l3-azabicyclo[7.3.1]-
tridican-5-one (112) (90).
 6. ALKALOIDS UNCLASSIFIED AND OF UNKNOWN STRUCTURE 285

69. Hotarrhena febrifuga Klotzsch (Apocynaceae) (IX, 3 18)

A reexamination of this plant yielded 2.4y0alkaloids from the bark.
The principal alkaloids were holafebrine and conessine (113), but the
following eight were also isolated: conessimine, isoconessimine, con-
arrhirnine, conessidine, conkurchine, holaminol, holarrhimine, and
holaphylline (91).

109 110 111 R = Me,R' = H

112 R = H,R' = Me

Me

113

R R' Ph
114 R =R' = P h 118
115 R = CsHll-, R' = CTHT5-
118 R = C,H:,-; R' = -CHz.CH(OH)(CHz),-Me
117 R = Ph, R' = -CHz.CH(OH)(CH2),.Me

70. Homaliurn pvonyense Guillaum (Flacourtiaceae) (Samydaceae)

(XII, 481; XIII, 409)
This plant, native to New Caledonia, has yielded four new alkaloids
which show affinities with spermine and spermidine.
Homaline (C,,H,,02N4; rnp 34";[a],,- 34")was given structure 114
although other possibilities were discarded only after careful study and
the final decision was based on the synthesis of a derivative.
286 R. H. F. MANSKE

Hopromine (C30H5,0,N4; oil; [.ID - lo") offered similar problems

concerning its structure but 115 is preferred. Hoprominol (C30K5803N4
oil; [a],,-19") and hopromalinol (C3,H5,03N4 oil; [a],,-17") are
hydroxy derivatives of similar structures represented by 116 and 117,
respectively (92).
The structure for homaline (114) was confirmed by a synthesis of
bisdihydrodioxohomaline. The diazacyclooctane (118) was reacted
with succinyl chloride and the bisamide reduced with LAH. The
product 114 was identical with that prepared from homaline (93).

71. Hypecoum erectum L. (Papaveraceae) (XII, 337)

Hypecorine (C2,H,,0,N; mp 154-156') and hypecorinine (CZoH,,O,N;
mp 197-198') from this plant were given structures 119 and 120,
respectively (94).

72. Isolongistrobine (XIV, 540)

Following an earlier synthesis of dehydroisolongistrobine (95) the
same authors have reported a synthesis of isolongistrobine (121) and

119 X = 2H 121 122 R = H

aw3
120 x = 0 128 R = -CO.CHz.CHz.CH=CHP
124 R = -CO .CH,.CHZ.CHO

R ) T k O R 1

CH2 * Ph 0 0
124a R = H,R' = -CO.Ph 125 126
lZ4b R = H,R1 = -CO*Me
124~ R = Ph.CO,-, R' = H
124d R = OH, R' = -CO*CH=CH.Ph
 6. ALKALOIDS UNCLASSIFIED AND OF UNKNOWN STRUCTURE 287
shown that the structure originally proposed is in error. The amino
alcohol 122 on reaction with 4-pentenoyl chloride generated 123. The
latter was first oxidized to the corresponding ketone with chromic
oxide in pyridine and then to the aldehyde 124 with sodium periodate
and osmium tetroxide. Compound 124 was identical with isolongi-
strobine (96).

73. Knightia dqdanchei Vieill. (Proteaceae)

The four alkaloids isolated from this plant are derivatives of the
structure shown. Mass spectra supplemented by other spectral studies
served to determine these. Alkaloid A (Gl5H2,ON; r n p 123-1Z4";
[.ID f0'; 124a);B (C1,&30N; oil; [a]D + O ; 124b); c (C2,HZ5O3N;
mp 168-170'; [.ID f O ; 142c); and D (C2*H2,03N; mp 174-175";
[.ID & 0; 124d). Some chemical reactions confirmed these structures
(96a).

74. Leontice darvasica (Auth. 2) (Berberideceae)

Darvasamine (Cl6HZ40N2;mp 102'; [.ID +72"), a new alkaloid,
was given structure 125 (97).

75. Leontice 1eonto.petalum Hook. f. et Thorns. (X, 570: XII, 486)

a-Isolupine, 3-(2-piperidiny1)quinolizidine (leontiformidine), ( + )-
lupanine, leontiformine, palmatine, and tetrahydropalmatine (98).

76. Leontidine (XII, 486)

The structure of leontidine (126),based on mass spectral evidence,
was confirmed by its preparation from cytisine (99).

77. Lindera oldhami Hemsl. (Lauraceae) (XIII, 412)

D-Dicentrine, N-methylnandigerine, N-methylovigerine, and the
first natural occurrence of O-methylbulbocapnine (mp 129°-1300;
+ 248'). Some others were not identified; dicentrinone was
probably present (100).

78. Litsea glutinosa Hook. (Lauraceae) (XIII, 412)

From the var, glabraria the following aporphines were isolated :
norboldine, boldine, laurotetanine, N-methyllaurotetanine, actino-
daphnine, and N-methylactinodaphnine (101).
288 R. H. F. MANSKE

79. Litsea leefeana Merr. and Cryptocarya foveobta White et Francis

The alkaloids of the former consisted essentially of boldine, lauro-
litsine, and ( + )-reticuline. The last named was the chief alkaloid in
C. foveolata (102).

80. Litsea sebifera Pers., L. wightiana, Hook. f., and Actinodaphne

obovata Bl. (IX, 1 7 )
The first plant yielded boldine, laurotetanine, N-methyllaurotetanine,
and actinodaphnine; the second yielded boldine and norboldine ; the
last yielded laurotetanine, N-methyllaurotetanine, and actinodaphnine
(103).

81. Lobelia nicotianaefolia Heyne (Lobeliaceae) (XI, 462; XII, 488)

Lobeline constituted 20y0 of the total alkaloids (103a).

82. Lobelia polyphylla Hook. & Am. (VI, 126)

The main alkaloid, in amounts up to 1.4Oj,, was norlobelanidine
(mp 254') (104).

83. Lophanthera lactescens Ducke (Malpighiaceae)

An amorphous base, lophanterine, of undisclosed formula ([.IF
- 92.7") forming a hydrochloride (mp 188-189") sparingly soluble in
cold ethanol. It is intensely bitter and the plant is used as a tea by some
Amazonians (105).

84. Lunaridine (X, 572)

An exhaustive spectral study, particularly of mass spectra, has
indicated that lunaridine has structure 127. It is thus isomeric with
lunarine 128 (106).

85. Mandragora autumnalis Bertol. and M . vernalis Bertol. ( M .

oficinarum L.) (Solanaceae)
The same alkaloids (hyosciamine, hyoscine, cuscohygrine, apo-
atropine, 3a-tigloyloxytropane, and 3,6-ditigloyloxytropane) and
approximately to the same extent were found in the roots of these two
species. This is the first known occurrence of tiglic acid esters in the
genus Mandragora (107).
 6. ALKALOIDS UNCLASSIFIED AND OF UNKNOWN STRUCTURE 289

NH I

127 n = 4,n1 = 3 129

128 n = 3, n1 = 4

Me0

Me0
OH
130

86. Maytenus chuchuhuasha Raymond-Hamet et Calas (XIV, 541)

Maytenine (C,,H,,O,N,; mp 158") was shown by exhaustive spectral
methods to be di-transcinnamoylspermidine (129) (108).It i s evidently
not related to the tumor-active alkaloids which have been isolated from
M . ovatus (109, 110). A synthesis of HN[(CH,),NH.CO-CH:Ph],,
which was stated to be maytenine, was achieved by treating spermidine
with 1-cinnamoyloxypiperidine (111).

87. Merendera raddeana Regel (Liliaceae) (XI, 412)

The new alkaloid merenderine from this plant was given structure
130 (112).
88. Mitrella kentii ( B l . ) Miq. (Anonaceae)
Liriodenine, anonaine, asimilobine, and egeline (113).
89. Monnieria trifolia L. (Rutaceae) (XIII, 414)
Arborinine (mp 176-178") (114).

90. Monodora angolensis Welw. (Anonaceae)

The main alkaloid was isoboldine (115).
290 R. H. F. MANSKE

91. Mucuna spp. (Leguminosae) (VIII, 12; XI, 12)

A procedure for the isolation of L-dopa from Mucuna seed has been
reported. Of the nine species examined eight gave recovery of 3.1 to
6.1 from mature seeds (116).

92. Murrayacine (XII, 491; XIII, 282)

The synthesis of this base (131) has been achieved by a series of
reactions in which the phenylhydrazone 132 was prepared by a Japp-
Klingemann reaction of the appropriate compounds and subsequently
subjected to ring closure. Though the subsequent steps present no
novel features i t is evident that their execution demanded considerable
manipulative skill (117).

93. Murraya koenigii Spreng. (Rutaceae) (XII, 491; XIII, 274, 414)
Murrazoline isolated from the stem bark has structure 133 as deter-
mined by spectral studies which chemical reactions confirmed (118).

OMe Me0
Me

OH
133 1a4
Me

HO GQ Me
iaa 136
 6. ALKALOIDS UNCLASSITIED AND OF UNKNOWN STRUCTURE 291

94. Nandina domestica Thunb. (Berberidaceae) (IX, 13)

Isocorydine, as well as a number of bases previously reported, was
isolated (119).
95. Nelumbo nucifera Gaertn. (Nymphaeaceae) (X, 410; XIV, 544)
I n addition t o a number of previously recognized alkaloids the
following were isolated: dehydroroemerine, dehydronuciferine, de-
hydroanonaine, and N-methylisococlaurine (120).
96. Nemuaron vieillardii Baill. (Monimiaceae)
The known alkaloids laurotetanine, N-methyllaurotetanine, noriso-
corydine, atheroline, and O-methylflavinantine were isolated. A new
alkaloid, nemuarine (C3,H4006N2; mp 222-223"; - 42.7'; 0-
methyl, mp 154-156'; [a]$0-43.8")) which is the major constituent of
the leaves, has structure 134 (121).

97. Nitraria schoberi L. (Zygophyllaceae)

The alkaloid nitramine (CloH,,ON) was given structure 135. De-
hydrogenation in the presence of Pd/C generated 8-methylquinoline
(122).

98. Nuphar luteum Sibth, et Sm. (Nymphaeaceae) (IX, 441; XIV,

545)
Neothiobinupharidine (136)and the isomeric thionuphlutine A were
isolated from plants grown in Poland. They were not obtained from
plants of American origin. Thionuphlutine A is identical with thio-
lunupharidine (123).

99. Obregonia denegrii Fri6. (Cactaceae)

Small yields of tyramine, N-methyltyramine, and hordenine were
isolated by thin layer chromatography; TLC (124).

100. Ocotea variabilis Mart. (Lauraceae) (IX, 6; XII, 349, 492)

Glaziovine, apoglaziovine, nantenine, and a new base variabiline
(C,,H,,O,N,; mp 116'; [.ID 5 0") have been isolated from this plant.
Spectral examination pointed t o structure 137 for the new alkaloid and
its preparation from ( + )-glaziovine (138)by heating it with dibenzyl-
amine and the hydrochloride for 2 hr a t 200-210" confirmed the
structure (125).
292 R. H. F. MANSKE

101. Oldenlandia afinis DC. (0. dichotoma Kook. f.) (Rubiaceae)

(X, 574)
Serotonin(5-hydroxytryptamine) was isolated from the dried aerial
parts of this plant (126).

102. Oricia suaveolens Verdoorn (Teclea smveolens Engl.) (Rutaceae)

The new alkaloid oricine (C,,H,,O,N; mp 150-152") was given
structure 139 on the basis of spectral evidence. A synthesis was reported.
The method was one (127) used earlier in an analogous base. Diethyl
y,y-dimethallylmalonate, when heated with aminoveratrol, gave an
intermediate which on cyclodehydration and subsequent methylation
generated oricine (128).

103. Orixa japonica Thunb. (Rutaceae) (IX, 227; XIV, 546)

&
Orixinone (Cl7Hl9O5N; mp 10ZO),a new alkaloid, was shown to
have structure 140, largely by means of spectral data and confirmed by

~~p~
dehydration of orixine (141). The quaternary 0-methylbalfouradinium
ion was also isolated as its perchlorate (129).
MHe 0 O T

Me0

Ph * CH2-T \
0
Me0 ' N
I
0

CHa. Ph Me
137 138 139

OMe OCH@Me

\
Q-0 L O N
140 141 142

R 0
I

143 R = OH 145
144 R -CHI. CO .M e
E
 6. ALKALOIDS UNCLASSIFIED AND OF UNKNOWN STRUCTURE 293

104. Pedicularidine (X,575;XIII, 416;XIV, 548)

The structure of this base (142) was determined by spectral methods
and the aldehyde portion was converted to carboxyl by oxidation with
silver oxide (130).

105. Peganum harmala L. (Zygophyllaceae) (XI, 14; XIV, 548; XII,

528)
Feganol (C,,H,,ON,; mp 178-180") is a new alkaloid of structure
143 from this plant (131).Also reported was deoxypeganidine (C14H,,-
ON,) (144), which on permanganate oxidation generated vasicinone
(145) (132).

106. Pelecyphora aselliformis Ehrenberg (Cactaceae) (IV, 8)

Hordenine, anhalidine, pellotine, 3-demethyltrichocereine, mescaline,
3,4-dimethoxyphenethylamine,and the N-methyl derivatives of the
last two. Several of these had not been isolated from plants other than
Lophophora species ( 133).

107. Phyllanthidine (IX,270; XIII, 417; XIV, 481)

This alkaloid (Cl3H1,O3N; mp 189-170"; [a]=-450") was first
obtained from Phyllanthus discoides Muell. Arg. (134) and presently
from Securinega suffruticosa Rehd. Its structure (146) was mooted on
the basis of a spectral study and confirmed when it was obtained in
excellent yield by the hydrogen peroxide oxidation of allosecurinine
(147) (135).

146 147

(o \ O P - 148
2 94 R. H. F. MANSKE

108. Piper sylvaticum Roxb. (Piperaceae) (XII, 495; XIII, 417; XIV,
557)
Sylvatine (C,,H3,03N; mp 112'; [a]D k 0') isolated from this plant
was shown to be an amide of piperic acid. Mass and other spectra
indicated structure 148 and confirmation was achieved by reduction,
hydrolysis, and/or oxidation, the product of the latter process being
5-methylhexanoic acid (136).
109. Pisum sativum L. (Leguminosae) (XIV, 551)
Cadaverine was present in concentration of 2 5 pg/g of fresh young
plants grown under various conditions (137).

110. Plantago arenaria Waldst. & Kit. (Plantaginaceae) (X, 5 7 5 )

The remarkable occurrence of narcotine in this plant is recorded.
A second base (C,,H,,ON,) appears to be a terpenoid (138).

11 1. Pogonopus patchouli Pellet (Labiatae) (XII, 496)

The alkaloids, guaipyridine (149) and epiguaipyridine (150), have
been synthesized from guaiol (151) and from a-gurjunene (152),
respectively (139).
112. Poranthera corymbosa Brogn. (Euphorbiaceae) (XIV, 5 5 7 )
The main alkaloid, porantherine (C,,H,,N; mp 36-40"; [a]D + 29")
was shown, by X-ray analysis, to have structure 153. Other spectral
studies are consonant therewith (140).Two further alkaloids have been
reported and their structures have also been elucidated by X-ray
methods. Poranthericine (C1,H,,ON; oil; [.ID - 20°; B.HBr, mp 308")
has structure 154. Its acetyl derivatives (oil) was also isolated from
the plant. Porantheridine (C1,H,,ON; oil; [a]=- 26"; B.HBr, mp
165-166"; [.ID - 19') has structure 155 (140-142).

11 3. Propylea quatuordecimpunctata L. (Coleoptera; Coccinellidae)

The structure of the alkaloid propyleine (C,,H,,N; amorphous;
levorotatory) (156) from this beetle was determined by spectral methods
supplemented by chemical methods. It is the dehydro derivative of
coccinellin (143) into which it was converted (144).

114. Prosopis alba Griseb. (Leguminosae) (XI, 12, 492)

Tyramine, 8-phenethylamine, and tryptamine were isolated (145).
 6. ALKALOIDS UNCLASSIFIED AND O F UNKNOWN STRUCTURE 295

Me
149 R = Me, R' = H 151 152
150 R = H, R' = Me

153 154 155

115. Pseudoprotopine (XIII, 427)

This is the name given to an alkaloid (mp 200-201") isomeric with
protopine, isolated from Zanthoxylum conspersipunctum Merr. ( l 4 6 ) ,
whose structure (157) has been confirmed by a synthesis. The reaction
sequence, beginning with the corresponding berberine, was essentially
that described in the original protopine synthesis (147).

116. Rhamnaceae from Chile (X, 407)

( - )-Friedelin was a common constituent of the following species. I n
addition the named alkaloids were identified. Colletia hystrix Clos,
( - )-magnocurarine; Retanilla ephedra Brongn., coclaurine. Neither
Colletia spinosa Lam., Trevoa trinervia Miers, nor Talguenea quin-
quinervia I. M. Johnston (Trevoa puinquinerwia Gill. & Hk.) yielded
alkaloids although an earlier examination indicated the presence of
D-( -)-magnocurine in C. spinosissima Gmel. ( = C . spinosa Lam.) (148).
296 R. H. F. MANSKE

117. Ruta graveolens L. (Rutaceae) (XII, 498)

Some quinolinium alkaloids related to those found in Balfourodendron
have been isolated (149).

118. Sarcopetalum harveyanum F. Muell. (Menispermaceae)

Stepharine and coclaurine were isolated (150).

119. Sarothamnus patens (Auth 1 ) (Cytisus striatus (Hill) Rothm.;

Genista straita Hill) (Leguminosae) (IX, 182; XIII, 418)
In addition to sparteine three derivatives of 13-hydroxylupanine
were isolated; namely, the veratric ester (cineverine), the trimethoxy-
benzoic ester (sarodesmine), and the isovanilic ester which is new and
named isocinevanine (151, 152).

120. Sceletium namaquense (L.) Bolus (Aizoaceae) (Ix,468; XIV, 553)

An alkaloid from this plant has been shown t o be identical with
Sceletium A, previously reported from Channa. Its structure was shown
to be 158 by an X-ray study of its crystals grown from an ethyl acetate
solution (153).

121. Schefferomitra subaequalis (Scheff.) Diels (Anonaceae) (XIV, 552)

Anonaine, liriodenine, asimilobine, isoboldine, and anolobine, all
known alkaloids, were isolated : in addition two potoberberine bases,
aequaline (C,,H,,04N; mp 232"; - 283") (159) and schefferine
(C,,H,,O,N; mp 176"; [a];, -303") (160). Both on methylation with
diazomethane generate ( - )-tetrahydropalmatine. A third base,
alkaloid Y (C,,H,,O,N; mp 257"), was obtained in amounts insufficient
for structural elucidation although it is apparently not a benzyliso-
quinoline, an aporphine, or a berberine type (154).
OMe

158 159 R =H lf3Oa

160 R =Me
 6. ALKALOIDS UNCLASSIFIED AND OF UNKNOWN STRUCTURE 297

122. Schelhammera undulata R.Br. (Liliaceae) (XIII,418; XIV, 271)

Alkaloids B (mp 152-153"; [elD+ 112') and E ([.ID + 125'; picrate
mp 169-172") from this plant had both been isolated from S. pendun-
culata F. Muell. and from S. muZtijZora R.Br. (255).

123. Senecio nemorensis L. (Compositae)

The alkaloid nemorensine (C,,H,,O,N; mp 132-134"; [a]E4 - 58")
was shown to have structure 160a on the basis of spectral and chemical
evidence. The basic moiety resulting from the alkaline hydrolysis could
not be crystallized either as such or as its picrate. The acidic fragment
was named nemorensic acid (mp 174-178'; [a]g4+87'). The same
alkaloid was isolated from a number of subspecies ( 2 5 5 ~ ) .

124. Senecio propinquus Schischk. (XII,251)

The main alkaloid proved to be seneciphylline (156).

125. Senecio taiwanensis Hayta & S. morrisonensis Hayata (XII,245)

Both plants yielded rosmarinine and integerrimine (157).

126. Shihunine (XIII,

426, 421)
Appropriately labeled 4,2'-carboxyphenyl-4-oxobutanoicacid (161)
was shown to be a precursor in the biosynthesis of shihunine (162) in
Dendrobium pierardi Roxb . (158).

SYL 161
COaH

mNH2
OAc

165
OAo

164

127. Slaframine (X,

579; XII,501)
An earlier synthesis of this base (163) (159) has been superseded by
a stereoselective one. The starting materials were glutamic acid and
298 R. H. F. MANSKE

acrylonitrile which generated an oxopyrrolidine. Dieckmann cycliza-

tion followed by hydrolysis, decarboxylation, catalytic reduction,
N-alkylation with methyl bromoacetate, another Dieckmann cycliza-
tion, more hydrolysis, decarboxylation, and acetylation gave 164.
The oxime of the latter on catalytic hydrogenation gave dl-slaframine
(160).

128. Sophora grifithii Stocks (Keyserlingia grifithii Boiss.) (Legumino-

sae) (XIV, 557)
Cytisine, N-methylcytisine, and matrine (161).

129. Spathelia sorbifolia (L) Fawc. & Rendle (Rutaceae) (XII, 480)
N-Methylflindersine (mp 83-85'), not previously recognized as a
natural product, was isolated by a procedure involving chromatography.
Spectral examination indicated its identity although no chemical
transformations were reported. This plant had at one time been placed
in Simarubaceae but the chemical constituents along with some
taxonomic studies indicate the above relegation (162).

130. Stemona japonica Miq. (Roxburghiaceae) (IX, 545; XII, 502;

XIII, 421; XIV, 5 5 8 )
Stemonamine (CI8Hz3O4N;mp 172-174'; hydrochloride (2H20),
mp 148-151') and isostemonamine (mp 165-169') are two new alkaloids.
The structure of the former (165) was revealed by an X-ray study of
its hydrochloride. Structure 166 is suggested for isostemonamine. Both
are optically inactive (163).

131. Tecoma stans Juss. (XI, 502)

A reexamination of this plant yielded the new A5-dehydroskytanthine
(liquid; [ c z ] ~-~ 89'; picrate, mp 167') and S-skytanthine (liquid;
+ 10.0";picrate, mp 144-146') (164).
132. Trichocereus chiloensis Britten & Rose (Cereus chiloensis DC.)
(Cactaceae) (XII, 506)
Candicine was identified as its iodide (165).

133. Tylophora asthmatica Wight et Am. (Asclepiadaceae)(XIII, 425;

XIV, 562)
The phenolic alkaloid tylophorinidine (C,,H,,04N; mp 216-218';
+105') was subjected to a spectral reexamination and the
 6 . ALKALOIDS UNCLASSIFIED AND OF UNKNOWN STRUCTURE 299

revised structure 167 has been suggested. Two minor alkaloids, also
isolated, were shown to be d-septicine and d-isotylocrebrine (166).

0
OMe

OM.3
165 166 167

v OMe
168
M e O - e C H . CHz. N H R

169
_ . I
OH
R = Ph.CO.
170 R = Ph.CH=CH.CO.

134. Urtica pilzclifera L. (Urticaceae)

Bufotenine was identified as a constituent of the leaves and stems
(162’).

135. Uvariopsis guineensis Keay (Anonaceae) (XIV, 563)

Five of the eight alkaloids isolated from this plant are derivatives
of aminoethylphenanthrene, “ open aprophines,” chief of which is
uvariopsine (168). The others of this type represent various 0-and
N-substituted bases. The remaining new alkaloids proved to be oxo-
aporphines in addition to which liriodenine and a methoxy and a
dimethoxy derivative of it were present (168).
136. Vandopsis gigantea Pfitz. (Orchidaceae) (XIV, 563)
Vandopsis gigantea yielded laburnine and lindelofidine as well as
their acetates. Vanda hindsii Lindl. and Vanda helvola B1. gave the
acetate of laburnine and the latter also gave laburnine. Vanda luzonica
Loher gave the acetate of either laburnine or of its enantiomer.
Vandopsis parishii Schltr. showed the presence of hygrine (169).
300 R. H.F. MANSKE

137. Verbascum songaricum Schrenk (Scrophulariaceae) (XIV, 563)

Anabasine, plantagonine, an unidentified base (mp 195-196"), and
acetamide were isolated (170).

138. Zanthoxylum inerme Koidz. (Fagara boninense Koidz.) (Rutaceae)

(XI, 13; XII, 506;XIII, 427)
The wood of this plant yielded, among other and neutral products,
4-methoxy-1-methyl-2-quinolone (mp 99-103'). The bark yielded
nitidine, aricine, chelerythrine, isolated as derivatives, and oxynitidine
(mp 283-285'). I n addition L-(+)-armepavine metho salt was also
found (171).

139. Zanthoxylum ocumarense (Pittier) Steyerm. (Fagara ocumarensis

Pittier)
I n addition t o neutral compounds the bark of this plant yielded
N-methyl-a-( - )-canadine, ( + )-laurifoline, chelerythrine, and two
bases (C,,H,,O,N. HC1, mp 245"; and C,,Hl103N, mp 216"). A number
of nonnitrogenous compounds were also isolated as well as two amides
169 (C,,H,,O,N; mp 149-151"), which proved to be tembamide (172),
and 170 (Cl,H,903N; mp 175-176'), which appears to be new (173).

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306 R. H. F. MANSKE

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