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1844 Short Reports

REFERENCES 6. Mabry. T. J, Markham, K. R. sod Thomas, M. B. (1970) 7lw

Syste&ic IdentjFcation ojFkwonoids. Springer, New York.
1. Alam, hi. S., Qasim, M. A., Kamil, M. and I&as, M. (1986)
7. Kutocy, J. P., Wanrock, W. D. C. and Gitbcrt, B. (1970)
F~~~~stry 23*2900.
P~~~~ry 9,1877.
2. Shiooda, J. (1928) J. Chem. PIuprn Sot. Japan 48,214.
8. Sherwood, R. T. and Sbarma, M. (1973) Phytdtembtry 12,
3. Hillis, W. E. and Urbacb, G. (1958) Noture 182,657.
4. Gupta, S. R, Shm T. R., Sharma, C. S. and Sharma, N.
9. Somogyi, M. (1952) J. Bioi. Ghan 1% 19.
D. (1975) Indian 1. C&m. 13, 785.
10. Lindberg, B., Longren, J. and lhompsoo, J. L. (1973)
5. Roskr, H, Mabry, T. J, Cmnmcr, M. F. sod Kagan, J. (1965)
Cmlw!tydr. Res. 28,351.
J. 0~. Chem. 30,4346.

Phytochemistry, Vol. 26, No. 6, pp. 1844-1845, 1987. 0031-9422/w s3.00 + 0.00
Printedin Great Britain. Q 1981PugamoaJounub Ltd.



Depertmcnt of Pharmacogwsy aad Botanics, Pharmaceutical Faculty, Odboj&rov lo,83232 Bratislava, czschoslovakia; *Chemical
Institute of the Chemical Research Cents of tbc Slovak Academy of sciences, 81238 Bratielava, Czechoslovakia

(Receiwd 16 SeptettW 1986)

Key Word l&x--I.&m candidw; Liliawae; flavonoid; alkaloid; 3,5,7,4’-tetrahydroxy-8-(3-methyl-2-oxo-S-

pyrrolidinyl)fIiwone; strwture determination.

Abetract-A new ilavonoid alkaloid, lilaline, was isolated from the aerial part of fiiinm can&fnm. Its structure has been
elucidated as 3,5,7,4’-te~ydroxy-8-(3-methyl-2sxo-pyrrolvone.

IMRODUCTION It is evident from the ‘HNMR spectrum of lilaline

that the alkaloidal moiety contains the fragment
During our search for new medicinal plant components,
CH,-/-CH-CH,-CH-/-heteroatom. This fact and the
we investigated the aerial part of Lilium cdidum L.
IR and MS data indicate the presence of a 3-methyl-2-
growing in Czechoslovakia. In a previous publication [l]
oxo-5-py~olidinyl group. The remaining signals in the
we described the isolation of a substance with the
‘H NMR spectrum belong to the tlavonoid moiety and
composition C,,H, ,N07, while in this paper we describe
characteristic for kaempferol substituted in position C-8
its structure determination.
or C-6 (singlet at 66.24). A comparison of the correspond-
ing signals in the i3C NMR spectra of lilaline at 699.3 (C-
RESULTS AND DISCUSSION 6) resp. 6 106.9 (C-8) and kaempferol [3] at 698.2 (C-6)
resp. 693.5 (C-8) favour C-8 substitution. The signal at
A floral extract of white lily afforded an alkaloid which
6 183.9 (C-2’) confirms the presence of pyrrolidinone in
crystallixes from acetone in the form of yellow prisms,
the molecule of lilaline. Thus lilaline is 3,5,7.4’-tetra-
&,H,,NO,. The substance does not react with
hydroxy-8-(3-me~yl-Z-oxo-5-pyrroli~nyl~vone (1).
Dragendorffs reagent, but it gives a positive reaction with
ferric chloride and aluminium chloride. in UV light the
compound displays a yellow fluorescence, which becomes
more intensive after exposure to ammonia In the UV
spectrum the absorption maxima at 272,322 and 371 mu
are characteristic of flavonols with a free 3-OH and
spectral shift reagents 123 indicated free hydroxyl groups
at the 5, 7- and Y-positions. The IR spectrum shows
hands at 33OOcn- * (OH), 1690 cm-’ (c--O in a five-
membered lactamk 1640 cm - ’ (GO of benxopyrone)
and 800 and 840 cm-’ (aromatic nucleus). The mass
spectrum displays peaks at M’ 383 for CzoHi7N07,
calculated 383.3610, and further important fragment ion
peaks at m/z 339 (C,,H,,O,), 286 (CiSHi006) and 176
(C,BH,aNOr). The presence of the fragment ion 286 may
be due to kaempferol while that at m/z97 (C,H,NO)
corresponds to the alkaloidal moiety. 1
short Reports 1845

This represents the 6rst example ofa pyrrolidin*flavonol. CD,OD): 61.29 (3H, d, I = 7.4 Hz CHs), 2.17 (lH, ddd, J
So far four flavonoid alkaloids have been described: ficine = 12.9, 8.9 and 4.9 Hz, H-&x”), 2.57 (lH, ddd, J - 12.9, 9.7 and
and isoficine from Ficus pantonicrnr [4], phyllospadine, 5.9 Hz, H-4b”). 2.77 (lH, dqd, J = and 4.9 H& H-3”), 5.56
from Pkyllosphadix iwatensis [S] and vochysine from (lH,dd,J = 8.9,and 5.9 IiqH-5”),6.24(1H,s,H-6),6.91 (ZH,d,
Vochysia g uaianensis [6]. The first three are N-methyl- J - 9.0 Hz, H-3’ and H-5’), 8.01 (2H. d, I = 9.0 Hq H-2’ and H-
pyrrolidinotlavones and vochysine is a pyrrolidinotlavan. 6’). “CNMR (75.47 MHz. CD,OD): d17.5(CH,), 35.9 (C-t”),
38.5 (C-3”),48.1 (C-5’),99.3 (C-6), 104.8 (C-ta), 106.8 (C-8), 116.5
(C-V, C-5’), 123.6 (C-l’), 130.8 (C-2, C-6’), 137.1 (C-3), 148.5 (C-
2), 155.9 (C-5), 160.7 (Gt’), 161.8 (C-8a), 163.7 (C-7), 177.5 (C-4),
183.9 (C-2”).
The plant material, Liliwn candidtan L, was collected in South
Slovakia and the herbarium specimen is deposited in the Ac&.nowIed~munt-The authors thank Dr L. DolejS of the
Department of Pharmacognosy and Botanics of the Institute of Organic Chemistry and Biochemistry, Cxechoslovak
Pharmaceutical Faculty, Comenius University, in Bratislava. Academy of Scienceq for the measurement of the mass spectrum.
Mps are uncorrected.
Extraction and isolation oflilaline. Dty flowers (1500 g) were
macerated several times at room temp. with a 96 % and 70 %
EtOH [l]. The filtered extract was evaporated and then freexe- 1. EinreichovB, E., Maliterowi, I., Bu&ovti, A. and Tomko, J.
dried. The substances present in the ethanohc macerate were (1985) Ceskoslou. Famt. 34,408.
extracted successively with petrol, ether, chloroform and 2. Markham, K. R. (1982) Techniques o/F&wnoid Idmtjfication.
chlorofonn+thanol (2: 1). Academic Press, New York.
Chromatography on silica gel of the ethereal extract using 3. Wagner, H, Chati, V. M. and Sonnenbichler, J. (1976)
benzene-acetone for clution gave a fraction rich in lilaline. Tetrahedron Letters 1799.
Rechromatography of this fraction on Sephadcx LH-20 with 4. Johns, !I. R, Russel, J. H. and He&man, M. L. (1965)
methanol and crystallixation from acetone afforded 26 mg of Tetr;Jtedron Letters 1987.
yellow crystals of lilaline. Mp 247”, [a]& + 65” (methanol, c 5. Tak& M., Funahsshi, S., Ohta, K. and Nakabayashi, T.
0.2), Cx,,H,,NO,. UVlz” nm (log e): 272 (4,36), 322 (4, lo), (198C) A&. B&l. C/tent. 44, 3019.
371 (4.31), + NaOMe: 285,322,424. + AlCl,: 276,312,357,436 6. Baudouin, G, Tillequin, F, Koch. hi., Vuilhorgne, M,
+ AIt&-HCI: 273, 308, 353, 432 +NaOAc: 282, 322, 402 L&tnand, J.-Y. and Jacquemin, H. (1983) J. Nar. Prod. 46,
+H,BO,-NaOAc: 272, 320, 372. ‘HNMR (300.13 MHz. 681.

Phytochemimy, Vol. 26. No. 6, pp. 1845-1846. 1987. 003 I -9422/87 33.00 + 0.00
Printed in Great Britain. Fergamon



CentralResearch Laboratory, Noristan Limited, Private Bag X516, Silverton 0127, Republic of South Africa

(Receiwd 2 October 1986)

Key Word Idex-Capparis totnentoq Capgmmxac; root; new oxindok; 13CNMR.

Abstract-The structure of 3-hydroxy-3-methyl4methoxyoxindole isolated from the roots of Capparis tomentosu

has hem determined by spectrometric methods.

INTRODUCTION This paper deals with the structural elucidation of a new

oxindole 1 from the roots C. tomentosu. Anticonvulsant
Capparis tomentosa Lam. (woolly caper-bush) is one of the
properties have been reported for a number of 3alkylated
best-known trees among African peoples for its supposed
magico-medicinal properties and has the reputation of 3-hydroxyoxindoles 12.33. Compound 1, however,
curing a variety of complaints ranging from coughs and showed only slight, if any, anticonvulsant activity.
colds to barrenness and impotence [l].

*part 5 in the seriesStudits of South African Medic&al

Plants”. For Part 4 set S. Afi. J. Gent. (1987) (submitted for
publication) The IR spectrum (Nujol) of 1 exhibited absorptions
tTo whom correspondence should he w. characteristic for the hydroxy group (3375 cm- ‘) and the