Phytochemistry. Vol. 30, No. 12, PP. 4195 4196, 1991 003 l-9422:9 I $3 00 +0.

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Pnnted in Great Britain. @>1991 Pergamon Press plc
AROMATIC COMPOUNDS FROM DELPHINIUM VENULOSUM
A. H. MERICLI, F. MERICLI, A. ULUBELEN and R. ILARSLAN*
Faculty of Pharmacy, University of Istanbul, Istanbul, Turkey; *Faculty of Sciences, University of Ankara, Ankara, Turkey
(Received in reoisedform 29 May 1991)
Key Word Index-Delphinium uenuloswn; Ranunculaceae; aromatic compounds; 2,5,6-trihydroxypiperonylic acid
methyl ester.
Abstract-From the non-alkaloidal fractions of Delphinium uenulosum, four known aromatic compounds cis and trans
p-coumaric acids, phydroxybenzoic acid, protocatechuic acid methyl ester and a new aromatic compound 2,5,6-
trihydroxypiperonylic acid methyl ester were isolated together with kaempferol, sitosterol and sitosteryl 3-glucoside.
The structures of the compounds were established by spectral data.
INTRODUClION
Delphinium species have been extensively studied for their
diterpenoidal alkaloids which possess neurotoxic, in-
secticidal, growth inhibiting and curare-like properties
[l-4]. However, there are only a few investigations of
their non-alkaloidal compounds [S, 63. In the present
study with the aerial parts of an endemic Delphinium
species, D. venulosum, we have obtained a new and four
known aromatic compounds after the separation of the
alkaloids.
RESULTS AND DL5CUSION
The acidic aqueous solution of the aerial parts of
Delphinium uenulosum Boiss. was extracted with benzene
and afforded five aromatic compounds, one of them being
the new 2,5,6-ttihydroxypiperonylic acid methyl ester (1).
Compound 1 showed IR bands at 3500,3450,3050,1605,
1595, 1550 and 15lOcm-. The first two resonances
corresponds to hydroxyl(s), and the rest are indicative of
an aromatic ring. UV maximum at 286 nm correlated the
presence of an aromatic system. The H NMR spectrum
(CD,OD) showed signals at 63.58 (3H, s, CO,Me), 6.02
(2H, s, OXH,-0). 6.42 (lH, s, OH) (D20 exchange), 5.20
(IH, s, OH) (D,O exchange), 14.10 (lH, s, OH) (D,O
exchange). The latter signal indicated the hydrogen bond
formation between one of the hydroxyls vicinal to car-
boxy1 with the carbonyl of the carboxymethyl. Acetyl-
ation of 1 yielded its triacetate (la). The IR spectrum of la
showed resonances at 1730, 1725, 171Ocn- for acetyl
carbonyls, while the hydroxyl resonances at 3500 and
3450 cm- in the IR spectrum of 1 disappeared. The
HNMR spectrum of la (CDCI,) exhibited signals at
63.50 (3H, s, CO,Me), 5.92 (2H, s, O-CH,-O). 2.25 (9H, s,
3 x OCOMe). When the H NMR spectrum was recorded
in benzene-d, the peaks were shifted to 65.82 (2H, s), 3.58
(2H, s), I.68 (9H, s). The t3C NMR, SFORD and APT of
la (CDCI,) indicated the presence of four methyl, one
methylene and ten quaternary carbon atoms. The acetyl
carbonyl resonances were at 6170.6, 171.3 and 172.5, a
carboxyl resonance was observed at 6166.8. The high
resolution mass spectrum of la did not yield the molecu-
lar ion peak, but the degradation peaks as well as the
OH
1
elemental analysis together with the 3C NMR spectrum
indicated the molecular formula C1 gH ,,O t o for la.
The spectral data indicated two structural possibilities
for 1, 2,5,6-trihydroxypiperonylic acid methyl ester and
2,3,6-trihydroxy-5,6-dioxymethylenebenzoic acid methyl
ester. The COSY spectrum of la (C,D,) showed the
relations between dioxymethylene (65.82) and acetyl
(61.68) as well as between carboxymethyl (63.58) and
acetyl (6 1.68). NOE experiment carried out with la did
not show a relation between carboxymethyl and di-
oxymethylene indicating the first structure for 1. An
FeCI, (5% aq. ale. solution) test with 1 produced a deep
green colour on TLC plates and on paper. In the case of
the latter structure the colour should be almost black as
observed in gallic acid [7]. Hence 1 is 2,5,6_trihydroxy-
piperonylic acid methyl ester.
EXPERIMENTAL
Plant material. Delphinium wtulosum Boiss. (Ranunculaceae)
was collected from Ulukisla, Nigde. Turkey in July 1990 and
identified by one of us (RI). A voucher is deposited in the
Herbarium of the Faculty of Science, University of Ankara
(Ilarslan 1613).
Extraction and isolution. The dried and powdered plant (500 g)
was extracted with 70% EtOH by percolation at room temp., the
solvent was evapd under vacuum. The extract was treated with
1.5% H,SO, and extracted with C,H, to clean it before alkaloid
extraction. The alkaloids were sepd from the remaining aq. soln
as described in ref. [8]. After neutralization the aq. soln was
4195
4196 Short Reports
extracted with EtOAc. The C,H, fr. was sepd in a silica gel Acknowledgements-This study is supported by TUBITAK
column (4 x 60 cm) eluting with petrol, a gradient of Et,0 was (Ankara) Grant No. TBAG-908). The authors thank TUBITAK-
added up to lOO%, followed by EtOH up to 100%. The new Gebze for H, C NMR and COSY, APT, NOE experiments,
compound 1 (15 mg), protocatechuic acid methyl ester (10 mg), Prof. Dr S. Matlin (City University, London) for MS, and the
sitosterol (20mg) were obtained from this column. When the International Organization for Chemical Sciences Development
EtOAc fr. was sepd in a Polyclar column (5 x 60 cm) eluting with for support.
CHCI,-EtOH (2: 1) cis-p-coumaric acid (25 mg), trans-p-coum-
aric acid (20 mg), p-hydroxybenzoic acid (7 mg), sitosteryl 3-
glucoside (15 mg) and kaempferol (20 mg) were Isolated.
2,5,6-Trihydroxypiperenc,Irc arid methyl ester I. Needles, mp
253-255. UV iz::nrn (log E): 286 (3.60). 218 (3.50). IR
,, F;I:p 3 (.m
: 3500, 3450, 3050, 2950, 2820, 1720, 1605, 1595,
1550, 1510, 1440, 1420, 1380, 1290, 1240, 1170, 1100, 930, 850.
H NMR (given in the text).
2,5,6-Triacetylpiperenolic acid methyl ester (la). IR
v~Ilf,l,cm-:
3050, 2980, 2850, 1730, 1725, 1710, 1250, 1210,
1080. 940, 860. H NMR given in the text. % NMR (CDCI,)
6: 172.5 (OCOMe), 171.3 (OCOMe), 170.6 (OCOMe), 166.8
(CO,Me), 150.8, 150.2, 149.6, 149.2, 147.8 (6x Arm. C), 103.2
(OXH,-0). 51.8 (CO,Me), 22.5 (OCOMe), 21.5 (OCOMe), 21.0
(OCOMe). MS 70 eV (probe) m;z (rel. int.): 264 [M - HOAc- 2
x Me] (100). 220 [264-CO,] (15). 176 [220-CO,] (48),
151 (30), I II (13). 98 (13). 85 (25). 69 (19). 58 (32), 55 (16).
2.
3.
4.
5.
6.
7.
8.
REFERENCES
Majak, W. and Engelsjord, M. (1988) J. Range Manage. 41,
224.
Schneider, G. (1985) Pharmazeutische Ei ol oyi e, p. 454. Biblio-
graplusches Institut, Zurich.
Wailer, G. R. and Burstrdm, H. (1969) Nature 222, 576.
Gubanow, 1. A. (1965) Planta Med. 13, 200.
Arazashvili, A. I., Moniava, I. I. and Kemertelidze, E. P. (1974)
Khim. Prir. Soedin. 10, 251.
Warnock, M. J., Liu, Y. L. and Mabry, T. J. (1983) Phyto-
chemistry 22, 1834.
Paech, K. and Tracey, M. V. (1955) Moderne Methoden der
PJanzen-analyse Vol. 3, p. 467. Springer, Berlin.
Pelletier, S. W., Joshi, B. S. and Desai. H. K. (1985) Adoances
in Medicinal Plant Research (Vlietick, A. J. and Domisse,
R. A., eds), p. 156. Wissenschaftliche, Stuttgart.
Phyrorhrmisrry, Vol. 30. No 12. pp. 4196 41Y7. 1991 0031 9422,91 f3.00+0.00
Printed m Great Bntam $. 1991 Pergamon Press pit
A FURANOCOUMARIN FROM DORSTENIA CONTRAJERVA
LEE A. SWAIN, J. M. E. QUIRKE.* STEPHEN A. WINKLE* and KELSEY R. DowruuMt
Department of Biological Sciences, University Park, Florida International University, Miami, FL 33199, and Fairchild Tropical
Garden, 10901 Old Cutler Road. Miami, FL 33156, U.S.A.; *Department of Chemistry, University Park, Florida International
Umversity, Miami, FL 33199, U.S.A.
(Received in reoisedform 3 May 1991)
Key Word Index-Dorsrmia; Moraceae: Icaves; furanocoumarin; phototoxins.
Abstract-A new furanocoumarin, 5-[3,4-epoxy-2,7-dimethyl-6,7-octenoyl]psoralen was isolated and identified from
Dorstenia contrajerva.
I NTRODUCTI ON
In our search for photobiocides from tropical plants, we
discovered furanocoumarins in a number of species of the
Moraceae. Furanocoumarins had been previously isol-
ated from a few genera in this family [I]. Dorstenia, a
herbaceous genus found throughout the Old and New
World tropics [2] is particularly rich in furanocoumarins
[3,4] and we recently described the distribution of these
tAuthor to whom correslxmdence should be addressed.
chemicals and discussed possible ecological and evolu-
tionary aspects [3]. This report describes the isolation
and structural elucidation of a new natural furanocoum-
arin, S-[3,4-epoxy-2,7-dimethyl-6,7-octenoyl]psoralen
(5EDOP) from leaves of Dorstenia contrajeta.
RESULTS AND DI SCUSSI ON
S-[3,4-epoxy-2,7-dimethyl-6,7-octenoyl]Psoralen (1)
was isolated as pale yellow needles. High-resolution mass
spectrometry established the molecular formula as
C,, H,,Ob (observed: 368.1252; calculated: 368.1260).