Letters 232
Alkaloids from Papaver rhopalothece Used as Folk Medicine in Anatolia Günay Sartyar"2 and YusufNur Kalav' 1 Department of Pharmacognosy, Faculty of Pharmacy, University of Istanbul, Istanbul, Turkey 2 Address for correspondence Received: January 30, 1989
The plant material was collected from Marmaris (Mula, Turkey) in May 8, 1983. Avoucher specimen ISTE 50557 is retained at the University of Istanbul, Faculty of Pharmacy. Pow-
dered aerial parts (14 kg) were extracted by percolation in methanol. The filtered extract was concentrated under reduced pressure and the residue was taken up in 5 % acetic acid. The alkaloidal extracts A and B were obtained from the acid extract in the usual manner (5).
TLC systems a—c were carried out on silica gel
GF254 Merck. The solvent systems were a —
ben-
zene: acetone : methanol (7 : 2: 1); b — benzene: ethanol: conc. ammonia (8 : 2 0.03); c — benzene : ethyl acetate: diethylamine :
(5:4: 1)(10).
Extract A (19.17 g) was separated on a column of silica gel (Kieselgel 60, size 0.063—0.125 mm, Merck) eluting with
The alkaloids of P. rhopalothece have now been examined for the first time. The major alkaloids were the aporphine (÷)-isocorydine (2) and phthalideisoquinoline (—)-ct-narcotine. Alkaloids also present in relatively large amounts were the berbinium salts berberine and coptisine,
the protopines protopine and cryptopine, the dihydro-
oxepine (+)-cularine, the aporphine (+)-roemerine, a new alkaloid (+)-rhopalotine [1; (+)-4-hydroxyisocorydine], and the phthalideisoquinoline narceine (4). The finding of a cularine-type in a Papaver species is somewhat surprising since in recent years cularine-type alkaloids had been detected only among Corydalis and Dicentra species within the Papaveraceae (6). Narcotine has been isolated together with narceine for the first time from a species in the section Rhoeades. The presence of narcotine as the major alkaloid in the species most probably is responsible for the antitussive property of the plant.
system a. (—)-cz-Narcotine (7.1 g), (+)-isocorydine (9.5g), (+)roemerine (0.2 g), protopine (1.1 g), (+)-rhopalotine (0.03 g), (+)cularine (0.008 g), cryptopine (0.09 g), and berberine (0.09 g) were obtained. Extract B (7.9 g) was separated on a column of silica gel eluting with benzene : acetone : chloroform (6 : 3: 1 and 5 : 3 : 2, re-
spectively). (—)-u-Narcotine (2.4g), (+)-isocorydine (2.5g), protopine (0.36g), narceine (0.1 g), and coptisine (0.1 g) were obtained. (-#)-Rhopalotine (4-hydroxyisocorydine) (1): col-
ourless crystals from methanol, m.p. 191 °C. UV 270 and 306nm, UV ?MOOH 274 and 308nm. 1H-NMR (100MHZ in CDC13) ô in ppm: 2.70 (3H, s, NMe), 3.72 (3H, s, OMe), 3.95 (3H, s, OMe), 3.98 (3H, s, OMe), 4.55 (1H, t, H-4), 6.97 (2H, s, H-8 and H-9),
7.20 (1H, s, H-3). MS, nile (%): 357 (M, 72), 342 (100), 340 (45), 326 (76), 314 (38), [czI: + 162° (C 0.2, MeOH). The other alkaloids were determined by direct comparison (UV, IR, NMR, MS, and TLC)
with authentic samples. R1values: in a, b, c: berberine 10.17 (c)], coptisine
[0.19 (c)], cryptopine (0.36, 0.36, 0.38), (+)-cularine (0.47, 0.54, 0.57), (+)-isocorydine (0.52, 0.74. 0.70), narceine (0.015, 0.23),
narcotine (0.78, 0.88, 0.90), protopine (0.40, 0.51, 0.56), (+)rhopalotine (0.50, 0.45, 0.39), roemerine (0.64, 0.63, 0.85).
Acknowledgements We express our sincere thanks to Prof. Dr. J. D. Phillipson for spectroscopic (NMR and mass) measurements and to Prof. A. Baytop for the identification of the plant material. We are most grateful to Prof. Dr. Bilge Sener for supplying the reference sample of cularine.
References 1 IR ° OH) l+)-rhopalotine
2 (R ° H) )+)-isoc0rydine
The UV spectrum of the new alkaloid (+)-
rhopalotine (1) which showed maxima at 270 and 306 nm
is consistent with a c-i, 2,10,11 tetrasubstituted aporphine (7), and its phenolic nature was established by a bathochromic shift in the UV spectrum when alkali was present. The 1H-NMR spectrum indicates the presence of one Nmethyl and three 0-methyl signals. The spectrum also exhibited a triplet centered at ô = 4.55 ppm and a singlet at ô = 7.20 ppm,
corresponding to the H-3 resonance shifted
downfield by the presence of a hydroxyl group at C-4, as is always the case in 4-oxygenated aporphinoids (8, 9).
Cullen, J. (1965) Papaveraceae in: Flora of Turkey and the East Aegean Islands (Davis, P. H., ed.), Vol. 1, p. 219, Edinburgh University Press. 2 Baytop, A., Saracoglu, M. (1982) J. Fac. Pharm. Istanbul 18. 25. Kiger, W. (1973) Taxon, 22(5—6), 579. Kalav, Y. N. (1986) Dissertation, University of Istanbul, Istanbul, Turkey. Kalav, Y., Sariyar, G. (1989) Planta Med. 55, 488. 6 Gözler, B., Shamma, M. (1984) J. Nat. Prod. 47, 753. Shamma, M. (1960) Experientia 16, 484. 8 Ribas, I., Suerias, J., Castedo, L. (1972) Tetrahedron Lett. 2033. Guinaudeau, H., Leboeuf, M., Cave, A. (1983) J. Nat. Prod. 46, 325. 10 Pfeifer, S., Kuhn, L. (1966) J. Chromatog. 24—364.
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Papaver rhopalothece Stapf (Sect. Rhoeades Bernh.) is an annual species which is endemic to Western Anatolia (1— 3). During our botanical excursion, we have observed that this species is used together with P. rhoeas L. in folk medicine against cough (4, 5).
Alkaloids from Papaver rhopalothece Used as Folk Medicine in Anatolia Günay Sartyar"2 and YusufNur Kalav' 1 Department of Pharmacognosy, Faculty of Pharmacy, University of Istanbul, Istanbul, Turkey 2 Address for correspondence Received: January 30, 1989
The plant material was collected from Marmaris (Mula, Turkey) in May 8, 1983. Avoucher specimen ISTE 50557 is retained at the University of Istanbul, Faculty of Pharmacy. Pow-
dered aerial parts (14 kg) were extracted by percolation in methanol. The filtered extract was concentrated under reduced pressure and the residue was taken up in 5 % acetic acid. The alkaloidal extracts A and B were obtained from the acid extract in the usual manner (5).
TLC systems a—c were carried out on silica gel
GF254 Merck. The solvent systems were a —
ben-
zene: acetone : methanol (7 : 2: 1); b — benzene: ethanol: conc. ammonia (8 : 2 0.03); c — benzene : ethyl acetate: diethylamine :
(5:4: 1)(10).
Extract A (19.17 g) was separated on a column of silica gel (Kieselgel 60, size 0.063—0.125 mm, Merck) eluting with
The alkaloids of P. rhopalothece have now been examined for the first time. The major alkaloids were the aporphine (÷)-isocorydine (2) and phthalideisoquinoline (—)-ct-narcotine. Alkaloids also present in relatively large amounts were the berbinium salts berberine and coptisine,
the protopines protopine and cryptopine, the dihydro-
oxepine (+)-cularine, the aporphine (+)-roemerine, a new alkaloid (+)-rhopalotine [1; (+)-4-hydroxyisocorydine], and the phthalideisoquinoline narceine (4). The finding of a cularine-type in a Papaver species is somewhat surprising since in recent years cularine-type alkaloids had been detected only among Corydalis and Dicentra species within the Papaveraceae (6). Narcotine has been isolated together with narceine for the first time from a species in the section Rhoeades. The presence of narcotine as the major alkaloid in the species most probably is responsible for the antitussive property of the plant.
system a. (—)-cz-Narcotine (7.1 g), (+)-isocorydine (9.5g), (+)roemerine (0.2 g), protopine (1.1 g), (+)-rhopalotine (0.03 g), (+)cularine (0.008 g), cryptopine (0.09 g), and berberine (0.09 g) were obtained. Extract B (7.9 g) was separated on a column of silica gel eluting with benzene : acetone : chloroform (6 : 3: 1 and 5 : 3 : 2, re-
spectively). (—)-u-Narcotine (2.4g), (+)-isocorydine (2.5g), protopine (0.36g), narceine (0.1 g), and coptisine (0.1 g) were obtained. (-#)-Rhopalotine (4-hydroxyisocorydine) (1): col-
ourless crystals from methanol, m.p. 191 °C. UV 270 and 306nm, UV ?MOOH 274 and 308nm. 1H-NMR (100MHZ in CDC13) ô in ppm: 2.70 (3H, s, NMe), 3.72 (3H, s, OMe), 3.95 (3H, s, OMe), 3.98 (3H, s, OMe), 4.55 (1H, t, H-4), 6.97 (2H, s, H-8 and H-9),
7.20 (1H, s, H-3). MS, nile (%): 357 (M, 72), 342 (100), 340 (45), 326 (76), 314 (38), [czI: + 162° (C 0.2, MeOH). The other alkaloids were determined by direct comparison (UV, IR, NMR, MS, and TLC)
with authentic samples. R1values: in a, b, c: berberine 10.17 (c)], coptisine
[0.19 (c)], cryptopine (0.36, 0.36, 0.38), (+)-cularine (0.47, 0.54, 0.57), (+)-isocorydine (0.52, 0.74. 0.70), narceine (0.015, 0.23),
narcotine (0.78, 0.88, 0.90), protopine (0.40, 0.51, 0.56), (+)rhopalotine (0.50, 0.45, 0.39), roemerine (0.64, 0.63, 0.85).
Acknowledgements We express our sincere thanks to Prof. Dr. J. D. Phillipson for spectroscopic (NMR and mass) measurements and to Prof. A. Baytop for the identification of the plant material. We are most grateful to Prof. Dr. Bilge Sener for supplying the reference sample of cularine.
References 1 IR ° OH) l+)-rhopalotine
2 (R ° H) )+)-isoc0rydine
The UV spectrum of the new alkaloid (+)-
rhopalotine (1) which showed maxima at 270 and 306 nm
is consistent with a c-i, 2,10,11 tetrasubstituted aporphine (7), and its phenolic nature was established by a bathochromic shift in the UV spectrum when alkali was present. The 1H-NMR spectrum indicates the presence of one Nmethyl and three 0-methyl signals. The spectrum also exhibited a triplet centered at ô = 4.55 ppm and a singlet at ô = 7.20 ppm,
corresponding to the H-3 resonance shifted
downfield by the presence of a hydroxyl group at C-4, as is always the case in 4-oxygenated aporphinoids (8, 9).
Cullen, J. (1965) Papaveraceae in: Flora of Turkey and the East Aegean Islands (Davis, P. H., ed.), Vol. 1, p. 219, Edinburgh University Press. 2 Baytop, A., Saracoglu, M. (1982) J. Fac. Pharm. Istanbul 18. 25. Kiger, W. (1973) Taxon, 22(5—6), 579. Kalav, Y. N. (1986) Dissertation, University of Istanbul, Istanbul, Turkey. Kalav, Y., Sariyar, G. (1989) Planta Med. 55, 488. 6 Gözler, B., Shamma, M. (1984) J. Nat. Prod. 47, 753. Shamma, M. (1960) Experientia 16, 484. 8 Ribas, I., Suerias, J., Castedo, L. (1972) Tetrahedron Lett. 2033. Guinaudeau, H., Leboeuf, M., Cave, A. (1983) J. Nat. Prod. 46, 325. 10 Pfeifer, S., Kuhn, L. (1966) J. Chromatog. 24—364.
Downloaded by: Universite Laval. Copyrighted material.
Papaver rhopalothece Stapf (Sect. Rhoeades Bernh.) is an annual species which is endemic to Western Anatolia (1— 3). During our botanical excursion, we have observed that this species is used together with P. rhoeas L. in folk medicine against cough (4, 5).
