A4LKXLOIDS OF PAPA VER L-4 CERU31 Gi' SIT P.IRII-.~R Depiirtnient of Plicirnincognos?,
Plinrniacj, L7ni;'ersit? oj' Istcinbirl, T i i r k e j and J. D.ii-1~PHILIJPSOY F t r c l i l t ~of
D e p n r f n i e n t o.f Plinrmocognos!, Tlie S c h o o l of Piiiirntnc?, l - n i ; , e r s i t j of L o n d o n , 29-90, Briinsirick Spiiiire, Londoti 11-CI S 1.i :', l..h-.
There are no previous reports on the chemical constituents of Papaw lacerum Popov. (syn. P . laezigatzim auct. non Bieb.), a species ivhich is native t o Turkey and Soviet Xrmenia (1). This comniunication reports the preeence of four allinloids extracted from the stems and capsules of a Turkish sample of P.lacerzim collected in -\nntolia. The major alkaloid \vas the aporpliine, roemerine (1); Tvhile another nporphine. .\'-methyl asimilobine (2). and the proaporphines mecnnibrine (3) and pronuciferine (1)
ferine. have been ixolated from a number of Papaier .pecie, ( 2 - 5 ) ; Smethyl asimilobine doe.; not appear t o be a common alkaloid. although it haq been reported recently to be t h e major alkaloid of an Egyptian -ample of P.rhoeas (6). P.lacerum ic in the section Papaver ( E Orthorhoeade; Fedde) TI hich include. P. rhoeas. P. commtitatiim, P. postii, P. dubiiim. P. aretiarium, P. stylatum and P . cla.iatiim. Morphologically. P. lacerzim i.; finiilar t o P. dubium L. (*yn. P . laeiigatiim
F-M RF-Me R1
Rl
R2
9 /
0
1 2
N
R1-R2 = OCH20 R 1 = O H ; R 2 = OMe
N
were obtained ai. minor a1l;aloid.;. Tlie :~lli:iloicl.~ \Yere identified by their ultrn-\-iolet, ma.+ and proton magnetic iwonance ,-pectrn and hj. chromatogi~ipliic eonip:ii,i>o~i\\-it11 i.eference compound c . Tlie proton magnetic m-onxnce ipectrum of the iGolnted .l.-methj.l :\,-imilobine (2) clearly diff'ei'riitinted i t fi.oni the col.I.esponc1iiig 1 -Ii\.cli,os!.-. ?-met iios!.-:\nnlogue. 1ii.iniciiiie ( 2 i . Tile :~lli:il~ids.i ~ e niei,iiie. niecnnibi,iiie and pi~onuci-
/ l2
3 RI-R2= OCH2O 4 R1 = R 2 = OMe
N
N
Bieb.), ivhicli i,s A widespread, variable species found in Europe and in -Asia. Ilecambrine and roenierine have been reported from P. tizibiiim. together ivitli the rhoeadine-type alkaloids, i,hoendine. isorhoeadine. rhoeagenine, s e v e i ~paparerrubines. ~l berberine. copti..ine, protopine and *anguinaritie (7-11). In vieiv of the variable alkaloid con>tituent~reported from .sevei~l>pecies of tlie section Pnpaver, tlie po>-ibilit>- of chemicnl race, of
240
JOURSAL OF SATURAL PRODUCTS
P. lacerum cannot be ignored. Hence it n-ould be of interest to investigate further samples of P. l a c e r u m from other parts of Turkey and Soviet Armenia for the presence of alkaloids.
EXPERIMEXTAL PL.AST sI.\TERI.%L.-The plant material was collected at Kayser, Turkey, by G. Sariyar and A. Baytop, June 21, 1977. Identifcation as P. lacerum Popov. was determined b y Professor A. Baytop, and a reference sample is retained in t h e herbarium of t h e Faculty of Pharmacy, University of Istanbul.
ISOL.LTIOS OF . % L K . I L ~ I D s . - ~ ) I ’ ~capsules ~~ and stems (130 g) were macerated (3 x ) with methanol, and t h e combined filtered est r a c t s were concentrated to dryness under reduced pressure. T h e residue was estracted with 3 5 acetic acid (5 x 25 m l ) ; t h e combined acid extracts were washed with light petroleum, made alkaline with 25% ammonium hydroxide solution, and estracted with diethylether (3 x 40 m l ) . T h e combined ethereal extracts, when washed, dried and concentrated t o dryness under reduced pressure, yielded 207 m g of t o t a l crude alkaloid (0.16Yc). Preparative tlc with absorbent Silica gel G (Rlerck) and t h e solvent system, benzene-ace t one-ammonium hydroxide (90:10:1), yielded amorphous roemerine (105 mg) and a pale brown solid (46 m g ) . .4fter further preparative tlc with alumina G (“lrck) and t h e solvent system benzene-acetone-methanol (7:2:1), t h e solid yielded t h e amorphous alkaloids mecambrine (19 mg), pronuciferine (5 mg), and AT-methyl asimilobine (1 mgj. IDENTIFICATIOS OF .~LltaLoIDs.-Roemerine (1) exhibited uv, ms (12), and 1H nmr spectra (13) identical with those reported in t h e literature and Rfvalues on tlc identical with those of t h e reference alkaloid. Mecambrine (3) exhibited uv (14) and ms (15) spectra identical with those reported in t h e literature. 1H nmr, 60 M H z (CDC1,) 6 6.92 (2H, m , J a , 1 2 2Hz, Js,g 8 H z ; C-8H, C-l2H), 6.32 (2H, m , Jg.11 1 H z , 18.9 8 Hz; C-gH, C - l l H ) , 6.53 ( l H , S: C-3H), 5.83 (2H, q ; ur OCH,O), 2.37, (3H, s; NLfe); tlc R f values identical with those of t h e reference sample. Pronuciferine (4) exhibited uv (14), ms (16) and ’H nmr spectra identical with those reported in t h e literature and tlc Rr values identical with those of t h e reference sample.
[VOL.
44, so. 2
IV-methylasimilobine (2) exhibited uv, ms, and lH nmr spectra identical with t h e literature values (6) and tlc R f values identical with those of t h e reference sample. ilCKSOWLEDGMENTS We are grateful t o Professor F. Santav); (roemerine, pronuciferine, mecambrine) and Professor A . CavC (X-methylasimilobine) for gifts of reference compounds and t o Professor A . Baytop for identification of t h e plant material. We thank J l r . 11. C a r t e r and M r . W .Baldeo for determination of ms and 1H nmr spectra. Receiced 16 S e p t e m b e r 1980 LITERATURE CITED 1. .J. Cullen in P. H. Davis ( e d . ) , Florii of T u r k e y n n d the .4egeiix Islonds, 1.01. 1, 1965, Edinburgh University Press, pp. 219-236. 2. H. Guinaudeau, 11. Lehoeuf and A . CavC, Lloydici, 38, 275 (1975). 3. H . Guinaudeau, I f . Leboeuf and A . CayC, J . IYfI!. Prod., 42, 325 (1979). 4. F . SantavJl in R . H . F. Manske (ed.), T h e I k f i l o ~ d s - C h e ~ i ~ s t riind y Physiology, 1.01. 12, 1970, Academic Press, London and New York, pp. 333-454. 5. F. Santavg in R . H. F . Manske and R . Rodrigo (eds.), T h e Alkriloids-Chemi s t r y and Physiology, 1701. 17, 1979, rlcademic Press, London and S e w York, pp. 385-544. 6. S. El Masrv. Ril. G . El Ghazoolv. A. A . Omar, S. Rf.’Khafagy and J . D.-Phillipson, Plantu J l e d . , 41, 61 (1981). H. G. Boit and H . Flentje, ~\‘aturwisI . senschaflen, 47, 180 (1960). 8. A. NEmeEkovi and F. Santav);, Coll. Czech. C h e m . Commun., 27, 1210 (1962). 9. A . NEmeEckov6, F. SantavS; and D . Walterova, Coll. Czech. Chenr. Commun., 35, 1733 (1970). 10. J. Slavik, Coll. Czech. C h e m . Commun., 28, 1738 (1963). 11. S. Pfeifer and S. K. Banerjee, Die Phnrmazze,19, 286 (1964). 12. S. Pfeifer and L . Kuhn, Die Phurmazie, 23, 199 (1968). 13. S. R . Johns, J. A. Lamberton and A. A . Sioumis, A u s t r . J . C h e m . 22, 1311 ~
-
(1969) --, \ - -
14. K. L . S t u a r t and M. P. Cava, C h e m . Ret’., 68, 321 (1968). 15. L . DolejS. Coll. Czech. C h e m . Commun., 39, 571 Cl974). 16. hl. Tomita. A . K a t o . T . Ibuka. H. Furakawa ’and bl. Kozuka, Tetrahedron Letts. 2825 (1965).
