Pergamon 0031-9422(94)00673-3 Phyrochemistr1, Vol. 38, No, 4, pp. 1049 1051, 1995 Copyright ,(5 1995 Elsevier Science ktd Printed in Great Britain. All rights reserved 0031 9422/95 $9.50 + 0110 ( -t- )-8-OXOHYPECORININE FROM HYPECOUM PROCUMBENS VAR. GLA UCESCENS HASSAN-ELRADY A. SAAD Department of Pharmacognosy, Faculty of Pharmacy, University of Mansoura, EI-Mansoura 35516, Egypt (Received 21 June 1994) Key Word Index--Hypecoum procumbens var. 91aucescens; Hypecoaceae; isoquinoline alkaloids; secoberbines; ( + )-8-oxohypecorinine; ( + )-hypercorinine; aporphines; isocorydine; protopines; allo- cryptopine; cryptopine; protopine. Abstract--A new secoberbine alkaloid, (+)-8-oxohypecorinine, together with (_+)-hypecorinine, isocorydine, allocryptopine, cryptopine and protopine were isolated from Hypecoum procumbens var. 91aucescens and spectro- scopically characterized. INTRODUCTION The genus Hypecoum [1] comprises ca 15 species growing in the Mediterranean region, central Asia, Pakistan and northern China [2]. It is represented in Egypt by nine species [1]. Although nothing could be traced in the current literature about the phytochemical study of H. procumbens var. 91aucescens native to Egypt, the alkaloids of H. procumbens growing in different localities has been the subject of several investigations [3-10]. Protopines, berbines, secoberbines, benzophenanthridines and apor- phines were reported as major groups [4]. In continua- tion of our work on Hypecoum species of Egypt [11], the alkaloids of H. procumbens var. 91aucescens were investig- ated. It afforded, in addition to (+_)-hypecorinine (1), isocorydine, allocryptopine, cryptopine and protopine, the new secoberbine alkaloid ( + )-8-oxohypecorinine (2), whose structure elucidation is described herein. RESULTS AND DISCUSSION From whole plants of H. procumbens var. glaucescens, the new optically inactive secoberbine alkaloid, ( + )-8- oxohypercorinine (2), and five known tertiary bases be- longing to the secoberbine (( + )-hypercorinine I [11, 12]) aporphine (isocorydine [13]) and protopine (allocrypto- pine [14], cryptopine [14], protopine [14]) groups were isolated. (+)-8-Oxohypecorinine (2), was obtained as an amorphous orange powder from the chloroform-isopro- panol extract by column chromatography and prepara- tive TLC. It showed UV maxima of a secoberbine alkaloid of the hypercorinine type, but with a strong bathochromic shift for the band at longer wavelength. The IR spectrum demonstrated two carbonyl adsorption bands at 1665 and 1645 cm- 1 of a six-membered lactone o 3 RI +R2=H 2 I RI +R2 =O 2 and a conjugated ketone [10]. The El-mass spectrum displayed a weak [M] + at m/z 381 consistent with the molecular formula C2oHlsNO7 (calcd 381.08484) with an unsaturation number of 14. The 1H NMR (Table 1) showed close resemblance with ( ___ )-hypecorinine (1) by signals for four aromatic protons at 66.61 (H-I), 6.73 (H-4), 7.01 (H-11) and 7.90 (H-12) of two tetrasubstituted benzene rings and two methylenedioxy protons at 6 5.99 and 6.1 t. However, it was significantly different from 1 by the absence of the CH2-8 proton resonances of 64.79 (1H, d, J = 15.9 Hz) and 5.14 (1H, d, J = 15.9 Hz), the strong downfield shift of N-Me protons to 62.71 and the reson- ance of the other protons at lower fields by ca 0.1-0.2 ppm. These features together with an extra oxy- gen atom in the molecular formula of 2 indicate that the two methylene hydrogens in ( + )-hypecorinine 1 were replaced by an oxygen atom as part of a lactone fragment in 2. Structure 2 was finally established by detailed analysis of its 13C NMR and DEPT spectra (Table 1). It revealed 1049 PHY 38:4-Q