Phytochemistry, Vol. 34, No. 6, PP. 1656 1658, 1993 Printed in Great Britain. 0031-9422/93 S6.00+0.00 Q 1993 Pergamon PressLtd zyxwvutsrq ALKALOIDS FROM zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHG NARCISSUS LEONENSIS* JAUME BASTIDA, FRANCESCVILADOMAT, SALVADOR BERGORON, JUAN MARCOS FERNANDEZ,CARLES CODINA,~ MARIO RUBIRALTA: and JEAN-CHARLES QUIRION$ Department de Productes Naturals; SLaboratori de Quimica Orgkdca, Facultat de FarmLcia, Universitat de Barcelona, 08028 Barcelona, Spain; $Institut de Chimie des Substances Naturelles, C.N.R.S., 91198 Gif-sur-Yvette Cedex, France (Received in reoisedform 7 June 1993) Key Word Index-Narcissus leonensis; Amaryllidaceae; alkaloids; epinorgalanthamine; epinorlycora- mine. Abstract-The new alkaloids epinorgalanthamine and epinorlycoramine have been isolated from whole plants of Narcissus leonensis. Their structures and stereochemistry were established by physical and spectroscopic methods. INTRODUCTION Carrying out chemical investigations on Narcissus alkal- oids, we have studied N. leonensis a hexaploid species belonging to the Pseudonarcissi DC. section and a native of the Cantabric chain (north of Spain). Narcissus nobilis and N. primigenius are two very closely related species, differing in their ploidy level and habitat [2, 31. RESULTS AND zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHGFEDCBA DISCUSSION Total alkaloids were isolated from fresh aerial parts and bulbs of N. leonensis by extraction with ethanol. After evaporation, the alkaloids were obtained by routine acid-base work-up procedures (see Experimental) to give two extracts. From extract I, epinorgalanthamine (l), epinorlycoramine (2) and norgalanthamine (3) were isol- ated. Extract II was found to contain lycorine. The concentration of total alkaloids on a fresh weight basis was 0.019%. For the characterization of 1 and 2, IR, mass, ‘H, 13C and 2D NMR spectrometry were used. The identification of the other two alkaloids was made by comparison of their spectral data with those of authentic samples and the literature [4,5]. Compound 1, with a [M]’ at tn/z 273 (100%) analysed for C,,H,,NO,, it was obtained by preparative chro- matography from an equimolecular crystalline mixture with 2. In the sixties, a similar mixture of 3 and norlycora- mine (4) was defined as a ‘quasi-racemic’ alkaloid [6]. The IR spectrum of 1 showed a hydroxyl band at 3550 cm- ‘. The aromatic part of the ‘HNMR spectrum (Table 1) displayed an AB system at 66.68 and 6.62 corresponding *Part 19 in the series ‘Narcissus alkaloids’. For part 18 see ref. [l]. tAuthor to whom correspondence should be addressed. zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHGFEDC 2 1 3 @ 4 0 Me0 lo l ..;: ‘;-R2 9 8 I <" lob ; J /& N."12 7 6 1 R, = H. R2= OH EPINORGALANTHAMINE 3 R,;. OH, R2 = H NORGAIANMAMINE Ml?0 2 R, = H, R2 = OH EPINORLYCORAMINE 4 R, = OH, R2 = H NORLYCORAMlNE to the ortho protons (H-8 and H-7) of the A ring, as well as two doublets at S 6.05 and 5.98 for the olefinic protons H- 4a and H-4; the assignment of H-4a at higher fields was made by the 2D COSY technique. At lower fields, the most interesting signals were: (i) two doublets at 64.04 and 3.93 for the methylene protons at the benzylic position, (ii) one singlet at 63.84 due to the methoxy group, and (iii) two signals at 63.38 and 3.22 for the protons /? and CL to the C-12 position; the difference 1656