Short Reports (rel. int.) 293 [M] + (C17H110,N)(4.6), 279 [M--CH2] + (100), 264 [M-COH] + (3.5), 250 [M-CO-Me] + (15), 220 (19.2), 206 (25.5), 191 (53.9), 178 (45.1), 151 (16.1). Rutalpinin 2, U V 2 ~ °n nm 293 (loge 4.2), 235 (loge 4.5). IR vc~cl3 cm- 1 3050, 2950, 2840, 1720 (sh), 1705, 1680 (sh), 1600, 1500, 1480, 1440, 1355, 1240, 1180, 1030, 930, 860, 800. 1HNMR see text. MS, 70eV (proble) m/z (rel. int.) 258.75 [M] + (C15H1,O,) (75), 243 [M-Me] + (8), 230 [M-CO] + (10), 215 [M-CO-Me] + (10), 135 [CsnTO2] + (100), 105 [C6H50 ] + (40), 77 [C6H5] + (45). 651 REFERENCES 1. Ulubelen, A., Terem, B., Tuzlact, E., Cheng, K. F. and Kong, Y. C. (1986) Phytochemistry 25, 2692. 2. Reisch, J., Rozsa, Zs., Szendrei, K., Novak, I. and Minker, E. (1976) Phytochemistry 15, 240. 3. Reisch, J., Mester, I., Kapoor, S. K., Rozsa, Z. and Szendrei, K. (198t) Ann. Chem. 85. 4. Mitaku, S., Skaltsounis, A.-L., Tillequin, F., Koch, M., Pusset, J. and Chauviere, G. (1985) J. Nat. Prod. 49, 1091. 5. Tillequin, F., Baudouin, G., Koch, M. and Svenet, T., (1980) J. Nat. Prod. 43, 498. 0031-9422/88 $3.00+ 0.00 © 1988 Pergamon Journals Ltd. Phytochemistry,Vol. 27, No. 2, pp. 651 653, 1988. Printed in Great Britain. ALKALOIDS OF TECLEA NOBILIS ABIY YENESEW and ERMIAS DAGNE* Department of Chemistry, Addis Ababa University, P.O. Box 1176, Addis Ababa, Ethiopia (Received 7 May 1987) Key Word lndex--Teclea nobilis; Rutaceae; quinoline alkaloids; no6iline; isoplatydesmine; ribalinine; edulinine; montrifoline; skimmianine; flindersiamine; maculine. Abstract--A new furoquinoline alkaloid to which we have assigned the trivial name nobiline, and seven other quinonline alkaloids were isolated and identified from the leaves and fruits of Teclea nobilis, an African medicinal plant. INTRODUCTION Teclea nobilis is a rutaceous plant widely distributed in tropical Africa and is known in many African societies as a medicinal plant. In South Africa the bark is reported to be a remedy for gonorrhoea while in Tanzanian folk medicine the leaves are used as cure for fever I-l]. Similarly in Ethiopian traditional medicine the bark and leaves are used as analgesics. Although many species of the genus Teclea have been investigated for their alkaloidal composition [2, 3], there is no prior report on the chemical constituents of T. nobilis. We therefore examined the leaves and fruits of this plant, since preliminary chemical screening showed both to be rich in alkaloids. RESULTS AND DISCUSSION TLC examination of the alkaloidal fraction of the leaves of T. nobilis revealed the presence of at least nine alkaloids. Upon silica gel chromatography and crystalliz- *Author to whom correspondence should be addressed. ation a hitherto unreported alkaloid named nobiline (1), ClsH19NO4 (['M-I + 313), mp 117-119 ° and seven other known alkaloids were ioslated. The identities of the known alkaloids were determined by spectroscopic means and in some cases by comparison with authentic samples. Spectroscopic evidence, especially UV and N M R , indicated that the new compound was a 4-methoxyfuroquinoline alkaloid. The mass spectrum of compound (1) showed in addition to the I-M] +, significant peaks at m/z 298 [,M - 15] +, 284, 245 [,(M - 6 8 ] + 100%) and 230 [M - 83] +. Loss of a fragment of m/z 68 is characteristic of compounds having a prenyloxy moiety. The 1H N M R spectrum of (1) in CDC13 showed the presence of two methyl groups appearing as a singlet at 61.76, strongly suggesting their attachment to an olefinic functional group, an assignment further supported by signals appearing as a doublet at 4.73 and a triplet at 5.62 ppm caused respectively by methylene protons and an olefinic proton ofa dimethylallyloxy side chain. Two O M e groups appear at 4.0 and 4.42 ppm, the latter signal indicative of a methoxy group at C-4, based on chemical shift data reported for 4-methoxyfuroquinoline alkaloids [-4]. A pair of AB doublets at 7.04 and 7.58 ppm ( J = 3 Hz) corresponded to the two furan protons, while the two 652 Short Reports OMe OH f R3 Rt = ~ Me OMe R2 = (Me)2C~--CHCH20-- R3 = H R1 = (Me)2COHCHOHCH20-- 0 R 2 = OMe R3 = H Rl = H, R2 = R l R2 = R3 = R3 = OMe --OCH20~ OMe OMe 8 R l R2 = R3= ~OCH20-- H I Me 4 singlets at 7.36 and 7.49 ppm represented H-8 and H-5 protons, respectively. The positions of the prenyloxy and the normal methoxy groups were established by an N O E study. Irradiation of the OMe group appearing at 4.0 ppm resulted in a 20.7% signal enhancement of H-5 clearly showing that this methoxy group is located at C-6. This then leads to placing the prenyloxy group at C-7. Isoplatydesmine (2) and ribalinine (3) were readily isolated from both the leaves and fruits of T. nobilis and gave rise to spectral characteristics identical to those reported in the literature [5, 61. The latter compound, by far the most abundant of the T. nobilis alkaloids, was identical except with respect to rotation to an authentic sample [6"1 isolated from Araliopsis soyauxii. Varying rotation values have been reported for ribalinine. Ribalinine, first isolated [5"1 from the Argentinian plant Balfourodendron riedelianum was reported to be racemic, whilst a laevorotatory compound was isolated from A. soyauxii, with [~X']D - 10°. Interestingly dextrorotatory ribalinine, [Ct]D+ 8°; was also isolated from A. tabouensis [7]. The ribalinine isolated here from T. nobilis had an [ct]D of - 7 8 ° indicating the partial racemic nature of ribalinine obtained from A. soyauxii. To our knowledge, this is the first report on the occurrence of compounds (2) and (3) in the genus Teclea. The leaves and fruits of T. nobilis also yielded edulinine (4). It has been previously reported that edulinine can be isolated in many instances only under basic conditions and not at neutral or acidic pH values and because of this it has been indicated that it may be an artefact of isolation [8-11"1. We could also isolate edulinine only under basic conditions. The occurrence of the furoquinoline alkaloids montri- foline (5) skimmianine (6), flindersiamine (7) and maculine (8) in the leaves of T. nobilis further attest to how rich this plant is in quinoline alkaloids. These alkaloids were readily identified by spectroscopic methods and, in the case of montrifoline and flindersiamine, by comparison with authentic samples. EXPERIMENTAL General. M p s : u n c o r r . 1H N M R w e r e m e a s u r e d in C D C I 3 w i t h TMS as int. std on 90 MHz instruments. The NOE study was conducted on a 360 MHz NMR instrument. Plant material. T. nobilis Delile leaves and fruits were collected from Menagesha, Lepis and Harena State Forests, Ethiopia at altitudes of 2800, 2100 and 1400 m, respectively. The plant was identified by Mr Zemde Asfaw and a voucher specimen is kept at the National Herbarium of Ethiopia (Zemde 535). Extraction and fractionation. Air-dried finely ground leaves were extracted for 12 hr in a Soxhlet using EtOH; the solvent was removed in vacuo. The alkaloid fraction was sepd from the crude extract by usual methods. TLC of the alkaloidal fraction using CHCI3-MeOH (9:1) showed the presence of nine alkaloids, which were sepd by silica gel CC eluting with CHC13 followed by CHC13-MeOH (19:1). Final purification in some cases was achieved by prep. TLC using benzene-EtOAc (4:1). Nobiline (1). Mp 117-119°; [~]24 0o (CHCI3; c0.1). UV 2~tspHnm (log e): 243 (4.7),249 (4.7), 282 (3.8) sh, 293 (3.9), 307 (4.0), 319 (4.0), 333 (4.5). IR Vkm~cm -1 3175, 2950, 2890, 1640, 1600, 1519, 1490, 1380, 1330, 1270, 1220, 1100, 840. 1H NMR (see text). MS 70 eV m/z (rel. int.): 313 [M] +, 298, 284, 245 (100), 230 (40). Isoplatydesmine (2). Mp 189-191° (lit. 191° [6]). [ct]24+50 ° Short Reports (CHCI3; c 1), (lit. +60 ° [6]). IR, UV, NMR and MS identical to lit. [6]. Ribalinine (3). Mp 232-234 ° (lit. 232° [5, 6]). [Ct]2D4--78° (CHC13; c 1), (lit. 0 ° [5], - 1 0 ° [6]). Other spectroscopic data identical to lit. cited in text. Edulinine (4). Identified by spectroscopic data and also comparison with authentic sample (co-TLC). Montrifoline (5). Mp 188-189 ° (lit. 189-190 ° [4] ). Identified by NMR and MS data; identical with an authentic sample of montrifoline (romp, co-TLC). Skimmianine (6). Mp 168-170 ° (lit. 170-172 ° [12]), flindersiamine (7): mp 207-209 ° (lit. 207-208 ° [13]) and maculine (8): mp 197-199 ° (lit. 198° [14]) were identified based on their spectroscopic data which were in good agreement with the lit. Acknowledgements--We are grateful to Prof. W. Steglich (Bonn University) for NMR and MS and Dr P. G. Waterman for the NOE study on nobiline. We also extend our thanks to Prof. Cav6 (University of Paris) for an authentic sample of ribalinine, Prof. Okogun (Ibadan University) for montrifoline and Prof. Scheuer (University of Hawaii) for edulinine.This work was supported by a research grant from SAREC (Sweden). 653 REFERENCES 1. Watt, J. M. and Breyer-Brandwijk, M. G. (1962) The Medicinal and Poisonous Plants of Southern and Eastern Africa, p. 923. E. S. Livingstone, Edinburgh. 2. Mester, I. (1973) Fitoterapia XLIV 123. 3. Mester, I. (1983) in Chemistry and Chemical Taxonomy of the Rutales (Waterman, P. G. and Grundon, M. F., eds) p. 31. 4. Ayafor, J. F. and Okogun, J. I. (1982) J. Nat. Prod. 45, 182. 5. Corral, A. R. and Orazi, O. O. (1967) Tetrahedron Letters, 583. 6. Vaquette, J., Hifnawy, M. S., Pousset, J. L., Fournet, A., Bouquet, A. and Cav6, A. (1976) Phytochemistry 15, 743. 7. Fish, F., Meshal, I. A. and Waterman, P. G. (1976) Planta Med. 29, 130. 8. Toube, T. P., Murphy, J. W. and Cross, A. D. (1967) Tetrahedron 23, 2061. 9. Iriarte, J., Kincl, F. A., Rosenkranz, G. and Sondheimer, F. (1956) J. Chem. Soc. 4170. 10. Boyd, D. R. and Grundon, M. F. (1970) J. Chem. Soc. C 556. 11. Higa, T. and Scheuer, P. J. (1974) Phytochemistry 13, 1269. 12. AI-Shama, A., Al-Douri, N. A. and Phillipson, J. D. (1979) Phytochemistry 18, 1417. 13. Ayafor, J. F. and Okogun, J. I. (1982) J. Chem. Soc. Perkin, I. 909. 14. Fish, F., Meshal, I. A. and Waterman, P. G. (1977) Fitoteropia XLVIII, 170. 0031 9422/88$3.00+0.00 © 1988PergamonJournals Ltd. Phytochemistry,Vol. 27, No. 2, pp. 653 655, 1988. Printed in Great Britain. (+)-3',4'-DIHYDROSTEPHASUBINE, A BISBENZYLISOQUINOLINE ALKALOID FROM STEPHANIA HERNANDIFOLIA AMARENDRA PATRA, TARUN KUMAR MANDAL, PRABIR K. MUKHOPADHYAY* and BRINDABANC. RANU~" Department of Chemistry, University College of Science, Calcutta 700009, India; lDepartment of Chemistry, Narajole Raj College, Midnapore, India; tDepartment of Organic Chemistry, Indian Association for Cultivation of Science, Calcutta 700032, India (Received 16 March 1987) Key Word Index--Stephania hernandifolia; Menispermaceae; dihydrostephasubine; stephasubine; epistephanine. bisbenzylisoquinoline alkaloid; 3',4'- Abstract--A new bisbenzylisoquinoline alkaloid has been isolated from the stems of Stephania hernandifolia and its structure established as (+)-Y,4'-dihydrostephasubine. This is accompanied by the known alkaloid (+)-stephasubine (+)-Epistephanine has been found in the roots of the plant. INTRODUCTION Recent phytochemical investigation on Stephania suberosa [1-3] prompted us to reinvestigate the alkaloid contents of S. hernandifolia Walp. We report here the isolation of a new bisbenzylisoquinoline alkaloid, the structure of which has been established as (+)-3',4'dihydrostephasubine (1), along with (+)-stephasubine (2) [ 1] from the stems of S. hernandifolia. (+)-Epistephanine (3) occurs in the roots of the same plant, RESULTS AND DISCUSSION C o m p o u n d 1, C36H36N206, exhibited a strong [M] + at rn/z 592 (38%) with m/z 591 as the base peak. The fact