The structure of vinerinine

THE STRUCTURE OF VINERININE UDC 547.944.1.92 M. M. Khalmirzaev, V. M. Malikov, K. L. Seitanidi, M. R. Yagudaev, a n d S. Y u , Y u n u s o v It h a s been shown p r e v i o u s l y [1] that the new oxindole alkaloid vinerinine (I) i s o l a t e d f r o m Vinca e r e c t a is a m o n o m e t h y l d e r i v a t i v e of majdine, but the mutual positions of the OCH 3 and OH groups in the a r o m a t i c r i n g of (I) r e m a i n e d u n d e t e r m i n e d . In o r d e r to e s t a b l i s h the position of the OCH 3 group we have studied the NMR s p e c t r u m of (I) in d e u t e r o c h l o r o f o r m and deuterobenzene (the s p e c t r a w e r e obtained on a J N M - 4 H - 1 0 0 / 100 MHz s p e c t r o m e t e r ; c 5%; 0 - TMS; 6 scale). On p a s s i n g f r o m d e u t e r o c h l o r o f o r m to deuterobenzene the d i f f e r e n c e in the c h e m i c a l shift (CF) of the protons of the OCH 3 group in (I) was A =0.31 ppm. On the b a s i s of file r e s u l t s of an a n a l y s i s Ofcthi~ CS of the OCI~ g r o u p s of majdine it has been e s t a b l i s h e d p r e v i o u s l y that for the 11-OCH 3 group ACDC13 6 6 is 0.52 ppm, and in the case of the 12-OCH 3 group it is 0.26 ppm. The r e s u l t s o f a comparison of the v a l u e s of A CDC1 C6D6 f o r the OCH 3 g r o u p s of majdine and vinerinine shows that in (I) the O C H 3 group is present in position 12 and the substance has the structure of ll-demethylmajdineo 10 g __. 7 SN I A confirmation of this is the fact that in the NMR s p e c t r u m of the d e u t e r i u m d e r i v a t i v e of vinerinine obtained by d e u t e r a t i n g vinerinine with h e a v y w a t e r in d i m e t h y l f o r m a m i d e , the signal of the only a r o m a t i c p r o t o n a p p e a r s in the f o r m of a singlet with 6 6.82 p p m the CS of which c o r r e s p o n d s to the proton at C9, which shows the r e p l a c e m e n t of the hydrogen a t o m by d e u t e r i u m at C10 in the ortho position to an OH group [3]. In addition, the location of the CH3 group at position 12 is also shown by the a b s e n c e f r o m (D of an i n t r a m o l e c u l a r n u c l e a r O v e r h a u s e r effect between the signals of the A r - O C I t 3 protons and the a r o m a t i c p r o t o n s . Thus, as a r e s u l t of the a n a l y s i s of the c h a r a c t e r i s t i c s of the NMR s p e c t r a in CDCI 3 and C6D ~ solutions, a n d also of the d e u t e r i u m d e r i v a t i v e the mutual positions of the OH and OCH 3 g r o u p s in v i n e r i n i n e have been e s t a b l i s h e d unambiguously. LITERATURE 1. 2. 3. CITED M. M. K h a l m i r z a e v , V. M. Malikov, and S. Yu. Yunusov, Khim. Prirodn.Soedin., 411 (1974). K. L. Seitanidi, M. R. Yagudaev, and V. M. Malikov, Khim. P r i r o d n . Soedin., 360 (1977). G. W. K i r b y and L. Ogunkova, J. Chem. Sot., 6914 (1965). Institute of the C h e m i s t r y of Plant Substances, A c a d e m y of Sciences of the Uzbek SSR, Tashkent. T r a n s Luted f r o m K h i m i y a P r i r o d n y k h Soedinenii, No. 5, pp. 718-719, S e p t e m b e r - O c t o b e r , 1977. Original a r t i c l e s u b m i t t e d June 27, 1977. 0009-3130/77/1305- 0605 $07.50 © 1978 Plenum Publishing C o r p o r a t i o n 605  (...truncated)