PHYTOECDYSONES OF S e r r a t u l a

IV. SOGDYSTERONE

I . L . N o v o s e l ' s k a y a , M. B. G o r o v i t s , a n d N. K . A b u b a k i r o v

UDC 547.926:591.147

Previous ly , f rom S. sogdiana Bge. family Composi tae we isolated ecdys te rone [1] and v i t icos terone E [2]. Subsequently, by repea ted r e c h r o m a t o g r a p h y on s i l ica gel and a lumina of a methanolic ex t r ac t f rom the f lowers of the plant we have obtained a new phytoecdysone which we have cal led sogdysterone. Yield 0.003 %.

Sogdysterone (I), C2zH4408, is an amorphous substance, [ol]~ + 43.9 ° (c 0.41" methanol); ~C2HsOI-I 242 nm ' " " I n a x

(log e 3.98); -vKBr 3300-3500 (OH), 1665 cm -1 ( C ~ C - C ~ O ) . It is a more po la r compound than the o ther " m a x

phytoecdysones isola ted f rom _S" sogdiana - Rj 0.16 [SiO2/gypsum; c h l o r o f o r m - m e t h a n o l (4 : 1)]. The op- t ical r o t a to ry d i spers ion curve of (I) (dioxane) showed posi t ive ([M]358 + 3520°; [M]315 - 622°; a = +41 °) and negative ([M]260 -3800° ; [M]233 + 14,300°; a = - 1 8 1 °) Cotton effects . This nature of the curve showed the p re sence of a 5 f l - j - 6 - o x o - 1 4 - h y d r o x y grouping in sogdysterone [3].

In the h i g h - m a s s region of the m a s s spec t rum of (I) there a r e peaks of ions with m / e 478 (M-I-I20), 460 (M-2H20) , 442 (M-3 H~O),424 ( M - 4H20), 409 ( M - 4 H 2 0 - C I-Is ) and 406 ( M - 5 ~ O ) , due to p r o c e s s e s involving dehydrat ion and the spli t t ing off of one of the methy l groups . The peaks of ions with m / e 379, 361,343, and 325 show the p r e s e n c e of four hydroxy groups in the s te ro id skeleton of the new phytoeodysone [4-6].

The f ragmenta t ion of the side chain of (i) is s im i l a r to the decomposi t ion of the side of ecdys te rone and is c h a r a c t e r i z e d by ions with m / e 99, 81, and 69 [7, 8].

NMR spec t rum of (I) (C~HsN , 100 MHz; HMDS, 5, ppm): 1.06 (3 H at C18, s), 1.25 (6 H at C26 and C2z , s), 1.46 (3 H at C21, s), 3.50 (H at Cg, m), 3.75 (H at C22, m), and 6.15 (H at C7). A broad four-pro ton mul t i - plet in the 4.07-4.40 ppm region shows the p re sence of protons at C~, C 3, and Cts. The absence f rom the NM:R spec t rum of I of the absorpt ion of a C19-methyl group p e r m i t s the assumpt ion that one of the hydroxy groups is located at C19.

The acetylat ion of sogdys terone gave a mix tu re of the amorphic 2 ,3 ,19 ,22- te t raace ta te (II), C35HszOt2 (M + --AcOH - H 2 0 ; m / e 586); [~]]~ + 56.4 ° (c 0.39; methanol) and the amorphous 2,3,19,22,25-pentaacetate 011), C37H54013 (M + - A c O H - 2H20; m / e 610). N1VIR spec t rum of (i-I) (CDC13): 0.80 (3 H at Cts, s), 1.18 and 1.15 (6 H at C26 and C27, s), 1.22 (3 H at C2t , s).

In solution in dry acetone under the action ofphosphotungst ic acid, phytoecdysone (I) f o r m s an a m o r - phous diacetonide (IV), C33H5208 (M + 576), [o~]~ + 50.0 ° (c 0.48; methanol). The production of the d iace to - hide (IV) shows the cis or ienta t ion of the hydroxy g r o u p s at C~ and C 3. Bear ing in mind the fact that the same plant contains ecdys te rone and v i t i cos te rone E, the glycol grouping in sogdysterone can be ass igned the 2fl,3fl-configuration.

The r e s u l t s of a compar i son of the chemica l shifts of the C18 , C21 , C25 , and C27 methyl groups of the new phytoecdysone with ecdys te rone and of the t e t r aace ta t e of (II) with the t r i ace ta te of ecdys te rone [1, 2, 7], and also the facts given above on m a s s - s p e c t r o m e t r i c f ragmenta t ion and optical r o t a to ry d i spers ion p e r - mit the s t ruc tu re of 19,20R-dihydroxyecdysone to be proposed for sogdysterone:

Inst i tute of the Chemis t ry of Plant Substances , Academy of Sciences of the Uzbek SSR. Trans la t ed f rom Khimiya Pr i rodnykh Soedinenii, No. 3, pp. 429-430, May-June, 1975. Or ig inal a r t i c le submit ted F e b - rua ry 20, 1975.

©19 76 Plenum Publishing Corporation, 22 7 West 17th Street, New York, N. Y. 10011. No part o f this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, microfilming, recording or otherwise, without written permission o f the publisher. A copy o f this article is available from the publisher for $15.00.

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L I T E R A T U R E C I T E D

I. L. Z a t s n y , M. B. G o r o v i t s , and N. K. A b u b a k i r o v , Kh im. P r i r o d n . Soed in . , 840 (1971). L L. Z a t s n y , M. B. G o r o v i t s , and N. K. A b u b a k i r 0 v , Kh im. P r i r o d n . Soedin . , 175 (1973). H. S c h e r r e r , He lv . Ch im. A c t a , 52_, 2428 (1969). J . J i z b a , V. He rou t , and F. S o r m , T e t r a h e d r o n Le t t . , 5139 (1967). K. Nakan i sh i , P u r e Appl . C h e m . , 25._, 167 (1971). B. Z. U s m a n o v , M. B. G o r o v i t s , and N. K. A b u b a k i r o v , K h i m . P r i r o d n . Soed in . , 125 (1973). N. N. G a l b r a i t h and D. H. S. Horn , Aus t . J . C h e m . , 2__.2, 1045 (1969). I. L. Z a t s n y , M. B. G o r o v i t s , Ya. V. R a s h k e s , and N. K. A b u b a k i r o v , K h i m . P r i r o d n . Soedin . , 155 (1975).

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