Synthesis of some new C ring steroidal derivatives

In this paper, the synthesis of some new C ring steroidal derivatives from -pregnyne has been described. They are 9 -brom-17 -pregn-4-en-11 ,17 -diol-3-on-20-yne; 11 -formiat-9 - brom-17 -pregn-4-en-17 -ol-3-on-20-yne; 17 -pregn-11 ,17 -diol-4-en-3-on-20-yne; 9 ,11 - epoxy-17 -pregn-4-en-17 -ol-3-on-20-yne and 9 ,11 -epoxy-17 -pregn-4-en-17 -ol-3-on-20- yne. Structure of the products has been elucidated by IR, MS and 1 H-NMR methods.
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Synthesis of some new C ring steroidal derivativesJournal of Chemistry, Vol. 43 (2), P. 250 - 252, 2005 synthesis of some new c ring steroidal derivatives Received 10th-April-2004 Luu duc Huy Institute of Chemistry,Vietnamese Academy of Science and Technology Summary In this paper, the synthesis of some new C ring steroidal derivatives from 9-pregnyne has been described. They are 9 -brom-17 -pregn-4-en-11 ,17 -diol-3-on-20-yne; 11 -formiat-9 - brom-17 -pregn-4-en-17 -ol-3-on-20-yne; 17 -pregn-11 ,17 -diol-4-en-3-on-20-yne; 9 ,11 - epoxy-17 -pregn-4-en-17 -ol-3-on-20-yne and 9 ,11 -epoxy-17 -pregn-4-en-17 -ol-3-on-20- yne. Structure of the products has been elucidated by IR, MS and 1H-NMR methods. I - Introduction the 9-pregnyne which is obtained from sterols via 17-ketosteroid (and- rostadiendion ADD) by Because the invention of microbial degra- the base-catalyzed condensation of the ADDdation of sterols which are recovered from a with acetylene [3, 4]. The C ring derivatives ofwaste of paper and soya industries provides an pregnyne are very valuable intermediates in theinexpensive source of 17-ketosteroids [1, 2], it synthesis of corticoidal medicines, such asis now a tendency to use plant sterols for cortisone and hydrocortisone.semisynthesis of steroidal medicines instead ofold materials such as diosgenin and solasodin. II - Materials and methodsThis has a great signification for Vietnam, anagricultural and developing country. Starting material 9-pregnyne, all reagents, In Vietnam, now there are some large paper solvents, adsorbents were purchased from Aldrichfactories and soybean is one of the most Co. (USA) and Merck Clevenot Co. (France).important agricultural produces (many hundreds Solvents were purified, distilled prior to use.thousand tons per year). Meanwhile, every year Melting points were determined on BoetiusVietnam must import a large quantity of apparatus. IR spectra were recorded on FT-IR-steroidal medicines because of lack the raw IMPACT-410 with KBr pellets. Optical rotationsmaterial necessary for synthesizing ones. were obtained on a Polartronic D (Schmidt + Besides the price of diosgenin and solasodin Haensch). 1H-NMR spectra were recorded onin the world market is very high because Bruker WM-250, Bruker AM 500 spectrometer inDioscorea and Solanum plants are cultivated on CDCl3 with TMS as internal reference. MS spectrathe agricultural land. were recorded on MS-5989B in CHCl3. Analytical thin-layer chromatography was performed using We have involved in the elaboration on Merck 60 GF254.some new methods for synthesis of corticoidsfrom sterols via 17-ketosteroids and the 17 - III - Experimental, Results andhydroxy-17 -ethynylsteroids since 1988. discussion In this paper we presents the synthesis ofsome new C ring derivatives of pregnyne from The methods employed in this conversion250are summarized in the scheme 1. C CH RO OH O i MeONa ii Br O O O 9 Pregnyne (1) R = H (83%) (3) (50 - 70% ) - (2) R = COH (90%) MCPBA HO O O O (4) (60%) (5) (80%) i: CH3CONHBr (R = H); ii: H2NOC(CH2)2CONHBr (R = COH) Scheme 1 The first step in the present sequence is IR ( , cm-1): 1065, 1620, 1640, 1655, 2100,transformation of 9-pregnyne into bromhydrin 3255, 3370, 3590.(1) and bromformiat (2) by treatment with 1 H-NMR ( , ppm): 1.16s (18 Me), 1.77d (19CH3CONHBr or H2NOC(CH2)2CONHBr corres- Me, j = 0.5 Hz), 2.67s (H21), 4.68q (H11, j = 5.75 ...