Abstract：A simple and effective route for the synthesis of mibolerone was described starting from the estr-5(10)-en-3,17-dione in four steps with the overall yield of 47.0 %. Thus, two methods for key intermediate methylnorandrost were investigated: one(method A) starting from estr-4-en-3,17-dione underwent 3-keto group protected with ethyl orthoformate to give 3-ethoxy-3,5-dien-estr-17-one, the other(method B) from estr-5(10)-en-3,17-dione and protected 3-keto group to give 3,3-dimethoxy-estr-5(10)-7-one in a mild acidic condition. Then, two intermediates were subsequently reacted with methyllithium followed by a mild hydrolytic procedure and gave methylnorandrost with total yield 25.0% and 86.0 %, respectively. In the preparation of 6-dehydrogenation product of methylnorandrost, two procedures(method C and method D) were investigated: one was the protected 17α-methyl-17β-hydroxy ∆ 3,5 -enol ethers estrendiene brominated and the resulting 6-bromo-19-methylnortestosterone was then immediately dehydrohaloenated to give 6-dehydro-19-methylnortestosterone, the total yield only reaches 36.0%; the other was directly dehydrogenated with chloranil and the yield reaches 75.6% under the optimum conditions: in refluxing tetrahydrofuran, the molar ratio of methylnorandrost to chloranil is 0.66 and reaction time of 5 h. The titled compound and intermediates were characterized by 1 H and 13 C NMR, IRMS and elemental analysis.

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TANG Rui-ren(Nt~{2.) l'z , GUO Can-cheng(!~llt~) 1 ,FAN Bo-lin(~;t~l~k) z (1.Abstract: 17a-actoxy-19-nor-progesterone was synthesized by a new efficient stereoselective asymmertric pathway from 19-nor-androst-4-en-3,17-dione in 5-steps reactions with overall yield 63.3~. Consequently, a strategy was used to produce of 17-a-hydroxyl compound stereoselectively by addition 17-keto steroid with hydrogen cyanide, at the same time, the conditions of this asymmertric reaction were optimized. The titled compound and the intermediate were fully characterized by ;H, one dimension and two dimension 13C-nuclear magnetic resonance, and infrared spectrum. The results show that the rate of 17-~-hydroxyl compound isomeride is sensitively affected by the solution system and the best volume ratio of CH3 OH to H2 O is 36 ~. After the carbonyl and hydroxyl groups were protected by ethylenediol and vinyl butyl ether respectively, organometallic addition to CN group with CH3Li, androstance compound was converted to pregnane compound. After removing the protective groups by a mild hydrolytic procedure with high yield, the titled compound was obtained by esterified the above intermidiate. The new pathway gives a good purity of 98N as determined by high performance liquid chromatography. TANG Rui-ren, et al.. Stereoselective asymmertric synthesis and characterization of 17a-acetoxy-19-nor-progesterone • 301 • • 302 •

Fused pyridine derivatives R 0450Novel Synthesis of Aza-phthalimidine Hydroxylactams. -A convenient and mild method for the synthesis of the title compounds involves the substitution reaction of substrates such as (III) with NBS via an unstable intermediate bromide which is rapidly hydrolyzed into the hydroxyl product during the work-up process. A different reaction course is observed in the case of substrate (VI). The yields of (IV) can be improved with NCS/Bz-O-O-Bz. -(FAN, B.; LIU, Z.; TANG, M.; XU, Y.; TANG, X.; MAO*