Use Of Natural Sterol Resources

Most steroidal drugs are produced by semisynthesis, using the rare and expensive diosgenin as starting material with multiple steps and in low yield. Bravery sterol, bean sterol and sitosterol are rich in China and can be converted to androst-4-ene-3,17-dione (4-AD) and androst-1,4-diene-3,17-dione (ADD) in high yield by cutting off their17-position side chain.4-AD and ADD are key intermediate compounds in the synthesis of almost all steroidal drugs.Therefore, the dissertation is focused on synthesizing key intermediate compounds of betamethasone and dexamethasone in the foundation of previous work in our group, using4-AD as starting material, which produced from industrial waste. What have been accomplished are as follows:1. Introduced16β-methyl in the16-position of4-AD in the yield of82%, gained our target compound------17a-hydroxy-16β-methyl-pregn-4-ene-3,20-dione, which laid foundation for industrial production.2. Have found suitable conditions to transform16β-methyl into16a-methyl, and gain androst-16a-methyl-17a-cyano-17β-hydroxy-4-ene-3-one in the yield of75%, which provides useful information for the synthesizing of androst-16a-methyl-17β-cyano-17a-hydroxy-4-ene-3-one.3. Gained androst-3-methoxyl-16,16-dimethyl-17-alkynyl-17-hydroxy-4,6-diene, which has a similar structure of progesterone drugs and can be used for further biological active test.4. In addition, a compound was synthesized by using the same materials and react conditions in literature (J. Org. Chem.1987,52,1670), and its X-ray diffraction confirmed its benzo-2H-thiopyran-2-one structure, instead of benzo-4H-thiopyran-4-one as reported. The mechanism of this reaction was supplemented.