3- Methyl octahydrophenanthrene

Other attempts at the synthesis of possible degradation products of morphine have been made by Ganguly [49], who prepared 13-methyl-octahydrophenanthrene-10-carboxylic acid, and by Sengupta, Ganguly, and Banerjee [50], who synthesized a hydrogenated phenanthrylene oxide. 

The angular methyl octahydrophenanthrene depicted, a 2-isopropylphenol derivative, upon ozonation at -78°C in dichloromethane/methanol for 22 hours, followed by warming to ambient temperature and finally treatment with sodium borohydride in aqueous ethanol over 2 hours, has been reported to result in a decalenofuranone in 49% yield (ref.63), apparently by preferred cleavage at the di- and trisubstituted double bonds. 

Ginsburg<29 31) took advantage of a preformed octahydrophenanthrene, 40 (Scheme 3.6). Conventional chemistry gave the ketal, 41, but an attempt to ketalize the free ring carbonyl caused cyclization to the trioxomorphinan, 42. Sequential reduction and N-methylation gave the previously described 4. 

The crude tertiary alcohol (5 g) was dissolved in 50 mL benzene and added to 107 g 90% sulfuric acid. The reaction mixture was stirred for 1 h at 0-2°C and then poured onto ice. After processing and evaporatively distilling at 150-155°C (0.15 mmHg), 1 g 2,5-dimethoxy-8-bromo-4a-methyl-10a-carbethoxy-l,2,3,4,4a,9,10,10a-octahydrophenanthrene was obtained. 

Whitlock, H. W., P. B. Reichardt, and F. M. Silver Synthesis and Solvolytic Rearrangement of Epimeric 4-Methanesulfonyloxy-4a-methyl- ra .y-1,2,3,4,4a,9,10,1 Oa-octahydrophenanthrene and Their 7-Methoxy and 1,1-Dimethyl Derivatives. Confor-mationally Rigid Homobenzylic Systems. J. Amer. Chem. Soc. 93, 485 (1971). 

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