Efficient synthesis of 14-hydroxymorphinans from codeine.

M A Schwartz; R A Wallace

doi:10.1021/jm00144a032

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PubMed · 7310832

Efficient synthesis of 14-hydroxymorphinans from codeine.

M A Schwartz·R A Wallace

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Abstract

Codeine is converted to 7,8-dihydro-14-hydroxynorcodeinone (noroxycodone) in six steps and 52% overall yield of the noroxymorphone in seven steps and 43% overall yield. N-Demethylation and oxidation of codeine afford N-(ethoxycarbonyl)norcodeinone, which is converted to its dienol acetate derivative and oxidized with singlet oxygen to give N-(ethoxycarbonyl)-14-hydroxynorcodeinone in the key step. Hydrogenation of the latter affords N-(ethoxycarbonyl)noroxycodone, which upon acid hydrolysis yields noroxycodone. Alternatively, O-demethylation of N-(ethoxycarbonyl)noroxycodone with boron tribromide and subsequent acid hydrolysis gives noroxymorphone. The results of the singlet oxygen oxidation of the pyrrolidine dienamine derived from N-(ethoxycarbonyl)norcodeinone are also described.

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Chemical Phenomena Chemistry Codeine Morphinans Journal Article Research Support, U.S. Gov't, P.H.S.

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M A Schwartz, R A Wallace. 1981. Efficient synthesis of 14-hydroxymorphinans from codeine.. https://doi.org/10.1021/jm00144a032

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