GB763203A - Polyhydrophenanthrene derivatives - Google Patents

Abstract

Polyhydrophenanthrenes of the formul <FORM:0763203/IV(b)/1> (the 7-position in formula Ia is occupied either by a divalent group or a pair of univalent groups which is convertible to a single keto group by acid hydrolysis, and the 7-position in formula Ib by a univalent group convertible to keto by acid hydrolysis) are prepared by treating a 4b-methyl - 7 - disubstituted - 1,2,3,4,4a,4b,5,6,7,8, 10,10a - dodecahydrophenanthrene - 4 - ol - 1 - one or the corresponding 7-mono-substituted-1,2,3,4,4a,4b,5,6,10,10a - decahydro derivative with an alkali metal, or its alkoxide or phenoxide, and intimately contacting the resulting reaction product with a methyl halide or methyl sulphate. The products may then be hydrolysed with acid to form 2:4b-dimethyl-1:7-diketo - 4 - hydroxy - 1,2,3,4,4a,4b,5,6,7,9,10,10a-dodecahydrophenanthrene. The initial treatment is preferably effected in a solvent, e.g. benzene, toluene, xylene, petroleum hydrocarbons, or an alcohol, e.g. t.-butanol when an alkoxide is used. Specified blocking groups in position 7 are enol ethers, e.g. ethyl enol ether, cyclic ketals, e.g. ethylenedioxy, ethylene dithioketal, ethylene hemithioketal, and noncyclic ketals, e.g. dimethyl ketal. In an example 4b - methyl - 1 - keto - 4 - hydroxy - 7 - ethylenedioxy - 1,2,3,4,4a,4b,5,6,7,8,10,10a - dodecahydrophenanthrene in benzene is treated with potassium t.-butoxide in t.-butanol and then refluxed with methyl iodide in benzene to yield the corresponding 2 : 4b-dimethyl derivative. Other examples illustrate the use of potassium or sodium-potassium alloy in benzene for the initial reaction step. Specifications 763,204, 763,206, 763,207 and 763,208 are referred to.