GB791771A — Steroid compounds

USPTO Abstract

D 9(11) - Anhydro - cyclopentanophenanthrene compounds are prepared by reacting an 11b -hydroxycyclopentanophenanthrene compound having a hydrogen atom attached to the 11-carbon atom with an alkyl sulphonyl chloride, e.g. a sulphonyl chloride containing 1 to 8, preferably 1 to 4, carbon atoms. It is preferable to use the sulphonyl chloride in amounts from 1 to 10 mols. per mol. of cyclopentanophenanthrene reactant. A solvent such as a hydrocarbon or chlorinated hydrocarbon may be used in the process. The reaction may be carried out in the presence of a tertiary amine and/or an amide of a secondary amine, suitable tertiary amines being pyridine, N-methyl- and N-ethyl-morpholine, a ,g -lutidine, collidine, nicotine, trimethyl-, triethyl- and tripropyl-amine, dimethyl- and diethyl-aniline, and N-heptyl-, N-amyl-, N-butyl-, N-propyl-, N-ethyl- and N-methyl-piperidine, and suitable amides being dimethylformamide and dimethylacetamide. The amine and/or amide may be solvents or a solvent for the 11b -hydroxy-cyclopentanophenanthrene reactant e.g. from 1 to 10 mols. of said amine or said amide or a mixture thereof per mol. of 11b -hydroxy-cyclopentanophenanthrene reactant may be used. The reaction may be carried out in an organic solvent which does not consist wholly of the tertiary amine and/or amide, e.g. the solvent may comprise a hydrocarbon or chlorinated hydrocarbon such as a mixture of benzene and pyridine, or a mixture of methylene chloride and pyridine. Other solvents which may be used are chloroform, acetone, propylene glycol and methyl ethyl ketone and mixtures thereof. Cyclopentanophenanthrene reactants which may be used in the above process are pregnanes and pregnenes, particularly the D 4-pregnenes. Substituents other than the 11b -hydroxy group which may be present in the steroid reactants are 3,20-keto groups and 3,17a -hydroxy groups. It is desirable to convert a 21-hydroxy group into an ester thereof before reaction with the sulphonyl chloride. Reactants specifically mentioned are the 21-esters of D 4-pregnene-11b ,17a ,21-triol-3,20-dione-particularly the acetate, propionate, formate, butyrate, benzoate, t-butyl-acetate, hemisuccinate and phenylacetate esters, D 4 - pregnene - 11b ,17a - diol - 3,20 - dione, D 4-pregnene - 11b - ol - 3,20 - dione, D 4 - pregnene-11b ,21 - diol - 3,20 - dione - 121 - acetate, acetate esters of D 4 - pregnene - 11b ,17a ,20,21 - tetrol3,20 - dione, D 4 - androstene - 11b - ol - 3,17-dione, D 4 - pregnene - 11b ,17a ,21 - triol - 3,20-dione, pregnane - 11b - ol - 3,20 - dione, pregnane - 11b ,21 - diol, 3,20 - dione - 21 - acetate, pregnane - 11b ,17a ,21 - triol - 3,20 - dione, allopregnane - 11b ,17a ,21 - triol - 3,20 - dione, D 5-pregnene - 3b ,11b - diol - 20 - one, and D 5-pregnene - 11b ,17a ,21 - triol - 3,20 - dione - 21-acetate - 3,20 - bis - ethylene ketal. In the examples, D 4,9(11) - pregnadiene - 17a ,21 - diol-3,20 - dione - 21 - acetate is prepared. Specification 750,866 is referred to.