GB883611A - Improvements in or relating to steroid derivatives - Google Patents

Abstract

The invention comprises compounds of the general formulae <FORM:0883611/IV (b)/1> <FORM:0883611/IV (b)/2> <FORM:0883611/IV (b)/3> wherein X represents fluorine, chlorine or bromine, Z represents a carbonyl, b -hydroxy-methylene or b -alkanoyloxymethylene radical, containing less than 10 carbon atoms, Y represents hydrogen or the methyl radical, and R represents an alkyl radical containing less than 9 carbon atoms. The compounds are prepared by acylating the required 9a -halo-17a -hydroxypregn-4-ene-3,11,20-triones and oxidizing these compounds with selenious acid to form rhe 11-keto compounds of the first general formula, or with chloranil in a non-polar solvent such as xylene to form the 11-keto compounds of the second general formula, or with an excess of chloranil and n-amyl alcohol to form the 11-keto compounds of the third general formula. The 11b -hydroxy and 11b -alkanoyloxy compounds of the above general formulae are prepared by similar methods by first acylating or diacylating the required 9a -halo-11b ,17a -dihydroxy-pregn-4-ene-3,20-diones to form 17a -alkanoates and 11b ,17a -dialkanoates and then dehydrogenating as above. Detailed examples are given. 9a - Halo - 17a - alkanoyloxypregn - 4 - ene - 3,11,20-triones, wherein the halogen atom is fluorine, chlorine or bromine, are prepared by reacting the required 9a -halo-17a -hydroxypregn-4 - ene - 3, 11, 20 - triones with alkanoic acid anhydrides in the presence of an acid catalyst such as p-toluenesulphonic acid, and hydrolysing the resulting enolacetates with mineral acid. Detailed preparations are given. 9a - Halo - 11b , 17a - dihydroxypregn - 4 - ene - 3,20-diones 17a -alkanoates and 11b ,17a -dialkanoates, wherein the halogen atom is fluorine, chlorine or bromine, are prepared by partially or completely acylating the required 9a -halo-11b , 17a - dihydroxypregn - 4 - ene - 3,20 - diones. Detailed preparations are given.