GB926472A - New halogen-pregnenes and a process for their manufacture - Google Patents

Abstract

The invention comprises compounds of the formula: <FORM:0926472/IV(a)/1> in which R represents a free or esterified hydroxyl group, Y represents an oxo group or a hydrogen atom together with a free or esterified hydroxyl group, X1 represents a hydrogen atom or a chlorine or fluorine atom and X2 represents a chlorine or fluorine atom, and 1-dehydro-derivatives of these compounds, pharmaceutical preparations thereof and a process for the manufacture thereof wherein a compound of the formula: <FORM:0926472/IV(a)/2> in which R and Y are as defined above, X represents hydrogen or a chlorine or fluorine atom and which compound contains in the 3-position a ketalised oxo group and in 20-position a free or ketalised oxo group, is treated with hydrogen chloride or hydrogen fluoride or with an agent yielding one of these compounds, a ketalised oxo or groups in the 3- or 3 : 20-positions is or are converted into a free oxo group or groups, the 5a -hydroxy-6b -halogen compound is dehydrated, the resulting D 4-3-oxo-6b -halogenpregnene is isomerised in the 6-position and, if desired, the resulting compound is dehydrogenated in the 1,2-position, and at any stage in the process esterified hydroxyl groups are hydrolysed or free hydroxyl groups esterified and/or an 11-hydroxy-compound is dehydrogenated to an 11-oxo-compound. 1,2-Dehydrogenation may be effected by means of selenium dioxide, or by means of a microorganism, e.g. Fusarium solani, Fusarium caucasicum, Calonectra decora, Alternaria passiflorae, Phiobolus heterostrophus, Phiobolus miyabeanus, Didymella lycopersici or Corynebacterium simplex. The treatment with hydrogen halide may be effected in glacial acetic acid or in a mixture of glacial acetic acid and chloroform. Esterification of the 21-hydroxy products may be carried out to obtain the corresponding 21-trimethyl acetate, 21-cyclopentylacetate, 21b -phenylpropionate, 21-hemisuccinate, 21-cyclopropylcarboxylate or 21-hemisulphate. Said pharmaceutical preparations having a high activity in the liver glycogen and granuloma tests are employed enterally or parenterally in the forms of tablets, dragees, solutions, suspensions, emulsions and ampoules. Specification 924,252 is referred to.