Patent GB-838228-A (GB)
Title: Steroid compounds
IPC: C12P33/00
Filed: 1956-11-28
Abstract: The invention comprises 1,4-pregnadienes of the general formula <FORM:0838228/IV (b)/1> wherein X represents hydrogen or fluorine, Y represents hydrogen or a keto or hydroxy group, R represents an alkyl group and Z represents a hydrogen atom, or a hydroxy, a monocarboxylic acyloxy group or a phosphoryloxy group with the proviso that when X is hydrogen and Y is a hydroxy group, Z represents a t-butylacetoxy or phosphoryloxy group or a hydrogen atom and a process that comprises bringing a D 4-pregnene of the general formula <FORM:0838228/IV (b)/2> wherein R, X and Y have the above significance and Z* is a hydrogen atom, a hydroxy group, a monocarboxylic acyloxy group or a phosphoryloxy group into contact with (1) the dehydrogenating activity obtainable in a medium fermented by micro-organisms of the class Schizomycetes to form a compound of the general formula <FORM:0838228/IV (b)/3> wherein R, X and Y have the above significance and Z1 represents a hydroxy group if Z* is an acyloxy or hydroxy group, or is the same as Z* if Z* is hydrogen or a phosphoryloxy group, or (2) selenium dioxide to form the corresponding 1,4-pregnadiene.  Suitable micro-organisms belong to the orders Actinomycetales and Eubacteriales.  The preferred micro-organisms of the order Actinomycetales are of the genus Nocardia and of the genus Mycobacterium, and of the order Eubacteriales are of the genus Acetobacter and of the genus Bacillus. The following species are specifically referred to: A. xylinum, A. aerogenes, B. sphaericus, N. erythropolis, N. blackwellii, N. asteroides, N. monima, N. globerula, N. leishmanii, N. formica, N. convoluta, N. corallina, M. smegmatis, M. phlei, M. lacticola, and M. tuberculolsis.  The species Bacillus sphaericus comprises several varieties such as the rotans variety and the fusiformis variety. The invention also includes a process for the preparation of a compound of the general formula <FORM:0838228/IV (b)/4> wherein R represents an alkyl group, X represents hydrogen or fluorine atom, Y represents hydrogen or a keto or hydroxy group and Z DEG  represents a monocarboxylic acyloxy group with the proviso that when X is hydrogen and Y is hydroxy, Z DEG  is t-butylacetoxy, by reacting the corresponding 21-hydroxy compound with an acylating agent.  The corresponding 21-hydroxy compound may also be converted to a 21-phosphate by a method claimed in Specification 805,828.  A number of detailed examples are given.  2-Alkyl-4-pregnenes of the general formula <FORM:0838228/IV (b)/5> wherein X represents hydrogen or fluorine, Y represents hydrogen or a keto or hydroxy group, R represents an alkyl group and Z* represents hydrogen or a hydroxy, monocarboxylic acyloxy or phosphoryloxy group, are prepared by reacting the corresponding 20 - ethylene - 4 - prenene - 17a  - ol - 3 - ones with dimethyl oxalate in the presence of sodium methoxide to form the corresponding 2-methyloxalyl derivatives, reacting these compounds with alkyl iodide in the presence of a base to form the corresponding 2-alkyl-2-methyloxalyl derivatives and reacting these compounds with (a) an alkaline hydrolysing agent thereby hydrolysing the 2-methyloxalyl group, and (b) an acidic hydrolysing agent thereby hydrolysing the 20-ethylenedioxy group. Specifications 805,829, 805,830, 824,348 and 830,921 also are referred to.  Reference has been directed by the Comptroller to Specification 794,485.