GB812690A - New halogen-testanes and process for their manufacture - Google Patents

Abstract

The invention comprises saturated and unsaturated 3,11,17-trioxygenated 9a -halogen testanes and functional derivatives thereof, particularly D 4 - 3 - oxo - 11b ,17b - dihydroxy - 9a -halogentestenes, their 17a -methyl derivatives and 17-esters thereof; also a process for their preparation by treating a D 9(11)-3,17-dioxygenated testane or functional derivative thereof with a halohydrin-forming agent, e.g. a hypohalous acid or one of its salts, ethers, or esters, a haloacetamide, haloimide or haloamine, and if desired treating the resulting 9,11-halohydrin with a dehydrohalogenating agent and reacting the 9,11b -epoxide formed with a hydrohalic acid, after which hydroxy and/or oxo groups may be liberated or functionally converted. Suitable dehydrohaloegnating agents are hydroxides or oxides of metals of Groups 1 and 2 of the Periodic System, e.g. silver oxide, also tertiary amines and aluminium oxide. Specified functional derivatives include esters, ethers, acetals, ketals, their thio analogues, enol derivatives, hydrazones, and semicarbazones. Subsequently the hydroxyl groups may be esterified, e.g. with acetic, trimethylacetic, propionic, valeric, enanthic, undecylenic, benzoic, phenylpropionic, cyclopentylpropionic and polycarboxylic acids, or etherified, e.g. with carbohydrates. In examples: (1) D 4,9(11)-3-oxo-17b -propionyloxy-testadiene in t-butanol is treated with N-bromoacetamide and dilute H2SO4 giving D 4 - 3 - oxo - 11b - hydroxy - 17b - propionyloxy - 9a - bromotestene, which is agitated in darkness in pyridine with dried silver oxide living D 4-3-oxo-17b -hydroxy- and 17b -propionyloxy - 9,11b - oxido - testenes; treatment of the latter in dioxane with dilute HCl gives D 4 - 3 - oxo - 11b - hydroxy - 17b - propionyloxy - 9a - chlorotestene, while HF gives the corresponding 9a -fluoro compound; the corresponding 17b -cyclopentylpropionoxy compounds are similarly prepared; (2) D 4,9(11)-3-oxo - 17b - hydroxy - 17a - methyltestadiene treated as in (1) yields D 4-3-oxo-11b ,17b -dihydroxy-17a -methyl-9a -bromotestene and subsequently the corresponding 9a -chloro and 9a -fluoro analogues.