GB1040177A - New 3:6-dioxo-a-nor-b-homo-steroids and process for their manufacture - Google Patents

Abstract

Novel 3,6-dioxo-A-nor-B-homo-steroids and their enol-esters, enol-ethers and thio-enol-ethers, and their salts, are prepared by irradiating 3 - oxo - 4a ,5a - oxido - steroids or 3 - oxo - 4b ,5b -oxido-steroids or mixtures thereof with ultra-violet light and, if desired, converting the resulting 3,6-dioxo-A-nor-B-homo-steroids into the afore-mentioned enol derivatives and/or metal salts. The starting materials may be D 1-steroids and the double bond in the 1-dehydro-products resulting therefrom may be hydrogenated. Ester or ketal groups in the products may be hydrolysed and free hydroxy groups oxidized to oxo groups. The steroids may be of the androstane, pregnane, cholane, cholestane, spirostane or cardanolide series or the corresponding 19-nor-compounds and may contain alkyl, alkenyl or alkynyl groups which may be halogenated, halogen atoms, oxo or alkylenedioxy groups or free, esterified or etherified hydroxyl groups, or lactone groups, in the nucleus or 17-side chain. Examples are given, and also described is the reductive desulphurization of D 3(5)-3-methylmercapto-6-oxo-17b -acetoxy - A - nor - B - homo - androstane to 6 - oxo - 17b - acetoxy - A - nor - B - homo - androstane and hydrolysis of this to the 17b -ol. 3 - Oxo - 4,5 - oxido - steroids are prepared from D 4-3-oxo-steroids and alkaline hydrogen peroxide or peracids, or by hydrogenation of D 1-3-oxo-4,5-oxido-steroids, themselves prepared from D 1,4-3-oxo-steroids and per-acids, or by dehydrogenation of 3-oxo-4,5-oxido-steroids. 3 - Oxo - 4,5 - oxido - 20b - acetoxy - pregnane is prepared by acetylation of the 20b -ol. The A-nor-B-homo-steroids of the invention, which variously are stated to have anabolic, anti-inflammatory, anti-oestrogenic and progestative action may be made up into pharmaceutical or veterinary preparations suitable for parenteral, enteral and particularly oral, or topical administration. In addition to carriers they may contain preserving, stabilizing, wetting or emulsifying agents, salts for regulating the osmotic pressure, or buffers.