Patent GB-1037162-A (GB)
Title: Improvements in or relating to 19-oxo-androstane compounds and derivatives thereof
IPC: C07J7/00
Filed: 1963-05-24
Abstract: The invention comprises steroids of the formulae <FORM:1037162/C2/1> (wherein R and R1 are hydrogen or hydrocarbon carboxylic acyl groups of less than 12 carbon atoms which may be substituted, R2 is alkyl, alkenyl or alkynyl of at most 8 carbon atoms, and X is alkyl of at most 8 carbon atoms); the preparation of the 19-alkyl-19-oxo-compounds by treating D 5 - androstene - 3b ,19 - diol - 17 - one 3-acetate with ethylene glycol in the presence of p-toluenesulphonic acid, oxidizing the resulting 17-ketal with chromium trioxide in a nuetral or basic medium, saponifying the resulting 17 - cycloethylenedioxy - D 5 - androsten-3b -ol-19-al acetate, treating the obtained 3-ol with dihydropyran in the presence of p-toluenesulphonic acid, reacting the so-formed 3-tetrahydropyranyl ether of 17-cycloethylenedioxy - D 5 - androsten - 3b  - ol - 19 - al with an alkyl magnesium bromide, acylating the thus-formed 3-tetrahydropyranyl ether of a 17-cycloethylene dioxy-19-alkyl-D 5-androstene-3b ,19-diol, treating the 19-acylate with acid to give the 19-acylate of a 19-alkyl-D 5-androstene-3b , 19-diol-17-one, treating this (a) with a double metal hydride, treating the formed 19-acylate of a 19-alkyl-D 5-androstene-3b ,17b ,19-triol with dihydropyran in the presence of p-toluenesulphonic acid, saponifying the 3,17-bis-tetrahydropyranyl ether obtained, oxidizing with chromium trioxide in a neutral or basic medium the thus-produced 3,17-bistetrahydropyranyl ether of a 19-alkyl-D 5-androstene-3b ,17b ,19-triol to give the 19-one and reacting this with a mineral acid to give a 19-alkyl-D 5-androstene-3b , 17b -diol-19-one; or (b) with dihydropyran in the presence of p-toluene sulphonic acid, treating the produced 3-tetrahydropyranyl-ether-19-acylate of a 19-alkyl-D 5-androstene-3b ,19-diol-17-one with an alkyl, alkenyl or alkynyl magnesium halide, oxidizing with chromium trioxide in a neutral or basic medium the obtained 3-tetrahydropyranyl ether of a 17a -(alkyl, alkenyl or alkynyl)-19-alkyl-D 5-androstene-3b ,17b ,19-trio to give the corresponding 19-one, treating this with acid to give the free 3-ol, and treating this by the Oppenauer method to give the corresponding 17a -substituted-19-alkyl-D 4-androsten - 17b  - ol - 3,19 - dione; and the preparation of the 19-oxo compounds by treating the 3-acetate of D 5-androstene-3b ,19-diol-17-one with dihydropyran to give the 19-tetrahydropyranyl ether and reacting this (a) with an alkyl, alkenyl or alkynyl magnesium halide in an inert solvent to form a 17-(alkyl, alkenyl or alkynyl) - D 5 - androstene - 3b ,17b  - triol - 19 - tetrahydropyranyl ether, acylating this in pyridine to give a 3-acylate, hydrolysing this in acid to give the free 19-ol, oxidizing this with chromium trioxide in a basic or neutral medium and saponifying the 17a -substituted-D 5-androstene - 3b ,17b  - diol - 19 - al - acylate to give the free 3b -ol which can optionally be oxidized by the Oppenauer method to the corresponding D 4-ketone; or (b) with a double metal hydride to give the 19-tetrahydropyranyl ether 3-acetate of D 5 - androstene - 3b ,17b ,19 - triol, acylating this to the 17-acylate, treating this with a mineral acid to give the free 19-ol, oxidizing this with chromium trioxide in a neutral or basic medium to give the corresponding diacylate of D 5-androstene-3b ,17b -diol-19-al and optionally saponifying this to give the free 3b ,17b -diol.  Hydroxyl groups in the products may be esterified by conventional means. Examples are given and a list of esterifying acids is provided.