Patent GB-459759-A (GB)
Title: Process for the separation of hydroxy compounds of the cyclopentano polyhydro phenanthrene series
IPC: C07J75/00
Filed: 1936-03-19
Abstract: Hydroxy compounds of the cyclopentanopolyhydro-phenanthrene series are separated from one another by adding a saponine to the mixture and separating the reaction products thus obtained by means of their different solubility.  Suitable saponins are digitonine, solanine, cyclamine and dioscine.  The types of compounds which may be separated by the present invention include (1) the mixture of androsterone and dehydroandrosterone obtained by extracting the urine of males with solvents.  In this case dehydroandrosterone forms a difficulty soluble addition compound, where androsterone does not combine at all with saponins; (2) the various isomeric hydroxy ketones, androstanolones having the general formula C19H30O2 and obtained either by oxidizing a mixture of isomeric hydrogenated sterols, or by partially hydrogenating the saturated and unsaturated diketones androstandiones and androstendione of the general formul C19H28O2 and C19H26O2\t   respectively.  In these cases it is the trans isomer which forms the difficulty soluble addition compound which is removed by filtration; (3) the various isomeric di-alcohols androstandiols having the general formula C19H32O2 as are obtained by completely hydrogenating the saturated and unsaturated diketones androstandiones and androstendione.  In this case also it is the trans compound which forms the difficulty soluble addition product. The saponin addition compound is decomposed either by heating with a high boiling solvent such as xylene, or by the use of pyridine and like bases.  By means of the present invention the various isomeric hydroxy compounds of the androstan series may be separated, and the less active trans compounds so isolated may be transformed by isomerization processes into mixtures of isomeric compounds which may in turn be subjected to the separation process of the present invention.  In examples: (1) the hormone oils obtained from the urine of men according to the process described in Specification 392,434, [Group VI], are treated in alcohol solution with digitonine, after some hours at room temperature the white precipitate is filtered, dried, and decomposed with boiling xylene to yield dehydroandrosterone.  The alcoholic filtrate is treated with ether and extracted with water to remove the digitonine.  On evaporation of the ether-alcohol solution, androsterone is separated; (2) an alcoholic solution of the saturated di-alcohols C19H32O2 obtained by p  hydrogenating androstandiones or androstendione are treated with digitonine and the precipitate which forms dissolved in pyridine and ether added.  The digitonine so precipitated is filtered and the filtrate evaporated to yield trans-androstandiol.  The alcoholic filtrate is treated as in example (1).  Samples have been furnished under Sect. 2 (5) of (1) androsterone, and (2) dehydroandrosterone which have been separated from each other by means of solanine.  The original mixture was obtained from purified hormone oils.  A mixture of cis and trans androstandiols obtained by the complete hydrogenation of androstandione were separated by the use of digitonine and the cis-androstandiol and trans-androstandiol so obtained furnished as samples (3) and (4) respectively.