Patent GB-813845-A (GB)
Title: Improvements in cyclopentanophenanthrene compounds
IPC: C07J1/00
Filed: 1956-03-27
Abstract: The invention comprises cyclopentanophenanthrene compounds of the general formula <FORM:0813845/IV (b)/1> wherein X represents hydrogen or a methyl, ethyl, propyl, butyl, amyl, isoamyl, vinyl, cyclopentylpropionyl, palmitoyl, benzyl, tolyl or naphthyl radical, and the preparation thereof by reducing D 5-androsten-3b -ol-16-one or the required 3-carboxylic ester or ether thereof with an alkali metal borohydride or an alkali metal aluminium hydride.  The above process may be modified in that the D 5-androsten-3b ,16b -diol is subsequently acylated or etherified in the 3- and 16-positions or a 3-carboxylic ester or ether of D 5-androstene-3b ,16b -diol may be acylated or etherified in the 16-position.  The above process may also be modified in that the D 5-androstene-3b ,16b -diol is reacted with an aryl sulphonyl halide to form D 5-androstene-3b ,16b  - diol - di - arylsulphonate, the di-arylsulphonate is selectively hydrolysed with dilute sulphuric acid to form D 5-androstene-3b ,16b -diol-16-arylsulphonate, the 16-arylsulphonate is reacted with an alkali metal acetate in acetic acid to form the 16-acetic acid ester of D 5-androstene-3b ,16a -diol which is then hydrolysed to form D 5-androstene-3b ,16a -diol, or the 3-carboxylic ester or ether of D 5-androstene-3b ,16b -diol is reacted with an aryl sulphonyl halide to form the corresponding 16-arylsulphonic acid ester, this ester is reacted with an alkali metal acetate in acetic acid to form the corresponding 16-acetic acid ester of the 3-carboxylic ester or ether of D 5-androstene-3b ,16a -diol which is then hydrolysed to form D 5-androstene-3b ,16a -diol or to the 3-ether thereof.  The additional modified processes referred to above may be extended by acylating or etherifying D 5 - androstene - 3b ,16a  - diol in the 3-and 16-positions, or by acylating or etherifying a 3-ether of D 5-androstene-3b ,16a -diol in the 16-position. In the examples: (1) D 5-androstene-3b ,16b -diol is prepared by reducing D 5-androsten - 3b - ol - 16 - one with sodium borohydride and is converted into the corresponding diacetate and dibenzoate; (2) D 5-androstene - 3b ,16a - diol is prepared by reacting D 5 - androstene - 3b ,16b  - diol with p-toluene sulphonyl chloride to form D 5-androstene - 3b ,16b  - diol - di - p - toluene sulphonate, partially hydrolysing the di-sulphonate to form D 5-androstene-3b ,16b -diol-16-p-toluene sulphonate, epimerizing the monosulphonate by heating with acetic acid and sodium acetate to form D 5 - androstene - 3b ,16a  - diol - 16 - acetate and hydrolysing the 16-acetate; (3) D 5 - androstene - 3b ,16a  - diol is prepared by acetylating D 5-androsten-b -ol-16-one to form 3b -acetoxy- D 5-androsten-16b -ol, treating this compound with p-toluenesulphonyl chloride to form D 5 - androstene - 3b ,16b - diol - 3 - acetate-16 - p - toluenesulphonate, heating this compound with sodium acetate and acetic acid to form D 5 - androstene - 3b ,16a  - diol - diacetate and acetic acid to form D 5-androstene-3b ,16a -diol-diacetate and then hydrolysing this product to form the required diol, and, if necessary, esterifying the diol to form the diacetate or dibenzoate thereof; (4) 3b -methoxy- D 5-androsten-16b -ol is prepared by reducing 3-methoxy-D 5-androsten-16-one with sodium borohydride; (3) 3b  - methoxy - D 5 - androsten - 16a  - ol is prepared by treating 3b -methoxy- D 5-androsten-16b -ol with p-toluenesulphonyl chloride to form the corresponding 16-p-toluenesulphonate, fusing the sulphonate with sodium acetate in acetic acid to form 3b -methoxy-16a -acetoxy-D 5-androstene, and hydrolysing this compound to form the desired 16a -ol.  Specification 813,333 is referred to.