GB516888A - Manufacture of derivatives of the saturated and unsaturated cyclopentanopolyhydrophenanthrene series - Google Patents

Abstract

516,888. Cyclopentanophenanthrene ketones. SOC. OF CHEMICAL INDUSTRY IN BASLE. July 12, 1938, Nos. 20640 and 20641. Convention dates, July 12, 1937, and June 9, 1938: Sample furnished. [Class 2 (iii)] Nuclear saturated or unsaturated ketones of the cyclopentanopolyhydrophenanthrene series are prepared from the corresponding aldehydes of this series by reaction with an aliphatic diazo compound. Parent materials include aldehydes derived from aetio-cholane, pregnane, oestrane, hydro-oestrane and their sterio-isomers. The parent aldehydes may contain a nuclear keto group. Diazo compounds mentioned include diazomethane and its di-, and monosubstitution products, such as mono- and di-alkyl-, cycloalkyl-, aralkyl-, and aryl-diazo compounds Examples specified include diazoethane, diazobutane, diazopropylene, phenyldiazomethane, diazo-mono-, and di-carboxylic acid derivatives such as diazoacetic acid esters, amides or nitriles, diazomalonic acid esters and diazosuccinic acid esters. In the latter cases saponification and decarboxylation may follow the reaction with the aldehyde group. The compound prepared according to this invention possess the general formula where R is a residue containing the cyclopentanopolyhydrophenanthrene nucleus, R1 and R2 represent hydrogen or radicals containing carbon such as substituted or unsubstituted hydrocarbon residues or substituted carboxyl groups. The ketones are isolated and purified by means of the usual ketone reagents. In examples : (1) An ethereal solution of the trityl ether of #<5>.<6>-3-oxyaetiocholene-17-aldehyde is treated with diazomethane and after standing some days warmed with alcoholic hydrochloric acid to give A <5>.<6>-pregnenol-3-one-20 which is purified by reaction with the chloride of trimethylaminoacetic acid hydrazide. (2) An ethereal solution of #<4>.<5>-3-keto-aetio-cholene- 17-aldehyde is treated with diazomethane to give #<4>.<5>-pregnene-dione. A sample has been furnished under Sect. 2 (5) prepared in accordance with the following schedule : an ethereal solution of A <5>.<6>-3- acetoxy-aetiocholene-17-aldehyde is treated with an ethereal solution of diazoacetic ester, and then refluxed with methyl alcoholic potassium hydroxide. After acidification with dilute sulphuric acid and extraction with ether there is obtained #<5>.<6>-pregnenol-3-one-20.