IL38339A - 5,10-epoxy-19-nor steroids and process for their preparation - Google Patents

Description

NOR AND QCESS FOR THEIR present invention relates to a novel process for the preparation of of and to the novel compounds thus The novel epoxides are valuable intermediates in steroid and of especially in the or alkenyl steroids described and claimed in the copending patent application from the present patent application has been divided process of the invention comprises the epoxidation of steroids by the action of peracids with preponderant formation of the corresponding bitertiary epoxides at The result could not be foreseen with certainty because a priori it was not obvious that there would be formed in a preponderant manner the rather than the The invention has as object a process for preparing the bitertiary epoxides at of characterized essentially in that one 9 steroids to the action of obtains a mixture of corresponding and 5 which one if need into the desired epoxide and The said process is applied more particularly to the steroids which carry at the a lower alkyl radical having 1 to 6 carbon the said steroids able to carry on the carbon at the groups such cyclic or or a hydroxy and on the carbon at the groups such as Epoxida One dissolves 3 of i in French Patent in 13 of methylene adds then introduces at in about 40 minutes a concentrated solution of perphthalic acid i ether One agitates overnight then pours the mixture into i aqueous solution of sodium extracts with methylene washes the organic solution with salt j dries and distils to One obtains j i of a mixture of and used as it is the ext As as is two products are not described in the Reduction of the ketone at i One puts 1 of the mixture obtained above j suspension in 10 of adds at of sodium One agitates for minutes under dilutes with water admixed with of acetic extracts with methylene washes the solution with an solution of sodium then with dries and distils to One obtains a mixture of j which one it is for the next stage of the As far as is two compounds are j described in r one sso g o 3 dimethoxy 17 oxo estra diene French Patent one cools to and in about a concentrated solution of perphthalic acid in ether One maintains overnight washes the filtrate with an solution sodium with salt dries on sulphate and distils to One pastes the residue in 8 of isopropyl adds 2 petroleum ether for 2 filters vacuo and washes the precipitate with an isopropyl ethe ether The isopropyl ether mother liquors are recovered with view to the later isolation of the The produc thus obtained is purified by dissolving in methylene then in isopropyl One obtains o as it is for the next The product is soluble in chloroform and it is soluble in isopropyl ether end spectrum at at far as io known this compound is not described triethylamine one obtains successively ι 188 of after crystallization in isopropyl melts at j i The product is soluble in it is insoluble in As far as is this is not described in the literature i 867 of crude pyl which one purifies by pasting in filterin and washing with cooled One obtains of product melting at soluble in methylene chloride and insoluble in far as is this compound is described j in the literature The starting product edio can be obtained in the ing wa ropyl Qne introduces 1 described in French Patent into 10 of One adds of acetic under agitation and and maintains at for 2 One then pours the solution into 150 of One leaves at rest for filters in washes and dries in one obtains of One takes reflux for 6 a mixture of Analysis spectrum λ at Inflexion at about 21 at λ at 280 19 As far as is this compound is not described in the literature and then of product which one dissolves in 80 of boiling isopropyl one filters and concentrates the filtrate to about 35 One for minutes and filters in One obtains 673 16 The product is soluble in chloroform and Found spectrum λ at 229 378 Inflexion at about 267 22 λ at 273 λ at 280 19 As far as is this compound is not described in literature Stage 1 introduces of in French Patent 1 into 226 of and of water and adds at and while agitating sodium maintains for under nitrogen at then allows to return to ambient One dilutes with of water and adds 3 of acetic One extracts with methylene washes the methylene i extracts with an aqueous solution of sodium bicarbonate and again with One dries on sodium sulphate and distils to The product thus obtained is pasted in the ethyl mixture then crystallized in ethyl acetate in the The mother liquors deriving from the pasting and the crystallization in ethyl acetate are distilled to One treats the ith 80 of pyridine and 40 acetic anhydride and leaves overnight under One decomposes the excess reagent by adding extracts with methylene washes the organic phase with with N hydrochloric an aqueous solution of sodium bicarbonate and finally with dries and distils to pastes the residue 60 of isopropyl ether at boiling pools and isolates a crude product which one recrystallizes by dissolving in of isopropyl ether the concentrates to 0 and obtains 12 of 1 As far as is compound is not described in the 2 One takes to reflux 1 hour under 12 of 5 of methanol and 29 of a solution of potassium One with water and the chloroform by of One leaves overnight then filters pin vacuo and washes with The product thus obtained is recrysfcallized in then in ethyl One obtains of estra j r C As far as is this compound is not described in the insufficientOCRQuality

Claims (1)

1. WHAT IS CLAIMED Process for preparing characterized in that one subjects a to the action of a and obtains a mixture of the and compounds of corresponding Λ nor which one if need into the desired and 5β Process according to Claim 1 characterized in that the lower alkyl radical at the contains 1 to 6 carbon Process according to Claims 1 and characterized in that the starting steroid carries on the carbon at the a substituent chosen from the group consisting of a a cyclic or the and on the carbon at the a substituent chosen from the group consisting of the keto acetyl the keto group of which has previously been blocked in the form of a Process according to Claims 1 and characterized in that the peracid used for the epoxidetion is chosen from the group consisting of perbenzoic performic acid and peracetic Process according to Claims 1 and 2 characterized in that the is effected in an organic solvent chosen from the group consisting of an aromatic a chlorinated solvent and an Process for preparing steroids substantially as hereinbefore described and with reference to any of the The steroids in which is found on the carbon at the a chosen from the group consisting of a cyclic or or a and on the carbon at the a acetyl keto group Of which has previousl been blocked in the or a or a keto acetoxygont 3 Box 33116 Attorneys for Applicant insufficientOCRQuality