Patent GB-950614-A (GB)
Title: Improvements in or relating to the process for the preparation of conanine derivatives and iminopregnenes
Inventor: GEORGIAN VLASIOS
IPC: C07J41/00
Filed: 1960-09-02
Abstract: The invention comprises (1) steroids of the formula: <FORM:0950614/C2/1> (wherein A and B are hydroxy, acyloxy or keto; R and R10 are hydrogen, hydroxy or acyloxy; R1 is hydrogen, hydroxy, acyloxy or methyl; R2 is hydrogen, fluoro, hydroxy, acyloxy or methyl; R3 is hydrogen or methyl; R5 is hydrogen or fluoro; and Z is C1-6 alkyl); (2) steroids of the formulae: <FORM:0950614/C2/2> <FORM:0950614/C2/3> (wherein R, R10, R1, R2, R3, R5 and Z have the above-defined meanings, except that at least one of R, R1, R2, R10 and R5 must be other than hydrogen, and D is hydroxy or acyloxy); (3) steroids of the formula: <FORM:0950614/C2/4> (4) steroids of the formula: <FORM:0950614/C2/5> <FORM:0950614/C2/6> <FORM:0950614/C2/7> (wherein X and Y are hydrogen, hydroxy, acyloxy or keto; R and R4 are hydrogen, hydroxy or acyloxy; W is a halogen of atomic weight less than 80; and R1, R2, R3 and R5 have the meanings defined in (1) above); (5) steroids of the formula: <FORM:0950614/C2/8> (wherein V and T are hydrogen, hydroxy or keto; R6 and R9 are hydrogen or hydroxy; R7 is hydrogen, hydroxy or methyl; R8 is hydrogen, hydroxy, methyl or fluoro; and R3 and R5 are as defined in (1) above; (6) the process of preparing steroid of formula XVI by irradiating with ultra-violet light in the presence of trifluoroacetic acid a steroid of the formula: <FORM:0950614/C2/9> (wherein X and W have the meanings defined under (4) above; Y is hydrogen, acyloxy or keto; R, R1, R2, R3, R5 and Z have the meanings defined under (1) above; and R4 is hydrogen or acyloxy) to form a steroid of the formula: <FORM:0950614/C2/100> treating this with an alkali to form a steroid of the formula: <FORM:0950614/C2/111> (in which V, T, R3, R5, R6, R9, R7 and R8 are as defined under (5) above; and Z is C1-6 alkyl), treating this with cyanogen bromide to form the corresponding N-cyano steroid, hydrolysing this to form the corresponding N-unsubstituted steroid, treating this with a halogenating agent to form the corresponding N-halo steroid and dehydrohalogenating this; and (7) the process of preparing a steroid of formula III by the first three stages of the process outlined under (6). Acyl radicals are defined as those derived from organic carboxylic acids of at most 6 carbon atoms.  In the third stage of the process, the precise nature of the product depends on the amount of alkali used, the use of more than one equivalent resulting in the hydrolysis of one or more acyloxy substituents. Resulting free hydroxy groups may subsequently be re-acylated. Similarly hydrolysis of acyloxy groups may occur in other stages of the above synthesis where alkaline conditions are employed. Products containing 3- or 11-hydroxy substituents may be oxidized to the corresponding ketones, or the ketones may be reduced to the ols.  Detailed examples are provided, a by-product in one cyanation process being 3-acetoxyconanine methobromide.  20a methylamino -19- nor -3- allopregnanone is prepared by oxidation of the 3b -ol.  Specifications 950,615, 950,616 and 950,617 are referred to.