Patent GB-998980-A (GB)
Title: Improvements in or relating to the hydrocyanation of ª,ª-unsaturated ketones
IPC: C07D221/22
Filed: 1963-03-01
Abstract: The invention comprises the process of reacting a polycyclic a ,b -unsaturated ketone with the complex anion [AlRR1R11CN]- (wherein R is C1- 5 alkyl or alkoxy and R1 and R11 are C1- 5 alkyl or alkoxy, halogen or cyano; the anion being produced by treating the aluminium compound AlRR1R11 in a substantially anhydrous medium with hydrocyanic acid or a compound AlRR1CN) in a substantially anhydrous medium followed, if necessary, by hydrolysis, to produce the corresponding polycyclic a ,b -saturated ketone in which the cyano group is present at the b -position to the carbonyl group.  The compound AlRR1CN is prepared in situ from the compound AlRR1H and hydrocyanic acid.  The reaction medium is preferably an inert, non-polar, organic solvent, and the process may be carried out at temperatures of from room temperature to 100 DEG  C. Examples describe the preparation of dl-2-oxocis-and trans-decahydronaphthalene-8a-carbonitriles, this cis-compound being characterized as a semicarbazone; dl-7a -acetyloxy-2-oxotetradecahydrophenanthrene - 10aa - and 10ab -carbonitriles, the isomers being isolated via their ethylene ketals; dl-1-oxo-7-methoxy-1,2,3,4,9, 10 - hexahydro - phenanthrene - 4aa - and 4ab -carbonitriles, isolated via their semicarbazones; 1,1,4ab -trimethyltetradecahydrophenanthren-7-one - 8ab  - carbonitrile; 3b - acetyloxy - 20 - oxo - 5 - pregnene - 16a  - carbonitrile; 3 - oxo - 5a - and 5b -cholestane - 5 - carbonitriles; 17b -acetoxy -3-oxo-5a - and 5b -estrane-5-carbonitriles; dl - 3b  - acetoxy - 17 - oxo - D - homo-5a  - androstane - 18 - nitrile and dl - 3b  - acetoxy - 17 - oxo - D - homo - 5a ,13a  - androstane-18-nitrile and the corresponding ethylene ketals (produced by ketalization) and their free 3b -ols, and their conversion to 3B-hydroxy-20-oxo-5a -16-pregnene 3-acetate by the following process <FORM:0998980/C2/1> 3,17 - dioxo - 5a  - 9(11) - androstene - 5 - carbonitrile and the bis-ethyleneketals of the 5a  and 5b -forms thereof (produced by ketalization); dl - 3a  - acetoxy - 17 - oxo - D - homo - 5b  - 9(11) - androsten - 18 - nitrile and its conversion to dl - 3a  - acetoxy - 5b  - 9(11),16 - pregnadien-20-one by the following process <FORM:0998980/C2/2> dl - 3 - methoxy - 20 - oxo - 19 - nor - 1,3,5(10) - pregnatriene - 18 - nitrile and dl - 3 - methoxy - 20 - oxo - 19 - nor - 13#x,17#x - 1,3,5(10) - pregnatriene - 18 - nitrile, and their conversion to dl-estrone 3-methyl ether by the following process <FORM:0998980/C2/3> 3b  - acetoxy - 7 - oxo - 5a  - cholestane - 5 - carbonitril and the corresponding 3b -ol, and, as a byproduct, 3,5 - cholestadien - 7 - one; 3,3 - ethylenedioxy - 17a  - hydroxy - 11 - oxo - D - homo-5 - androstene - 18 - nitrile, and its conversion to 3,20 - dioxo - 11b ,21 - dihydroxy - 4 - pregnen-18-oic acid lactone 21-acetate by the following process <FORM:0998980/C2/4> 8 - cyano - 11 - oxo - tigogenin acetate; 3b  - acetoxy - 8 - cyano - 5a  - pregnane - 11,20 - dione; 3b  - acetoxy - 11 - oxo - 5a  - 22 - ergostene - 8 - carbonitrile 3,3 : 17,17 - bisethylenedioxy - 8 - cyano - 5 - androsten - 11 - one; 17,20 : 20,21-bismethylenedioxy - 3,3 - ethylenedioxy - 8 - cyano - 5 - pregnen - 11 - one; and N - methanesulphonyl - 1 - methyl - 8ab  - cyano - 1,2,3,4,4b, 5,6,7,8,8a,9,10 - dodecahydro - 1,4a(10aH) -methanoiminomethanophenanthrene - 7 - one and the corresponding 8aa -isomer.  Starting materials for the preparation of the above-named products are prepared by the following eight processes <FORM:0998980/C2/5> Specifications 915,892, 948,114, and U.S.A. Specifications 2,666,770, 2,678,932, 2,752,370 and 3,050,518 are referred to.