GB476189A - Improvements in the manufacture and production of secondary, mixed aliphatic-cyclic alcohols - Google Patents

Abstract

Secondary mixed aliphatic-cyclic alcohols are manufactured by treating, in the liquid phase, with hydrogen under a pressure of at least 20 atmospheres, preferably 100--200 atmospheres, in the presence of a hydrogenation catalyst containing metallic nickel, which may be distributed on a carrier, at temperatures between about 100 and 250 DEG C., ketones which contain at least two rings in the molecule and in which the carbonyl group is not directly connected with a ring, e.g. unsaturated ketones formed by reacting aliphatic ketones, containing reactive alkyl groups, twice with aromatic aldehydes, such as dibenzylidene-, p-dianisylidene-, dicinnamylidene- or di-a -naphthylideneacetone, or analogous saturated ketones, or also unsaturated ketones formed by multiple reaction of cycloaliphatic ketones or of heterocyclic aldehydes with aliphatic ketones containing reactive alkyl groups, such as dicyclohexylidene- or bis-furfurylidene-acetone. In many cases a preliminary hydrogenation of the olefinic double linkage may be effected. The products are useful as perfumes, softening agents and additions to wax preparations, or for the preparation of assistants for the textile and related industries by the introduction of solubilizing groups, e.g. by the action of alkylene oxides or sulphonating agents such as chlorosulphonic acid. In examples: (1) dibenzylidene-acetone is treated in methanol solution with hydrogen under 200 atmospheres pressure, first at ordinary temperature and then at 160 DEG C., in the presence of a nickelchromium catalyst (prepared by treating a mixture of nickel carbonate and chromic acid with nitrogen at 300 DEG C. and then with hydrogen at 350 DEG C.), to produce di-(cyclohexylethyl)-carbinol; dicinnamylidene-acetone similarly yields di-(cyclohexylbutyl)-carbinol; (2) bis-(p - dimethylaminobenzylidene) - acetone is treated in ethyl alcohol solution with hydrogen under 200 atmospheres pressure, at 160--170 DEG C., in the presence of a nickel catalyst (prepared by precipitating nickel hydroxide on silica gel and reducing with hydrogen at 400--600 DEG C.), producing bis - (p - dimethylaminocyclohexylethyl) - carbinol; p - dianisylidene - acetone similarly yields di-(p-methoxycyclohexylethy)-carbinol; (3) difurfurylidene-acetone is treated in ethyl alcohol with hydrogen under 200 atmospheres pressure, the temperature being slowly raised to 140--150 DEG C., in the presence of the catalyst of (1), to produce di-(tetrahydrofurfurylethyl)-carbinol; (4) di-a -naphthylidene-acetone is treated in methanol with hydrogen under 50 atmospheres pressure, first at ordinary temperature and then at 160--170 DEG C., in the presence of a nickel catalyst.