Patent GB-471483-A (GB)
Title: Improvements in the manufacture and production of products suitable as assistants forthe textile, leather, lacquer and like industries
IPC: C07C45/74
Filed: 1936-03-02
Abstract: Assistants for the textile, leather and lacquer industries are obtained by treating with alkaline agents or dehydrating catalysts the unsaturated ketones obtainable by condensing an aliphatic aldehyde containing from 4 to 8 carbon atoms in the molecule with ketones having from 3 to 5 carbon atoms in the molecule, whereby two molecules of the unsaturated ketones condense with simultaneous removal of water.  If desired, the products may be reduced to secondary alcohols, which again may be converted into soluble compounds having wetting, washing and emulsifying properties by sulphonation or by the introduction of residues of polyhydric alcohols.  The aldehydes used for the preparation of the unsaturated ketones may be obtained by catalytic dehydrogenation of the oxygen containing products obtained from carbon monoxide and methanol by hydrogenation.  In order to effect the union of the two molecules of unsaturated ketones, ammonia, alkali hydroxides, mono and dimethylamines, piperidine, and alcoholic caustic alkali are suitable.  Alumina, thoria and silica gel are mentioned as dehydrating catalysts.  The secondary alcohols obtained by catalytic hydrogenation of the condensation products may be sulphonated in the presence of solvents, organic acid chlorides or anhydrides or phosphorus pentoxide, and the sulphonated products may be neutralized with alkalies, ammonia or amines..  Solubility of the secondary alcohols may also be effected by treatment with alkylene oxides, e.g., ethylene oxide or glycide, or with polyglycols or glycerols in which one hydroxy group has been replaced by chlorine.  In examples: (1) isohexylaldehyde is condensed with acetone in the presence of barium hydroxide and the resulting 5-methyloctylene-3-one-2 is converted into 4 : 9 : 12-trimethylpentadecatriene-5 : 8 : 10-one-7 by heating with caustic potash; by reducing with hydrogen using nickel oxide as catalyst, 4 : 9 : 12-trimethylpentadecanol-7 is obtained; the latter is solubilised by sulphonation, by treating with ethylene oxide or by heating first with propylene oxide and then with ethyleneoxide: (2) isoamylaldehyde is condensed with acetone and the resulting 5 - methylheptylene - 3 - one - 2 is converted into the unsaturated ketone 3 : 8 : 11 - trimethyltridecatriene-4 : 7 : 9-one-6; the latter is reduced to the alcohol and sulphonated: (3) normal or isobutyraldehyde is condensed with acetone and the resulting 5-methyl-hexylene-3-one-2 treated as in the previous examples to double the molecule and prepare the sulphuric ester of the corresponding alcohol: (4) isoheptylaldehyde is condensed with acetone and the resulting ketone converted into 2 : 4 : 9 : 12 : 14-pentamethylpentadecatriene-5 : 8 : 10-one-7; the latter is reduced and the alcohol either sulphonated or treated with ethylene oxide: (5) ethylhexylaldehyde is condensed with acetone and the resulting ketone converted into 5 : 13-diethyl-10-methyl heptadecatriene-6 : 9 : 11-one-8; the corresponding alcohol is formed by hydrogenation and is sulphonated or treated with ethyleneoxide: (6) methylhexenylaldehyde is condensed with acetone and the resulting ketone converted into 4 : 9 : 12-trimethylpentadecapentiene-2 : 5 : 8 : 10 : 12-one-7; the latter is reduced to 4 : 9 : 12-trimethyl pentadecanol-7: (7) isoheptylaldehyde is condensed with methyl-ethylketone and the resulting ketone converted into 2 : 4 : 6 : 7 : 10 : 12 : 14-heptamethylpentadecatriene-5 : 8-10-one-7 by doubling the molecule; the latter is reduced and sulphonated. Specification 436,214 is referred to.ALSO:Products stated to have emulsifying properties are obtained by solubilizing the secondary alcohols derived from the ketones which are prepared by treating with alkaline agents or dehydrating catalysts, the unsaturated ketones obtainable by condensing an aliphatic aldehyde containing from 4 to 8 carbon atoms in the molecule with ketones having from 3 to 5 carbon atoms in the molecule.  Solubility of the alcohols is effected by sulphonation or by introducing residues of polyhydric alcohols, e.g. glycol, glycerol, di- and tri-ethyleneglycol or polyglycerol.  In examples: (1 isohexylaldehyde is condensed with acetone and the resulting 5-methyloctylene-3-one-2 is converted into 4 : 9 : 12-trimethylpentadecatriene-5 : 8 : 10-one-7 by heating with caustic potash; by reducing with hydrogen, 4 : 9 : 12-trimethyl pentadecanol-7 is obtained; the latter is solubilized by sulphonation, by treating with ethylene oxide or by treating first with propylene oxide and then with ethylene oxide; (2) isoamylaldehyde is condensed with acetone and the resulting 5-methylheptylene-3-one-2 converted into 3 : 8 : 11-trimethyltridecatriene-4 : 7 : 9-one-6; the latter is reduced and sulphonated; (3) butylaldehyde is condensed with acetone and the product treated as in the previous examples to prepare the sulphuric ester of the corresponding alcohol; (4) heptylaldehyde is condensed with acetone and the resulting ketone converted into 2 : 4 : 9 : 12 : 14-pentamethylpentadecatriene-5 : 8 : 10-one-7; the latter is reduced and the alcohol either sulphonated or treated with ethyleneoxide; (5) ethylhexylaldehyde is condensed with acetone and the resulting ketone converted into 5 : 13-diethyl-10-methylheptadecatriene - 6 : 9 : 11-one-8; the corresponding alcohol is formed by hydrogenation and is sulphonated or treated with ethyleneoxide; (6) isoheptylaldehyde is condensed with methylethylketone and the resulting ketone converted into 2 : 4 : 6 : 7 : 10 : 12 : 14 - heptamethylpentadecatriene-5 : 8 : 10-one-7 by doubling the molecule; the latter is reduced and sulphonated.  Specification 436,214, [Group IV], is referred to.