Patent GB-461662-A (GB)
Title: Improvements in the preparation of oxygenated aliphatic compounds
IPC: C07C45/74
Filed: 1935-12-18
Abstract: An aliphatic aldehyde having at least 4 carbon atoms is condensed in the presence of alkali with an aliphatic ketone to give a ketol composed of equimolecular amounts of aldehyde and ketone and having atleast 10 carbon atoms, which ketol is dehydrated to the corresponding unsaturated ketone.  The condensation may be effected using aqueous or alcoholic caustic alkali below 40 DEG  C., preferably 20--25 DEG  C.  The product is acidified and fractionally distilled to dehydrate the ketol and remove water and unreacted materials.  The unsaturated ketone is recovered by distillation in vacuo.  It can be hydrogenated at 20--200 DEG  C., preferably not above 150 DEG  C., and at 1--100 atm. using active Ni, Pt or Cu as catalyst to give first the saturated ketone and finally the corresponding alcohol.  The latter can be sulphated, e.g. with H2SO4 + (CH3CO)2O at 0--10 DEG  C., and the acid sulphate ester neutralized with caustic alkali, ammonia or amines such as ethanolamines.  The sulphate esters are employed as detergents, and as wetting, emulsifying, or impregnating agents, e.g. in the textile and leather industries. Example (1) describes the condensation of methylethyl ketone and ethylhexaldehyde to give 6-ethyldecene-4-one-3 which is hydrogenated to 6-ethyldecanol-3.  This is treated with chlorsulphonic acid in b .b <1>-dichlorethyl ether at about 15 DEG C. and the sodium salt of the sulphate isolated.  Other suitable starting materials are unsaturated ketones produced by condensing butyraldehyde or other higher aldehyde with acetone or its homologues such as methylethyl ketone and dehydrating, or saturated ketones produced by hydrogenation of these, e.g. butylidene acetone, methylamyl ketone, dipentenyl ketone, methylheptenone or methylheptanone.  Other examples describe the condensation of (2) methylamyl ketone and butyraldehyde to yield undecene-4-one-6; (3) methylisobutyl ketone and butyraldehyde to give 2-methylnone-5-one-4; (4) methylamyl ketone and ethylhexaldehyde giving 9-ethyl-tridecen-7-one-6; (5) butylidene acetone and ethylhexaldehyde to form 9-ethyltridecadiene-4.7-one-6; (6) dipropyl ketone and ethyl-hexaldehyde to give 5.7-diethylundecen-5-one-4; (7) methylheptenone and ethylhexaldehyde to form 9-ethyl-5-methyltridecadien-4.7-one-6; (8) 3-methylheptanone-2, prepared from butyraldehyde and methylethyl ketone, and ethylhexaldehyde yielding 9-ethyl-5-methyltridecen-7-one-6.  The ketones obtained are in each case hydrogenated to the saturated ketone and the alcohol, the latter then being sulphated.  In place p of the initial ketones, reactants yielding them may be used, e.g. methylethyl ketone and butyraldehyde in example (7). Specifications 440,539, 446,026, 446,084, and 453,151 are referred to.ALSO:Sulphate esters of alcohols obtained by condensing an aliphatic aldehyde having at least 4 carbon atoms with an aliphatic ketone in the presence of alkali to give a ketol of at least 10 carbon atoms, dehydrating, and then hydrogenating, are employed as emulsifying agents, e.g. in the textile and leather industries.  Examples describe the preparation of the sulphate esters of 6-ethyldecanol-3, undecanol-6, 2-methylnonanol-4, 9-ethyltridecanol-6, 5.7-diethylundecanol-4, and 9-ethyl-5-methyltridecanol-6.