Patent GB-446084-A (GB)
Title: Improvements in the preparation of oxygenated aliphatic compounds derived from 2-ethylbutyraldehyde
IPC: C07C45/74
Filed: 1935-12-18
Abstract: 2-Ethylbutyraldehyde is condensed with an aliphatic ketone in presence of alkali to form a ketol which is heated with a catalyst to give an unsaturated ketone.  This is hydrogenated to a saturated ketone and further to a secondary alcohol.  The latter is sulphated to form an acid sulphate ester which is neutralized with a base such as an alkali or alkaline earth metal compound, ammonia, an amine or substituted amine.  The unsaturated and saturated ketones may be further condensed with aldehydes such as butyraldehyde or ethylhexaldehyde and the ketol converted into an unsaturated ketone and finally a secondary alcohol.  The initial condensation may be effected at 20--30 DEG  C., the presence of air and metals catalyzing oxidation being avoided.  Intermittent or slow addition of the alkali is advantageous.  The ketol is heated above 100 DEG  C. with, for example, 0,1--0,2 per cent by weight of sulphuric, phosphoric, or hydrobromic acid or iodine.  To prevent polymerization, weak acids such as acetic, carbonic or tartaric are preferred.  The unsaturated ketone is hydrogenated with 1--10 per cent by weight of catalysts such as Ni, Pt or Cu at about 60--75 DEG  C. and 800 lbs./sq. in. if a saturated ketone is desired, or up to 150 DEG  C. and 900 or 1000 lbs./sq. in. for the secondary alcohol.  The product is filtered and fractionated. Sulphation is effected with sulphuric acid or sulphur trioxide, or preferably chlorsulphonic acid.  The saturated ketones are used as lacquer solvents particularly with natural or synthetic resins. The alcohols and their sulphates are employed as wetting, foaming, emulsifying and impregnating agents, as detergents, and in treatment liquors in the textile, leather, and other industries. In examples: (1) acetone and 2-ethylbutyraldehyde are condensed by adding methanolic NaOH, the mixture neutralized, filtered and fractionated to remove unreacted starting materials, methanol, and water.  Sulphuric acid is added and fractionation continued under reduced pressure to yield 3-ethylhepten-4-one-6.  Distillation without acidifying gives 3-ethylheptanol-4-one-6.  The unsaturated ketone is hydrogenated to 3-ethylheptanone-6.  Both ketones on further hydrogenation give 3-ethylheptanol-6.  This is dissolved in b b <1>-dichlorethyl ether and treated at 10 DEG  C. with chlorsulphonic acid while passing air or inert gas.  The product is poured into cold water, neutralized with NaOH, the salt extracted with water and the solution evaporated after addition of NaHCO3; (2) acetone and 2-ethylbutyraldehyde are condensed, acidified, and fractionated to obtain the unsaturated ketone as in (1).  A higher boiling fraction is obtained consisting of a 15 carbon ketone, apparently 3.9-diethylundecadien-4.7-one-6, formed by condensation of a second molecule of 2-ethylbutyraldehyde with the 9 carbon ketol or ketone.  Hydrogenation gives the corresponding saturated ketone and alcohol.  The unsaturated or saturated ketone of (1) may be substituted for the acetone to give the same 15 carbon ketone, or 3.9-diethylundecen-4-one-6 respectively.  Also, the unsaturated or saturated ketone of (1) may be condensed with another aldehyde, for example, ethylhexaldehyde which yields a 17 carbon doubly or singly unsaturated ketone; (3) 2 - ethylbutyraldehyde and methylisobutyl ketone yield 3-ethyl-9-methylnonene-4-one-6 which gives the corresponding alcohol on reduction.  Methylisobutyl ketone can be made by condensing acetone with an alkali, hydrogenating the mesityl oxide, and dehydrating the diacetone alcohol formed.  (4) Using methylamyl ketone the product is apparently 3-ethylundecen-4-one-6. Methylamyl ketone may be prepared by condensing acetone and butyraldehyde and hydrogenating the butylidene acetone produced.  (5) With 5-ethylnonene-3-one-2, the product appears to be 3.9-diethyltridecadien-4-7-one-6.  This can be hydrogenated and the alcohol sulphated as in (1).  (6) 5-Ethylnonanone-2 gives 3.9-diethyltridecen-4-one-6.ALSO:Saturated ketones obtained by condensing 2-ethylbutyraldehyde with an aliphatic ketone, heating the resultant ketol to give an unsaturated ketone, and then hydrogenating, are used as lacquer solvents.  3-ethylheptanone-6, 3.9-diethylundecanone-6, and p  3.9-diethyltridecanone-6 are given as examples.