Patent GB-737528-A (GB)
Title: Improvements in or relating to method of forming esters
Inventor: CUMMINGS LOWELL OSCAR
IPC: C07C59/00
Filed: 1953-08-01
Abstract: Alkyd resins are heated with esters of b -keto-carboxylic acids having at least one hydrogen atom in a -position and lower aliphatic monohydric alcohols, to effect ester interchange at the free hydroxy groups.  In examples: (1) a resin prepared from soya oil, pentaerythritol, glycerine, and phthalic anhydride is heated with methyl acetoacetate, and the product chlorinated; and (2) a resin prepared from linseed oil, glycerine, and phthalic anhydride is heated with methyl acetoacetate and after-treated with paraformaldehyde, crotonaldehyde, acrolein, furfural, and acetaldehyde.  Esterification of polyethylene glycol and polyethylene oxide is referred to.ALSO:Esters of higher alcohols with b -keto carboxylic acids containing at least one hydrogen atom in a -position are made by heating a mixture of said higher alcohol and an ester of a lower aliphatic monohydric alcohol and such an acid, at least in molecular equivalency of said higher alcohol, to effect ester interchange between said higher alcohol and said ester of a lower alcohol, reducing the concentration of evolved lower alcohol sufficiently low to maintain the desired ester interchange, maintaining the reaction temperature below the decomposition temperatures of the alcohols and b -keto esters until the reaction is substantially completed, and recovering the resulting ester of the higher alcohol.  Excess of the ester of the lower alcohol may be employed, and the evolved lower alcohol may be removed with the assistance of a current of inert gas, or of reduced pressure.  An inert solvent, e.g. xylene, may be present.  In examples, the following alcohols were heated with excess methyl or ethyl acetoacetate, in absence of a catalyst, to give their acetoacetates: (1) cholesterol, (2) stigmasterol, (3) b -sitosterol, (4) cholestanol, (5) epidehydroandrosterone, (6) octadecyl alcohol, (7) castor oil (details of the plasticizing action of the product on a nitrocellulose lacquer and a vinyl chloride vinyl acetate copolymer, (8) decamethylene glycol, (9) cyclohexanol, (10) polyethylene glycol, (11) diethylene glycol monobutyl ether, (12) n-octanol, (13) menthol (molecular equivalent or excess of the ester, (14) lauryl alcohol, (15) the unsaponifiable fraction of tall oil, (16) stearyl alcohol, (17) diacetone alcohol, (18) 12-hydroxy-stearic, glycolic, lactic, ricinoleic, or tartaric acid, and (19) cortisone, and (20) diacetone alcohol.  Also in examples (21) cholesterol and stearyl alcohol are each heated with excess ethyl benzoylacetate, and (22) stearyl alcohol and cholesterol are each heated with excess ethyl acetone dicarboxylate, and with excess diethyl acetyl succinate. Also in examples, cholesterol is heated with excess methyl acetoacetate in presence of the following as catalysts: triethylamine, sulphuric acid, sodium cholesterate, benzene sulphonic acid.  Other alcoholic compounds and b -keto acids are specified.  Reference is made to reaction of the keto group in the products with hydrazines, hydroxylamines, and semicarbazide, to give hydrazones, oximes and semicarbazones, and with ammonia, ammonium salts, or amines to esters of unsaturated amino-acids. Reference is also made to the bromination of the products, and to the treatment of them with triphenylmethyl chloride and diazonium salts.