Patent GB-817000-A (GB)
Title: Improvements in the production of esters of beta-substituted glycidic acid
IPC: C07D303/48
Filed: 1958-03-10
Abstract: Esters of beta-substituted glycidic acid are produced by condensing an alpha-halogencarboxylic acid ester with a carbonyl compound in the pressure of a condensing agent comprising a sodium or potassium alcoholate of a primary or secondary alcohol having at least 5 carbon atoms in the molecule and which is difficulty soluble or practically insoluble in water.  Suitable alcoholates are those of pentanols, hexanols, cyclohexanols, heptanols, octanols and nonanols, which may be branched with aliphatic or araliphatic side chains and which preferably have the hydroxy group in the alpha or beta position.  The said alcoholates are preferably used in 20 to 50 per cent solution in the alcohol corresponding to the alcoholate.  Suitable alpha-halogencarboxylic acid esters are the esters of monochloracetic acid, alpha-halogenpropionic acid, alpha-halogen-butyric acids or alpha-halogen-substituted araliphatic carboxylic acids, e.g. alpha-halogenphenylacetic acid.  In general the alcohol moiety of the ester corresponds to the alcoholate used, but in the case where esters of other alcohols are used, ester interchange may take place during the process to give the glycidic ester of the alcohol corresponding to the alcoholate.  Suitable carbonyl components are acetone, ethyl methyl ketone, cyclohexanone, benzophenone, acetophenone, butyraldehyde, benzaldehyde, furfural, 2-ethylhexanal and 2-ethylhexenal.  The reaction may be effected by allowing the alpha-halogen carboxylic acid ester and the carbonyl compound to flow into a solution of the condensing agent at a temperature between - 10 DEG  and +20 DEG  C., preferably at 0 DEG  to 8 DEG  C.  A diluent such as benzene, toluene, or cyclohexane may be present.  In examples: (1) beta, beta-dimethylglycidic acid 2 - ethylhexyl ester is obtained by reacting monochloracetic acid 2-ethylhexyl ester with acetone at 5 DEG  C. in a solution of sodium 2-ethylhexylate in 2-ethylhexanol; (2) beta, beta-cyclohexylideneglycidic acid 2-ethylhexyl ester is obtained by reacting monochloracetic acid 2-ethylhexyl ester with cyclohexanone at 5 DEG  C. in a solution of sodium 2-ethylhexylate in 2-ethylhexanol; the following esters are prepared in a similar manner using the alcoholate corresponding to the alcohol radical of the ester: alpha-methyl-beta, beta - cyclohexylideneglycidic acid 2 - ethylhexyl ester; beta - phenylglycidic acid 2 - ethylhexyl ester; beta - (n - heptene - D  - 3,4-yl-3) glycidic acid 2-ethylhexyl ester; beta-(n-heptyl - 3) - glycidic acid and 2 - ethylhexyl ester, beta, beta - cyclohexylideneglycidic acid n - hexyl ester; beta, beta-cyclohexylidene 2-ethylbutyl ester; beta, beta-cyclohexylidene-3-methylhexyl ester; beta, beta-cyclohexylideneglycidic acid n-octyl ester; (3) beta, betacyclohexylideneglycidic acid cyclohexyl ester is obtained from cyclohexanone and cyclohexyl monochloracetate with sodium cyclohexylate in cyclohexanol; (4) beta, beta-cyclohexylidene glycidic acid 2-ethylhexyl ester is obtained from cyclohexanone and ethyl monochloracetate with sodium 2-ethylhexylate in 2-ethylhexanol with interchange of ester radicals; (5) beta, beta-dimethylglycidic acid 2-ethylhexyl ester is obtained from acetone and ethyl monochloracetate with sodium 2-ethylhexylate in 2-ethylhexanol; (6) beta, beta-cyclohexylideneglycidic acid nonyl ester is obtained from cyclohexanone and nonyl monochloracetate (obtained by esterification of monochloracetic acid with a mixture of isomeric nonanols obtained by the oxoprocess from octenes) with a mixture of the corresponding sodium nonylates in the nonanols.