Improvements in the process of replacing active hydrogen by a hydrocarbon group

Compounds of general formula :- wherein R is a hydrogen atom or a hydrocarbon group, R1 is an ester, cyano or phenyl group or a group containing a keto group or the vicinal carbon atom, R11 is an alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl or aralkyl group and X is an organic esterifying group, are prepared by reacting a metallo ester of formula :- wherein M is an alkali or alkaline earth metal, with an alkylating agent R11 Y, wherein Y is a halogen atom or an alkyl sulphate, alkenyl sulphate, aryl sulphate or aralkyl in the presence of one or more organic catalysts devoid of active or acidic hydrogen atoms and which contain within their respective molecules an electrically rigid, unbranched diatomic or triatomic dipole possessing as its negatively charged terminus an oxygen atom with sufficient electron donor capacity to be potentiometrically titrated with perchloric acid in an acetic anhydride medium. Catalysts specifically claimed as suitable are :-pyridine N-oxide, trimethylphosphine oxide, hexamethylphosphoramide, N-methyl-o -caprolactam, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N-methyl-2-piperidone, tetramethylurea, N-formylpiperidine, N,N-dimethylbenzamide and N-formylpyrrolidine. Other substances whose catalytic activity is evaluated are:-N-formylmorpholine, N-acetylmorpholine, N-vinyl,-2-pyrrolidone, trimethylacetic acid dimethylamide, diethyl carbonate, acetonitrile acetone, dimethyl-nitrosamine, nitrobenzene, ethanol, benzonitrile, diphenyl-formamide, methylphenylformamide, dimethylglycine ethyl ester, dimethylcyanamide, trifluoroacetic acid dimethylamide, 2,4-dimethyltetrahydrothiophen dioxide and N-thioacetylmorpholine.