EFFECT OF DIPOLAR APROTIC SOLVENTS ON NUCLEOPHILIC ADDITION OF ALCOHOLS TO ACTIVATED OLEFINS

The effect of dipolar aprotic solvents on the alkoxide-catalyzed addition of methanol and ethanol to methyl esters and nitriles of acrylic and methacrylic acid was investigated kinetically. The rate equation found was R = (kobsd [olefin] [alkoxide])/[ROH]n. Rates of addition were relatively very high in solvent mixture poor in alcohol. The order of reaction in alcohol was dependent only on the type of the aprotic solvent used; its absolute value increased with increasing the hydrogen-bonding capability of the aprotic solvent. It is suggested that mainly one and the same nucleophile is involved in the addition reaction, in both pure alcohol and in alcohol dipolar aprotic solvent mixtures poor in alcohol. © 1969, American Chemical Society. All rights reserved.