Reactions of carbonyl compounds in basic solutions. Part 28.¹ The alkaline hydrolysis of 2-formylbenzonitrile, N-(2-formyl and -acetylphenyl)acetamides, N-(2-formylphenyl)-substituted benzamides, 4-(2-formylbenzoyl)morpholine, 3-(4-morpholino)- and -(N-methylanilino)-phthalides and -naphthalides

Abstract

Rate coefficients have been measured for the alkaline hydrolysis of 2-formylbenzonitrile 1, N-(2-formyl and -acetylphenyl)acetamides 2, N-(2-formylphenyl)-3-substituted benzamides 3,4-(2-formylbenzoyl)morpholine 4, 3-(4-morpholino)- and -(N-methylanilino)-phthalides 5 and -naphthalides 6 in 70% (v/v) dioxane–water at various temperatures. The enthalpies and entropies of activation have been evaluated. The hydrolysis of the nitrile is second order in base and that of the amides is first order in base. The relative rates of hydrolysis, activation parameters and substituent effects have been used to suggest the mechanisms of the reactions. Intramolecular catalysis by the neighbouring carbonyl group occurs in the alkaline hydrolysis of 1–4. The alkaline hydrolysis of 5 and 6 is rapid due to their lactone structures.

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