Reactivity of 2-Sulfobenzoic Acid Imide and Benzenesulfonamide in Arenesulfonylation

Reactivity of Benzamide toward Sulfonylation

“…Furthermore, the former could create steric hindrances to attack of nucleophilic nitrogen atom on the sulfonyl group of acylating agent 2. Thus, on the basis of our present results and reported data [5], the reactivity series of carboxylic and sulfonic acid amides toward sulfonylation can be represented as 1 > 3 > 4.…”

“…Comparison of our experimental data with the kinetic parameters of related reactions involving benzenesulfonamide (3) and saccharin (4, o-sulfobenzoic acid imide) in aqueous 1,4-dioxane (20 wt % of water) [5] showed that the rate constant for the reaction with benzamide (1) is more than 200 times higher than the rate constant for the reaction with saccharin (4) and more than 10 times higher than the rate constant for the sulfonylation of sulfonamide 3. The activation barrier for the reaction with 1 is lower by 10 kJ/mol than that for the reaction with 4 and is similar to the activation barrier found for the reaction with 3.…”

“…Compounds containing an amino group have long been the subjects of our studies, as they are substrates of acylation reactions, including sulfonylation. We previously performed systematic studies of the kinetics and mechanisms of acylation of various amines such as ammonia, α-amino acids, dipeptides, benzoic and benzenesulfonic acid hydrazides, benzenesulfonamide, and 2-sulfobenzoic acid imide [4][5][6][7][8]. Among amino compounds that are promising as substrates for sulfonylation, arenecarboxylic acid amides remain almost unstudied.…”