Catalytic properties and acidity of 1,2-benzenedisulfonimide and some of its derivatives. An experimental and computational study

1,2-Benzenedisulfonimide (1) has previously been found to be an excellent and, importantly, safe Brønsted acid catalyst. In this work we present the results of a search for derivatives of 1 that are more acidic and effective. Instead of blindly synthesizing a series of analogues, we have carried out a screening process in which the pKa of 1 and a set of its derivatives were calculated. The calculated pKa values were confirmed experimentally by carrying out determination through potentiometric titrations of some of the compounds: 1, 4-methyl and 4-nitro derivatives of 1. The calculations indicated that the dinitro and 4-nitro derivatives are among the best candidates for the synthesis. The latter was obtained in good yields and tested as a catalyst. Results were excellent as the reactions took place more quickly and at lower temperatures in all cases, and in a number of cases it was even possible to reduce the amount of catalyst.

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