Mechanistic Studies of the Solvolyses of 4-(Acetylamino)-1-Naphthalenesulfonyl Chloride
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First-order rate constants (kobs) have been obtained for the solvolyses of 4-(acetylamino)-1-naphthalenesulfonyl chloride (C12H10ClNO3S, 1) in a variety of organic and aqueous-solvents. These have been used to set up a scale of solvent nucleophilicities based upon the extended Grunwald-Winstein equation. The twenty-four kinds of solvents gave a reasonably precise extended Grunwald-Winstein plot, with a correlation coefficient (R) of 0.941. The sensitivity values (l = 0.760.07 and m = 0.370.03) for 1 were smaller than those obtained for benzenesulfonyl chloride (C6H5SO2Cl, 2; l = 1.01 and m = 0.61) as indeed, for which a normal SN2 mechanism has been proposed. According to the previous research, when the l/m value obtained is greater than 1, it is known to be an SN2 mechanism in which bond formation and bond destruction occur simultaneously. In this study, since the l/m value is 2.1, it can be seen that the solvolysis of 1 is an SN2 mechanism. The kinetic solvent isotope effect (KSIE) of 1.75 is in accord with a bimolecular mechanism, probably assisted by general-base catalysis.
Abstract
First-order rate constants (kobs) have been obtained for the solvolyses of 4-(acetylamino)-1-naphthalenesulfonyl chloride (C12H10ClNO3S, 1) in a variety of organic and aqueous-solvents. These have been used to set up a scale of solvent nucleophilicities based upon the extended Grunwald-Winstein equation. The twenty-four kinds of solvents gave a reasonably precise extended Grunwald-Winstein plot, with a correlation coefficient (R) of 0.941. The sensitivity values (l = 0.760.07 and m = 0.370.03) for 1 were smaller than those obtained for benzenesulfonyl chloride (C6H5SO2Cl, 2; l = 1.01 and m = 0.61) as indeed, for which a normal SN2 mechanism has been proposed. According to the previous research, when the l/m value obtained is greater than 1, it is known to be an SN2 mechanism in which bond formation and bond destruction occur simultaneously. In this study, since the l/m value is 2.1, it can be seen that the solvolysis of 1 is an SN2 mechanism. The kinetic solvent isotope effect (KSIE) of 1.75 is in accord with a bimolecular mechanism, probably assisted by general-base catalysis.
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