Application of the Extended Grunwald-Winstein Equation to the Solvolyses of 4-(Chlorosulfonyl)biphenyl
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Solvolyses with the reaction center being the sulfur of 4-(chlorosulfonyl)biphenyl (C6H5C6H4SO2Cl, 1) was studied under solvolytic conditions and the extended Grunwald-Winstein equation was applied. The thirty five kinds of solvents gave a reasonable extended Grunwald-Winstein plot with a correlation coefficient (R) of 0.940. The sensitivity values (l = 0.60 and m = 0.47) of 1 were smaller than those obtained for benzenesulfonyl chloride (C6H5SO2Cl, 2; l = 1.10 and m = 0.61) proposed to undergo dissociative SN2 mechanism. These l and m values for the solvolyses of 1 can be considered to support a SN2 pathway with some ionization reaction. The activation parameters, ΔH≠ and ΔS≠, were determined and they are also in line with values expected for a bimolecular reaction. The kinetic solvent isotope effect (KSIE) of 1.26 is also in accord with a bimolecular mechanism, probably assisted by general-base catalysis.
Abstract
Solvolyses with the reaction center being the sulfur of 4-(chlorosulfonyl)biphenyl (C6H5C6H4SO2Cl, 1) was studied under solvolytic conditions and the extended Grunwald-Winstein equation was applied. The thirty five kinds of solvents gave a reasonable extended Grunwald-Winstein plot with a correlation coefficient (R) of 0.940. The sensitivity values (l = 0.60 and m = 0.47) of 1 were smaller than those obtained for benzenesulfonyl chloride (C6H5SO2Cl, 2; l = 1.10 and m = 0.61) proposed to undergo dissociative SN2 mechanism. These l and m values for the solvolyses of 1 can be considered to support a SN2 pathway with some ionization reaction. The activation parameters, ΔH≠ and ΔS≠, were determined and they are also in line with values expected for a bimolecular reaction. The kinetic solvent isotope effect (KSIE) of 1.26 is also in accord with a bimolecular mechanism, probably assisted by general-base catalysis.
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