The acidities of 4-arylsulfonylmethylpyridines and N-methyl and N-benzyl 4-arylsulfonylmethylpyridinium cations in aqueous solution

Abstract

The pKa values for the deprotonation of a series of 4-(X-phenylsulfonylmethyl)pyridines (6) (pKa = 19.89 (X = H); ρ = 3.0) were determined in aqueous dimethyl sulfoxide solutions at 25 °C using the H0q acidity function. The pKa values were also measured for the corresponding series of N-mefhyl 4-(X-phenylsulfonylmethyl)pyridinium cations (2) (pKa = 11.27 (X = H); ρ = 1.45) and also for a series of N-(X-benzyl) 4-phenylsulfonylmethylpyridinium cations (7) (pKa = 10.70 (X = H); ρ = 0.65) in aqueous solution (ionic strength 0.1 at 25 °C). Comparison of the substituent effects upon the pKa values of the sulfonyl-activated carbon acids 2, 6, and 7 with the substituent effects upon the pKa values of the corresponding three series of ketones gives insight into the electron-density distribution in the carbanionic conjugate bases of sulfone and ketone carbon acids. Extrapolation of a linear free energy relationship between the pKa values of neutral sulfones and ketones allows the estimation of pKa = 28.7 for the deprotonation of methyl phenyl sulfone in aqueous solution.