Nucleophilic substitution at the pyridine ring. Kinetics of the reaction of 2-chloro-3,5-dinitropyridine with arylthiolates in methanol

The reaction rates of 2-chloro-3,5-dinitropyridine 1 with a series of arylthiolates 2a-h in methanol have been measured at 25°C. The products are the corresponding 2-thioaryl-3,5-dinitropyridine 3a-h. Good Hammett correlation with ρ value −1.19 was obtained suggesting an elimination-addition mechanism SNAr and the formation of Meisenheimer-like intermediates. Plot of log k2 vs. pKa values of arylthiols gave straight line with β=0.38 indicating that the π-bond breaking in the pyridine ring is so much advanced over bond making between the nucleophile and the carbon that bears the chlorine atom. Excellent correlation between log k2 and log K (carbon basicity of arylthiolates) was obtained.