The α-effect in the SNAr reaction of 1-(4-nitrophenoxy)-2,4-dinitrobenzene with anionic nucleophiles: effects of solvation and polarizability on the α-effect

Abstract

A kinetic study on SNAr reactions of 1-(4-nitrophenoxy)-2,4-dinitrobenzene (1a) with various anionic nucleophiles in 80 mol% water – 20 mol% DMSO at 25.0 °C is reported. The Brønsted-type plot for the reaction of 1a with a series of substituted phenoxides and HOO− results in an excellent linear correlation with βnuc = 1.17. However, OH− exhibits dramatic negative deviation from the Brønsted-type plot, while N3−, C6H5S−, and butane-2,3-dione monoximate (Ox−) deviate positively from linearity. HOO− is 680-fold more reactive than OH− but does not exhibit the α-effect. In contrast, Ox− is 166-fold more reactive than isobasic 4-Cl−C6H4O− and exhibits the α-effect. Differential solvation effects have been suggested to be responsible for the α-effect in this study, i.e., Ox− exhibits the α-effect, since it is 5.7 kcal/mol less strongly solvated than 4-Cl−C6H4O− in the reaction medium, while HOO− does not show the α-effect due to a strong requirement for partial desolvation before nucleophilic attack. The highly enhanced reactivity of polarizable N3− and C6H5S− and extremely decreased reactivity of nonpolarizable OH− are in accord with the hard–soft acid and base principle.