Kinetic and equilibrium studies of the reactions of some thiolate ions with trinitro-aromatic compounds: intrinsic reactivities

Abstract

Kinetic and equilibrium data are reported for the formation of 1 :1 and 1 : 2 adducts from 1,3,5-trinitrobenzene (TNB) and 2,4,6-trinitrotoluene with thiolate ions derived from mercaptoacetate, mercaptosuccinate, and glutathione. The results are used to determine intrinsic reactivities for the thiolate ions in adduct-forming reactions at the nitro-activated aromatic ring. The values for the three thiolate ions are all ca. 5 × 10⁴ and are considerably higher than comparable values, calculated from literature data, for the sulphite ion (300) and the hydroxide ion (10).

The results for the glutathione anion show that results reported previously for reaction with TNB refer to formation of the 1 : 2 adduct rather than 1 : 1 adduct formation.