Collect. Czech. Chem. Commun. 2000, 65, 35-46

Effects of ortho-Substituents in Protonolysis of Arylmercuric Chlorides with Hydrochloric Acid

Yulan Wanga,* and Yangjie Wub

a Institute of Chemical Metallurgy, Chinese Academy of Sciences, Beijing, 100080, China
b Zhengzhou University, Zhengzhou, 450052, China


The kinetics of reaction of ortho-substituted phenylmercuric chlorides, 2-R-C6H4HgCl (R = H, CH3, CH3O, C2H5O, CF3, COOC2H5, Cl, Br, F, NO2), with hydrochloric acid in absolute ethanol in the presence of sodium iodide has been studied. The reaction is of the overall second order, first order with respect to each reactant. The rate constant determined at a fixed temperature decreases in the order of R: C2H5O > CH3O > CH3 > H > COOC2H5 > F > Cl > Br > CF3 > NO2. The role of inductive, resonance and field effects of the ortho-substituents, and the relation between steric demands of the ortho-substituents and volume of attacking species are discussed. The underlying mechanism is proposed on the basis of experimental results.

Keywords: Reaction kinetics; Arylmercuric halides; Substituent effects; Protonolysis; Mercury.

References: 11 live references.