Solvolysis of 1-aryl-1-tert-butylmethyl chlorides. Solvent effects on the Hammett-type correlation analysis

摘要

A series of 1-aryl-1-tert-butylmethyl chlorides were prepared, and their rates of solvolysis in a variety of solvents were measured. Correlation analyses using the single-parameter Grunwald-Winstein equation against Y-BuCl showed excellent linear relationships in every case. Hammett-type analysis of rate data against Brown-Okamoto's sigma(+) constants gave excellent linear correlations with rho values dependent upon the range of substitutents and the type of solvents used. Similar results were observed when the Yukawa-Tsuno equation was employed. The use of solvent-dependent sigma(+) constants also yielded comparable results, although with smaller variation. The function of solvents on the solvolytic mechanism was discussed. [References: 23]