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 YBnCl showed excellent linear relationships in every case. Hammett‐type analysis of rate data against Brown‐Okamoto's σ+ constants gave excellent linear correlations with ρ 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 σ+ constants also yielded comparable results, although with smaller variation. The function of solvents on the solvolytic mechanism was discussed.
The solvolysis of a series of l-aryl-l-tert-butylmethyl bromides (la-lg) in a variety of solvents were carried out. Linear relationships were observed from Hammett-type analysis of logarithm of rate constants using single-parameter Brown-Okamoto equation (Eqn. 1) and dual-parameter Yukawa-Tsuno equation
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