The rates of solvolysis of twenty-two m-and p-substituted α-methylbenzyl chlorides were determined in 80% aqueous acetone. The relative rates at 45° C are not correlated linearly with σ 0 or σ. The use of Brown's σ+ improves the fit but the resulting correlation is still concave. An excellent correlation, logk⁄ k 0=− 4.950 (σ 0+ 1.147Δ\ barσ R+), was obtained by applying the LArSR equation. The r value 1.15 suggests that the π-electronic contribution ...
