Solvent effects on the steric course of the solvolysis of tertiary acyclic derivatives

The solvolysis of (R)-3-chloro-3,7-dimethyloctane (2), of the corresponding hydrogen phthalate (S)-4g, and of the p-nitrobenzoate (S)-4h proceeds with up to 87% inversion of configuration in solvents such as methanol or ethanol. The degree of inversion decreases in more dissociating solvents. In 2,2,2-trifluoroethanol (TFE), up to 40% retention of configuration occurs.