K. Okamoto, T. Kinoshita
Sep 1, 1972
Citations
0
Influential Citations
11
Citations
Journal
Bulletin of the Chemical Society of Japan
Abstract
As tertiary and secondary systems with optical activity, tetrahydrolinalyl (methylethylisohexylcarbinyl) chloride or p-nitrobenzoate and 2-octyl p-toluenesulfonate have been selected, and their titrimetric and polarimetric rate constants (kt and kp) for SN1 phenolyses have been measured in the presence of triethylamine (or sodium phenoxide) in 50 wt% phenol–benzene. At higher amine (or phenoxide) concentrations, the kt and kp coincide with each other for tetrahydrolinalyl chloride (at 25.0°C) or p-nitrobenzoate (at 100.0°C), and also for 2-octyl tosylate (at 75.0°C), exhibiting the typical features of the nN1 solvolysis rate constant. In the absence of the amine (or sodium phenoxide), the kt diminishes to show a gap between the kp and the kt, indicating the occurrence of an ion-pair return in the phenolysis for both systems. Under the same reaction conditions as those of the rate measurement, tetrahydrolinalyl chloride and p-nitrobenzoate yield the phenyl ether, with a predominant racemization accompanied...