Rates of solvolyses of 2-（4-methylphenyl）-2-propyl benzoate （2b）, 2-（4-methylthiopheny1）-2-propyl benzoate （3b） and 2,2-dimethy1-1-（4-methoxypheny1）-1-phenyl-1-propy1 benzoate （4b） were measured, respectiv...Rates of solvolyses of 2-（4-methylphenyl）-2-propyl benzoate （2b）, 2-（4-methylthiopheny1）-2-propyl benzoate （3b） and 2,2-dimethy1-1-（4-methoxypheny1）-1-phenyl-1-propy1 benzoate （4b） were measured, respectively, in ten or more different solvent systems. Additional YBnOPXB and Y, BnOPNB values in binary trifluoroethanol-water systems were determined, Grunwald-Winstein type correlation analysis showed that YBaIOBB values were applicable to benzylic benzoates. The rate ratio, koPNB/KOBZ, was found to be solvent-dependent in the range of 29 for 4 in ethanol to 4 for 2 in trifluoroethanol-water. Non-limiting mechanism, including both nucleophilic and electrophilic solvent assistance, in the solvolysis of 2b was discussed,展开更多
文摘Rates of solvolyses of 2-（4-methylphenyl）-2-propyl benzoate （2b）, 2-（4-methylthiopheny1）-2-propyl benzoate （3b） and 2,2-dimethy1-1-（4-methoxypheny1）-1-phenyl-1-propy1 benzoate （4b） were measured, respectively, in ten or more different solvent systems. Additional YBnOPXB and Y, BnOPNB values in binary trifluoroethanol-water systems were determined, Grunwald-Winstein type correlation analysis showed that YBaIOBB values were applicable to benzylic benzoates. The rate ratio, koPNB/KOBZ, was found to be solvent-dependent in the range of 29 for 4 in ethanol to 4 for 2 in trifluoroethanol-water. Non-limiting mechanism, including both nucleophilic and electrophilic solvent assistance, in the solvolysis of 2b was discussed,
