RATES OF SOLVOLYSIS OF SOME DEUTERATED 2-PHENYLETHYL p-TOLUENESULFONATES
Rates of solvolysis of 2-phenylethyl (Ia), b 2/ (Ic) p-toluenesulfonates were determined in formic and in acetic acid. In formolysis Ia and Ic react at the same rate, but Ia reacts 17 plus or minus 2% faster than Ib. In acetolysis small effects are observed with both deuterated com. pounds: Ia is 3 plus or minus 1% faster than Ib and 4 plus or minus 3% faster than Ic. The formates and acetates produced in the solvolyses were converted to the corresponding 2phenylethanols II. Comparison of the infrared spectra of the products with those of synthetic mixture of IIb and IIc revealed that ca. 45% phenyl migration had occurred in the formolysis and ca. 10% phenyl migration in acetolysis. These results suggest that phenyl participation predominates in formolysis, but is unimportant in acetolysis. The nature of the transition state in phenyl- participation reactions and the factors contributing to secondary deuterium isotope effects are discussed. (auth)
- Research Organization:
- Univ. of Rochester, N.Y.
- Sponsoring Organization:
- USDOE
- NSA Number:
- NSA-12-012272
- OSTI ID:
- 4336413
- Journal Information:
- Journal of the American Chemical Society (U.S.), Journal Name: Journal of the American Chemical Society (U.S.) Vol. Vol: 80; ISSN JACSA
- Country of Publication:
- Country unknown/Code not available
- Language:
- English
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