Deuterium Oxide Solvent Isotope Effects in the Nucleophilic Reactions of Phenyl Esters
Deuterium oxide solvent isotope effects in two intramolecular and three intermolecular nucleophile-catalyzed hydrolyses of phenyl esters were determined. Reactions utilizing carboxylate ion as a nucleophile resulted in ratios of k/sup H2 O//Kd2 O/ of l.8 while reactions utilizing a tertiary amine as a nucleophile gave ratios of 0.9 to 1.0. Values of the isotope effect in the carboxylate ion reactions calculated on the basis of the consideration of the secondary deuterium isotope effects were 1.5 to 1.6 in reasonable agreement with the experimental values. A comparison is made of kinetic isotope effects in general base- and nucleophile-catalyzed hydrolyses, reflecting primary and secondary deuterium isotope effects, respectively. While there is ambiguity in distinguishing between these isotope effects, they may be used in certain restricted situations as an empirical criterion in distinguishing between general base- and nucleophile-catalyzed hydrolyses.
- Research Organization:
- Illinois Inst. of Tech., Chicago; Northwestern Univ., Evanston, Ill.
- Sponsoring Organization:
- USDOE
- NSA Number:
- NSA-16-011616
- OSTI ID:
- 4800822
- Journal Information:
- Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 4 Vol. 84; ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- Country unknown/Code not available
- Language:
- English
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