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Mechanisms of elimination reactions. 35. Deuterium kinetic isotope effects and tunneling in the reaction of (2-(p-(trifluoromethyl)phenyl)ethyl)trimethylammonium ion with hydroxide ion in mixtures of water and dimethyl sulfoxide

Journal Article · · J. Org. Chem.; (United States)
DOI:https://doi.org/10.1021/jo00334a028· OSTI ID:5723684
;
The rates of reaction of (2-((p-trifluoromethyl)phenyl)ethyl)trimethylammonium (1h) and (2-((2-trifluoromethyl)phenyl)ethyl-2,2-d/sub 2/)trimethylammonium (1d) iodides with hydroxide ion in mixtures of dimethyl sulfoxide and water were determined as a function of temperature. A maximum in k/sub h//k/sub D/ (7.25 at 50/sup 0/C) is observed at 35% dimethyl sulfoxide. The Arrhenius parameters provide qualitative evidence for tunneling, and fitting the Bell theory expression for tunneling to the observed temperature dependence gives tunnel corrections, Q/sub tH//Q/sub tD/, of 1.6 to 1.8 at 50/sup 0/C. Equations for calculating the effect of error in the Arrhenius preexponential factor, A/sub aH//A/sub aD/, on the tunnel correction are derived. The error in Q/sub tH//Q/sub tD/ (3 to 18%) is less than the error in A/sub aH//A/sub aD/ (10 to 50%) but is still enough to render uncertain the significance of observed variations in Q/sub tH//Q/sub tD/. These results are compared with earlier results on the (2-phenylethyl)trimethylammonium ion, and the effect of the p-trifluoromethyl substituent on the structure of the transition state for elimination is discussed. The application of Marcus theory to k/sub H//k/sub D/ variation in these reactions is considered.
Research Organization:
Univ. of Rochester, NY
OSTI ID:
5723684
Journal Information:
J. Org. Chem.; (United States), Journal Name: J. Org. Chem.; (United States) Vol. 46:21; ISSN JOCEA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400302* -- Organic Chemistry-- Isotope Effects-- (-1987)
AMINES
AMMONIUM COMPOUNDS
CHARGED PARTICLES
CHEMICAL REACTIONS
DATA
DEUTERIUM
DMSO
EXPERIMENTAL DATA
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
HYDROXIDES
INFORMATION
IONS
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LIGHT NUCLEI
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OXYGEN COMPOUNDS
QUATERNARY COMPOUNDS
REACTION KINETICS
SOLVENT PROPERTIES
STABLE ISOTOPES
SULFOXIDES
WATER