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Deuterium isotope effects in the solvolysis of benzal chlorides. 4. Salt effects and. cap alpha. -deuterium isotope effects

Journal Article · · J. Am. Chem. Soc.; (United States)
DOI:https://doi.org/10.1021/ja00394a026· OSTI ID:6570841
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The effect of LiClO/sub 4/, Bu/sub 4/NClO/sub 4/, LiCl, Bu/sub 4/NCl, and mixtures of these salts on the rate and ..cap alpha..-deuterium isotope effects are reported for the solvolysis of p-methoxybenzal chloride in 75% and 85% (v/v) dioxane-water mixtures at 25/sup 0/C. In the less polar of these solvents (85D), k/sub ext//sup 0/ values from the Winstein equation for the two salts LiClO/sub 4/ and Bu/sub 4/NClO/sub 4/ are the same, and very little common-ion rate depression is observed although induced common-ion rate depression is observed. In the more polar solvent (75D), extensive common-ion rate depression is observed for both LiCl and Bu/sub 4/NCl. k/sub ext//sup 0/ values for Bu/sub 4/NClO/sub 4/ and LiClO/sub 4/ are not the same in this more polar solvent. These results are interpreted by using Winstein's ion-pair mechanism for this solvolysis.

Research Organization:
Univ. of Maryland, Catonsville
OSTI ID:
6570841
Journal Information:
J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 103:4; ISSN JACSA
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)
ALKALI METAL COMPOUNDS
BINARY MIXTURES
CHEMICAL REACTIONS
CHLORIDES
CHLORINE COMPOUNDS
DATA
DECOMPOSITION
DEUTERIUM
DIOXANE
DISPERSIONS
EXPERIMENTAL DATA
HALIDES
HALOGEN COMPOUNDS
HETEROCYCLIC COMPOUNDS
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
INFORMATION
ISOTOPE EFFECTS
ISOTOPES
LIGHT NUCLEI
LITHIUM CHLORIDES
LITHIUM COMPOUNDS
LITHIUM HALIDES
LITHIUM PERCHLORATES
MIXTURES
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXYGEN COMPOUNDS
PERCHLORATES
SALTING-OUT AGENTS
SOLVOLYSIS
STABLE ISOTOPES
WATER