Hydrolysis of acetaldehyde diethyl acetal and ethyl vinyl ether: secondary kinetic isotope effects in water and aqueous dioxane and the stability of the ethoxyethyl cation
Secondary deuterium isotope effects on the hydronium ion catalyzed hydrolysis of acetaldehyde diethyl acetal and ethyl vinyl ether were determined in wholly aqueous and aqueous dioxane solutions by comparing rates of reaction of the normal substrates with those of CD/sub 3/CH(OC/sub 2/H/sub 5/) and CH/sub 3/CD(OC/sub 2/H/sub 5/) and of CD/sub 2/=CHOC/sub 2/H/sub 5/ and CH/sub 2/=CDOC/sub 2/H/sub 5/. All of the isotope effects observed are consistent with the values expected on the basis of the changes in hyperconjugation, bond hybridization, and inductive effect which occur during the course of these reactions. The solvent dependence of the isotope effects, however, suggests that the ethoxyethyl cation intermediate generated in these reactions becomes sufficiently unstable in aqueous dioxane to require the conventional mechanisms for these reactions to give way to concerted pathways. 23 references, 2 tables.
- Research Organization:
- Univ. of Toronto, Ontario
- OSTI ID:
- 5961644
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 106:23; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400302* -- Organic Chemistry-- Isotope Effects-- (-1987)
ABSORPTION SPECTROSCOPY
ACETALS
ALDEHYDES
AQUEOUS SOLUTIONS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CORRELATIONS
DATA
DECOMPOSITION
DEUTERIUM
DEUTERIUM COMPOUNDS
DIOXANE
DISPERSIONS
ETHERS
EXPERIMENTAL DATA
HETEROCYCLIC COMPOUNDS
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
HYDROLYSIS
INFORMATION
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LEAST SQUARE FIT
LIGHT NUCLEI
LYSIS
MATHEMATICAL MODELS
MAXIMUM-LIKELIHOOD FIT
MIXTURES
MONITORING
NUCLEI
NUMERICAL DATA
NUMERICAL SOLUTION
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
QUANTITY RATIO
REACTION INTERMEDIATES
REACTION KINETICS
SOLUTIONS
SOLVENT PROPERTIES
SOLVOLYSIS
SPECTROSCOPY
STABILITY
STABLE ISOTOPES