Secondary deuterium isotope effects in the solvolysis of cyclopropyl triflates
..cap alpha.. Deuterium isotope effects have been measured for solvolysis of cyclopropyl triflate, exo-bicyclo(4.1.0)hept- 7-yl triflate, exo-bicyclo(3.1.0)hex-6-yl triflate, and endo-tricyclo(3.2.1.0/sup 2/ /sup 4/)oct-exo-3-yl triflate in acetic acid. The respective values are 1.07, 1.08, 1.18, and 1.24. These values are discussed in terms of increasing cyclopropyl cationic character in the cationic intermediates. ..beta..-Deuterium isotope effects were determined for 1-methyl cyclopropyl triflate (8) and endo-6-methyl-exo-bicyclo(3.1.0)hex-6-yl triflate (9). Values were 1.12 and 1.42, respectively. The former value was considered to implicate a concerted ionization ring opening in 8. The latter value was consistent with a stepwise ionization, ring opening mechanism for 9. The ..beta.. effect of 1.42 was considered small in view of the instability of the cation derived from 9 and rationalized in terms of an early transition state.
- Research Organization:
- Univ. of Notre Dame, IN
- OSTI ID:
- 7334385
- Journal Information:
- J. Org. Chem.; (United States), Vol. 41:23
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
DEUTERIUM
ISOTOPE EFFECTS
ORGANIC FLUORINE COMPOUNDS
SOLVOLYSIS
SULFONIC ACID ESTERS
ACETIC ACID
HETEROCYCLIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
SOLVENT PROPERTIES
CARBOXYLIC ACIDS
CHEMICAL REACTIONS
DECOMPOSITION
ESTERS
HYDROGEN ISOTOPES
ISOTOPES
LIGHT NUCLEI
MONOCARBOXYLIC ACIDS
NUCLEI
ODD-ODD NUCLEI
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
STABLE ISOTOPES
400302* - Organic Chemistry- Isotope Effects- (-1987)