Secondary deuterium isotope effects in the solvolysis of cyclopropyl triflates

Journal Article · Fri Nov 12 04:00:00 EST 1976 · J. Org. Chem.; (United States)

DOI:https://doi.org/10.1021/jo00885a019· OSTI ID:7334385

Creary, X

..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), Journal Name: J. Org. Chem.; (United States) Vol. 41:23; ISSN JOCEA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400302* -- Organic Chemistry-- Isotope Effects-- (-1987)
ACETIC ACID
CARBOXYLIC ACIDS
CHEMICAL REACTIONS
DECOMPOSITION
DEUTERIUM
ESTERS
HETEROCYCLIC COMPOUNDS
HYDROGEN ISOTOPES
ISOTOPE EFFECTS
ISOTOPES
LIGHT NUCLEI
MONOCARBOXYLIC ACIDS
NUCLEI
ODD-ODD NUCLEI
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC FLUORINE COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
SOLVENT PROPERTIES
SOLVOLYSIS
STABLE ISOTOPES
SULFONIC ACID ESTERS