Thermolysis of (1R,2R)-1,2-dideuteriocyclobutane. An application of vibrational circular dichroism to kinetic analysis
The relative rates of geometric isomerization to racemization have been studied for the title compound by using a combination of infrared (IR) and vibrational circular dichroism (VCD) spectroscopies, respectively. The results are interpreted with a kinetic and mechanistic scheme which parallels that used by Berson, Pedersen, and Carpenter on a similar study of chiral cyclopropane-d/sub 2/ thermolysis. Relative rates of isomerization to stereomutation of 1.5 +/- 0.4 were obtained which can be interpreted to be consistent with a mechanism best described by random methylene rotation in tetramethylene-d/sub 2/. This is the first application of VCD to kinetic analysis, and the advantages of IR techniques over the more usually employed UV spectroscopies to this type of basic mechanistic problem are illustrated.
- Research Organization:
- Univ. of Missouri, St. Louis
- OSTI ID:
- 5455251
- Journal Information:
- J. Am. Chem. Soc.; (United States), Vol. 108:15
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
BUTANE
ISOMERIZATION
PYROLYSIS
CYCLOALKANES
DEUTERIUM COMPOUNDS
ISOTOPE EFFECTS
CHEMICAL REACTION KINETICS
EXPERIMENTAL DATA
HIGH TEMPERATURE
INFRARED RADIATION
INFRARED SPECTRA
MAGNETIC CIRCULAR DICHROISM
STRUCTURAL CHEMICAL ANALYSIS
ALKANES
CHEMICAL REACTIONS
DATA
DECOMPOSITION
DICHROISM
ELECTROMAGNETIC RADIATION
HYDROCARBONS
HYDROGEN COMPOUNDS
INFORMATION
KINETICS
NUMERICAL DATA
ORGANIC COMPOUNDS
RADIATIONS
REACTION KINETICS
SPECTRA
THERMOCHEMICAL PROCESSES
400302* - Organic Chemistry- Isotope Effects- (-1987)