Thermolysis of (1R,2R)-1,2-dideuteriocyclobutane. An application of vibrational circular dichroism to kinetic analysis

Journal Article · Wed Jul 23 04:00:00 EDT 1986 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00275a028· OSTI ID:5455251

Chickos, J S; Annamalai, A; Keiderling, T A

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), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:15; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400302* -- Organic Chemistry-- Isotope Effects-- (-1987)
ALKANES
BUTANE
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CYCLOALKANES
DATA
DECOMPOSITION
DEUTERIUM COMPOUNDS
DICHROISM
ELECTROMAGNETIC RADIATION
EXPERIMENTAL DATA
HIGH TEMPERATURE
HYDROCARBONS
HYDROGEN COMPOUNDS
INFORMATION
INFRARED RADIATION
INFRARED SPECTRA
ISOMERIZATION
ISOTOPE EFFECTS
KINETICS
MAGNETIC CIRCULAR DICHROISM
NUMERICAL DATA
ORGANIC COMPOUNDS
PYROLYSIS
RADIATIONS
REACTION KINETICS
SPECTRA
STRUCTURAL CHEMICAL ANALYSIS
THERMOCHEMICAL PROCESSES