Thermal unimolecular decomposition of bicyclopropyl and deuterated analogues: infrared photoactivation as a diagnostic tool in mechanistic organic chemistry
- Univ. of Minneapolis, MN.
The infrared photochemistry of bicyclopropyl yields product mixtures that are not easily rationalized on the basis of the mechanistic scheme suggested by previous pyrolysis work. As a result of this inconsistency the thermal chemistry of bicyclopropyl and analogues deuterated specifically on one ring has been reexamined. A significant new reaction channel involving the chemically activated decomposition of cyclohexene to ethylene and butadiene has been demonstrated. Evidence for the involvement of chemically activated cyclohexene is as follows: (1) isotopic labeling studies implying a symmetric intermediate, (2) a pressure-dependent ratio of cyclohexene to butadiene and ethylene, (3) good agreement between experimental and calculated values for the unimolecular rate constant for retro-Diels-Alder decay of ''hot'' cyclohexene. A comprehensive mechanism for the unimolecular decay of bicyclopropyl is proposed. The important elements of this mechanism are a single first-formed 1,3 biradical common to all products and the intervention of chemical activation in the generation of several of the secondary products.
- DOE Contract Number:
- AC02-80ER10592
- OSTI ID:
- 6347381
- Journal Information:
- J. Org. Chem.; (United States), Journal Name: J. Org. Chem.; (United States) Vol. 47:25; ISSN JOCEA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400303* -- Organic Chemistry-- Isotope Exchange & Isotope Separation-- (-1987)
ALKENES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CYCLOALKENES
DECOMPOSITION
DEUTERIUM
ENTHALPY
HYDROCARBONS
HYDROGEN ISOTOPES
INFRARED SPECTRA
ISOTOPES
ISOTOPIC EXCHANGE
KINETICS
LABELLING
LIGHT NUCLEI
NUCLEI
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
PHYSICAL PROPERTIES
PYROLYSIS
REACTION KINETICS
SPECTRA
STABLE ISOTOPES
THERMOCHEMICAL PROCESSES
THERMODYNAMIC PROPERTIES