Dioxetane chemiluminescence. The effect of deuterium substitution on the thermal decomposition of trans-3,4-diphenyl-1,2-dioxetane
trans-Diphenyl-1,2-dioxetane was prepared by cyclization of the corresponding ..beta..-bromohydroperoxide. Thermal decomposition of this compound proceeds with an activation energy of 23.6 +- 1.6 kcal/mol to yield benzaldehyde, 10 +- 2% of which was in an excited triplet state. The effects of replacement of a dioxetane ring proton with a deuterium were investigated. No detectable partitioning between electronically excited protio- and deuteriobenzaldehyde was detected. The secondary deuterium isotope effect on the rate of thermal decomposition of this dioxetane was found to be 1.01 +- 0.02. We suggest that the absence of an isotope effect is consistent with a stepwise decomposition for 1,2-dioxetanes.
- Research Organization:
- Univ. of Illinois, Urbana
- OSTI ID:
- 7087552
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 99:16; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400302* -- Organic Chemistry-- Isotope Effects-- (-1987)
ACTIVATION ENERGY
CHEMICAL REACTIONS
DECOMPOSITION
DEUTERIUM
ENERGY
EPOXIDES
HYDROGEN ISOTOPES
ISOTOPE EFFECTS
ISOTOPES
LIGHT NUCLEI
NUCLEI
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
PYROLYSIS
STABLE ISOTOPES