Infrared photochemistry of oxetanes: mechanism of chemiluminescence

Journal Article · Wed Feb 19 04:00:00 EST 1986 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00264a033· OSTI ID:6962018

Farneth, W E; Johnson, D G

The infrared multiphoton (IRMP) induced photolysis of several oxetanes is examined at low pressures (ca. 100 mtorr) while experimental variables such as laser frequency, laser energy, bath gas, and bath gas pressure are altered. The products of the IRMP induced photolysis of 2-acyl-3-ethoxy-2-methyloxetane, Ox1, are primary biacetyl and ethyl vinyl ether. When the photolysis is run with the collimated beam of a CO/sub 2/ laser (1-3 J/cm/sup 2/) luminescence is observed. The intensity of the luminescence varies with the efficiency of the unimolecular decomposition of the oxetane. On the basis of the spectral distribution and temporal behavior of the luminescence following irradiation of Ox1, the emitter is believed to be vibrationally hot electronically excited biacetyl. Similar experiments with 2,2-dimethyl-3-ethoxyoxetane give a weaker emission apparently due to excited-state acetone. Results are discussed in terms of the reverse of the Paterno-Buchi reaction - a diabatic retrophotocycloaddition. 52 references, 6 figures, 3 tables.

• Research Organization: Univ. of Minnesota, Minneapolis
• OSTI ID: 6962018
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:4; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
CHEMICAL REACTIONS
CHEMILUMINESCENCE
CHEMISTRY
DATA
DECOMPOSITION
ELECTROMAGNETIC RADIATION
ENERGY LEVELS
ETHERS
EXCITED STATES
EXPERIMENTAL DATA
HETEROCYCLIC OXYGEN COMPOUNDS
INFORMATION
INFRARED RADIATION
LASERS
LOW PRESSURE
LUMINESCENCE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PHOTOLYSIS
RADIATIONS