Chemiluminescence in the infrared photochemistry of oxetanes: the formal reverse of ketone photocycloaddition

Journal Article · Wed Mar 21 04:00:00 EST 1984 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00318a074· OSTI ID:6139427

Farneth, W E; Johnson, D G

Oxetanes were prepared by the photochemical cycloaddition of biacetyl and acetone, respectively, with ethyl vinyl ether. The oxetanes were irradiated in the gas phase with the collimated beam of a grating-tuned CO/sub 2/ TEA laser. Reaction conditions employed 0.1 torr of oxetane and 1 J/cm/sup 2/ fluence with a beam dia of 6 mm, constant through the cell at a frequency of 969.15/cm. Progress of the reaction was followed by monitoring the pressure in the cell. For up to 25% conversion, the pressure data provide a good fit to a calculated first-order rate constant. The products were analyzed by gas chromatography and IR spectra. IR spectra show the growth of absorption features assigned to the ketone and olefin. The rate of photodecomposition of the oxetanes appears to respond, as expected from previous results, to changes in fluence, frequency, and bath gas pressure.

• OSTI ID: 6139427
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 106:6; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400500 -- Photochemistry
ACETONE
ALKENES
CARBON DIOXIDE LASERS
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CHEMILUMINESCENCE
CHROMATOGRAPHY
DATA
DECOMPOSITION
ELECTROMAGNETIC RADIATION
ETHERS
EXPERIMENTAL DATA
GAS CHROMATOGRAPHY
GAS LASERS
HETEROCYCLIC OXYGEN COMPOUNDS
HYDROCARBONS
INFORMATION
INFRARED SPECTRA
KETONES
KINETICS
LASER RADIATION
LASERS
LUMINESCENCE
MEDIUM VACUUM
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
PRESSURE DEPENDENCE
RADIATIONS
REACTION KINETICS
SEPARATION PROCESSES
SPECTRA
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
YIELDS