Thermal decomposition of allylbenzene ozonide
- Louisiana State Univ., Baton Rouge (USA)
Thermal decomposition of allylbenzene ozonide (ABO) at 98{degree}C in the liquid phase yields toluene, bibenzyl, phenylacetaldehyde, formic acid, and (benzyloxy)methyl formate as major products; benzyl chloride is formed when chlorinated solvents are employed. These products, as well as benzyl formate, are formed when ABO is decomposed at 37{degree}C. When the decomposition of ABO is carried out in the presence of 1-butanethiol, the product distribution changes: yields of toluene increase, no bibenzyl is formed, and decreases in yields of (benzyloxy)methyl formate, phenylacetladehyde, and benzyl chloride are observed. The decomposition of 1-octene ozonide (OTO) also was studied for comparison. The activation parameters for both ABO and OTO are similar (28.2 kcal/mol, log A = 13.6 and 26.6 kcal/mol, log A = 12.5, respectively); these data suggest that ozonides decompose by homolysis of the O-O bond, rather than by an alternative synchronous two-bond scission process. When ABO is decomposed at 37{degree}C in the presence of the spin traps 5,5-dimethyl-1-pyrroline N-oxide (DMPO) or 3,3,5,5-tetramethyl-1-pyrroline N-oxide (M{sub 4}PO), ESR signals are observed that are consistent with the trapping of benzyl and other carbon- and oxygen-centered radicals. A mechanism for the thermal decomposition of ABO that involves peroxide bond homolysis and subsequent {beta}-scission is proposed. Thus, Criegee ozonides decompose to give free radicals at quite modest temperatures.
- OSTI ID:
- 6971148
- Journal Information:
- Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 111:15; ISSN 0002-7863; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
Similar Records
Ozonation of methyl oleate in hexane, in a thin film, in SDS micelles, and in distearoylphosphatidylcholine liposomes: yields and properties of the Criegee ozonide
Ozonides and epoxides from ozonization of pyrethroids
Related Subjects
400500* -- Photochemistry
54 ENVIRONMENTAL SCIENCES
540110
AMINES
ATMOSPHERIC CHEMISTRY
BENZOINOXIME
CHEMISTRY
DATA
DATA ANALYSIS
EXPERIMENTAL DATA
HYDROXY COMPOUNDS
INFORMATION
MEASURING INSTRUMENTS
MEASURING METHODS
MEDIUM TEMPERATURE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIMES
OZONE
THERMAL DEGRADATION