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The kinetic regularities, products, and mechanism of the thermal decomposition of dimethyldioxirane. The contribution of molecular and radical reaction channels
被引:9
作者:
Khursan, SL
[1
]
Grabovskii, SA
[1
]
Kabal'nova, NN
[1
]
Galkin, EG
[1
]
Shereshovets, VV
[1
]
机构:
[1] Russian Acad Sci, Ufa Res Ctr, Inst Organ Chem, Ufa 450054, Russia
关键词:
dimethyldioxirane;
thermolysis;
kinetics;
reaction mechanism;
D O I:
10.1007/BF02495074
中图分类号:
O6 [化学];
学科分类号:
0703 ;
摘要:
The products and kinetics of the thermal decomposition of dimethyldioxirane (DMDO) were studied. The reaction proceeds via three parallel pathways: isomerization to methyl acetate, oxygen atom insertion into the C-H bond of a solvent molecule (acetone), and the solvent-induced homolysis of the O-O bond in the DM DO molecule. The contribution of the latter reaction channel is cn. 23% at 56 degrees C. The overall kinetic parameters of DMDO thermolysis in oxygen atmosphere were determined. The free radical-induced DMDO decomposition occurs in an inert atmosphere. The formal kinetics of this reaction was investigated. The mechanism of the DMDO thermolysis is discussed.
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页码:1338 / 1348
页数:11
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