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1.
D. V. Kazakov A. I. Voloshin N. N. Kabal'nova V. V. Shereshovets V. P. Kazakov 《Russian Chemical Bulletin》1997,46(6):1089-1093
The reaction of dimethyldioxirane (1) with the RuII trisbipyridyl complex accompanied by chemiluminescence (CL) was studied. It is established that the intensity of CL and the
rate of its decay increase proportionally with the concentration of RuII. The bimolecular rate constant (k
2) of the reaction of1 with RuII was determined. The activation parameters (E
a and logA) for this reaction were calculated from the temperature dependence ofk
2. The excitation yield of RuII* (η
Ru
*
) was estimated. The quenching of RuII* by dioxirane was studied, and the bimolecular quenching constant and the coefficient of excitation regeneration were determined.
It was suggested that the catalysis of the decomposition of1 and the excitation of RuII occurvia a mechanism of chemically initiated electron exchange.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1138–1142, June, 1997. 相似文献
2.
D. V. Kazakov D. R. Khusnullina N. N. Kabal'nova S. L. Khursan V. V. Shereshovets 《Russian Chemical Bulletin》1997,46(10):1690-1693
The kinetics of the reaction between dimethyldioxirane and 2-methylbutane in acetone solutions were studied spectrophotometrically
at 25 °C. The radical-chain induced decomposition of dioxirane proceeding with the participation of the carbon-centered radicals
follows the first-order kinetic law. The reaction is inhibited by dioxygen. In the presence of O2, the dimethyldioxirane consumption is due to the homolysis of the O−O bond (at a rate constant of 6.3·10−4 s−1) followed by attack of the C−H bond of 2-methylbutane by the biradical formed. The rate constant of the reaction between
the alkyl radical and dimethyldioxirane was estimated.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1785–1788, October, 1997. 相似文献
3.
D. I. D'yachenko A. G. Mustafin V. V. Shereshovets N. N. Kabal'nova V. P. Kazakov I. B. Abdrakhmanov G. A. Tolstikov 《Russian Chemical Bulletin》1998,47(8):1611-1612
An unusual direction of the reaction of 2-(cyclopent-2-enyl)aniline hydrochloride with dimethyldioxirane was found: the formation
of two isomeric products,viz., 3- and 6-chloro-2-(cyclopent-2-enyl)anilines, was observed.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1654–1655, August, 1998. 相似文献
4.
S. L. Khursan S. A. Grabovskii N. N. Kabal'nova E. G. Galkin V. V. Shereshovets 《Russian Chemical Bulletin》2000,49(8):1338-1348
The products and kinetics of the thermal decomposition of dimethyldioxirane (DMDO) were studied. The reaction proceedsvia 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 DMDO molecule. The contribution of the latter reaction channel isca. 23% at 56°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.
Dedicated to Professor E. T. Denisov on the occasion of his 70th Birthday.
Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1344–1354, August, 2000. 相似文献
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Grabovskiy SA Antipin AV Ivanova EV Dokichev VA Tomilov YV Kabal'nova NN 《Organic & biomolecular chemistry》2007,5(14):2302-2310
Dimethyl- (DMD) and methyl(trifluoromethyl)-dioxiranes were used for oxyfunctionalization of spiro{1',7-cyclopropan-(E)-2-methylbicyclo[2.2.1]heptane} (), tricyclo[3.2.2.0(2,4)]nonane (), exo-endo-endo- () and exo-exo-exo- () heptacyclo[9.3.1.0(2,10).0(3,8).0(4,6).0(5,9).0(12,14)]pentadecane, yielding tertiary alcohols as the main products. The rate constants for oxidation of by DMD were measured and the Arrhenius parameters determined. The DFT theory (B3LYP and B3PW91) using restricted and unrestricted methods was employed to study the oxidation reaction of the C-H bond of cage hydrocarbons , adamantane, and acetone with DMD. The kinetic isotopic effect calculated using unrestricted methods agreed with experiment. The reaction mechanism in terms of the concerted oxygen insertion vs. the radical part is discussed. 相似文献
9.
D. V. Kazakov A. I. Voloshin N. N. Kabal'nova V. V. Shereshovets V. P. Kazakov 《Russian Chemical Bulletin》1996,45(10):2452-2453
Chemiluminescence (CL) was found upon the isomerization of dimethyldioxirane in the gas phase under argon atmosphere. The intensity of CL increases as temperature increases and decreases with time at constant temperature. If Silipor is placed in a cell containing the dimethyldioxirane vapor in argon, the intensity of CL sharply increases (more than 10 times) and then decreases following the exponential law. In all cases tripletly excited methyl acetate is the emitter of chemiluminescence.[/ p]Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2582–2583, October 1996. 相似文献
10.
Z. F. Akbalina N. N. Kabal'nova S. S. Zlotskii I. A. Grigor'ev S. A. Kotlyar V. V. Shereshovets G. A. Tolstikov 《Russian Journal of General Chemistry》2002,72(3):447-448
2,2,5,5-Tetramethyl-4-phenyl-3-oxo-35-imidazolin-1-yloxyl catalyzes oxidation of 2-isopropyl-1,3-dioxolane, 2-phenyl-1,3-dioxolane, 2-phenyl-4-chloromethyl-1,3-dioxolane, and 2-phenyl-1,3-dioxane with 15-crown-5 complexes of potassium chlorodiperoxochromate (KCrO5Cl·2C10H20O5) and potassium chlorochromate (KCrO3Cl·2C10H20O5). 2-Isopropyl-1,3-dioxolane is oxidized to the corresponding monoester in quantitative yield, and the 2-phenyl derivatives yield benzaldehyde. The spiro ketal, 2,2-pentamethylene-4-methyl-1,3-dioxane, is decomposed to cyclohexanone. 相似文献