R. N. Zaripov

Kinetics of copper(II)-catalyzed cyclopropanation of olefins

Kinetics of the copper(II) acetylacetonate-catalyzed cyclopropanation of styrene and 2,5-dimethylhexa-2,4-diene is reported. A kinetic analysis of a catalytic olefin cyclopropanation scheme is suggested.

Kinetics of oxidation of alkanes and their derivatives byn-decanepersulfonic acid

The kinetics of interaction ofn-decanepersulfonic acid with linear, branched, and substituted hydrocarbons was studied. The oxidation ofcyclo-C6H12/C6D12 occurs with a moderate kinetic isotope effect,kH/kD=2.2±0.3. A satisfactory correlation between the partial rate constants and the structure of hydrocarbons in terms of the Okamoto-Brown equation was found.

THE KINETICS OF ACID-CATALYZED DECOMPOSITION OF DECANEPERSULFONIC ACID

The kinetics of thermal decomposition of decanepersulfonic acid (RSO2OOH, R=C10H21) in CCl4 in the presence of cyclohexanesulfonic and trifluoroacetic acids at 323–343 K was studied. The reaction has an autocatalytic character. The kinetics of consumption of the persulfonic acid is described by the equation-d[RSO2OOH]/dt=k1[RSO2OOH]+k2[RSO2OOH]·[HX].

The Kinetics of Thermal Decomposition of Acetyl-cyclo-hexylsulfonylperoxide

The kinetics of the decomposition of acetyl-cyclo-hexylsulfonylperoxide (SP, RS(O2)OOC(O)CH3, R = cyclo-C6H11) was studied in a C6H4Cl2 solution in an O2 atmosphere at 323–353 K and in an Ar atmosphere at 323–343 K. The rate constants of SP monomolecular decomposition (k1) and SP reaction with CH3· radicals (k3) were determined. The temperature dependences of these rate constants are described by equations log k1 = (14.5 ± 2.9) – (115.4 ± 19.0) – (2.3RT) and log k3= (11.6 ± 2.2) – (44.6 ± 14.2)/(2.3RT), where the activation energies are expressed in kJ/mol.

Effect of the solvent on the kinetics of thermal decomposition of acetylcyclohexylsulfonyl peroxide

The kinetics of the decomposition of acetylcyclohexylsulfonyl peroxide (ACSP) in CCl4, benzene, toluene, ethylbenzene, cumene, acetonitrile, ethanol, and 2-propanol in an atmosphere of O2 were studied at 40–70 °C. The rate constants (k0) and activation parameters of the monomolecular decomposition of ACSP were determined. A linear dependence between logA0 and activation energyE0 (compensation effect) was established. The dependence ofk0 on the nature of a solvent is described by the four-parameter Koppel-Palm equation.

Induced decomposition of acetylcyclohexylsulfonyl peroxide

The kinetics of thermal decomposition of acetylcyclohexylsulfonyl peroxide is studied in an-decane solution in an oxygen atmosphere (303–333 K) and under anaerobic conditions (313–333 K); the reaction products are also studied in a cyclohexane solution under oxygenfree conditions (323 K). In the absence of oxygen, the reaction is found to proceedvia a chain-radical mechanism. Some kinetic parameters of the process are determined.

Kinetics of the reaction of decanesulfoperacid with SO2 in the presence of water

A study has been made of the kinetics of the oxidation of SO2 by decanesulfoperacid in the presence of water in a medium of CH3CN. Retardation of the process by acids has been observed, the retarding effect decreasing with decreasing strength of acid. A mechanism for the reaction has been suggested which explains the experimental results obtained.

Hydroxylation of saturated hydrocarbons by alkanesulfonic peracids

Trifluoroperacetic acid oxidizes hydrocarbons, containing secondary and tertiary CH bonds, to the corresponding alcohols under mild conditions in high yield [ i]. In the present work, we were the first to show that alkanesulfonic peracids, RSO~H, which are available intermediates in the sulfooxidation of saturated hydrocarbons [2], are also efficient hydroxylating reagents for saturated hydrocarbons (rH).