Aminolysis ofO-alkylO-4-nitropyenyl chloromethylphosphonates in reverse micellar solutions of the nonionic surfactant

The reaction ofn-hexylamine withO-alkylO-4-nitrophenyl chloromethylphosphonates in toluene solutions of poly(ethylene glycol)-600 monolaurate (PM) has been studied by spectrophotometry. The reverse micelles of the nonionic surfactant increase more than tenfold the observed rate constant of aminolysis. The catalytic activity of the surfactant is practically independent of the alkyl radical length of phosphonate. An increase in the concentration of amine results in a decrease in the catalytic efficiency. The character of the dependence of the rate constant on the concentration of PM is affected by the alkyl chain length of the substrate. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1735–1738, September, 1998.     

Application of the Monte Carlo Method to Modeling Kinetic Processes of Polyatomic Molecules and Clusters: III. Kinetics of Reversible Reactions of Polyatomic Molecules

The Monte Carlo simulations of the reversible isomerization is carried out. The rate constants for the forward and reverse reaction of dichloroethylene cis–trans isomerization are determined for a broad range of initial conditions. Its is shown that the mutual effect of two actively interacting reactions occurring with energy exchange leads to a number of kinetic features of the process: characteristic changes in the rate constants during the process and the dependence of the equilibrium values of rate constants on pressure. The physical nature of these features associated with the disturbance of the function of distribution over vibrational energy due to the reaction is discussed.     

Inverse Micellar Catalysis of Phosphorylation of Hydroxybenzylated Polyethylenimines

The aggregation in polyethylenimine-chloroform and cetyltrimethylammonium bromide-polyethylenimine-chloroform systems is studied by dielcometric titration. Inverse micelles of cetyltrimethylammonium bromide catalyze the phosphorylation of hydroxybenzylated polyethylenimines in chloroform. The dependence of parameters of the micelle-catalyzed reaction on the structure and concentration of polyethylenimine and on the reaction temperature is studied. The inverse micelles affect the complexation of polyethylenimines with 4-nitrophenol.     

Kinetics of alkaline hydrolysis of ethylp-nitrophenyl ethylphosphonate in the reverse micellar system: sodium dodecyl sulfate-hexanol-water

The kinetics of alkaline hydrolysis of ethylp-nitrophenyl ethylphosphonate in the reverse micellar system sodium dodecyl sulfate—hexanol—water was studied. At high pH and low water content, the process occurs at the surface layer and can satisfactorily be described by the pseudo-phase model equation. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp 262–266, February, 2000.     

Application of the Monte Carlo Method to Modeling Kinetic Processes of Polyatomic Molecules and Clusters: II. Kinetics of Unimolecular Reactions of Polyatomic Molecules

The method for statistical modeling of the kinetics of unimolecular decomposition of polyatomic molecules based on the construction of nonequilibrium functions of the distribution over the energies of the vibrational excitation of molecules is developed. The rate constants for the two-channel decomposition of a model molecule depending on temperature and pressure are reported. The relaxation characteristics for the dissociation of the model molecule are determined.     

Micelle-Forming and Catalytic Properties of n-Alkyl(2-hydroxyethyl)dimethylammonium Bromides in the Phosphorylation of Tetrakis(dimethylaminomethyl)calixresorcin[4]arene

Micelle formation by n-alkyl(2-hydroxyethyl)dimethylammonium bromides in chloroform was studied by dielcometric titration and kinetic method. Increase in the length of the hydrocarbon chain leads to reduced critical micelle concentration. The region of structural reorganization of micelles was determined. n-Alkyl(2-hydroxyethyl)dimethylammonium bromides catalyze phosphorylation of tetrakis(dimethylamino- methyl)calixresorcin[4]arene. The catalytic activity of micelles depends on the hydrophobic properties and concentration of the surface-active substance, as well as on structural features of its aggregates.     

The inverted micellar catalysis of the reaction of 2-aminomethylphenols with 4-nitrophenyl bis(chloromethyl)phosphinate

The parameters of the reaction ofpara-substituted 2-aminomethylphenols with 4-nitrophenyl bis(chloromethyl)phosphinate in toluene catalyzed by reversed micelles of polyethylene glycol-600 monolaurate depend on the nucleophile structure. The efficiency of the catalytic action increases in the series of substitutes C₉H₁₉ ⁱ<H<Cl. An increase in the catalytic activity of micelles in the region of structural rearrangement of micelle aggregates was observed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 275–278, February, 1999.     

Catalytic Effect of Reverse Micelles of a Cationic Surfactant on the Reaction of Calix[4]resorcinolarenes with 4-Nitrophenyl Bis(chloromethyl)phosphinate

The presence of the aminomethyl fragment in the calix[4]resorcinolarene molecule favors its phosphorylation in chloroform. Reverse micelles of (2-hydroxyethyl)dimethylpentadecylammonium bromide catalyze this reaction, the catalytic effect being dependent on the length of the hydrocarbon chain of a calixarene and detergent concentration.