Dealkylation ofpara-nitrophenyldimethyl thiophosphate in micellar and liquid-crystalline media of then-decylammonium chloride-n-decylamine-water system

The kinetics of decomposition of p-nitrophenyldimethyl thiophosphate (1) were investigated spectrophotometrically in the n-decylammonium chloride-n-decylamine-water system (DAC-DA-H₂O), in which micellar or lamellar liquid-crystalline phases are formed as a function of the concentration of components. It was shown that1 is dealkylated in both phases. An increase in the surface charge density of associates decreases the rate of dealkylation. The activation energy in the lamellar phase is significantly higher than in the micellar phase.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center, Russian Academy of Sciences, 420083 Kazan'. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1042–1048, May, 1992.     

Calculation of the enthalpy of formation of polyatomic molecules in the CNDO/2 approximation

Conclusions By taking the nonvalence interactions into account when determining the enthalpies of formation of polyatomic molecules in the CNDO/2 approximation it becomes possible to noticeably improve the agreement of theory with experiment.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1157–1159, May, 1978.     

Reaction of Methyl Diazoacetate with Amines Catalyzed by Ru<Subscript>2</Subscript>(OAc)<Subscript>4</Subscript>Cl

Reactions of primary and secondary amines with methyl diazoacetate in the presence of Ru₂(OAc)₄Cl gave the corresponding N-substituted glycine methyl esters in almost quantitative yield. Catalytic decomposition of methyl diazoacetate generates methoxycarbonylcarbene which is inserted into the N-H bond of amines with high regioselectivity.     

Coprecipitation of titanium(IV) and Iron(III) complex salts from peroxide-fluoride solutions

Because the salts (NH₄)₃TiO₂F₅ and (NH₄)₃FeF₆ are isostructural, precipitation of the titanium peroxy salt from the (NH₄)₂TiF₆-(NH₄)₃FeF₆-NH₄F-H₂O₂ system is accompanied by crystal-chemical substitution of ions. As a result of partial peroxolysis, the iron salt coprecipitates with ammonium peroxypentafluorotitanate. If the degree of precipitation is higher than 20%, TiO₂ samples of high whiteness can be prepared from the hydrolysis product isolated from such solutions, after annealing at 850°C.     

The catalytic effect of the cationic surfactant-polyethylene imine-water system in the hydrolysis ofO-alkylO-p-nitrophenyl chloromethylphosphonates

The kinetics of the hydrolysis ofO-alkylO-p-nitrophenyl chloromethylphosphonates in the cationic surfactant—polyethylene imine—water system was studied. The catalytic effects of the nature of the surfactant and substrate and the surfactant—polyethylene imine ratio were found. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1510–1514, September, 2000.     

Influence of the fluoride ion on the aggregation and catalytic properties of micellar solutions of cetyltrimethylammonium bromide

The influence of the fluoride ion on the aggregation behavior and catalytic properties of neutral and alkaline aqueous solutions of cetyltrimethylammonium bromide in nucleophilic substitution reactions of phosphorus acid esters was studied by tensiometry, small-angle neutron scattering, and UV spectrophotometry. The critical micelle concentrations and the radii, aggregation numbers, and shape of micelles forming in these systems, as well as the kinetic parameters of the nucleophilic substitution reactions of phosphorus acid esters, were determined.     

Micellar,Liquid Crystalline and Polymer Systems Based on Surfactant and Polyethylene Imine as Nanoreactors for the Transfer of Phosphoryl Group

Abstract

In the kinetic study of the hydrolysis of p-nitrophenyl alkyl chloromethylphosphonates and p-nitrophenyl diphenyl phosphate in the cationic surfactant-polyethylene imine-water system the dependence of the catalytic effect of the system on the nature of surfactants and substrates and the surfactant-polyethylene imine ratio was found. An appearance of liotropic mesophase in the surfactant -polymer solutions results in alteration in the reactivity of the substrates.     

The effect of a liquid crystal medium on the decomposition ofρ-nitrophenyl dimethylthiophosphate

The lamellar liquid crystal meso phase formed in the cetyltrimethylammonium bromide-1-hexanol-water system assists the reaction of p-nitrophenyl dimethyl thiophosphate with a charged nucleophile (hexanolate anion) and uncharged nucleophile (ethylenediamine) with the loss of the p-nitrophenylmethylthiophosphate anion, i.e., the reaction at the carbon atom and not at the phosphorus atom.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1165–1167, May, 1990.