Catalysis of nucleophilic substitution reactions in supramolecular systems

The factors determining the catalytic effect of supramolecular systems on the nucleophilic substitution reactions are analyzed. The role of the structural and phase transitions of nanoaggregates in the catalytic mechanism are determined. The substrate specificity is shown for different structures of the supramolecular composition.     

Influence of the Structure of Cetyltrimethylammonium Bromide Based Microemulsions on Base Hydrolysis of Carboxylic Acid Esters

The structure of water/cetyltrimethylammonium bromide/n-butanol/hexane microemulsions was studied by conductometry, viscometry, and Fourier transform ¹H NMR spectroscopy with pulse magnetic field gradient. The regions of phase inversion from inverse micelles in hexane through a bicontinual structure to a dispersion of normal micelles in water were determined. The influence of the structure of the microemulsions on the rate of hydrolysis of carboxylic acid p-nitrophenyl esters was analyzed. The hydrolysis rate constants considerably increase in going from inverse to normal microemulsions.     

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.     

Basicities of phosphinylalkylamines in water and ethanol

Conclusions The pK_a values of various phosphinylalkylamines in water and ethanol were determined. The inductive effect of phosphinyl groups on the basicities of the investigated amines was demonstrated. The inductive constants of a series of substituents were estimated.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1265–1267, June, 1982.     

Hydrolysis of phosphorus acid esters in the sodium bis(2-ethylhexyl)sulfosuccinate—<Emphasis Type="Italic">n</Emphasis>-nonane—polyethylene glycol—water supramolecular system before and after the percolation threshold

The kinetics of alkaline hydrolysis of O-ethyl O-p-nitrophenyl chloromethylphosphonate in a sodium bis(2-ethylhexyl)sulfosuccinate—n-nonane—polyethylene glycol—water reverse micellar system was studied in a wide range of concentrations of the surfactant and water. The sign of the catalytic effect of micelles is inverted in the presence of the polymer. A sharp change in the apparent rate constant of hydrolysis of the phosphonate was found in a region of the temperature percolation threshold. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 60–67, January, 2007.     

Reactions of esters of tetracoordinated phosphorus acids with nucleophilic reagents in highly organized media

Characteristic features of reactions involving esters of phosphorus-containing acids in highly organized media (micelles, liquid crystals, vesicles, and emulsions) are surveyed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 298–312, February, 1996.     

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.     

Hydrolysis of bis(chloromethyl)phosphonic acid p-nitroanilide in aqueous micellar surfactant solutions

The hydrolysis of bis(chloromethyl)phosphonic acid p-nitroanilide has been studied in the pH range 6.86–13.0 and the effects of ionic surfactant micelles on this process have also been examined. The nature of the micellar effects of cetyltrimethylammonium bromide (CTAB) and sodium dodecylsulfate (SDS) on this reaction lead us to conclude that both the neutral and anionic forms of the substrate are reactive, and that in the range of pH > pK_a hydrolysis of the ionic form of the anilide predominates, while at pH < pK_a the reaction of the neutral form is predominant. The binding constants for both the neutral and anionic forms of bis(chloromethyl)phosphonic acid p-nitroanilide in micellar CTAB and SDS solutions have been determined using a kinetic method, as well as by measuring the changes in the acid-base properties of the substrate resulting from the influence of micelles.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1718–1722, August, 1990.     

Mixed micelles of cetyltrimethylammonium bromide and poly(ethylene glycol)-600 monolaurate as catalysts of polyethylenimine phosphorylation in chloroform

Micelle formation in a cetyltrimethylammonium bromide-poly(ethylene glycol)-600 monolaurate-chloroform system in the absence and presence of hydroxybenzylated polyethylenimines (PEI) was studied by dielcometric titration, NMR self-diffusion, light scattering, and kinetic methods. A catalytic effect of mixed micelles on the reaction of 4-nitrophenylbis(chloromethyl)phosphinate with PEI was shown. The catalytic effect depends on the degree of substitution of PEI and composition of a surfactant mixture. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1359–1365, August, 2006.