The reactivity of phosphonic esters in aqueous micellar solutions of cationic surfactants

The micellar effect of cationic surfactants in alkaline hydrolysis of O-alkyl-O-aryl-chloromethyl phosphonates involves a positive contribution of concentrating the reagents and a negative effect of the micellar environment due to a loss in the activation entropy. The reactivity of substrates in micelles depends on both electronic and hydrophobic characteristics of substituents in the aryl group.     

Influence of temperature on the reactivity of phosphorus acid esters in reverse micellar systems based on sodium bis(2-ethylhexyl)sulfosuccinate

A change in the reactivity of ethyl p-nitrophenyl chloromethylphosphonate in the sodium bis(2-ethylhexyl)sulfosuccinate-n-nonane-water system around the percolation threshold was found. Study of location sites of the reactants by NMR self-diffusion and optical spectroscopy and modeling of the kinetic data in terms of the pseudophase approach demonstrated that below the percolation threshold, the reaction occurs in the surface layer. The observed rate constant for substrate hydrolysis in a microemulsion below the percolation threshold is described by the Arrhenius equation, like that in aqueous solutions. Above the percolation threshold, the slope of the Arrhenius plot sharply changes, which is apparently due to a change in the reactant location pattern and, hence, the microscopic properties of the medium in the region of their solubilization. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1407–1414, June, 2005.     

Catalytic activity of aminomethylated calix[4]resorsinolarene aggregates in hydrolysis of esters of phosphorus acids

The reaction kinetics of aminomethylated calix[4]resorcinolarenes (AMC) withp-nitrophenyl esters of phosphorus acids (EPA) in a water—DMF solution (30 vol.% DMF) was studied by spectrophotometry and³¹P NMR spectroscopy in the presence and absence of the nonionic surfactant Triton X-100. The AMC form aggregates of micellar and nonmicellar types and are the catalysts for EPA hydrolysis. The catalytic activity of the aggregates depends on their structure, pH of the medium, and the nature of the solvent. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1361–1365, August, 2000.     

Control of the catalytic effect of cetyltrimethylammonium bromide micelles by the addition of background electrolyte and nonionic surfactant

The variation of the microscopic properties (surface potential, micropolarity, etc.) of the interface of cetyltrimethylammonium bromide micelles upon the addition of a background electrolyte or the nonionic surfactant Triton X-100 decreases the rates of ion-molecular reactions, namely, alkaline hydrolysis of carboxylic acid esters and tetracoordinate phosphorus acid esters, and results in the shift of acid-base equilibria. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1933–1940, October, 2007.     

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.     

Catalytic hydrolysis of phosphate esters in microemulsions

We have continued our kinetics investigation of the iodosobenzoate (IBA) catalysis of the hydrolysis of p-nitrophenyl diphenyl phosphate (PNDP), in microemulsion media composed of hexadecane in water stabilized by cetyltrimethylammonium bromide and 1-butanol over a range of water mass fractions. We have examined two iodosobenzoic acid derivatives (5-nitro-2-iodosobenzoic acid and 5-octyloxy-2-iodosobenzoic acid) as catalysts. In addition, we have determined by³¹P FT-NMR techniques that the major product of the hydrolysis of PNDP, both in IBA catalyzed and in uncatalyzed media, is diphenylphosphate.     

Interaction between primary aliphatic amines and carboxylic acid esters in aqueous micellar solutions of cationic surfactants

The effects of cetylpyridinium bromide (CPB) on the acid-base equilibria of primary aliphatic amines and on the kinetics of reactions of the amines withp-nitrophenyl acetate (PNPA) andp-nitrophenyl caprylate (PNPC) were studied by potentiometric titration and UV spectroscopy. The values of apparent pK _a of the amines in the micellar phase, binding constants of their neutral forms, and the surface potentials of micelles were determined. Cetylpyridinium bromide accelerates the aminolysis of PNPA by factors of 3 to 8 by forming mixed micellar aggregates with the amines. The shift of pK _a values of the amines in micellar solutions is not the only factor that enhances their reactivity. The substrate specificity was found: in contrast to the reaction with PNPA, CPB accelerates (by factors of 15 to 65) or retards (by factors of 4 to 6) the aminolysis of PNPA depending on the hydrophobicity of the nucleophilic reagent. The binding constants of substrates, the rate constants in the micellar phase, and the critical concentrations of micellization were determined from the data obtained. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1333–1338, July, 1998.     

The influence of the structure of tetracoordinate phosphorus acid esters on the catalytic effect of the sodium dodecyl sulfate-hexanol-water ternary reverse micellar system

The catalytic effect of the sodium dodecyl sulfate-hexanol-water ternary reverse micellar system in the alkaline hydrolysis ofO-alkylO′-aryl chloromethylphosphonates as a function of the substrate structure was studied. The micellar effect is mainly determined by a change in the electronic properties of the substituents, while the hydrophobicity plays a secondary role. The kinetic data were examined in the framework of the pseudo-phase model of micellar catalysis. The rate constants of the reaction in the surface layer and the partition constants of the reactants were calculated. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1366–1370., August, 2000.     

阳离子表面活性剂金属胶束作为模拟磷酸酯水解酶的研究

在模拟水解酶的研究中,模拟模型中配体的功能已经受到普遍重视,冠醚是外腔疏水而内腔亲水的物质,因此已被用作模拟水解酶模型中的配体。这些模型可以分为两类,一是金属离子镶嵌在冠醚环中所形成的穴状配合物模型,二是以冠醚基作为支链的冠醚化Schiff碱配合物。穴状配合物模型作为模拟水解酶用于催化磷酸酯的研究已经取得了一定的进展。     

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.     

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.     

Kinetics of alkaline hydrolysis of esters of phosphorus acids in micellar and hexagonal phases in the cetyldimethylethylammonium bromide—NaOH—water system

The influence of micellar (Mi) and hexagonal (E) mesophases of the cetyldimethylethylammonium bromide—NaOH—water system (I) on the rates on alkaline hydrolysis ofO-p-nitrophenyl-O,O-diethyl phosphate (2),O-p-nitrophenyl-O-ethylethyl phosphonate (3), andO,O-di(p-nitrophenyl)methyl phosphonate (4) was studied by UV spectrophotometry. The binding constants of the substrates, critical micelle concentrations, and rate constants of reactions in the micellar phase were determined. In micellar solutions of systemI, a tenfold increase in the rates of alkaline hydrolysis of2–4 was observed. An increase in the degree of medium ordering during the formation of the E-phase results in a twofold acceleration of alkaline hydrolysis of2 and3 and in the inhibition of this process in the case of4. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1499–1504, August, 1998.     

Kinetics of the transesterification of para-nitrophenyl esters of phosphorus acids in water and aqueous hexamethylphosphorotriamide

The rate constants for the substitution of the para-nitrophenoxide ion by the phenoxide and hydroxide ions in phosphates and phosphonates are enhanced upon the addition of hexamethylphosphorotriamide (HMPTA) to water. The lack of alkaline hydrolysis of the esters in 90% aqueous HMPTA containing PhONa is a consequence of the formation of the PhOH... OH complex, which is nonreactive.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Science Center, Russian Academy of Sciences, 420083 Kazan. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 456–459, February, 1992.     

Electrochemical synthesis of phosphorus esters from white phosphorus in the presence of copper complexes and ethanol

In the presence of white phosphorus the redox potentials of the copper ions change and the potential of the reduction wave of Cu^I/Cu⁰ shifts noticeably toward more positive values. The Cu^I—P₄ complex is characterized by a lower value of the electrochemical gap, that is, higher polarizability and reactivity compared to those of the free Cu^I cation. Phosphorus esters can be synthesized from P₄ and ethanol. The latter is in the composition of the copper(ii) complexes, which act as a catalyst-charge mediator.     

The effect of cyclodextrins on the hydrolysis of carboxylic acid esters

Cyclodextrins and their derivatives act as inverse phase-transfer catalysts in the hydrolysis of carboxylic acid esters. The reaction is affected by temperature, choice of cyclodextrin and also by the stirring rate. Lipophilic esters are better hydrolyzed under inverse phase-transfer catalysis conditions than under classic phase-transfer catalysis (PTC) conditions. Some typical features of the reaction are emphasized and compared with classical PTC reactions.     

The effect of self-association on the reactivity of calix[4]resorcinolarene anions with respect to esters of phosphorus acids

The kinetics of reactions of amphiphilic anions derived from calix[4]resorcinolarenes and their aggregates withp-nitrophenyl esters of phosphorus acids were studied by spectrophotometry. The effect of hydrophobicity of the substituent R and of the composition of aqueous dimethylformamide solvent (30, 50, 80% (v/v) DMF) on these processes was investigated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 275–279, February, 1998.     

A nucleophilic substitution reaction in microemulsions based on either an alcohol ethoxylate or a sugar surfactant

A nucleophilic substitution reaction between 4-tert-butylbenzyl bromide and a series of iodide salts has been performed in oil-in-water microemulsions based on either a fatty alcohol ethoxylate or a sugar surfactant. The reaction kinetics was compared with the kinetics of the same reaction performed in a microhomogeneous reaction medium, d-MeOH. Previous results showing a particularly high reactivity in the microemulsion based on the fatty alcohol ethoxylate was confirmed. It was shown that in both microemulsions the reaction rate was almost independent of the choice of counterion to iodide. This indicates that complexation of the cation with the surfactant headgroup, which, in particular, could have taken place with surfactants containing oligooxyethylene chains (a “crown ether effect”), seems not to be of importance.

¹²⁷I NMR studies, as well as quadrupole splitting experiments performed by ²H NMR, indicate that there is a certain accumulation of iodide at the oil–water interface of the microemulsions. It is difficult to draw any quantitative conclusions in this respect, however.

The results obtained in this study, combined with results from previous investigations of the same reaction, indicate that the unexpectedly high reactivity obtained in the microemulsion based on a surfactant containing an oligooxyethylene headgroup is most probably due to the nucleophile being poorly solvated when present in the headgroup layer of such a microemulsion. Poorly solvated anions are known to be highly reactive nucleophiles.     

The effect of electrolytes on the reaction rates and acid-base equilibria in ionic micelles

The influence of a number of electrolytes on the micellar effect of cetyltrimethylammoniurn bromide (CTAB) in the hydrolysis ofp-nitrophenyl acetate (1) and bis(p-nitrophenyl) methylphosphonate (2) and in the course of the acid-base dissociation of thep-nitroanilide of bis(chloromethyl)phosphinic acid (3) has been examined. The activity of the salts studied increases in the following order: MeCOOK2CO₃3<p-MeC₆H₄SO₃K. It has been found that in the presence of electrolytes the catalytic effect of CTAB micelles in the hydrolysis reactions of esters1 and2 decreases, and the pK _a value of anilide3 increases. The results obtained are interpreted in terms of the pseudophase model of micellar catalysis. The analysis of the experimental data carried out using logarithmic coordinates revealed a relationship between phase transitions in micellar catalysis and in micellization.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1396–1400, August, 1993.     

The micellar effect of the sodium bis(2-ethylhexyl)sulfosuccinate—decane—water reverse system on the hydrolysis of phosphonic acid esters

The reactivity of alkyl aryl chloromethylphosphonates in alkaline hydrolysis in the sodium bis(2-ethylhexyl)sulfosuccinate—decane—water reverse micellar system is mainly determined by the electronic properties of substituents and depends only slightly on their hydrophobicity. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1712–1715, October, 2000.     

Protolytic properties and reactivity of aminomethylated calix[4]resorcarenes in reactions with esters of phosphorus acids

The acid-base properties and the kinetics of reactions of aminomethylated calix[4]resorcarenes (AMC) withp-nitrophenyl esters of phosphorus acids in aqueous solutions of propan-2-ol (80 vol.% PrⁱOH) were studied by potentiometry, UV spectrophotometry, and³¹P NMR spectroscopy. The effect of the length of the hydrocarbon radical and substituents at the nitrogen atom on the protolytic properties and reactivity of AMC was studied. The reactions studied occur in two stages. At the first stage, phosphorylated AMC are formed, which are hydrolyzed to the corresponding acids at the second stage. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 456–461, March, 1999.