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.     

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.     

Nucleophilic Substitution in Carboxylic Esters in Oil-In-Water Microemulsions

In hydrolysis and aminolysis of p-nitrophenyl esters of carboxylic acids in oil-in-water microemulsions on the basis of surfactants of various nature, a complex mechanism of the effect of the medium is operative, including shift of acid-base equilibria in the nucleophile. The rate constants of the processes studied are quantitatively related to the surface potential of the microdroplet. Varied hydrophobicity of the nucleophile and substrate changes the site of the reaction act and the relative contributions of aminolysis and hydrolysis.     

The influence of micellization ofn-decylamine on its basicity and reactivity toward carboxylic acid esters

Micellization ofn-decylamine in aqueous solution leads to substantial decrease in its pK _a, and increase in its reactivity in the nucleophilic substitution ofp-nitrophenylic esters of carboxylic acids (up to 70 times compared to ethylamine which forms no micelles). The influence of cetylpyridinium bromide on the acid-base properties ofn-decylamine and its reactivity was investigated. It was found that the reaction withn-decylamine can be accelerated or retarded depending on the hydrophobicity of the esters. The quantitative characteristics of the mieellar catalytic processes were estimated.Translated fromIzvestiya Akademii Nauk Seriya Khimicheskaya, No. 2, pp. 366–370, February, 1996.     

Effects of solubilized dodecylamine on the microstructure of cetylpyridinium bromide-<Emphasis Type="Italic">n</Emphasis>-butanol-hexane-water system studied by pulsed-gradient spin echo NMR and ESR spin label methods

The effect of solubilized dodecylamine (DDA) on the structure of the cetylpyridinium bromide-n-butanol-hexane-water microemulsions has been studied by the Fourier-transform pulsed-gradient spin-echo¹H nuclear magnetic resonance and the electron spin resonance spin label method. The sample compositions were chosen to examine three different microemulsion structures: oil-in-water, water-in-oil and bicontinuous. In all systems the DDA molecules are shown to be incorporated into the oil-water interface, resulting in essential changes in the microemulsion structure. In the micellar systems the DDA emergence in the interface causes an increase of the micelle size and a redistribution of butanol and water between micelle and bulk phases. In the oil-in-water microemulsions of amine-containing systems the quantity of micellized butanol and water decreases. In the water-in-oil microemulsions the introduction of DDA leads to an increase of butanol and water involved in the micelle formation. The redistribution of butanol and water between polar and organic phases in the microemulsions would be expected to cause changes in the bicontinuous structure.     

Alkylation reaction of amines by dimethyl phosphite

The alkylation reaction kinetics of a series of amines of different structures by dimethyl phosphite have been studied. Two-parameter correlation equations have been deduced, relating reactivity to steric and inductive effects of substituent s attached to the nitrogen atom in the amine; a Swain-Scott equation has also been deduced, establishing a correlation between the rate of alkylation and the nucleophilicity of the reaction site. When steric conditions at the nitrogen atom are fixed, as in the case of orthoaminomethylphenols, the reactivity follows a Brönsted equation.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1129–1133, May, 1990.     

Aggregation behavior and solubilization properties of 3-hydroxypiperidinium surfactants

Russian Chemical Bulletin - Systematic data on the aggregation behavior of novel 3-hydroxypiperidinium surfactants in aqueous solutions were obtained. The ability of the surfactants to solubilize...     

Aggregation Behavior and Catalytic Action of Carbamate-Bearing Surfactants in Aqueous Solutions

Kinetics and Catalysis - The aggregation behavior of new cationic hexadecyl surfactants with one or two alkylcarbamate fragments in the head group in water was studied using conductometry,...     

Aggregation behavior of morpholinium surfactants in the presence of organic electrolytes

It was shown that the addition of organic electrolytes to aqueous solutions of morpholinium surfactants facilitates micellization, reduces the micellar surface potential, increases the hydrodynamic diameter of micelles and favors the formation of cylindrical micelles which behave as pseudoplastic fluids. At low shear rates, the viscosity is extremely large and changes insignificantly, and it decreases sharply with increase in shear rate. Significant decrease in viscosity upon the increase in shear deformations indicates the orientation of cylindrical micelles along the direction of the flow with the increase in shear rate.