Reactivity of 2-diethylaminomethylphenol and its copper(II) complex in the reaction with 4-nitrophenylbis(chloromethyl)-phosphinate

The kinetics of reactions of 2-diethylaminomethylphenol (I) and its Cu²⁺ complex (with a metal: ligand composition of 12) (II) with 4-nitrophenylbis(chloromethyl)-phosphinate have been studied in aqueous-ethanolic media (10–70 vol. % ethanol); bimolecular rate constants have been calculated for the reactions of different forms of compound (I) and complex (II). It was shown that compound (I) in aqueous-ethanolic media is a nucleophilic catalyst for hydrolysis of 4-nitrophenylbis (chloromethyl)-phosphinate. The reactivity of complex (II) is an order of magnitude greater than that of the zwitterion form of the ligand which exists in the same range of pH 7–9.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 555–560, March, 1991.     

Reaction of 2-alkylaminomethylphenols with 4-nitrophenyl-bis(chloromethyl)phosphinate in toluene micellar solutions of polyethylene glycol-600 monolaurate

The effect of polyethylene glycol-600 monolaurate (PEG-ML) reversed micelles on the reaction of 2-alkylaminomethylphenols (AMP) with 4-nitrophenyl-bis(chloromethyl) phosphinate in toluene has been investigated. PEG-ML increases the observed rate constant of the reaction by more than one order of magnitude. AMP concentration in solution affects the position of the maximum on the concentration dependence of the micellar-catalyzed-reaction rate constants. The reaction rate constant in the micellar phase and the binding constant of the substrate with micelles depend on the alkyl chain length and AMP concentration. Inhibition of the reaction studied is observed in the presence of high PEG-ML concentrations and low AMP concentrations.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2134–2138, December, 1994.     

Synthesis and Antibacterial Activity of 9-Oxo-9,10-dihydroacridinecarboxylic Acids Esters Bearing a Triazole Fragment

An effective method for the synthesis of new acridine-9(10H)-one (acridone) derivatives containing 1,2,3-triazole fragment was developed. A number of new triazole-containing compounds were synthesized from propargyl acridone acetate and their antimicrobial activity was studied.     

Reaction of p-menthadiene dioxide with hydrogen chloride

Conclusions When 1,2,8,9-diepoxy-p-menthane is reacted with HCl in ether under mild conditions, the 1,2-epoxy ring opens first in accordance with the conformational control of the reaction to form (–)-trans-2-hydroxy-1-chloro-8, 9-epoxy-trans-p-menthane from the cis dioxide or (–)-trans-1-hydroxy-2-chloro-8, 9-epoxy-trans-p-menthane from the trans dioxide. The opening of the 8,9-epoxy ring to form products of the addition of 2 moles of HCl takes place with difficulty.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 847–851, April, 1979.     

Aggregation of amphiphilic aminomethylated calix[4]resorcinarenes and the nonionic surfactant Triton-X-100 in organic solvents

Aggregation and intermolecular interactions of amphiphilic calix[4]resorcinarene (1), aminomethylated calix[4]resorcinarenes (AMC 2—7) with different structures of the upper rim (including the oxazine structure in 6 and 7) and hydrophobic substituents on the lower (2—5), upper (6), or both rims (7) in the absence and in the presence of the nonionic surfactant Triton-X-100 (8) and p-nitrophenol (9) in chloroform and 1,4-dioxane were studied by permittivity measurements and 2D ROESY ¹H NMR technique. The tendency of amphiphilic derivatives 1—7 toward self-aggregation and mixed aggregation with surfactant 8 primarily depends on the nature of both the solvent and the polar groups on the upper rim of calixarenes. In chloroform, AMC—8 aggregates show interactions of the methyl and methylene groups of the hydrophobic substituents of AMC with the ethyleneoxy fragments of surfactant 8, while in stable intermolecular complexes of 5 and 6 with compound 9, the methylene groups of the long-chain radicals of the AMC strongly interact with the aromatic protons ortho to the hydroxy group of 9. In 1,4-dioxane, calix[4]resorcinarenes 1 and 5 are bound in stable solvates, which prevents them from forming aggregates and mixed micelles.     

Hydrodynamic properties of rigid pyridine-containing poly(phenylene) dendrimers in solutions

The hydrodynamic properties of pyridine-containing polyphenylene dendrimers of the third and fourth generations in chloroform are studied by photon correlation spectroscopy and viscometry. It has been demonstrated that the hydrodynamic characteristics of these macromolecules in dilute solutions are similar to those of nondraining spheres. The hydrodynamic radius of these dendrimers is shown to be proportional to their molecular mass to a power of 1/3. It has been established that the macromolecules of the dendrimers under examination in solutions conserve the conformation and size over a wide temperature range. The detailed analysis of hydrodynamic data allowed a conclusion concerning an extremely low content of the polymer inside the equivalent sphere for the above dendrimers in solutions. The compounds of interest may be referred to as rigid dendritic systems.     

Phosphorylation of alkylated poly(ethyleneimine) in chloroform in the presence of cetyltrimethylammonium bromide and calix[4]resorcinarene

The phosphorylation of alkylated poly(ethyleneimine) with 4-nitrophenyl bis(chloromethyl)phosphinate in chloroform in the presence of cetyltrimethylammonium bromide (CTAB), calix[4]resorcinarene (CR), or their mixture was studied by UV spectrophotometry. The catalytic effect of CTAB and CR on the process of polymer phosphorylation was shown to depend on the concentration of the surfactant and poly(ethyleneimine) in solution. The catalytic effect of the system is ascribed to the formation of poly(ethyleneimine)-CTAB, poly(ethyleneimine)-CR, and poly(ethyleneimine)-CTAB-CR mixed aggregates. Their existence was confirmed by the methods of light scattering and UV spectroscopy. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 918–923, May, 2007.     

Aggregation and catalysis in a nonionic surfactant-polyethylenimine-chloroform system

The formation of polymer-colloid complexes (PCCs) of hydroxybenzylated polyethylenimines (PEIs) with poly(ethylene glycol-600) monolaurate (PM) in chloroform is established through dielcometric titration, light scattering, and viscometry. The effect of PCC on the PEI reactivity in phosphorylation with 4-nitrophenyl bis(chloromethyl)phosphinate is studied with spectrophotometry. It is found that the character of aggregates and the degree of their influence depend on the PM-to-PEI concentration ratio, polymer structure, and reaction temperature.     

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.