E. M. Kasymova

New P-Containing Linear and Macrocyclic Polyphenols

Abstract We synthesized new phosphorus-containing linear and macrocyclic polyphenols using organic compounds containing phosphorus-carbon bonds and the phosphorus atom of various coordination, and also with reactive acetal, aldehyde, vinylethoxy, and methylene quinone fragments as starting materials. These achievements are briefly summarized.

Alkylated polyethyleneimine-cationic surfactant-calix[4]resorcinarene-chloroform catalytic system

The kinetics of phosphorylation of alkylated polyethyleneimine in chloroform in the presence of cationic surfactants with a cyclic or bicyclic head group and alkylated calix[4]resorcinarenes has been investigated by UV spectrophotometry. The catalytic activity of individual and mixed solutions of the amphiphilic admixtures depends on the structure of the constituents of the composition, on their concentrations in the solution, and on their relative amounts. In the presence of a calixarene, a decrease in the surfactant and polymer concentrations enhances the catalytic effect of the system.

Phosphorylation of polyethyleneimine in the solutions of calyx[4]resorcinolarene and its mixture with the surfactant

Phosphorylation of alkylated polyethyleneimine in chloroform in the presence of alkylated calyx[4]-resorcinolarenes with 2-hydroxyethoxy- and phosphorus-containing substituents and cetyl(3-hydroxypropyl)-dimethylammonium bromide was studied by means of the UV spectrophotometry. It was found that the character and the degree of the effect of calyxarene and its mixture with the surfactant depend on the hydrophobicity of macroring and the ratio of concentrations of components in the solution. The increase in the content of calyxarene and decrease in the concentration of polymer leads to the transformation of the catalytic action into the inhibiting one.

Reaction of dichloronitrobenzofuroxanes with amines and their derivatives

Reactions of 4,6-dichloro-5,7-dinitrobenzofuroxane and 4,6-dichloro-5-nitrobenzofuroxane with some aliphatic amines were studied. In the reaction of 4,6-dichloro-5,7-dinitrobenzofuroxane with 2,2-dimetoxyethylmethylamine the monosubstituted product was formed for the first time. In the reactions of 4,6-dichloro-5-nitrobenzofuroxane with amines substitution only of one chlorine atom takes place.

2,6-Dinitrobenzofuroxanes containing aminoacetal fragments

Substituted benzofuroxanes present undoubted interest as biologically active compounds [1]. Therefore, introduction of functional groups providing possibilities for further structural modification of benzofuroxanes is an important problem. In thise connection of great interest are halogen-containing dinitrobenzofuroxanes. They can be used as starting biulding blocks. Recent studies of the reaction of 5,7-dichloro4,6-dinitrobenzofuroxanes with aromatic amines showed that substitution of chlorine at the C carbon atom proceeds in the first turn, and the resulting mixture contains monoand disubstituted products [2, 3]. With the purpose to prepare benzofuroxanes containing reactive acetal fragments, we have studied the reactions of 5,7-dichloro-4,6-dinitrobenzofuroxane (I) and 5,7-dibromo-4,6-dinitrobenzofuroxane (IV) with (2,2-dimethoxyethyl)(methyl)amine II.

New polyethers on the calix[4]resorcinarene platform

Presently calixarene chemistry attracts a wide attention of researchers. This is due to the fact that functionalized derivatives of calixarenes are of undoubted interest as complexing agents, metal extractants, polymer stabilizers [1–3]. An important feature of these compounds is the ability to form complexes of guest-host type with various organic substances and metal ions [3]. Recently we developed a synthesis method of calixarenes containing hydroxyethyl groups on the upper molecule rim, which are promising initial compounds for preparation of new type receptors on the calixarene matrix. This method involved acide-catalized condensation of 1,3-bis(2hydroxyethoxy)benzene with aliphatic aldehydes [4]. Aiming at examining the possibilities of calixarene Ia and Ib functionalization we studied their reactions with acetic anhydride and bromine. The acylation of calixarenes was carried out by the hours-long heating of the reaction mixtures. The bromination of calixarenes Iа and Ib was performed using a mixture of bromine and triethylphosphine in anhydrous acetonitrile according to the procedure tested earlier on the hydroxyethylated resorcinol [5]. The obtained calixarenes IIa, IIb, IIIа, IIIb are soluble in polar organic solvents. Their structures were determined by the Н, С NMR, and IR spectroscopy; their composition was proved by the elemental analysis data. DOI: 10.1134/S1070363210020295

Synthesis and some properties of tetrakis-3,5-di-tert-butyl-4-hydroxybenzylated calix[4]resorcinols

A method for the synthesis of new calix[4]resorcinols tetra-3,5-di-tert-butyl-4-hydroxybenzyl derivatives is developed. Their interaction with methyldichlorophosphonate, dimethyldichlorosilane in the presence of a base leads to formation of organophosphorus-organosilicon cavitands. Acetylation of hydroxybenzylated calix[4]resorcinols with acetic anhydride leads to products of either incomplete or full acetylation depending on experimental conditions.

Reactions of 4-acylresorcinol derivatives with 3,5 -di -tert -butyl -4 -hydroxybenzyl acetate

Reactions of hydroxyphenylcarbonyl derivatives with 3,5-di-tert-butyl-4-hydroxybenzyl acetate under mild conditions gave novel functionalized diarylmethanes.

Reaction of rhodium trichloride with oxyethylated calix[4]resorcinarene

Reaction of rhodium trichloride with a new ligand, oxyethylated calix[4]resorcinarene was examined in an inert atmosphere in different solvents (acetone, acetone + chloroform). The product was characterized by IR, Raman, 1H NMR, ESR, ESCA spectroscopy, conductometry. Its composition was proved by the data of elemental and X-ray fluorescent analyses. The solvent used does not affect the composition of the product but only its yield. The structure of the coordination node and the type of coordination of the rhodium-containing fragment was investigated by calculating the model molecules of the ligand and the complex using the molecular mechanics method (MM+).