N. I. Kharitonova

Synthesis and properties of N-[2,2-bis(2,4-dihydroxyaryl)ethyl]-N-methylamines and their hydrohalides

Condensation of one molecule of α-methylaminoacetaldehyde dimethyl acetal with two molecules of resorcinol or methylresorcinol in hydrohalogen acid solutions led to substituted N-(2,2-diarylethyl)-N-methylamine hydrohalides. Reactions of the corresponding amines with acetic anhydride, mono-and diisocyanates, and formaldehyde were studied. Conditions for formation of calixarene from resorcinol and α-methylaminoacetaldehyde dimethyl acetal were invented.

Facile synthesis of 2-(2-arylpyrrolidin-1-yl)pyrimidines via acid-catalyzed reaction of N-(4,4-diethoxybutyl)pyrimidin-2-amine with phenols

N-(4,4-diethoxybutyl)pyrimidin-2-amine undergoes acid-catalyzed intramolecular cyclisation in the presence of phenols leading to the formation of 2-(2-arylpyrrolidin-1-yl)pyrimidine derivatives. Target compounds were obtained with moderate to good yields by operationally simple one-step procedure.Graphical abstract

Reaction of α-aminoacetals with 2-methylresorcinol

The main method of synthesis of calix[4-resorcinols is the condensation of resorcinol and its derivatives with aliphatic or aromatic aldehydes [1–3]. We have recently extended synthetic opportunities of this method by involvement into the reaction with resorcinol of phosphorylated acetals to obtain calix[4] resorcinols with phosphorylalkyl substituents at the lower rim of the molecule [4]. A special attention should be paid to their aminoalkyl analogs that can serve as primary compounds (due to involvement of amino groups) in the syntheses of new cavitands, container compounds, and nanotubes. For the synthesis of the calixarenes of this type we studied reaction of aminoacetaldehyde diethylacetal (Ia) and dimethylaminoacetaldehyde diethylacetal (Ib) with 2-methylresorcinol. We found that synthetic result of this reaction depends considerably on the reaction conditions. The process carried out in dioxane in the presence of trifluoromethanesulfonic acid leads to formation of calix[4]resorcinols IIIa and IIIb as the final products. DOI: 10.1134/S1070363209090199

Reaction of 1-(2,2-dimethoxyethyl)-1-methyl-3-phenylurea with pyrogallol

Reaction of formaldehyde diethylacetal with resorcinol in acid medium leads to formation of a cyclic tetramer, calix[4]resorcinol [1]. In the reactions of phosphorylated acetals with resorcinol calixarenes were formed containing phosphorylalkyl or thiophosphorylalkyl groups at the bottom rim of the molecule [2–4]. The condensation of resorcinol with αmethylaminoacetic aldehyde dimethylacetal (I) in aqueous solutions of hydrochloric acid led to the formation of hydrochlorides of substituted polyphenolic products originating from two resorcinol and one aminoacetal molecules [5].

Sodium picrate effect on extraction of lanthanum and lutetium by aminophosphonate calix[4]resorcinarenes

Aminophosphonate calix[4]resorcinarene derivatives extract lanthanum and lutetium ions from aqueous solutions to chloroform much more efficiently than O,O-diethyl[(4-nitrophenyl)aminobenzyl] phosphonate does. In an excess of the metal ion in the aqueous phase with respect to the amounts of the extracting agent and sodium picrate, extraction occurs at the 1 : 1 molar ratio of the metal ion to extracting agent. In a twofold excess of the extracting agent and a considerable excess of sodium picrate over the metal ion, the composition of the extracted complex depends substantially on both the length of the alkyl substituent in the (AlkO)2P(O) group in the extracting agent and the number of lanthanide.

One-pot synthesis of novel s-triazine-containing polyphenols and imidazotriazinium salts

Study of the reaction of aminoacetal containing 1,3,5-triazine moiety with phenols is reported. Reaction conditions leading to the formation of either polyphenols modified with 1,3,5-triazine moiety or previously unknown 6-arylimidazo[1,2-a][1,3,5]triazin-5-ium salts with good yields are determined. Formation of triazinium salts proceeds via the dearylation of initially formed triazine-containing polyphenols.Graphical abstract.

Synthesis of benzooxadiazocines via the acid-catalyzed reaction of pyrimidine-containing acetals with resorcinol derivatives

Herein, we report the synthesis of heteroannelated benzooxadiazocines via unusual reaction of pyrimidine-containing acetal with resorcinol derivatives.Graphical abstract

Synthesis of new polyphenols containing aminoalkyl and ammonium fragments

Recently we have shown that the condensation of resorcinol and methylresorcinol with dimethylacetal of methylaminoacetic α-aldehyde in aqueous hydrochloric acid leads to the formation of the hydrochlorides of the substituted polyphenols as the products of the reaction between two resorcinol molecules and one aminoacetal molecule [1]. In this work we studied the synthetic opportunities of the derived polyphenols. For modifications of these compounds we used the Mannich reaction [2]. The initial 2,2-bis(2,4-dihydroxy-3-methylphenyl)-N,N-dimethylethylamine I was synthesized by the known method [1, 3] starting from 2-methylresorcinol and dimethylacetal of N,N-dimethylaminoacetaldehyde. The reaction of I with 2 equiv of formaldehyde in the presence of dimethylamine or morpholine results in compounds IIa and IIb in 98 and 84% yield respectively. In the presence of aromatic amines like aniline, diphenylamine, or benzidine the reaction affords a complex mixture of the unidentified products. DOI: 10.1134/S1070363213010234

Aminomethylated calix[4]resorcinolarenes with NH groups on the upper rim of the molecule

The reaction of calix[4]resorcinolarenes with N,N-dimethylethylenediamine and aqueous CH2O in a molar ratio of 1 : 5 : 5 affords calixarenes containing secondary amino groups arranged on the upper rim of the molecule. When the double amount (with respect to primary amine) of formalin is used (ratio of reactants 1 : 5 : 10), cavitands with four oxazinyl fragments are synthesized.