A Derivatives of 2-thiouracil are characteri­zed by wide spectrum of biological activity, which is characteristic of most representatives this heterocycles class. In particular, 2-(2-oxo-2-phenylethylthio)-pyrimi­din-4(3H)-ones belong to the group of non-nucleoside inhibitors of HIV-1 reverse transcriptase. The antimalarial properties of 2-(2-oxo-2-phenylethyl­thio)-4-R-pyrimidine derivatives, which proved to be effective inhibitors of CIpP protease of Plasmodium falciparum, are being studied. Known examples of 2-(2-oxo-2-phenylethyl­thio)-pyrimidines modification at the "4" position of the heterocycle are limited to use 4-chloro derivatives, which, in turn, are formed according to the classical method by reaction of pyrimidine-4(3H)-ones with POCl3 at boiling point of reaction mixture. In this work, we present an alternative version of modification the above-mentioned class of compounds. By amination amide function of 6-R-2-(2-oxo-2-arylethylthio)-pyrimidin-4(3H)-ones derivati­ves of with ethanolamine and 1-aminopropa­ne-2,3-diol using sulfonate method, synthesized and characterized new compounds a 6-R-2-(2-oxo-2-phenylethylthio)-pyrimidines series by spectral methods. The advantages of this scheme are discussed (the formation of intermediate sulfonates and the amination stage do not require harsh conditions and are carried out with satisfactory yields). The proposed scheme can be recommended in cases where the original substrate contains functio­nal groups that are labile at high temperatures and sensitive to an acidic environment.

Despite its wide application in industry, the effective use of glycerol growing volumes is very relevant, since «technical» glycerol with an acceptably high content of main substance can become an available and promising raw material for obtaining valuable chemical compounds, in particular cyclic glycerol ketals. Glycerol reaction with acetone in the presence of acid-modified clinoptilolite (CLI) as a catalyst for formation of cyclic ketals was studied. It was found that technology of acid modification doesn’t significantly affect the acidity of catalyst. For samples prepared by first method, with increasing time of acid modification, pH suspensions increase, namely the acidity decreases. As for catalysts prepared by second method, no such tendency is observed. The influence of modification time CLI samples has different effects on activity of prepared catalysts with different diameters. For CLI with a larger diameter (dav. = 1.5 mm) a minimum of activity is observed with increasing modification time (τH), namely the dependence of glycerol conversion (ZGL) on τH is extreme. For CLI of smaller dav. (0.05 mm and 0.75 mm) change of this factor has little effect on their activity. Comparing catalysts with same τH, but different dav. and method of preparation, it can be noted that the activity of catalyst with a higher d av. is higher than in samples with less. At the same time, two catalysts of same dav. (0.05 mm), but different methods of preparation practically don’t differ in their catalytic properties. CLI belongs to sorbents with a heterogeneous porous structure, catalytic activity of which depends on acidity, pore structure, and availability for diffusion of reagents. By method of planning two series experiments, according to a complete three-factor analysis, adequate models were obtained, according to which the pH of suspension and d av. are factors that have little influence on response function – ZGL. A linear (sympathetic) dependence is observed between glycerol conversion and initial rate of its loss, which is characteristic for most «families» of studied acid-modified CLI samples.

The reaction of 2-(1-hydroxyimino-2-oxo-2-phenylethyl)-6-R-pyrimidin-4(3H)-ones with an excess of p-toluenesulfochloride proceeds in two stages involving consecutive oxidation of the oxygen atom of the hydroxyimino group and the oxygen atom of the amide fragment of the pyrimidine ring. The reaction of the resulting ditosylates with ethylenediamine proceeds via replacement of the sulfonyl group in the 2-position of the pyrimidine ring. The examples of 2-[1-benzoyl-2-(2-furyl)vinyl]-6-methylpyrimidin-4(3H)-one, 2-[2-(4-nitrophenyl)vinyl]-6-methylpyrimidine-4(3H)-one, and 6-methyl-2-(2-oxo-2-phenylethylthio)pyrimidin-4(3H)-one were used to consider the relationship between the structure of the substrate and the direction of the tosylation reaction.

Reactions of 1,4-benzoquinone with 2-(2-oxo-2-arylethylidene)-2,3-dihydro-1H-pyrimidine-4-ones in glacial acetic acid proceed selectively to give 2-[1-(2,5-dihydrophenyl)-2-oxo-2-arylethylidene]-2,3-dihydropyrimidine-4(1H)-ones.

Попытка сокристаллизации N7,N16-бис(S-1-фенилэтил)-1,4,10,13-тетраокса-7,16-диазациклооктадекан-7,16-дикарбоксамида (1) с гидрохлоридами метиловых эфиров (ГХМЭ) L- и D-валина, а также L- и D-лейцина приводит к раздельной кристаллизации диазакраун-эфира 1 (или его моногидрата 1.H2O) и ГХМЭ соответствующих α-аминокислот. Ранее неописанные кристаллические структуры соединений 1, 1.H2O и ГХМЭ D-лейцина (2) определены методом монокристальной дифрактометрии.

An attempt to co-crystallize N7,N16-bis(S-1-phenylethyl)-1,4,10,13-tetraoxo-7,16-diazacyclooctadecane-7,16-dicarboxamide (1) with hydrochlorides of methyl ethers (HCMEs) of L- and D-valine and also L- and D-leucine results in separate crystallization of diazacrown-ether 1 (or its monohydrate 1·H2O) and HCMEs of respective α-amino acids. Crystal structures of D-leucine 1·H2O (1) and HCME (2) compounds, which were not described previously, are solved by single crystal X-ray diffraction.

It was established that unsubstituted amides of imidazole-4,5-dicarboxylic acid are characterized by large (up to 15000 cm–1) Stokes shifts. It was found that the structural factors determining the character of transitions of the molecules of esters and hydrazides in the initial and excited states are similar. The effect of the lipophilicity of the compounds on the Stokes shifts and fluorescence quantum yields is discussed.

Reaction of potassium thiocyanate with 2-[2-oxo-1-(1-tosyloxyimino)-2-phenylethyl]pyrimidin-4-(3H)-one derivatives led to the formation of a new fused heterocyclic system with a common nitrogen atom, substituted 7H-[1,2,5]thiadiazolo[2,3-a]pyrimidin-7-one.

Реакция роданида калия с производными 2-[2-оксо-1-(1-тозилоксиимино)-2-фенилэтил]пиримидин- 4(3Н)-она приводит к образованию новой конденсированной гетероциклической системы с общим атомом азота - замещённого 7Н-[1,2,5]тиадиазоло[2,3-а]пиримидин-7-она.

Features of the decomposition of H2O2 in the presence of polynuclear complexes with Co2Cu2 and Co3Cu2 metal cores with deprotonated and di- and triethanolamines (H2Dea and H3Tea), compounds with the composition (H2Tea)ConCumCl (m + n =1; n = 0.33, 0.5, 0.67), and mononuclear complexes (H2Tea)CuCl and (H2Tea)CoCl were examined. It is suggested that the reaction in the presence of poly- and mononuclear complexes has different mechanisms.

We considered the changes in the luminescent properties in the series of neodymium(III) complexes of various coordination types with different tetrapyrrole macrocycles ( porphyrins, phthalocyanines and corroles): mononuclear complexes (metal-ligand ratio 1: 1), sandwich type complexes (metal-ligand ratio 1: 2 or 2: 3), peripheral binding (on the basis of ditopic tetrapyrrole, metal-ligand ratio 1: 1). 4f-Luminescence in the near infrared region is observed in all studied Nd-complexes as a result of intramolecular transfer of excitation energy. Each kind of complexes has its unique features, which are discussed. The peripheral complexes are dual-emissive: they display both neodymium(III) 4f-emission and molecular fluorescence. The values of quantum yield of molecular fluorescence as well as 4f-luminescence are estimated. It was found that binding type plays a key role in excited state relaxation pathways in the molecule. Corroles have unusual behaviour in terms of Nd sensitization.

The reaction of 6-methyl-2-(2-oxo-2-phenylethylidene)-2,3-dihydropyrimidine-4(1H)-one with arylhydrazines leads in high yields to the corresponding hydrazones, in which the ethylidene fragment of the starting compound is transformed to the ethylene fragment. By oxidation of the hydrazones with hydrogen peroxide or selenium dioxide the corresponding 6-methyl-2-[2-phenyl-2-(arylhydrazono)acetyl]-3H-pyrimidine-4-ones were synthesized.

An attempt to consider the effect of the structure and composition of benzo-, dibenzo-, and aliphatic crown ethers (more than 40 compounds) on the characteristics of their interaction with surface groups of A-300 aerosil is carried out by comparing the Henry (K H ) and Langmuir (K L ) constants and analyzing the main factors and structural fragments that facilitate or hamper the formation of corresponding surface compounds by quantitative-structure-property-relationships method.

Основным продуктом окисления кислородом воздуха при комнатной температуре смеси комплекса состава (СоII)3( -OOCBut)6(NEt3)2 и дибензилового эфира (DBE) в растворе дихлорметан–бензол (4 : 1) является гексаядерный комплекс [(CoIII)6( 4-O)2( 3-O)2( -OOCBut)9(OH)2(HOOCBut)](HNEt3) · 0.5DBE · C6H6 (I). Mеталлоостов I, по данным РСА, содержит псевдокубановый фрагмент [Co4( 4-O)2( 3-O)2], связанный с двумя “периферийными” ионами кобальта(III). Обсуждаются возможность функционирования полученного комплекса в качестве интермедиата-катализатора жидкофазного окисления DBE и особенности конформационных изменений в молекуле DBE, обусловленные характером адаптации последней соответствующим металлокомплексом.

Room-temperature oxidation of a mixture of the complex (CoII)3(μ-OOCBu t )6(NEt3)2 and dibenzyl ether (DBE) with atmospheric oxygen in dichloromethane-benzene (4: 1) gave the hexanuclear complex [(CoIII)6(μ4-O)2(μ3-O)2(μ-OOCBu t )9(OH)2(HOOCBu t )](HNEt3) · 0.5DBE · C6H6 (I) as the major reaction product. According to X-ray diffraction data, the metal framework of complex I contains the pseudocubane fragment [Co4(μ4-O)2(μ3-O)2] linked with two “peripheral” cobalt(III) ions. The possibility of using complex I as an intermediate catalyst for liquid-phase oxidation of DBE as well as the conformational changes in the DBE molecule due to its adaptation to the metal complexes are discussed.

Methods for production of polymers and copolymers that contain fragments of crown ethers (CEs) and derivatives thereof, as well as methods for covalent and adsorption immobilization (fixation) of CEs on the surface of different silicas—silica gels, aerosils, silochromes, and so on—are considered. The efficiency and potential of the resulting materials as catalysts, specific sorbents, analytical reagents, extractants, stationary phases, etc., are demonstrated. The peculiarities and possible mechanisms of interaction of CE with the surface groups of the corresponding carriers are discussed.

2-(2-Oxo-2-arylethylidene)-2,3-dihydropyrimidine-4(1H)-ones react with aromatic and heteroaromatic aldehydes to form the unsaturated ketones, whereas in the case of 3- and 4-benzaldehydes the corresponding trans-2-styrylpyrimidine-4(3H)-ones were obtained. A possible mechanism of hydrolytic cleavage of the product of condensation of 2-(2-oxo-2-phenylethylidene)-2,3-dihydropyrimidine-4(1H)-one with paraformaldehyde under acid catalysis and mechanochemical activation has been discussed.

A reaction between palladium(II) acetate and aqueous cerium(III) acetate in acetic acid with subsequent boiling in benzene with excess pivalic acid is found to yield the complex Pd(μ-OOCBut)4Ce(OOCBut)(HOOCBut)3 (1). The liquid-phase thermolysis of complex 1 in dibenzyl ether (190°C) leads to the formation of the tetranuclear complex [Pd(μ-OOCBut)4Ce(HOOCBut)]2(μ-OOCBut)(μ-OH2) (2). The structure of the synthesized complexes is established by X-ray diffraction.