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.

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.

Реакции 1,4-бензохинона с 2-(2-оксо-2-арилэтилиден)-2,3-дигидро-1Н-пиримидин-4-онами в ледяной уксусной кислоте протекают селективно с образованием 2-[1-(2,5-дигидрофенил)-2-оксо-2-арилэтилиден]-2,3-дигидропиримидин-4(1Н)-онов.

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.

The reaction of 2-(2-oxo-2-phenylethylidene)-2,3-dihydropyrimidin-4(1H)-ones and ethyl cyanoacetate leads to the formation of 4-hydroxy-2,10-dioxo-5-phenyl-1,10-dihydro-2H-pyrimido[1,2-a][1,8]naphthyridine-3-carbonitriles.

This article describes the synthesis of 2-(2-oxo-2-arylethylidene)-2,3-dihydropyrimidin-4(1Н)-ones and provides details of their reactivity, such as nucleophilic and electrophilic substitution, as well as associated processes: acidic degradation, isomerization, and diazine ring cleavage.

Methods of synthesis of halogenated benzo-and dibenzocrown ether derivatives are surveyed: halogenation of benzo-and dibenzocrown ethers with molecular halogens, N-halosuccinimides in the solid phase and different media (water, ethanol, halohydrocarbons) and hypohalites in water, as well as the 'assembly' method. Reactions of these compounds are considered: synthesis of phosphorus-containing crown ethers, organometallic synthesis, the Heck and Sonogashira reactions, synthesis of acetylene derivatives and other reactions. Special attention is focused on the complexing properties of halogenated benzocrown ethers with respect to ionic guests and neutral organic molecules. The possibility of synthesis of complexes of such compounds in the solid phase is demonstrated. The extraction and sorption properties of halogenated benzo-and dibenzocrown ethers are considered. Examples of practical use of these compounds are presented. The bibliography includes 203 references.

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.

Peculiarities of benzo-15-crown-5 (I), [3.3]dibenzo-18-crown-6 (II), and [4.4]diben zo-24-crown-8 (III) nitration by the dilute nitric acid and the mixture HCl-HNO3(4:1, «aqua regia») at room temperature are discussed. It was revealed that the «reactivity» of studied crown ethers (symbatically/antisymbatic to their hydrophili ci ty/lipophilicity) is variated as follows: I>> III> II.

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.

Five oxonium tetrahalogenaurate(III) (Hal = Cl, Br) benzo-crown ether (BCE) complexes are prepared and reported. The new compounds are [(H3O)(B18C6)(0.58)(4 '-Cl-B18C6)(0.42)][AuCl4] 1, [(H3O)(B18C6)][AuCl4] 2, [(H3O)(4 '-Br-B18C6)][AuCl4] 3, [(H3O)(4 '-Br-B18C6)][AuBr4] 4, and [(H3O)(B18C6)][AuBr4] 5. The reaction medium, distinctive from the previously used aqua regia, allowed avoiding the unwanted nitration of initial macrocycles. The compositions and structures for 1, 3, 4, and 5 were proved by single crystal X-ray crystallography. The complete conversion of tetrachloroaurate(III) to the tetrabromoaurate(III) salts resulted in complex 4 isomorphous and isostructural to 3. All compounds form the laminated structures with alternation of cationic and anionic layers. The robustness of the anionic sheets is sustained by the halogen-halogen interactions and makes crucial impact on extraction of stoichiometric products in the case of tetrabromoaurate(III) salts.

It was found that both sodium hypochlorite and hypobromite can be used as mild and selective reagents for chlorination and bromination of benzocrown ethers (BCE) in water medium. The adjustment of pH in these processes enables the control of the resulting number of atoms of halogens in the aromatic fragment of BCE. Only mono halogen-BCE are found in the alkaline environment, while in the acidic medium there are only tetrachloride and dibromide BCE. The possibility of the use of elementary iodine in aqueous solution for the iodination of BCE by hypoiodite in situ was also demonstrated.

For the first time the reaction ability of bromoderivatives of benzoand dibenzocrown ethers at sorption of ~30 elements from the water solutions of nitric and muriatic acids was studied. It was found, that an introduction of one (in the case of benzocrown ethers) or two (dibenzocrown ethers) bromine atoms into the phenylene rings of macrocycle increases the sorption properties of the aimed bromides in comparison with the corresponding unsubstituted crown ethers. In this case the properties of dibenzocrown ethers differ rather strongly. So, 4’,4’’,(5’’)-dibromo[3.3]dibenzo18-crown-6 has low level of activity, but in going from [4.4]dibenzo-24-crown-8 to its 4’,4’’,(5’’)-dibromoderivative the sorption properties when extracting some elements from water solutions of hydrochloric acid increase in hundreds of times. Thus, a new highly selective agent for the extraction and separation of elements from multicomponent mixtures was found. Despite rather close spatial and electronic parameters, the reaction ability of 4’,4’’,(5’’)-dibromoand 4’,4’’,(5’’)-diiodo[4.4]dibenzo-24-crown-8 differs dramatically because the latter is absolutely unselective and extracts 28 elements of all studied to the same extent.

Iodination of benzo-12-crown-4, benzo-15-crown-5 and benzo-18-crown-6 by equimolar amounts of N-iodosuccinimide in ethanol in the presence of sulfuric acid additions proceeds quickly and selectively and results in corresponding 4I-iododerivatives with 78-86% yields. Reactivity of [3.3]dibenzo-18-crown-6 slightly differs from that of benzocrown ethers and diiodide (mixture of cisand trans-isomers) is obtained with 76% yield.

In the conditions of mechanochemical activation and without the solvent cis-syn-cis-isomer of dicyclohexano-18crown-6, 4I-bromobenzo-18-crown-6, 5,5I-dibromoderivatives of proximal [0.6]biphenyl-20-crown-6 and [1.5]dibenzo18-crown-6 form complexes with potassium chlorochromate (KCrO3Cl) with ratio of 1:1 and 87-99% yields. At the same time, reactivity of the cis-anti-cis-isomer of dicyclohexano-18-crown-6 is considerably lower: the yield of the (1:1) complex in the similar conditions is only 10%, and benzo-18-crown-6 and [3.3]dibenzo-18-crown-6 do not take part in the reaction.