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Modification of the upper rim of the lipophilic cone-shaped tetrapropoxycalix[4]arene with hydrophilic phosphine oxide groups or phosphinic acid groups yielded nano-sized water-soluble calixarenes that form supramolecular complexes with uracils, including active pharmaceutical ingredients of 5-Fluorouracil and 5-Methyluracil drugs. Stability constants of the formed complexes in an aqueous-organic medium were determined by the HPLC method. The most favored structures of the calixarenes and their uracil complexes were optimized at the DFT level of approximation. In in the most favored structures of all adducts, the uracil molecules coordinate via hydrogen bonding with the phosphorus-containing groups on the upper rim of the calixarene ligands.

3-Phenyl-2-(prop-2-en-1-ylsulfanyl)-5,6,7,8-tetrahydrobenzo[4,5]thieno[2,3-d]pyrimidin-4(3H)-one reacted with 4-methoxyphenyltellurium trichloride in a regioselective manner to give angularly fused 1-{[dichloro(4-methoxyphenyl)-λ4-tellanyl]methyl}-4-oxo-5-phenyl-1,2,4,5,6,7,8,9-octahydrobenzo[4,5]thieno[3,2-e][1,3]thiazolo[3,2-a]pyrimidinium chloride. Electrophilic cyclization of 2-(prop-2-en-1-ylsulfanyl)- and 2-(2-methylprop-2-en-1-ylsulfanyl)-5,6,7,8-tetrahydrobenzo[4,5]thieno[2,3-d]pyrimidin-4(3H)-ones with 4-methoxyphenyltellurium trichloride afforded linearly fused 3-{[dichloro(4-methoxyphenyl)-λ4-tellanyl]methyl}-2,3,6,7,8,9-hexahydro-5H-benzo[4,5]thieno[2,3-d][1,3]thiazolo[3,2-a]pyrimidin-5-one hydrochlorides. Regardless of the reactant ratio, the products were isolated as 1:1 complexes with 4-methoxyphenyltellurium trichloride.

Hydrazone [HydrHSal]∙Н2О is synthesized for the first time by the interaction of 2-(7-bromo-2-oxo-5- phenyl-3H-1,4-benzdiazepin-1-yl)acetohydrazide (gidazepam) with salicylic aldehyde and characterized by the elemental analysis, thermogravimetry, mass, electron, IR, and NMR spectroscopic techniques. The molecular and crystal structure is determined by single crystal X-ray diffraction.

The Host-Guest complexation of octakis(diphenoxyphosphoryloxy)tetramethylcalix[4]resorcinarene, 5,17-bis-(N-tolyliminomethyl)-25,27-dipropoxycalix[4]arene and 5,11,17,23-tetrakis(diisopropoxyphosphonyl)-25,26,27,28-tetrapropoxycalix[4]arene with a series of 11 phenols (phenol, p-fluorophenol, p-chlorophenol, p-bromophenol, pyrogallol, p-cresol, p-aminophenol, p-nitrophenol, salicylic aldehyde, guaiacol and veratrole) has been studied by the high-performance liquid chromatography (RP HPLC) method. Chromatographic characteristics and log P of industrial phenols have been determined. Using the relationship of the phenol retention factor k’ vs the calixarene concentration in the mobile phase the stability constants of the supramolecular complexes K A (29-331 M -1 ) have been determined. The stability constants of the calixarene complexes show that the Host-Guest interaction strongly depends on the nature of the substituents in the Host and Guest molecules. Calixresorcinarene functionalized by diphenoxyphosphoryl groups and calixarene containing tolyliminomethyl groups formed more stable complexes with some phenols compared to calixarene functionalized by diisopropoxyphosphonyl groups. In accordance with the molecular modeling data the complexation does not change the C2v flattened-cone conformation of the calixarene skeleton. The Host-Guest complexes are stabilized by the intermolecular hydrogen bonds of phenolic OH groups with oxygen atoms of P = O groups at the upper rim, and OH groups at the lower rim of the macrocycle. Hydrophobic interactions also participate in the complexation.

1-Aryl-4-chloro-5-(2-nitroethenyl)-1H-imidazoles reacted with thiols and aromatic amines via Michael addition to give 5-[(1-arylsulfanyl)-2-nitroethyl)]-4-chloro-1H-imidazoles and N-[1-(1-aryl-4-chloro-1H-imidazol-5-yl)-2-nitroethyl]anilines, respectively. [2 + 3]-Cycloaddition of the title compounds to sodium azide afforded 4-(4-chloro-1H-imidazol-5-yl)-1H-1,2,3-triazoles.

Комплексоутворення типу Гість-Господар oктакіс-(дифеноксифосфорилокси)-тетраметилкалікс[4]резорцинарену (CR) та 5,17-біс-(N-толілімінометил)-25,27-дипропоксикалікс[4]aрену (CA) з 6 дитерпеноїдними (смоляними) кислотами було досліджено методом обернено-фазної високоефективної рідинної хроматографії (ОФ ВЕРХ). Визначені хроматографічні характеристики (час утримання tR тa фактор утримання k’) смоляних кислот. Розраховано значення ліпофільності log P смоляних кислот тa констант зв’язування KA комплексів (395-682 М-1 для CR тa 844-1268 М-1 для CA), а також значення вільних енергій Гіббса ∆G (-14.79 – -16.14 кДж/моль для CR тa -16.70 – -17.67 кДж/моль для CA) із смоляними кислотами. Молекулярне моделювання комплексів CA вказало на присутність водневих зв’язків між карбоксильними групами кислот тa атомами азоту іміно-груп верхнього вінця CA макроцилу або атомами кисню ОН груп його нижнього вінця. Молекулярне моделювання комплексів CR вказало на присутність водневих зв’язків між карбоксильними групами кислот тa атомами кисню дифеноксифосфорилокси-груп верхнього вінця макроциклу CR. Здійснено оцінку впливу log P на константи зв’язування KA комплексів CR/CA. Лінійна залежність КА від log P кислот вказує на роль сольвофобних взаємодій на комплексоутворення. Встановлено взаємозв’язок між супрамолекулярними (KA) тa фізико-хімічними (log P, pKa) характеристиками кислот., The Host-Guest complexation of octakis-(diphenoxyphosphoryloxy)tetramethylcalix[4]resorcinarene (CR) and 5,17-bis-(N-tolyliminomethyl)-25,27-dipropoxycalix[4]arene (CA) with 6 diterpenoid (resin) acids has been studied by the reversed phase high-performance liquid chromatography (RP HPLC). The chromatographic characteristics (retention time tR and retention factor k’) of resin acids have been determined. The lipophilicity values log P of the acids, binding constants KA (395-682 M-1 for CR and 844-1268 M-1 for CA), as well as Gibbs free energies ∆G (-14.79 – -16.14 kJ/mol for CR and -16.70 – -17.67 kJ/mol for CA) of the complexes with resin acids have been calculated. Molecular modelling of CA complexes has revealed the presence of hydrogen bonds between carboxylic groups of acids and nitrogen atoms of imino groups at the upper rim or oxygen atoms of the hydroxyl groups at the lower rim of the CA macrocycle. Molecular modelling of CR complexes has shown the presence of hydrogen bonds between carboxylic groups of acids and oxygen atoms of diphenoxyphosphoryloxy groups at the upper rim of the CR macrocycle. The effect of log P values on KA values of the CR/CA complexes has been assessed. The linear dependence of the binding constants on the acid lipophilicity indicates a significant role of solvophobic interactions on the complexation. The relationship between supramolecular (KA) and physicochemical (log P, pKa) characteristics of acids has been determined., Комплексообразование типа Гость-Хозяин oктакис-(дифеноксифосфорилокси)-тетраэтилкаликс[4]резорцинарена (CR) и 5,17-бис-(N-толилиминометил)-25,27-дипропоксикаликс[4]aрена (CA) с 6 дитерпеноидными ( смоляными) кислотами было исследовано методом обращенно-фазной высокоэффективной жидкостной хроматографии (ОФ ВЭЖХ). Определены хроматографические характеристики (время удерживания tR и фактор удерживания k’) смоляных кислот. Рассчитаны значения липофильности log P смоляных кислот и констант связывания KA их комплексов (395-682 М-1 для CR и 844-1268 М-1 для CA), а также значения свободных энергий Гиббса ∆G (-14.79 – -16.14 кДж/моль для CR и -16.70 – -17.67 кДж/моль для CAL) со смоляными кислотами. Молекулярное моделирование комплексов CA показало наличие водородных связей между карбоксильными группами кислот и атомами азота имино-групп верхнего обода макроцикла CA или атомами кислорода гидроксильных групп его нижнего обода. Молекулярное моделирование комплексов CR показало наличие водородных связей между карбоксильными группами кислот и атомами кислорода дифеноксифосфорилокси-групп верхнего обода макроцикла CR. Оценено влияние log P на константы связывания KA комплексов CR/CA. Линейная зависимость КА от log P кислот свидетельствует о влиянии сольвофобных взаимодействий на процесс комплексообразования.

A method for the synthesis of 2-R-2-(1-aryl-7,8-dimethoxy-5H-2,3-benzodiazepin-4-yl)acetic acid esters from 2-R-2-(1-aryl-7,8-dimethoxy-5H-2,3-benzodiazepin-4-ylsulfanyl)acetic acid esters through Eschenmoser reaction has been developed.

The aminomethylation of 6-amino-4-aryl-2-thioxo-1,2-dihydropyridine-3,5-dicarbonitriles by the action of primary amines and an excess of formaldehyde under conditions of base catalysis was studied. It was found that the structure and yields of the products depend largely on the structure of the initial amine and also on the ratio of the reagents and reaction conditions. In the case of alkyl- or arylalkylamines, 8-aryl-3-alkyl(arylalkyl)-6-thioxo-1,3,4,6-tetrahydro-2H-pyrido[1,2-a][1,3,5]triazine-7,9-dicarbonitriles were obtained, whereas when aromatic amines were used 3,10-diaryl-1,8-dithioxo-5,6,12,13-tetrahydro-1H,8H-dipyrido[1,2-a:1′,2′-e][1,3,5,7]tetrazocine-2,4,9,11-tetracarbonitriles or their mixtures with the above-mentioned pyrido[1,2-a][1,3,5]triazines were obtained. Dipyrido[1,2-a:1′2′-e]-[1,3,5,7]tetrazocine derivatives were also synthesized by direct condensation of 6-amino-4-aryl-2-thioxo-1,2-dihydro-pyridine-3,5-dicarbonitriles with formaldehyde.

The reaction of 3-amino-4-(3,4-dimethoxyphenyl)maleimide and the methyl esters of 3-amino-4-(3,4-dimethoxyphenyl)-5-R-thiophene-2-carboxylic acids with carbonyl compounds and nitrous acid has been investigated. Dioxopyrrolo[3,4-c]- and thieno[3,4-c]isoquinolines and cinnolines were obtained.

Condensation of hetarene carboxaldehydes with phthalide gave 2-(3-hydroxy-1-oxoinden-2-yl)benzo[b]furan and 2-(3-hydroxy-1-oxoinden-2-yl)-5-ethylthieno[2,3-b]thiophene. Starting from hetaryl acetic acids gave 3-(3-hydroxy-1-oxoinden-2-yl)benzo[b]furan and 3-(3-hydroxy-1-oxoinden-2-yl)benzo[b]thiophene. Acylation of 3-hydroxy-1-oxoinden-2-yl-substituted heterocycles using acetic anhydride in the presence of 70% HClO4 leads to the formation of pentacyclic pyrilium salts. Pentacyclic indenopyridines are prepared by treating the pyrilium salts with ammonia. The reaction of the carbonyl group in the indenopyridines with hydroxylamine, hydrazine hydrate, and in reduction using NaBH4 has been studied.

The reaction of 3-acylamino- and 3-alkoxybenzo[c]pyrilium perchlorates with hydrazine has been studied. It was discovered that the direction of the recyclization of the pyran ring depends on the type of substituent in position 3 and on the ratio of reactants. Derivatives of isoquinoline and benzo-2,3-diazepine were obtained.

A method for the synthesis of 2-R-2-(1-aryl-7,8-dimethoxy-5H-2,3-benzodiazepin-4-yl)acetic acid esters from 2-R-2-(1-aryl-7,8-dimethoxy-5H-2,3-benzodiazepin-4-ylsulfanyl)acetic acid esters through Eschenmoser reaction has been developed.

The base-mediated aminomethylation of 6-amino-4-aryl-2-thioxo-1,2-dihydropyridine-3,5-dicarbonitriles (I) provides access to pyridotriazine and tetrazocine derivatives in ratios depending strongly on the structure of the initial amine, the ratio of regents, and the reaction conditions.

Treatment of N-phenyl-2-(1-R-indol-3-yl)succinimides with acetyl perchlorate leads to acylation of the benzene ring of the indole substituent.

Nitration, bromination, thiocyanation, and acylation of 1, 7-dimethyl-3(2H)-benzo[b]furo[2, 3-c]pyridone were investigated. It was shown that either the 4-nitro- or the 4,6-dinitro derivative is formed as a function of the nitration conditions. Bromination with bromine and thiocyanation with dithiocyanogen yields a bromo derivative at position 4. The product of substitution at the C(6), atom is obtained in acylation with acetyl chloride, and the product of substitution at atoms C(4) and C(6) is obtained with benzoyl chloride. The results of the calculations were generalized in the MNDO approximation.

The solubility of iodine in 30-55% nitric acid at 25°C was measured. Particular attention was given to the control of equilibration in the system. An equation was suggested for estimating the iodine solubility in nitric acid in the concentration range 0-70 wt % HNO3.

A study has been made of thenitrationand bromination of 1-oxo-3,3,6-trimethyl-1,2,3,4-tetrahydrobenzo[bjfuro-, benzo[b]thieno-, and indolo[2,3-c]quinolines. It has been shown that the nitration is directed to the benzene ring (position 10). Bromination by molecular bromine takes place at the 6-CH3 group of the pyridine fragment and yields a mixture of the corresponding nwnobromomethyl and dibromomethyl derivatives, whereas a dimethylacetamide-bromine complex bronzinates the methylene group in position 2, forming the α-bromoketone. The Schmidt reaction of 1-oxo-3,3,6-trimetliyl-1,2,3,4-tetrahydrobenzo[b]furo-, benzol[b]thieno-, and indolo[2,3-c]quinolines have been investigated, as well as conversions of their oximes under conditions of the Beckmann rearrangement.

By reacting propylene carbonate with epichlorohydrin 8-methyl-2-chloromethyl-1,4,6,9-tetra- oxaspiro[4.4]nonane was obtained that afforded 8-methyl-2-methylene-1,4,6,9-tetraoxaspiro[4.4]nonane on dehydrochlorination. The spirocompounds synthesized are composed of stereoisomers mixtures containing: cis,syn-, cis,anti-, trans,syn-, trans,anti-isomers and cis,syn-, cis,anti-isomers, respectively. These isomers are distinguished by a different orientation of substituents in positions 2 and 8 with respect to two five-membered rings.

A study has been made of thenitrationand bromination of 1-oxo-3,3,6-trimethyl-1,2,3,4-tetrahydrobenzo[bjfuro-, benzo[b]thieno-, and indolo[2,3-c]quinolines. It has been shown that the nitration is directed to the benzene ring (position 10). Bromination by molecular bromine takes place at the 6-CH3 group of the pyridine fragment and yields a mixture of the corresponding nwnobromomethyl and dibromomethyl derivatives, whereas a dimethylacetamide-bromine complex bronzinates the methylene group in position 2, forming the α-bromoketone. The Schmidt reaction of 1-oxo-3,3,6-trimetliyl-1,2,3,4-tetrahydrobenzo[b]furo-, benzol[b]thieno-, and indolo[2,3-c]quinolines have been investigated, as well as conversions of their oximes under conditions of the Beckmann rearrangement.

Treatment of N-phenyl-2-(1-R-indol-3-yl)succinimides with acetyl perchlorate leads to acylation of the benzene ring of the indole substituent.

A study has been made of the reaction of 1,3-disubstituted bezothieno[2,3-c]pyrylium salts with hydrazine. It has been shown that 1,3-dialkyl-substituted benzothieno[2,3-c]pyrylium salts interact with hydrazine to give N-amino-1,3-dialkylbenzothieno[2,3-c]pyridines. The presence of a pyrylium ring on one of the positions of the phenyl group leads to a mixture of N-amino derivatives and 5H-[2,3]benzothieno[2,3-e]diazepines. In contrast, 1,3-diphenylbenzothieno[2,3-c]pyrylium perchlorate gives exclusively 5H-[2,3]benzothieno[2,3-e]diazepine.

The recyclization reactions of 4-cyanobenzo[c]pyrylium salts with ammonia, primary amines, and hydrazines have been studied. New derivatives of isoquinoline, benzo-2,3-diazepine, and pyrazolo-[ 5,4-c]isoquinoline have been obtained.

The examples reported for the recyclization of 3-acylaminobenzo[c]pyrilium salts are limited to their reactions with ammonia [1] and ortho-phenylenediamine [2], although the structure of these compounds would lead us to expect a great variety of transformations. In a study of 3-acylaminobenzo[c]pyrilium salts with nitrogen-containing nucleophiles, we assumed that the formation of 1,3-aminonaphthol derivatives would be possible in their reactions with amines as in the case of 5-alkyl-2-oxobenzo[c]pyrrolo[3,2-e]pyrilium perchlorates [3]. The structure of the products of the reactions of 3-acylamino-1-alkylbenzo[c]pyrilium salts (1) with benzylamine was found to depend on the length of the alkyl substituent at C(1) in the benzo[c]pyrilium cation. Heating 3-acetylamino-6,7-dimethoxy-1-methylbenzo[c]pyrilium perchlorate (1a) with two equivalents of benzylamine gives 3-acetylamino-1-benzylamino-6,7-dimethoxynaphthalene (2), whose structure and composition were indicated by IR and H NMR spectroscopy and elemental analysis. Under the same conditions, salt 1b is converted into the "normal" product, aminonaphthol 3. Recyclization with retention of the acetylamino group was quite unexpected since the reported reactions of 1-acylaminobenzo[c]pyrilium cations feature either loss of the acylamino group [1, 2] or participation of this group in intramolecular recyclization to give 3-hydroxyisoquinoline derivatives [4].

The examples reported for the recyclization of 3-acylaminobenzo[c]pyrilium salts are limited to their reactions with ammonia [1] and ortho-phenylenediamine [2], although the structure of these compounds would lead us to expect a great variety of transformations. In a study of 3-acylaminobenzo[c]pyrilium salts with nitrogen-containing nucleophiles, we assumed that the formation of 1,3-aminonaphthol derivatives would be possible in their reactions with amines as in the case of 5-alkyl-2-oxobenzo[c]pyrrolo[3,2-e]pyrilium perchlorates [3]. The structure of the products of the reactions of 3-acylamino-1-alkylbenzo[c]pyrilium salts (1) with benzylamine was found to depend on the length of the alkyl substituent at C(1) in the benzo[c]pyrilium cation. Heating 3-acetylamino-6,7-dimethoxy-1-methylbenzo[c]pyrilium perchlorate (1a) with two equivalents of benzylamine gives 3-acetylamino-1-benzylamino-6,7-dimethoxynaphthalene (2), whose structure and composition were indicated by IR and H NMR spectroscopy and elemental analysis. Under the same conditions, salt 1b is converted into the "normal" product, aminonaphthol 3. Recyclization with retention of the acetylamino group was quite unexpected since the reported reactions of 1-acylaminobenzo[c]pyrilium cations feature either loss of the acylamino group [1, 2] or participation of this group in intramolecular recyclization to give 3-hydroxyisoquinoline derivatives [4].