This article describes the development of a method for the synthesis of benzo-15-crown-5, a promising extractant of lithium isotopes that are widely used in various fields of nuclear technology. The synthesis of benzo-15-crown-5 was carried out by the method of two-component condensation of pyrocatechol and tetraethylene glycol dichloride in the presence of a template agent sodium hydroxide, followed by extraction of crown ether by hexane or isolation by vacuum distillation. Optimal synthesis conditions were determined, impurities were chromatographically identified, the technological reaction time was determined and methods of introducing raw materials into the reaction mass were investigated. The study showed that the drip addition of tetraethylene glycol dichloride leads to the fact that the content of benzo-15-crown-5 reaches 82.1% in the reaction mass. The optimal holding time of the reaction mass is 7 h at boiling point. The processes of isolation of the target product (hexane extraction, vacuum distillation) were selected and studied. The proven technique has been fully adapted to a pilot industrial plant for the synthesis of crown ethers, consisting of three mixing reactors, nutch filters, measuring tanks and a vacuum distillation unit. The developed installation allows to receive up to 25 kg of high-quality product per month. The product was identified using NMR and IR spectroscopy and elemental analysis. At the pilot plant, it was possible to obtain a product whose yield was 41%, compared with 48% at the laboratory plant, which is a very good indicator for scaling, without loss of quality of the synthesis product. The purity of benzo-15-crown-5 was more than 98% according to gas-liquid chromatography.

Sequential reaction of 2-chlorobenzaldehyde, cyanothioacetamide, and malononitrile dimer in the presence of an excess of N-methylmorpholine resulted in the formation of N-methylmorphlinium salt of 2-amino-4-(2-chlorophenyl)-6-(dicyanomethyl)-1,4-dihydropyridine-3,5-dicarbonitrile. The resulting salt reacts under Mannich conditions with primary amines and an excess of formaldehyde to form substituted 2-alkylamino-4-(dicyanomethylene)-3,7-diazabicyclo[3.3.1]non-2-ene-1,5-dicarbonitriles. Structure of the key compound was confirmed by single crystal X-ray diffraction analysis.

N , N ′-Diphenyldithiomalonamide reacts with the 4-nitrobenzylidene derivative of Meldrum’s acid (or with Meldrum’s acid and 4-nitrobenzaldehyde) in the presence of a base to form crystalline Michael adducts. Structure of triethylammonium 2,2-dimethyl-5-(1-(4-nitrophenyl)-3-(phenylamino)-2-(phenylcarbamothioyl)-3-thioxopropyl)-4-oxo-4 H -1,3-dioxin-6-olate was studied by single crystal X-ray diffraction analysis.

trans-2-Amino-4-aryl-5-benzoyl-4,5-dihydrothiophene-3-carbonitriles were prepared either by the reaction of 3-aryl-2-cyanothioacrylamides with α-thiocyanatoacetophenone or by the Michael-type addition of cyanothioacetamide to α-bromochalcones followed by intramolecular cyclization. The mechanism of the first reaction was studied using high-level quantum chemical calculations. Density functional theory (DFT) studies were carried out to determine the mechanism of the first reaction. A new approach toward the construction of the thieno[2,3-d]pyrimidine core system was demonstrated by the reaction of the prepared dihydrothiophenes with HCHO and RNH2 under noncatalyzed Mannich conditions.

This microreview summarizes new data (2014–2019) on the use of 1-cyanoacetyl-3,5-dimethylpyrazole in organic synthesis.

The reaction of cyanothioacetamide with ethoxymethylenemalonate and triethylamine in ethanol upon heating is non-selective and leads to the formation of a mixture of triethylammonium 1,5-diamino-2,4-dicyano-5-thioxopenta-1,3-diene-1-thiolate and triethylammonium 6-oxo-3-cyano-5-ethoxycarbonyl-1H-pyridin-2-thiolate with a predominance of the latter. When treating with primary amines and 37% formalin in boiling aqueous alcohol, the reaction product gives only 4-(1,3,5-thiadiazinan-2-ylidene)-2-(3,4-dihydro-2H-1,3,5-thiadiazin-6-yl)pent-2-enedinitrile instead of the expected pyrido[2,1-b][1,3,5]thiadiazine derivatives. Triethylammonium 6-oxo-3-cyano-5-ethoxycarbonyl-1H-pyridin-2-thiolate does not react under these conditions.

( Е )-3-Арил-2-цианопроп-2-ентиоамиды легко гидроксиметилируются при нагревании с водно-спиртовым раствором формальдегида с образованием ( E )-3-арил- N -(гидроксиметил)-2-цианопроп-2-ентиоамидов. Проведен прогнозный анализ биологической активности полученных соединений in silico.

NpCdS nanocrystals are prepared by a microbial synthesis technique at the NRC “Kurchatov Institute”—GOSNIIGENETIKA. The stabilizing layer of nanocrystals consists of proteins, and the composition of the protein layer depends on the strain used in nanoparticle (NP) biosynthesis. The morphology and size, hydrodynamic diameter, zeta-potential, and luminescence properties of the biogenic NPs are investigated using electron microscopy, dynamic light scattering, and spectrofluorimetry, and the NPs are identified as quantum dots. The effects that temperature, pressure, and solvents have on the stability and luminescence intensity of biogenic NPs are studied in collaboration with the National Research Center Kurchatov Institute—IREA. For the aqueous NpCdS suspension, the dependence of luminescence intensity on the NP concentration range is established. The feasibility of incorporation and identification of NpCdS in an epoxy resin, polyimide, and polyvinyl alcohol is evaluated. Polymer nanocomposites find use in optoelectronics, biomedicine, and agriculture.

At the NRC “Kurchatov Institute” – GOSNIIGENETIKA, NpCdS nanocrystals were obtained by microbial synthesis. They were stabilized with proteins, which composition is determined by the strain used for biosynthesis of nanoparticles. Biogenic nanoparticles were studied and described by size, shape, hydrodynamic diameter, ζ potential, luminescence level, and defined as quantum dots applying methods of electron microscopy, dynamic light scattering, and spectrofluorimetry. The influence of temperature, pressure and solvents on the stability of biogenic nanoparticles and the luminescence intensity was evaluated in collaboration with IREA (NRC “Kurchatov Institute”). The luminescence intensity of the aqueous suspension of NpCdS was determined depending on the range of nanoparticle concentrations. The possibility of introducing and identifying NpCdS in epoxy resin, polyimide, and polyvinyl alcohol was assessed. Polymer nanocomposites are used for optoelectronic, biomedical and agricultural applications.

The review summarizes the results obtained by our research group over the past 15 years in chemistry of N -, S , N -, and Se , N -heterocycles resulted from aminomethlation of a wide range of acyclic and heterocyclic substrates derived from active methylene amides, thioamides, and selenoamides. A series of 1,3,5-thia(selena)diazines, 3,7-diazabicyclo[3.3.1] nonanes, 3,5,7,11-tetraazatricyclo[7.3.1.0 2,7 ]tridec-2-enes, 1,3,5,7-tetrazocines, and pyrido[1,2- a ][1,3,5]triazines were synthesized. The general regularities of the Mannich reaction in the series of N -, S , N -, and Se , N -containing pyridine substrates were discussed. Biological activities of some synthesized compounds were studied to reveal compounds with antiviral, analeptic, anti-inflammatory, and antipyretic activities.

3-Aminothieno[2,3- b ]pyridine-2-carboxylic acid esters readily reacted with 3,5-dimethyl-1-(cyanoacetyl)-1 H -pyrazole to give previously unknown N -(thieno[2,3- b ]pyridin-3-yl)cyanoacetamides. Reactions of the latter with 2-(arylmethylidene)malononitriles were nonselective, and mixtures of different heterocyclization products were generally formed. The cyclization of ethyl 4,6-dimethyl-3-[(cyanoacetyl)amino]thieno[2,3- b ]-pyridine-2-carboxylate afforded 2,4-dihydroxy-7,9-dimethylthieno[2,3- b : 4,5- b ′]dipyridine-3-carbonitrile whose tautomeric equilibrium was studied by DFT quantum chemical calculations. In silico analysis of biological activity of the synthesized compounds was performed.

The reaction of 5-amino-3-(cyanomethyl)-1H-pyrazole-4-carbonitrile with 3-aryl-5-hydroxy-5- methyl-2,4-di(ethoxycarbonyl)cyclohexanones in acetic acid furnished previously unknown 4,5,6,7,8,9-hexahydropyrazolo[1,5-a]quinazoline derivatives.

New polyheterocyclic ensembles of 8,9,10,11-tetrahydro-7-thia-1,4,6,8-tetraazabenzo[de]anthracenes were prepared by reaction of easily available 5Н-pyrido[2’,3’:2,3]thiopyrano[4,5-b]pyridines with Ас2О or acyl chlorides. The starting 5Н-pyrido[2’,3’:2,3]thiopyrano[4,5-b]pyridines were prepared by reaction of N-methylmorpholinium 4-aryl-3-cyano-6-oxo-1,4,5,6-tetrahydropyridine-2-thiolates with malononitrile dimer.

Three series of new cyclic sulfones have been prepared by a one-pot multi-component reaction (MCR) starting from the readily available dihydro-2H-thiopyran-3(4H)-one-1,1-dioxide. The in silico screening of the synthesized compounds revealed their high anti-inflammatory, antiarthritic, antiasthmatic and antiallergic potential coupled with the strong probability levels of cystinyl aminopeptidase inhibition. The key structures were confirmed by 2D NMR techniques.

The reaction of cyanothioacetamide with diethyl ethoxymethylenemalonate in the presence of triethylamine in hot EtOH proceeds non-selectively and leads to the formation of a mixture of triethylammonium 1,5-diamino-2,4-dicyano-5-thioxopenta-1,3-diene-1-thiolate (minor) and triethylammonium 3-cyano-5-ethoxycarbonyl-6-oxo-1Н-pyridine-2-thiolate (major). Upon treatment with primary amines and 37% aqueous HCHO in boiling aqueous ethanol, the reaction product affords only 4-(1,3,5-thiadiazinan-2-ylidene)-2-(3,4-dihydro-2H-1,3,5-thiadiazin- 6-yl)pent-2-enedinitrile derivatives, instead of the expected pyrido[2,1-b][1,3,5]thiadiazines. Triethylammonium 3-cyano-5-ethoxycarbonyl-6-oxo-1Н-pyridine-2-thiolate does not react under these conditions. The structure of the resulted products was confirmed by means of NMR, IR spectroscopy, and LCMS. The mechanism of the formation of the products is discussed.