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Abstract The reaction of 2-amino-1,1,3-tricyanopropene (malononitrile dimer) with isothiocyanates leads to 1-substituted 4,6-diamino-2-thioxo-1,2-dihydropyridine-3,5-dicarbonitriles or 4,6-diamino-2-(phenylimino)-2H-thiopyran-3,5-dicarbonitrile, depending on the conditions. Quantum-chemical modeling of the IR spectra and reaction routes for the synthesized compounds was carried out. In silico predictive analysis of potential protein targets, compliance with bioavailability criteria, and ADMET parameters was performed.

Bromination of (2E)-3-aryl(hetaryl)-2-[4-aryl(hetaryl)-1,3-thiazol-2-yl]acrylonitriles proceeds regioselectively at the C5 atom of the thiazole ring with the formation of new (2E)-3-aryl(hetaryl)-2-[5-bromo-4-aryl(hetaryl)-1,3-thiazol-2-yl]acrylonitriles. The latter were alternatively obtained by the reaction of aldehydes, cyanothioacetamide, α-bromoketones and bromine in the presence of triethylamine in DMF. Structure of the key compounds was confirmed using 2D NMR spectroscopy and single crystal X-ray diffraction analysis.

The reaction of cyanothioacetamide with aromatic aldehydes and 1,3-dicarbonyl compounds followed by aminomethylation or S-alkylation gave a series of heterocyclic derivatives with a 1,2,3,4-tetrahydropyridine or 1,4,5,6,7,8-hexahydroquinoline fragment. The resulting compounds were tested for analgesic activity in vivo. Some of the prepared compounds showed an antinociceptive effect superior to that of ketorolac in dynamics.

1,6-Diamino-2-oxo-1,2,3,4-tetrahydropyridine-3,5-dicarbonitriles under the action of primary aliphatic amines and an excess of 37% formalin in ethanol were converted into 2,3,8,9-tetrahydro-6,10-methano[1,2,4]triazolo[1,5-a][1,5]diazocine-6,10(7H)-dicarbonitrile derivatives. At the same time, the Mannich reaction in the case of 1,6-diamino-4-aryl-2-oxo-1,2-dihydropyridine-3,5-dicarbonitriles proceeds ambiguously, and, depending on the conditions, gives either N-ethoxymethylation products or 1,2,4-triazolo[1,5-a]pyridine derivatives. In silico predictive analysis of the biological activity of new compounds was carried out.

The sequential reaction of furfural with cyclic secondary amines and further with benzaldehyde and cyanoacetates affords new 2,4-dicyano-8-(R2N)-6-oxo-3-phenylbicyclo[3.2.1]-octane-2,4-dicarboxylates as rac-(1R,2R,3R,4S,5S,8R)-diastereomers. The structures of the reaction products were determined by X-ray diffraction.

The reaction of N-substituted amides of 3-amino-4,6-diarylthieno[2,3-b]pyridine-2-carboxylic acids with ninhydrin in the presence of catalytic amounts of sulfuric acid gave 1′-spiro[indene-2,2′-pyrido[3′,2′:4,5]thieno[3,2-d]pyrimidine]-1,3,4′(3′H)-triones. Structure of a number of key compounds was studied using 2D NMR spectroscopy; the bioavailability parameters of the obtained compounds in silico were calculated. In a laboratory experiment, a moderate antidote effect was revealed with respect to the 2,4-D herbicide for one compound.

New complex compounds LnL3·nH2O (n = 5–10) have been synthesized on the basis of Eu3+, Gd3+, and Tb3+ salts and quinoline-4-carboxylic acid derivatives obtained via the Pfitzinger reaction. Composition and structure of the ligands and the resulting complex compounds have been confirmed by NMR and IR spectroscopy, thermogravimetry, and complexometric titration. Europium complex with 1,2,3,4-tetrahydroacridine-9-carboxylic acid has exhibited efficient luminescence.

The reaction of 3-pentylpentane-2,4-dione with cyanothioacetamide afforded 4,6-dimethyl-5-pentyl-2-thioxo-1,2-dihydropyridine-3-carbonitrile. Alkylation of the latter led to the formation of 2-alkylsulfanyl-4,6-dimethyl-5-pentylpyridine-3-carbonitriles or 3-amino-4,6-dimethyl-5-pentylthieno[2,3-b]pyridines, depending on the alkylating agent and reaction conditions. The structures of the key compounds were proved by 2D NMR spectroscopy and X-ray analysis. Biological activity of the synthesized compounds was evaluated in silico. Some compounds were experimentally found to stimulate growth of sunflower seedlings.

A novel one-pot method based on the sequence of the Fisher reaction between nitroacetophenone and phenylhydrazines, the reduction with metallic tin directly in polyphosphoric acid, and acylation has been developed for the synthesis of indoloquinolines. The obtained indolo-[3,2-c]quinolines are precursors of the analogs of isocryptolepine alkaloid.

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.

2,4-Dioxo-3-azaspiro[5.5]undecane-1,5-dicarbonitrile reacted with primary amines and formaldehyde on heating in boiling ethanol to give mixtures of 7-alkyl-2,4-dioxo-3,7-diazaspiro[bicyclo[3.3.1]nonane- 9,1′-cyclohexane]-1,5-dicarbonitriles and their ammonium salts. The former were isolated in 26–71% after acidification of the reaction mixture.

Aminomethylation of xanthane hydride (5-amino-1,2,4-dithiazole-3-thione) with the RNH2–HCHO system has resulted in the formation of the derivatives of new heterocyclic system (3,7-dihydro-5H-[1,2,4]-dithiazolo[4,3-a][1,3,5]triazine) in low yields. The reaction of xanthane hydride with dicyandiamide has led to thioammeline [4,6-diamino-1,3,5-triazine-2(5Н)-thione]. Some practically important properties of xanthane hydride and its derivatives have been investigated. Xanthane hydride has efficiently exhibited carbon steel corrosion in neutral aqueous media. The prepared compounds have not exhibited growth-regulating or antidote activity to herbicide 2,4-D.

The aminomethylation of 4,4-dialkyl-2,6-dioxopiperidine-3,5-dicarbonitriles (Guareschi imides) was studied for the first time. When the Guareschi imides were treated with primary aliphatic amines and an excess of formaldehyde, 2,4-dioxo-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarbonitriles were obtained in varying yields (15–67%). The structure of 9,9-dimethyl-7-(2-methylpropyl)-2,4-dioxo-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarbonitrile was studied by X-ray diffraction analysis.

The review describes the history of development of organic chemistry in higher schools of Russia over a period of 170 years, since the emergence of organic chemistry in our country till now.

The aminomethylation reaction of 9-benzyl-2,4-dioxo-3,9-diazaspiro[5.5]undecane-1,5-dicarbonitrile hydrochloride in the presence of primary aliphatic amines and an excess of 37% aqueous formaldehyde led to the formation of 7-substituted 1'-benzyl-2,4-dioxo-1H,5Hspiro[3,7-diazabicyclo[3.3.1]nonane-9,4'-piperidine]-1,5-dicarbonitrile derivatives.

The reaction of tetra(phenylethynyl)tin with aromatic aldehydes in the presence of ZnCl2 afforded α-acetylene ketones in a yield of 77–98%.

A highly efficient synthetic route to 6,7-dihydro-1H-cyclopenta[gh]perimidines has been proposed on the basis of a novel reaction of nitroalkanes with 4,5-diaminoacenaphthene in the presence of polyphosphoric acid. The reaction involves phosphorylation of the aci-nitro compound, followed by intramolecular cyclization.

A highly efficient protocol for acid-mediated peri-annulation of perimidines with pyrimidines was developed. Pyrimidines, used as surrogates for 1,3-dicarbonyl compounds allow for furnishing benzo[gh]perimidines, including hardly available analogs, non-substituted, or mono-substituted at C-6, C-8. Limitations of reactions employing 5-bromopyrimidines are investigated.

The reaction of tetraalkynyltin with aldehydes was studied for the first time. The reaction was shown to proceed as a tandem process of nucleophilic addition of tin acetylide to aldehyde followed by Oppenauer-type oxidation of produced tin alcoholates, and may be used as a convenient one-pot approach to acetylenic ketones. The advantages and limitations of the proposed method are discussed.

A novel highly efficient preparative method for the synthesis of substituted indoles using conjugate addition of nucleophiles to 3-(2-nitrovinyl)indoles has been developed. The addition of nucleophiles generated in the presence of a base from CH acids was investigated. The studied reactions proceed quickly and smoothly under the conditions of microwave activation and do not require protection of the indole nitrogen atom.

A new, highly efficient method was developed for the synthesis of (3-indolyl)acetonitriles by reduction of readily available (3-indolyl)hydroxamic acids with phosphorus trichloride. The nitriles obtained according to this method are of significant interest for structure-activity studies of potential anticancer agents.