T. A. Volovnenko

4-Oxo-3,4-dihydroquinazolinyl- and Benzimidazolylacetonitriles in Annelation Reactions of a Haloquinoline Ring

The interaction of 4-oxo-3,4-dihydroquinazolinyl- and benzimidazolylacetonitriles with 2,6-dihalobenzaldehydes leads to 3-(2,6-dihalophenyl)-2-(4-oxo-3,4-dihydro-2-quinazolinyl)acrylonitriles and 2-(1H-benzo[d]imidazol-2-yl)-3-(2,6-dihalophenyl)acrylonitriles respectively. As a result of intramolecular cyclization of these nitriles 4-halo-12-oxo-12H-quino[2,1-b]quinazoline-6-carbonitriles and 4-halobenzo[4,5]imidazo[1,2-a]quinoline-6-carbonitriles respectively are formed.

Synthesis and Properties of 2-Amino-6-nitroindoles

A new method is proposed for the synthesis of 2-amino-6-nitroindoles, based on the reaction of 2-haloanilines and substituted acetonitriles. The reaction of 2-amino-6-nitroindoles with β-dicarbonyl compounds was studied.

Synthesis of 5-Amino-1-aryl-4-(4-aryl-1,3-thiazol-2-yl)- 2,3-dihydro-1H-pyrrol-3-ones*

Reactions of 2-(4-aryl-1,3-thiazol-2-yl)-3-oxo-4-chlorobutyronitriles with primary aromatic amines result in nucleophilic substitution of the chlorine atom by amino group, followed by intramolecular addition of the secondary amino group to the cyano group. The products are 5-amino-1-aryl-4-(4-aryl-1,3-thiazol-2-yl)- 2,3-dihydro-1H-pyrrol-3-ones which are structurally related to the known antiischemic drugs.

Synthesis of 2-(2-hetaryl)-6-hydroxy-3-(R-amino)-2-hexenenitriles

The reaction of 2-hetaryl-2-(tetrahydrofuran-2-ylidene)acetonitriles and 6-chloro-2-(2-hetarylidene)-3-oxohexanenitriles with amines was studied. It was shown that the reaction of primary aliphatic amines with 6-chloro-2-(2-hetarylidene)-3-oxohexanenitriles takes place through a stage involving the formation of 2-hetaryl-2-(tetrahydrofuran-2-ylidene)acetonitriles followed by opening of the furanylidene fragment of the latter and the formation of 2-(2-hetaryl)-6-hydroxy-3-(R-amino)-2-hexenenitriles.

The reaction of 2-hetarylacetonitriles with heterocyclic haloaldehydes

The reaction of 4-oxo-3,4-dihydroquinazolyl-and benzimidazolylacetonitriles with 2-chloro-2-quinolinecarbaldehydes and 1-aryl-5-chloro-3-methyl-1H-pyrazole-4-carbaldehydes gave the corresponding 3-(2-chloro-3-quinolyl)-2-(4-oxo-3,4-dihydro-2-quinazolyl)-2-propenenitriles and 3-(1-aryl-5-chloro-3-methyl-1H-4-pyrazolyl)-2-hetaryl-2-propenenitriles. Intramolecular cyclization of these compounds gives 15-oxo-15H-benzo[6,7][1,8]naphthyridino[2,1-b]quinazoline-6-carbonitriles, 1-aryl-3-methyl-11-oxo-1,11-dihydropyrazolo[4′,3′:5,6]pyrido[2,1-b]quinazoline-5-carbonitriles, and 1-aryl-3-methyl-1H-benzo[4,5]imidazo[1,2-a]pyrazolo[4,3-e]pyridine-5-carbonitriles.

Novel synthesis of 2-amino-3-hetaryl-4(5H)-oxothiophenes

Abstract3-Cyano-3-hetaryl-2-oxopropyl thioacetates were obtained by the acylation of hetarylacetonitriles with acetylmercaptoacetyl chloride. Their reaction with amines led to the formation of 2-amino-3-hetaryl-4(H)-oxothiophenes.

Synthesis and properties of 6,7,8-substituted 2-(4-oxo-3,4-dihydro-2-quinazolinyl)-acetonitriles

Abstract2-(4-Oxo-3,4-dihydro-2-quinazolinyl)acetonitriles have been obtained by the interaction of α-cyanoethylthioiminoacetate with substituted anthranilic acids. Prototropy became apparent in the series of synthesized compounds. Reactions of the 2-(4-oxo-3,4-dihydro-2-quinazolinyl)acetonitriles have been carried out with (hetero)aromatic aldehydes leading to the formation of 3-aryl-2-(4-oxo-3,4-dihydro-2-quinazolinyl)acrylonitriles.

Reaction of 2-(4-Arylthiazol-2-yl)-4-chloro-3-oxobutyronitriles with Secondary Aliphatic Amines

We have obtained 2-(4-arylthiazol-2-yl)-4-chloro-3-oxobutyronitriles by acylation of 4-aryl-2-cyanomethylthiazoles with α-chloroacetyl chloride. We have studied their reaction with secondary aliphatic amines, leading to formation of 4-dialkylamino-2-(4-arylthiazol-2-yl)-3-oxobutyronitriles, and also intramolecular alkylation with formation of 3-aryl-7-cyano-6(5H)-oxopyrrolo[2,1-b]thiazoles. We have determined some aspects of the tautomerism of the synthesized compounds.

Nucleophilic substitution in 1-alkyl-4,5-dichloro-3-nitropyridazin-6-ones

Treatment of 1-alkyl-4,5-dichloro-3-nitropyridazin-6-one with C-nucleophiles and with ambident nucleophiles (2-azahetarylacetonitriles) leads to a selective substitution of a chorine atom by the quaternary carbon atom of the carbanion formed from a substituted acetonitrile. The pKa of the CH-acid 2-(1-alkyl-5-chloro-3-nitro-6-oxo-1,6-dihydro-4-pyridazinyl)malononitrile was determined by potentiometric titration. Reaction of 2-(1-alkyl-5-chloro-3-nitro-6-oxo-1,6-dihydro-4-pyridazinyl)-2-hetarylacetonitriles with primary amines gives 6,7-dihydro-1H-pyrrolo[2,3-d]pyridazin-7-ones.

New method of synthesis of 2-amino-4(5H)-oxothiophenes

A new method is proposed for the synthesis of 2-amino-4(5H)-oxothiophenes with aryl and hetaryl substituents in position 3 of the molecule by the acylation of aryl- and 2-azahetarylacetonitriles with mercaptoacetic acid ethyl ester.