A. Yu. Alekseeva

Heterocyclization of michael adducts of β-diketones with arylmethylidene derivatives of malononitrile dimers

Reaction of arylmethylidene derivatives of malononitrile dimer with 1,3-cyclohexanediones in anhydrous methanol in the presence of sodium methylate as catalyst affords 4-amino-5-aryl-2-methoxy-6-oxo-5,6,7,8,9,10-hexahydrobenzo[b][1,8]naphthyridine-3-carbonitrile. In the presence of strong electron-donor substituents in the benzene ring the reaction takes another route resulting in 4-amino-2-aryl-6-methoxypyridine-3,5-dicarbonitriles.

One-step synthesis of chromeno[2,3-b]pyridines

Three-component condensation of aliphatic aldehydes with resorcinol and malononitrile dimer (2-aminoprop-1-ene-1,1,3-tricarbonitrile) afforded the corresponding 5-alkyl-2,4-diamino-8-hydroxy-5H-chromeno[2,3-b]pyridine-3-dicarbonitriles.

Synthesis of fluorescent alkoxybenzylidene derivatives of malononitrile dimer in water in the presence of Triton X-100

An efficient procedure has been developed for the synthesis of alkoxybenzylidene derivatives of malononitrile dimer in water in the presence of nonionic surfactant (Triton X-100). Depending on the number and position of alkoxy groups, the products showed solid-state fluorescence with the emission maximum in the range λ 491–560 nm.

Synthesis of polyfunctional 2-thionicotinonitriles

Reaction of 2-amino-4-arylbuta-1,3-diene-1,1,3-tricarbonitriles with sulfur in benzonitrile affords 4-amino-6-aryl-2-thio-1,2-dihydropyridine-3,5-dicarbonitriles. They also are synthesized by an authentic synthesis from 4-amino-6-aryl-2-bromopyridine-3,5-dicarbonitriles and sodium hydrosulfide.

Three-component synthesis of 5-aryl-1,8-naphthyridine-3-carbonitriles

A procedure has been developed for the synthesis of highly functionalized 1,8-naphthyridines by three-component condensation of aromatic aldehydes with malononitrile dimer and enamino ketones.

MIRC reactions of 4-aryl-2-aminobuta-1,3-diene-1,1,3-tricarbonitriles. Synthesis of 2-amino-6-aryl-5-cyano-4-(dicyanomethylidene)-3-azabicyclo[3.1.0]hex-2-ene-1-carboxylic acid esters and amides

Abstract4-Aryl-2-aminobuta-1,3-diene-1,1,3-tricarbonitriles (benzylidene derivatives of malononitrile dimer) reacted with bromo(cyano)acetic acid amide and esters to give the corresponding 2-amino-6-aryl-5-cyano-4-(dicyanomethylidene)-3-azabicyclo[3.1.0]hex-2-ene-1-carboxylic acid amides and esters.

Reaction of bromomalononitrile with 2-amino-4-arylbuta-1,3-diene-1,1,3-tricarbonitriles

Abstract3-Amino-4-aryl-1-dicyanomethylidene-1,3a,4,4a-tetrahydrocyclopropa[c]pyrrole-3a,4a-dicarbonitriles were synthesized by reaction of 2-amino-4-arylbuta-1,3-diene-1,1,3-tricarbonitriles (arylmethylidene derivatives of malononitrile dimer) with bromomalononitrile.

Synthesis of fused derivatives of 1,8-naphthyridine

Reactions of aromatic aldehyde, 2-aminoprop-1-ene-1,1,3-tricarbonitrile and cyclic enhydrazinoketones led to the formation of N-substituted 5-aryl-2,4-diamino-6-oxo-5,6,7,8,9,10-hexahydrobenzo[b][1,8]- naphthyridine-3-carbonitriles

Use of a water solution of surfactant in Knoevenagel reaction

In reaction of vanillin with active methylene compounds in the presence of detergent Oksipav AP the corresponding substituted alkenes were formed in high yields.

MIRC reactions of 4-aryl-2-aminobuta-1,3-diene- 1,1,3-tricarbonitriles. Synthesis of alkyl 6-aryl-5-cyano-4-(dicyanomethylidene)-2-oxo-3-azabicyclo[3.1.0]hexane-1-carboxylates

MIRC (Michael-initiated ring closure) reactions offer an elegant strategy for building up cyclic structures [1–5]. As a rule, these reactions lead to the formation of monocyclic compounds from simple substrates. While developing these strategy, we proposed to use polyfunctional Michael acceptors, which ensured conditions for tandem fusion of a second ring [6–13]. For example, our previous studies of the chemical behavior of 4-aryl-2-aminobuta-1,3-diene-1,1,3-tricarbonitriles showed that their reactions with CH acids (Michael donors) involve successive formation of fused systems (DHARMA synthesis) [6, 7]. It was also found that bromo-substituted methylene-active compounds as Michael donors reacted with activated alkenes via tandem formation of cyclopropane and pyrrole rings and that these reactions are diastereoselective (only one of possible isomers was formed). For example, 2-amino-6-aryl-4-(dicyanomethylidene)-3azabicyclo[3.1.0]hex-2-ene-1,5-dicarbonitriles were obtained from bromomalononitrile [12], and bromo(cyano)acetamide gave rise to 2-amino-6-aryl-5-cyano4-(dicyanomethylidene)-3-azabicyclo[3.1.0]hex-2-ene1-carboxamides [13]; the aryl substituent in the products was oriented trans with respect to the pyrrole ring. We continued studies in this line, and carried out reactions of 4-aryl-2-aminobuta-1,3-diene-1,1,3-tricarbonitriles 1a–1c with dimethyl and diethyl 2-bromomalonates under basic conditions. As a result, we isolated alkyl 6-aryl-5-cyano-4-(dicyanomethylidene)2-oxo-3-azabicyclo[3.1.0]hexane-1-carboxylates 2a– 2c in 78–83% yield. The structure of 2a–2c was confirmed by IR, H NMR, and mass spectra. The presence of a threemembered cyclopropane ring in their molecules