V. P. Sheverdov

Reaction of α,β-unsaturated ketones with tetracyanoethylene

Abstract Reaction of tetracyanoethylene with α,β-unsaturated ketones was investigated. 3-R1-4-R2-6-R3-5-oxo-1,1,2,2-cyclohexanetetracarbonitriles, unsaturated tetracyanoalkanones, 3-R-5,5-dihydroxy-1,1,2,2-cyclohexanetetracarbonitriles, 1,2,2-tricyano-3-R-5-oxo-1-cyclohexanecarboxamides, 3-R1-4-R2-8-R3-5-hydroxy-7-oxo-6-azabicyclo[3.2.1]octane-1,2,2-tricarbonitriles were synthesized.

The synthesis of 3-amidinio-2-aminopyridine-4-carboxylates

Abstract A new class of isonicotinic acid derivatives, 3-amidinio-2-aminopyridine-4-carboxylates, from aqueous ammonia and β,β,γ,γ-tetracyanoalkanones, is reported.

Reaction of tetracyanoethylene with aldehydes. Synthesis of 6-imino-2,7-dioxabicyclo[3.2.1]octane-4,4,5-tricarbonitriles

It was discovered by means of dynamic NMR that the 1-(cis-1-methylprop-1-en-1-yl)-1,2-dimethyl-acenaphthylenonium ion generated under conditions of “long life” for carbocations underwent fast (ΔG#35.8 kJ mol−1 at −103°C) degenerate 1,2-shift of the cis-dimethylvinyl group. Quantum-chemical calculations by DFT method predict lower rate of 1,2-shift for the trans-dimethylvinyl group compared to cis-dimethylvinyl group and dependence on the cations conformation of the rates of these processes and of the rearrangement mechanism into the ions of phenalenyl type.

Tricomponent domino synthesis of 6-hydroxy-2-chloro-1,4,5,6-tetrahydropyridine-3,4,4-tricarbonitriles

In reaction of tetracyanoethylene with ketones and HCl in 1,4-dioxane at 30–40°? 6-hydroxy-2-chloro-1,4,5,6-tetrahydropyridine-3,4,4-tricarbonitriles are formed.

ANTITUMOR ACTIVITY OF POLYCYANO-SUBSTITUTED CARBO- AND HETEROCYCLES PREPARED FROM 3-(2,2-DIALKYLHYDRAZINO)- 4-R-1,1,2,2-TETRACYANOCYCLOPENTANES

Anticancer activity tests have been carried out at the National Cancer Institute (USA) on a series of polycyano-substituted carbo- and heterocyclic compounds synthesized from 3-(2,2-dialkylhydrazino)-4-R-1,1,2,2-tetracyanocyclopentanes. It is established that 1,1,2,2-tetracyano-substituted derivatives are the most active, showing a high activity comparable with that of reference drugs with respect to colon, ovarian, prostate, and renal cancer. The antitumor effect of the investigated compounds is explained by the presence of dialkylhydrazino- and 1,1,2,2-tetracyanoethyl moieties in their structures.

Reactivity with respect to bases of 5-hydroxy-7-oxo-6-azabicyclo[3.2.1]octane-1,2,2-tricarbonitriles

We reported formerly on the synthesis of 5-hydroxy-7-oxo-6-azabicyclo[3.2.1]octane-1,2,2-tricarbonitriles (Ia3f) from tetracyanoethylene and appropriate a,b-unsaturated ketones [1, 2]. We found that at treating the azabicyclic compounds Ia3f with various bases, in particular amines, pyrrolidine ring underwent opening yielding 5-oxo-1,2,2-tricyano-1-cyclohexanecarboxamides ( IIa 3d) that furthercyclized into 3-amino-1,6-dioxo-3a,4,5,6,7,7a-hexahydro-1H-isoindole-3a,7a-dicarbonitriles ( IIIa 3f). The conversion is affected by the reaction temperature and amount of the base brought intoreaction. The use of equimolar quantity of sodium alcoholate in the corresponding alcohol at room temperature led to heterolytic cleavage of the N3C bond in azabicyclic compounds Ia3f to afford carboxamidesIIa 3d. At heating aza-

The interaction of 1,1,2-tricarbamoyl-2-cyanoethane with alkyl vinyl ketones — A new approach to [3.3.3]propellanes

Abstract Single-stage synthesis of 3,7-diacyl-2,6-diamino-9,11-dioxo-10-aza[3,3,3]propella-2,6-dienes from 1,1,2-tricarbamoyl-2-cyanoethane and alkyl vinyl ketones, is reported.

Antiproliferative Activity of Cyano-Substituted Pyrans and 1,2,5,6,7,8-Hexahydroquinoline-3,3,4,4-Tetracarbonitriles

The antiproliferative activity of methyl-6-amino-3-acyl-4-aryl-5-cyano-4H-pyran-2-carboxylates, 9-aryl-12-imino-10,11-dioxatricyclo[5.3.2.01, 6]dodecane-7,8,8-tricarbonitriles, and 1,2,5,6,7,8-hexahydroquinoline-3,3,4,4-tetracarbonitriles was investigated.

Compounds of the menthane series. Synthesis of unsaturated primary alcohols with the o- and p-menthane skeletons

Precursors to terpene alcohols of the o- and p-menthane series (o-cimen-7-ol and o- and p-cimen-9-ols) were synthesized, and their reduction with lithium in ethylenediamine was studied. The reduction of o- and p-cimen-9-ols in the presence of isopropyl alcohol selectively afforded the corresponding 1,4-dihydro derivatives. Under analogous conditions, o-cimen-7-ol was converted into a mixture of unsaturated hydrocarbons. The reduction with lithium in ethylenediamine in the absence of isopropyl alcohol in all cases gave mixtures of menthene alcohols.

Synthesis and Antimicrobial, Analgesic, Antipyretic, and Immunotropic Activity of Methyl 3-Aryl-6-Amino-4-Aryl-5-Cyano-4H-Pyran-2-Carboxylates

A series of methyl 3-acyl-6-amino-4-aryl-5-cyano-4H-pyran-2-carboxylates were synthesized using the reaction of methyl 2,4-dioxobutanoates with arylidenemalononitriles in EtOAc in the presence of catalytic amounts of morpholine or piperidine. The structures of the compounds were elucidated using IR, PMR, 13C NMR, and mass spectral data. The antimicrobial, analgesic, and antipyretic activities of the synthesized compounds and their influence on antibody response were studied.