A. V. Gutov

New viologen analogs: 1,4-bis[2-(pyridin-4-yl)ethenyl]benzene quaternary salts

Alkylation of 1,4-bis[2-(pyridin-4-yl)ethenyl]benzene with alkyl p-toluenesulfonates and dimethyl sulfate gave new viologen analogs, 1-alkyl-4-(2-{4-[2-(1-alkylpyridinium-4-yl)ethenyl]phenyl}ethenyl)-pyridinium bis(p-toluenesulfonates) and sulfate. Their derivatives with tetrafluoroborate and tetraphenylborate ions were also obtained. Spectral properties of the synthesized compounds were examined, and their structure was determined by X-ray analysis.

Synthesis and alkylation of 1-alkyl(aryl)-4-cyano-3-dicyanomethylene-substituted carbo[c]fused pyridines. Molecular and crystal structure of 2-(4-cyano-1-methyl-5,6,7,8-tetrahydroisoquinolin-3-yl)-2-(2-oxo-2-phenylethyl)malononitrile and 10-amino-8-phenyl-5-(2-chlorophenyl)-1,2,3,4-tetrahydro-7H-pyrido[2′,3′:3,4]cyclopenta[1,2-c]isoquinoline-7,7,9-tricarbonitrile

Condensation of 2-acyl-1-(N-morpholinyl)cycloalkene with malononitrile dimer results in 1-alkyl-(aryl)-4-cyano-3-dicyanomethylene-substituted carbo[c]fused pyridines. Reaction of the latter with alkyl halides affords the corresponding 2-alkyl-2-(3-isoquinolinyl)malononitrile, 1-amino-2-(4-bromobenzoyl)-5-(2-chlorophenyl)-6,7,8,9-tetrahydro-3H-cyclopenta[c]isoquinoline-3,3-dicarbonitrile and 10-amino-8-phenyl-5-(2-chlorophenyl)-1,2,3,4-tetrahydro-7H-pyrido[2′,3′:3,4]cyclopenta[1,2-c]isoquinoline-7,7,9-tricarbonitrile. Structure of the latter and of 2-(1-methyl-4-cyano-5,6,7,8-tetrahydroisoquinolin-3-yl)-2-(2-oxo-2-phenylethyl)-malononitrile was investigated by XRD.

Synthesis of 3,3-Bis(diethylphosphono)-1-(3H)-isobenzofuranone and Its Chemical Properties

Abstract The reaction of o-phthaloyl chloride with sodium diethylphosphite leads to the formation of cyclic bisphosphonate—a 3,3-bis(diethylphosphono)-1(3H)-isobenzofuranone. The hydrolysis of 1-(3H)-isobenzofuranone with aqueous potash results in the acyclic α−ketophosphonate. At the same time, hydrolysis with hydrochloric acid yields the bisphosphonic acid in a good yield. The reaction of 3,3-bis(diethylphosphono)-1-(3H)-isobenzofuranone with benzylamine in the presence of triethylamine passes with the replacement of endocyclic oxygen on PhCH2N group to give the bisphosphonate-phthalimide The structures of the compounds were confirmed by IR, 1Н, 13С, 31Р NMR spectroscopies, mass spectra, and in one case, a single crystal X-ray analysis. GRAPHICAL ABSTRACT

The mannich reaction in the synthesis of n,s-containing heterocycles 3*. Unexpected direction of the aminomethylation reaction of N-methylmorpholinium 1-amino-2,4-dicyano-4-ethoxycarbonyl-1,3-butadienethiolate. One stage cascade synthesis of new derivatives of pyrido[1,2 -a][1,3,5]triazine

The interaction of N-methylmorpholinium 1-amino-2,4-dicyano-4-ethoxycarbonyl-1,3-butadienethiolate with primary amines and formaldehyde leads to the formation of ethyl esters of 7-cyano-6-thioxo-1,3,4,6-2H-pyrido[1,2-a][1,3,5]triazine-9-carboxylic acid in place of the expected derivatives of pyrido[2,1-b][1,3,5]thiadiazine. The structure of the ethyl ester of 7-cyano-3-phenyl-6-thioxo-1,3,4,6-2H-pyrido[1,2-a][1,3,5]triazine-9-carboxylic acid was demonstrated by X-ray structural analysis.

Synthesis of 3-(4-chlorophenyl)oxirane-2,2-dicarboxamide

Oxidation of (E)-3-(4-chlorophenyl)-2-cyanoprop-2-enethioamide with hydrogen peroxide or the H2O2-KOH system gave 3-(4-chlorophenyl)oxirane-2,2-dicarboxamide. This compound was also obtained by an independent “one pot” synthesis from p-chlorobenzaldehyde and 2-cyanoacetamide through in situ oxidation of their adduct (E)-3-(4-chlorophenyl)-2-cyanoprop-2-eneamide with the H2O2-KOH system. The structure of 3-(4-chlorophenyl)oxirane-2,2-dicarboxamide was confirmed by X-ray diffraction and spectroscopic data.

2,2-Bis(trifluoromethyl)-2,3-dihydro-1H-1,5-benzodiazepines

A method for the cyclization of hexafluoroacetone N-phenylimine derivatives with the formation of benzodiazepine analogs containing trifluromethyl groups has been elaborated. The obtained compounds were characterized by the NMR and mass spectral analysis and by the data from X-ray structural analysis.

3,3-Bis(diethylphosphono)-1(3H)-isobenzofuranone and Its Properties

Abstract The reaction of o-phthaloyl chloride with sodium diethylphosphite led to the formation of new 3,3-bis(diethylphosphono)-1-(3H)-isobenzofurane 1. The reaction of bis-phosphonate with alkylamine occurs with replacement of an ester oxygen by an imine group to afford the crystalline isoindolyl-bis-phosphonate—a representative of this new type of organophosphorus heterocycles.

The radziszewski oxidation of (E)-3-aryl-2-(thiazol-2-yl)acrylonitriles: A convenient diastereoselective synthesis of (2S,3S)-3-aryl-2-(thiazol-2-yl)oxirane-2-carboxamides

The oxidation of organic compounds with hydrogen peroxide in an alkaline medium is widely used in synthetic practice, in particular, for the preparation of catechol derivatives by the Dakin reaction, as well as for the epoxidation of activated olefins and the oxidative hydrolysis of nitriles [1‐3]. The latter transformation is known as the Radziszewski reaction [1, 4] and provides a convenient method for the conversion of nitriles into the corresponding amides [5‐7]. Hydroperoxy anion, which can be readily generated from hydrogen peroxide in the presence of a strong base, is one of the most available epoxidation agents and is often used for the oxidation of polar olefinic bonds according to the Weitz‐Scheffer procedure [2, 8, 9]. In this context, α , β unsaturated nitriles are of special interest as substrates for oxidation with peroxide since the hydroperoxide anion in this case can initially attack both the carbon atom of the nitrile group and the electron-deficient β carbon atom. In 1932, Murray and Cloke found that α , β -unsaturated nitriles underwent epoxidation under the Radziszewski reaction conditions to give the corresponding oxirane-2-carboxamides [10]. Payne and coworkers showed later for a series of other examples [5, 7] that this reaction is not always stereospecific and often is not regioselective: it is complicated by the side reaction of formation of oxirane-2-carbonitriles. In continuation of our studies in the field of cyanothioacetamide chemistry [11], we studied the behavior of its derivatives, ( E )-3-aryl-2-(thiazol-2-yl)acrylonitriles 1a ‐ 1d , under the Radziszewski reaction conditions. The treatment of suspensions of nitriles 1 in EtOH with an excess of 35% H 2 O 2 in the presence of 0.5 equiv. of 10% KOH upon short heating was found to produce substituted oxirane-2-carboxamides 2a ‐ 2d in high yields (87‐90%) (Scheme 1). It was revealed that the reaction proceeds slowly at ambient temperature; the use of larger amounts of KOH obviously increases the oxidation rate but generally leads to a decrease in the yield of amides 2 , presumably, on account of partial hydrolysis of both the initial reagents and the reaction products. It follows from the literature [5, 7, 10] that the initial attack of the hydroperoxide anion is directed preferably at the carbon atom of the nitrile group rather than at the β carbon atom. Resulting peroxycarboximidic acid 3 , containing a prochiral olefin moiety, undergoes intramolecular stereospecific epoxidation of the multiple bond with the retention of the initial E configuration to produce corresponding compound 2a ‐ 2d as a single diastereomer. Scheme 1.