Synthesis of 2-aryl-6-(4-bromophenyl)-4-(2,2-dichlorovinyl)pyridines with the use of 1-aryl-5,5-dichloropenta-2,4-dien-1-ones

Heating 1-aryl-5,5-dichloropenta-2,4-dien-1-ones with 4-bromophenacylpyridinium bromide in AcOH in the presence of AcONH₄ gave 2-aryl-6-(4-bromophenyl)-4-(2,2-dichlorovinyl)pyridines. The reaction products were structurally characterized by¹H and¹³C NMR spectroscopy. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 955–957, May, 2000.     

Reactions of 1-aryl-2-bromodiazene 1-oxides with acids and bases

The reactions of 1-aryl-2-bromodiazene 1-oxides with HCl in nonaqueous media give aryldiazonium chlorides, while 1,3,3-substituted triazenes-1 are formed in the reactions with secondary amines. Using 2-{¹⁵N} label, it was shown that the aryl group does not migrate in these reactions. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 613–615, March, 1997.     

Interaction of decacarbonyldimanganese and decacarbonyldirhenium with 1-aryl-3-cyanoprop-2-en-1-ones

The reactions of M₂(CO)₁₀ (M = Mn, Re) withtrans-1-aryl-3-cyanoprop-2-en-1-ones in the presence of Me₃NO proceed with replacement of the CO ligand and lead to complexeseq-(1-aryl-3-cyanoprop-2-en-1-on)nonacarbonyldimanganese andeq-(1-aryl-3-cyanoprop-2-en-1-on)nonacarbonyldirhenium complexes where the metals are bonded with the ligand through the nitrogen atom of the cyanogroup. The treatment of (1-phenyl-3-cyanoprop-2-en-1-on)nonacarbonyldirhenium with a second equivalent of the ligand resulted in the disubstituted complex,eq,eq-bis(1-phenyl-3-cyanoprop-2-en-1-on)octacarbonyldirhenium in a good yield. The structures of the obtained complexes are discussed on the basis of¹³C,¹H NMR, and IR-spectroscopy.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1485–1487, August, 1994.This work was supported in part by the Russian Foundation for Basic Research (grant No 93-03-4028).     

Synthesis of 3-acetyl-4-amino-6-arylpyran-2-ones and ethyl 7-aryl-4,5(1H,5H )-dioxopyrano[4,3-b]pyridine-2-carboxylates

The reactions of aroylacetonitriles with the nickel chelate of ethyl acetoacetate afforded new block heterocyclic reagents, viz., 3-acetyl-4-amino-6-arylpyran-2-ones. The reactions of the latter with diethyl oxalate gave rise to ethyl 7-aryl-4,5(1H,5H)-dioxopyrano[4,3-b]pyridine-2-carboxylates.     

Stereochemicai study of 7-aryl-1,7,8,8a-tetrahydro-3(2H)indolizinones by1H and13C NMR

Stereochemistry of 7-aryl-1,7,8,8a-tetrahydro-3(2H)-indolizinones was studied by¹H and¹³C NMR. Complete assignment of¹H NMR signals and analysis of¹H-¹H coupling constants were performed using the iterative PANIC program. Values of³ J _6,7,³ J _7,8endo, and⁴ J _5,7 allow one to unambiguously identify the correspondingexo- andendo-stereoisomers. For stereoisomers with exo-orientation of H(7), complete assignment of¹³C NMR signals was performed on the basis of analysis of the¹³C-¹H coupling constants using two dimensional heteronuclear shift-correlating spectroscopy.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 591–593, March, 1996.     

1,4-二氢-4-芳基-3,5-吡啶二羧酸酯的合成及表征

基于二氢吡啶化合物的构效关系, 设计了一系列1,4-二氢-4-芳基-3,5-吡啶二羧酸酯新化合物. 含有易于水解基团的1,4-二氢-4-芳基-3,5-吡啶二羧酸酯类化合物在碱性条件下水解合成了重要中间体1,4-二氢-4-芳基-3,5-吡啶二羧酸单酯, 收率93%～99.8%. 该二羧酸单酯与α-溴代芳基乙酮在相转移剂催化下反应合成目标化合物, 收率74%～99%. 中间体和目标化合物经¹H NMR, ¹³C NMR, IR, MS和元素分析等确证.     

Synthesis of 2-iminoimidazolidin-4-one derivatives by cyclization of 2-aryl-1-(4,6-dimethylpyrimidin-2-yl)guanidines with ethyl bromoacetate, dimethyl acetylenedicarboxylate, and maleic anhydride

Derivatives of 2-iminoimidazolidin-4-one, (E)-methyl (2-imino-5-oxoimidazolidin-4-ylidene)acetate, and (2-imino-5-oxo-imidazolidin-4-yl)acetic acid were synthesized by the cyclization of 2-aryl-1-(4,6-dimethylpyrimidin-2-yl)guanidines with ethyl bromoacetate, dimethyl acetylenedicarboxylate, and maleic anhydride, respectively. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1372–1378, July, 2007.     

微波辐射下合成3-芳基-9-氨基-1,2,3,4-四氢吖啶-1-酮衍生物

在微波辐射和对甲基苯磺酸的催化作用下, 5-芳基-1,3-环己二酮与邻氨基苯甲腈进行缩合反应, 得到了N-取代的2-氨基苯甲腈衍生物, 在K₂CO₃和Cu₂Cl₂的催化作用下进一步合环, 得到3-芳基-9-氨基-1,2,3,4-四氢吖啶-1-酮衍生物, 用LiAlH₄还原羰基得到3-芳基-9-氨基-1,2,3,4-四氢吖啶-1-醇衍生物. 新合成化合物的结构均经元素分析、红外光谱和核磁共振光谱予以确认.     

Preparation of 3-Aryl-4-(5-ARYL-Δ2-1,2,4-Oxadiazolin-3-YL)Sydnones and their Conversion into 3-ARYL-4-(5-ARYL-1,2,4-Oxadiazol-3-YL)Sydnones

3-Aryl-4-(5-aryl-Δ²-1,2,4-oxadiazolin-3-yl)sydnones (5) were synthesized in high yields by the reaction of 3-arylsydnone-4-carboxamide oximes (prepared from the corresponding 3-arylsydnone-4-carbonitriles) with aromatic aldehydes in the presence of acid catalysts. No reaction occurred when aliphatic aldehydes were used. The oxadiazolin-3-ylsydnones (5) were easily converted into the corresponding 3-aryl-4-(5-aryl-1,2,4-oxadiazol-3-yl)sydnones by N-bromosuccinimide oxidation. The 3-arylsydnone-4-carbonitrile oxides were synthesized in good yields by N-bromosuccinimide oxidation of the corresponding 3-arylsydnone-4-carboxaldehyde oximes.     

Effective synthesis of 5-aryl-3-ethylidene-3H-pyrrol-2-ones

Substituted 5-aryl-3-ethylidene-3H-pyrrol-2-ones were synthesized by the reaction of the corresponding 4-aryl-4-oxobutanoic acids with ketones in the presence of aminating agents. The conditions of this reaction were developed with the use of both the conventional condensation technique and microwave activation. The structures of the reaction products were con-firmed by elemental analysis, IR spectroscopy, and ¹H NMR spectroscopy. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 693–696, April, 2006.     

Reduction of (<Emphasis Type="Italic">E</Emphasis>)-3-aryl-2-(thiazol-2-yl)acrylonitriles with lithium aluminum hydride

Reduction of (E)-3-aryl-2-(4-arylthiazol-2-yl)acrylonitriles with lithium aluminum hydride in dry ether afforded (Z)-1-amino-3-aryl-2-(thiazol-2-yl)prop-1-ene derivatives in 15 to 40% yields. The structure of (Z)-1-amino-3-(2-chlorophenyl)-2-[4-(4-methylphenyl)thiazol-2-yl]prop-1-ene was confirmed by X-ray diffraction analysis. Dedicated to Academician N. K. Kochetkov on the occasion of his 90th birthday. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1301–1303, May, 2005.     

Effects of different GIAO and CSGT models and basis sets on 2-aryl-1,3,4-oxadiazole derivatives

The direct molecular structure implementations of the gage-including atomic orbital (GIAO), individual gages for atoms in molecules (IGAIM) and continuous set of gage transformations (CSGT) methods for calculating nuclear magnetic shielding tensors at both the Hartree-Fock (HF) and density functional (B3LYP) levels of theory with 6-31G(d), 6-311G(d), 6-31++G(d,p), 6-311++G(d,p), and 6-311++G(df,pd) basis sets are presented. Dependence on the ¹H and ¹³C NMR chemical shifts on the choice of method and basis set have been investigated. Also, these chemical shifts of 2-aryl-1,3,4-oxadiazoles 5a–g have been performed related to dihedral angles (C4–C3–C2–O) of two conformers. The optimized molecular geometries and ¹H and ¹³C chemical shift values of 2-aryl-1,3,4-oxadiazoles 5a–g in the ground state have been obtained. The linear correlation coefficients of ¹³C NMR chemical shifts for these molecules were given. The new nuclear magnetic shielding tensors of tetramethylsilane (TMS) were calculated. The data of 2-aryl-1,3,4-oxadiazole derivatives display significant molecular structure and NMR analysis. Also, these provide the basis for future design of efficient materials having the 1,3,4-oxadiazole core.     

Reactions of 2-aryl-4-arylidene-4<Emphasis Type="Italic">H</Emphasis>-oxazol-5-ones with 3-amino-1,2,4-triazole, 5-aminotetrazole,and 2-aminobenzimidazole

The reactions of 3-amino-1,2,4-triazole, 5-aminotetrazole, and 2-aminobenzimidazole with 2-aryl-4-arylidene-4H-oxazol-5-ones (azlactones) were studied. The electron-releasing properties of the azole ring were demonstrated to influence the reaction pathway of azlactones with aminoazoles. The structures of the resulting compounds were established by ¹H and ¹³C NMR spectroscopy using spin-spin decoupling and the nuclear Overhauser effect.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2730–2733, December, 2004.     

Novel two step synthesis of bis/Mono 1-aryl-1H-tetrazole-5-carboxylic acid

Some novel compounds of bis/mono 1-aryl-1H-tetrazole-5-carboxylic acid are synthesized by the hydrolysis of two different synthesized esters, they are ethyl-1-aryl-1H-tetrazole-5-carboxylate and ethyloxo(1-aryl-1H-tetrazol-5-yl)acetate. The ethyl-1-aryl-1H-tetrazole-5-carboxylate is resistant to get hydrolyzed, whereas the ethyloxo(1-aryl-1H-tetrazol-5-yl) acetate undergoes hydrolysis process and converts the ester to title compound. All the synthesized compounds are characterized by IR, ¹H and ¹³C NMR, mass and elemental analysis.The ethyl-1-aryl-1H-tetrazole-5-carboxylateis optimized by DFT B3LYP method and the HOMO and LUMO energy is 5.14?eV and also there is a formation of a weak bond between O₁₈ and C₈ as observed from the AIM analysis result.     

Reactions of 4-Aryl-1,2,4-triazolidine-3,5-dithione with Some Electrophilic Reagents

Reaction of 4-aryl-1,2,4-triazolidine-3,5-dithiones in an alkaline medium with chloroacetic acid and its derivatives, as well as with -bromo ketones, results in their conversion to 4-aryl-1,2,4-triazole-3,5-bis(sulfides). The aminomethylation in a neutral medium leads to the formation of 1-(aminomethyl)-4-aryl-1,2,4-triazolidine-3,5-dithiones.     

A novel three-component reaction of 1, 1-dicyano-2-(trifluoromethyl)ethylenes,primary arylamines,and ketones

1, 1-Dicyano-2, 2-bis(trifluoromethyl)ethylene and 3, 3-dicyano-2-(trifluoromethyl)acrylates react with primary arylamines in the presence of ketones to form 1, 1-aryl-1, 4-dihydropyridme derivatives under mild conditions. The mechanism of this three-component reaction includes the formation of Schiffs bases as intermediates. 1, 4-Dihydropyridine derivatives, which are the products of three-component heterocyclization, were also obtained by reaction the corresponding Schiffs bases with 1, 1-dicyano-2-(trifluoromethyl)ethylenes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 552–559, March, 1993.For preliminary communication see Ref. 1.     

Determination of the structure of 7-diethylamino-4-(1,2,3-triazol-1-yl)-2H-1-benzopyran-2-one derivatives using two-dimensional heteronuclear chemical-shift correlated NMR techniques

¹H and¹³C NMR spectra of 7-diethylamino-4-(1,2,3-triazol-1-yl)-2H-1-benzopyran-2-one derivatives have been studied. The location of the substituent in the 1,2,3-triazole ring was determined by the 2D COLOC method. It was established that the H(3) and H(5) protons in the coumarin moiety experience anisotropic influence of the phenyl subsituent at the C(5) atom in the triazole ring.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1330–1332, July, 1994.     

The Synthesis and Reactions of N-Hydroxy-3-Arylsydnone-4-Carboxamide Oximes

N-Hydroxy-3-arylsydnone-4-carboxamide oximes (7) were prepared from the corresponding 3-arylsydnone-4-carbohydroximic acid chlorides (6) and hydroxylamine in high yield. The chemical reactivity of compound (2) is somewhat different from 3-arylsydnone-4-carboxamide oximes (2) in that the former compounds reacted with both aromatic and aliphatic aldehydes in the presence of acid catalyst to give 3-aryl-4-(5-aryl-1,2,4-oxadiazol-3-yl)sydnones (5) and 3-aryl-4-(5-alkyl-1,2,4-oxadiazol-3-yl)sydnones (3).     

4-甲基-苯磺酸-2-氧-2-[3-(5-芳基-[1,3,4]噁二唑-2-基)-硫脲]-乙基酯的合成及生物活性研究

合成了12个未见文献报道的4-甲基-苯磺酸2-氧-2-[3-(5-芳基-[1,3,4]噁二唑-2-基)-硫脲]-乙基酯, 其结构经元素分析、¹H NMR和IR确证. 初步活性测试结果表明: 部分化合物有较好的杀菌活性.     

UNPRECEDENTED OUTCOME OF BASE-PROMOTED NEBER REARRANGEMENT OF O-MESYLOXIME OF 2-ARYL-1,2,3,4-TETRAHYDRO-1-METHYLSUL FONYL-4-QUINOLONE- SYNTHESIS OF 4-AMINO-2-ARYLQUINOLINES

Abstract

O-Mesyloximes derived from 2-aryl-1,2,3,4-tetrahydro-1-methylsulfonyl-4-quinolones react with sodium ethoxide in ethanol to afford the 4-amino-2-arylquinolines in high yield. No traces of the 3-amino-2-aryl-4-quinolones expected from the Neber rearrangement of the substrates were detected or isolated from the reaction mixture. The structures of the products were determined using a combination of ¹H NMR, ¹³C NMR, IR and mass spectroscopic techniques.