N-azirin-3-yl and N-indol-3-yl azaxylylenes

Flash-vacuum pyrolysis of N-(2,3-diphenylazirin-3-yl)dihydrobenzoxainones leads to transient N-azirinyl- and N-indolylazaxylylenes which give 2-arylindoles (5) and dihydroindoloquinolines (8) respectively. 5H-1,4-Benzodiazepines are implicated as the precursors to the indoles via the methylene nitrile ylides (9) and an alternative route to the latter by flash pyrolysis of N-(2-methylphenyl)benzimidoyl chlorides (10) provides a new, simple route to 2-arylindoles.     

噁唑、苯并噁唑及1,3,4-噁二唑硫醚的合成及抗肿瘤活性研究

设计并以噁唑、苯并噁唑及1,3,4-噁二唑硫醇与卤代烃反应合成了14个硫醚类杂环化合物, 其中13个化合物未见文献报道. 目标化合物的结构均通过¹H NMR谱、MS和元素分析进行了表征. 采用MTT [3-(4,5-dimethylthiagol-2-yl)- 2,5-diphenyltetrogolium bromide]法对14个目标化合物进行了体外抗肿瘤活性测定, 结果表明: 在10^－5 mol/L 浓度下, 10个化合物对肿瘤细胞具有抑制活性.     

Beyond vinyl: electronic structure of unsaturated propen-1-yl, propen-2-yl, 1-buten-2-yl, and trans-2-buten-2-yl hydrocarbon radicals

Vertical excitation energies and oscillator strengths for several valence and Rydberg electronic states of vinyl, propen-1-yl, propen-2-yl, 1-buten-2-yl, and trans-2-buten-2-yl radicals are calculated using the equation-of-motion coupled cluster methods with single and double substitutions (EOM-CCSD). The ground and the lowest excited state (n <-- pi) equilibrium geometries are calculated using the CCSD(T) and EOM-SF-CCSD methods, respectively, and adiabatic excitation energies for the n <-- pi state are reported. Systematic changes in the geometries, excitation energies, and Rydberg state quantum defects within this group of radicals are discussed.     

Synthesis of D-Glucos-2-yl Sucros-2-yl Phosphate (Agrocinopin C) and bis(D-glucos-2-yl) Phosphate (Agrocinopin D)

Abstract

The synthesis of a substance with the revised structure proposed for agrocinopin C, D-glucos-2-yl sucros-2-yl phosphate, via the hydrogen-phosphonate approach to phosphodiesters is presented. Agrocinopin D, related to agrocinopin C by the lack of the fructofuranosyl part of the sucrose moiety, is synthesized via direct formation of hydrogen-phosphonate diesters from appropriately protected monosaccharides and phosphonic acid.     

Synthesis of (m-carboran-9-yl)ferrocene and (m-carboran-9-yl)cymantrene

Cross-coupling reactions of 9-iodo-m-carborane with ferrocenylzinc chloride or cymantrenylzinc chloride catalyzed by (Ph₃P)₂PdCl₂ result in the formation of (m-carbo ran-9-yl)ferrocene and (m-carboran-9-yl)cymantrene, respectively. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 542–543, March, 1998.     

Formylation of indol-1-yl acetates

Preparation procedure was developed for 3-formylindole-5,6-dicarbonitriles underlain by the treatment of 1-acetoxyindole-5,6-dicarbonitriles with Vilsmeier-Haack reagent; a special feature of this reaction consisted in a replacement of the OAc group for hydrogen. A probable mechanism was assumed of the formation of 3-formylindole-5,6-dicarbonitriles.     

Degenerate rearrangement of 9-isopropenyl-9,10-dimethyl-phenanthren-9-yl and 9,10-dimethyl-9-(trans-1-methylprop-1-en-1-yl)phenanthren-9-yl cations

¹H NMR study has shown that long-lived 9-R-9,10-dimethylphenanthren-9-yl cations (R = isopropenyl, trans-1-methylprop-1-en-1-yl) generated in the system HSO₃F-SO₂ClF-CD₂Cl₂ at ?130°C undergo degenerate rearrangement via 1,2-vinyl shifts (ΔG’ = 37 and 39 kJ/mol, respectively, at ?88°C). Analysis of the geometric parameters of the initial structures and transition states calculated by the DFT method indicates that unfavorable steric factors are responsible for the sharp deceleration of 1,2-shifts of the isopropenyl and trans-1-methylprop-1-en-1-yl groups as compared to vinyl and cis-1-methylprop-1-en-1-yl groups, respectively.     

(Pyrrol-1-yl)furazans

Short-time reactions of 3-amino-4-R-furazans with 2,5-dimethoxytetrahydrofuran in boiling acetic acid afford (pyrrol-1-yl)furazans. One of the products was characterized by X-ray diffraction analysis.     

1,2-Dicarba-closo-dodecaboran-1-yl naphthalene derivatives

1,2-Dicarba-closo-dodecaboranes (o-carboranes) and naphthalenes have potential value as components or building blocks for supramolecular systems. We have efficiently synthesized 1-(1,2-dicarba-closo-dodecaboran-1-yl)naphthalene and 2-(1,2-dicarba-closo-dodecaboran-1-yl)naphthalene derivatives by employing three preparative methods: cyclization of the corresponding acetylenes with decaborane(14), an Ullmann-type coupling reaction of carboranes with aryl halide, and the aromatic nucleophilic substitution (S(N)Ar) reaction of aryl-o-carboranes with nitrophenyl halide. The optimum conditions of each method for synthesis of the title compounds were also investigated.     

Synthesis of new (pyrazol-1-yl)(7-nitro-1h-indol-2-yl)ketone derivatives

The condensation of 7-nitroindole-2-carbohydrazide derivatives with acetylacetone lead to (pyrazol-1-yl)(7-nitroindol-2-yl)ketones.     

3-(Carbazol-2-yl)- and 3-(Carbazol-3-yl)-dl-alanines

A facile transformation of 2- and 3-methylcarbazoles into 3-(carbazol-2-yl)-and 3-(carbazol-3-yl)-dl-alanines compounds is described.     

Synthesis of S-(carboran-1-yl)thiophosphates and S-(carboran-1-yl)-thiophosphonates

Conclusions New S-(carboran-1-yl)thiophosphates and S(carboran-1-yl)thiophosphonates were obtained by the reaction of derivatives of lithiumcarboranes with bis(dialkoxythiophosphoryl)disulfides or halo derivatives of pentavalent phosphorus.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 194–197, January, 1989.     

A facile synthesis of novel benzofuran-2-yl(9-methyl-9H-carbazol-3-yl)methanones

A facile synthesis of hitherto unreported benzofuran-2-yl(9-methyl-9H-carbazol-3-yl)methanones (3a?Cl) is described. The synthesis mainly relies on the ultrasound-assisted Rap?CStoermer reaction of 3-chloroacetyl-9-methyl-9H-carbazole (1) with a variety of salicylaldehydes, as well as 2-hydroxy-1-naphthaldehyde (2) in CH₃CN, with the presence of PEG-400 as a catalyst. This procedure offers easy access to benzofuran-2-yl(carbazolyl)methanone derivatives in a short reaction time and the products are achieved in good yields.     

Reactions of some alken-1-yl and cycloalken-1-yl bromomethyl sulfones with dimethyl malonate and malononitrile

Bromomethyl cyclopent-1-enyl sulfone and bromomethyl cyclohex-1-enyl sulfone reacted with dimethyl malonate and malononitrile sodium salts in THF at 20?C50°C to give products of Michael-induced Ramberg-B?cklund reaction, functionalized derivatives of methylidenecyclopentane and methylidenecyclohexane. Reactions of bromomethyl hex-1-en-1-yl sulfone and bromomethyl hept-1-en-1-yl sulfones with the same sodium enolates followed the Michael-induced ring closure pattern with formation of tetrahydrothiophene 1,1-dioxide derivatives containing allylmalonic acid derivatives as impurities. Factors responsible for the different reaction pathways of cyclic and acyclic bromomethyl sulfones are discussed.     

Synthesis and properties of (1,2,3,7,9-pentamethyldipyrrolylmethen-8-yl)-(1,2,3,7,8-pentamethyldipyrrolylmethen-9-yl)methane and bis(1,2,3,7,9-pentamethyldipyrrolylmethen-8-yl)trifluoromethylmethane dihydrobromides

(1,2,3,7,9-pentamethyldipyrrolylmethen-8-yl)(1,2,3,7,8-pentamethyldipyrrolylmethen-9-yl)-methane and bis(1,2,3,7,9-pentamethyldipyrrolylmethen-8-yl)trifluoromethylmethane hydrobromides were synthesized and characterized spectrally (1H NMR, IR, electron absorption spectra). A comparative study was performed of the effect of the bonding site (??- or ??-position of the dipyrrolylmethene) with the methane structural fragment connecting two dipyrrolylmethene chromophores, and trifluoromethyl group on the spectral properties of the molecules of compounds dissolved in organic solvents of different nature and their resistance to thermal oxidative degradation.     

Selective synthesis of di(propen-1-yl)sulfone and di(propen-1-yl)sulfoxide

Convenient selective methods of synthesis of the title compounds, based on oxidation of di(propen-1-yl)sulfide with 30% H₂O₂, have been developed.Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, 664033 Irkutsk. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 675–679, March, 1992.     

Studies on Azolylacetonitriles: The Reactivity of Thiazole-2-yl,Thiadiazol-2-yl Acetonitriles Toward Electrophilic Reagents

5-Acetyl-2-cyanomethyl-4-methylthiazole, 2-aminothiazole, and 5-N-benzoylamino-1,3,4-thiadiazole-2-yl-acetonitrile react with acetone, and malononitrile derivatives in the presence of sulfur to yield the corresponding thiophene derivatives. Also, 4-furylmethylene-2-phenyl-2-oxazolin-5-ones react with thiophenol, and/or thionaphthol to give the thiolester derivatives in one-pot synthesis. The structures of the products were based on IR, 1 H NMR, and elemental analysis.