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.     

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.     

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.     

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.     

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.     

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.     

(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 6-Methyl-4-(1-methyl-2-buten-1-yl)-2-(2-cyclohexen-1-yl)- and 6-Methyl-4-(1-methyl-2-buten-1-yl)-2-(1-cyclohexen-1-yl)anilines

Alkenylation of 6-methyl-2-(2-cyclohexen-1-yl)- and 2-(1-cyclohexen-1-yl)anilines with piperylene in the presence of AlCl₃ and transformation of the resulting cyclohexenylanilines into carbazole structures were studied.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 3, 2005, pp. 441–443.Original Russian Text Copyright © 2005 by Gataullin, Ishberdina, Sotnikov, Abdrakhmanov.     

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.     

Synthesis of monofluorinated 1-(naphthalen-1-yl)piperazines

A series of regioisomerically monofluorinated 1-(naphthalen-1-yl)piperazines is described.     

2-(1H-Tetrazol-1-yl)­benzoic acid

In the title compound, C₈H₆N₄O₂, the tetrazole and benzene rings are planar to within 0.001 (1) and 0.007 (1) Å, respectively. These rings are not coplanar in the mol­ecule, the dihedral angle between them being 52.90 (4)°. Molecules are connected together by O—H⋯N and C—H⋯O hydrogen bonds, forming two-dimensional networks parallel to the xz plane with van der Waals interactions between them.     

Synthesis and in-vitro antitumor activity of 1-[3-(indol-1-yl)prop-1-yn-1-yl]phthalazines and related compounds

A series of novel 3-(indol-1-yl)prop-1-yn-1-yl-substituted phthalazines and related azines was prepared via a concise pathway by palladium-catalyzed cross-coupling of appropriate halo-azines and N-propargylindoles. Some of the compounds exhibited significant antitumor activity in an in-vitro assay.     

Bis (2,4,6,8-cyclononatetraen-1-yl)methane

Bis (2,4,6,8-cyclononatetraen-1-yl)methanes Bis (2,4,6,8-cyclononatetraen-1-yl)methanes ( 2a–c ) have been prepared by reaction of all-cis-cyclononatetraenide with 1,1-dichlorodimethyl ether as well as with carbenium ion precursors 9b and 9c . The title compounds 2 are attractive precursors of highly delocalised nonafulvenes of type 3 ; however, elimination experiments 2→3 failed so far.     

Functiaonalization of 2-(1-Cyclohexen-1-yl)aniline Derivatives

The reaction of 2-(1-cyclohexen-1-yl)aniline and -6-methylaniline with phthalic anhydride has afforded 2-(2-cyclohex-1-en-1-ylphenyl)- and 2-(2-cyclohex-1-en-1-ylphenyl)-6-methylphenyl)-1H-isoindole-1,3(2H)-diones. The reaction of the obtained isoindole-1,3-diones with bromine in dichloromethane in the presence of sodium bicarbonate has led to the formation of the product of pseudo-allylic halogenation. Replacement of the halogen atom by methoxy group has been performed by keeping 2-[2-(6-bromocyclohex-1-en-1-ylphenyl)-6-methylphenyl)]-1H-isoindole-1,3(2H)-dione in a methanolic solution in the presence of NaHCO₃. The reaction of 2-(2-cyclohex-1-en-1-yl-6-methylphenyl)-1H-isoindole-1,3(2H)-dione with molecular bromine in the presence of methanol has given a co-halogenation product, whereas the dibromination product has been obtained in the presence of octyl alcohol.