Carbon—carbon and carbon—nitrogen bond formation reactions catalyzed by the magnesium and calcium acenaphthene-1,2-diimine complexes

A mixture of allylbromide and diphenylacetonitrile is reduced to afford 2,2-diphenylpentene-4-nitrile as a major product in the presence of catalytic amounts of the magnesium complex (dpp-bian)Mg(thf)3 (dpp-bian is 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene dianion). The overall conversion of nitrile is 71% within 3 h at 85 °С. 4,4-Diphenylbutene-1 and diphenylmethane are by-products in this process. Complexes (dpp-bian)Mg(thf)₃ and (dpp-bian)Ca(thf)₄ (in an amount of 0.5—5 mol.%) catalyze the intramolecular hydroamination of some aminopentenes and aminohexenes with the conversion from 67 to 99%.     

Trifluoroacetylation of 3-halo-9-methylcarbazoles

Trifluoroacetylation of 3-halo-9-methylcarbazoles at 110C proceeds at 6-position. In the case of 3-bromo- and 3-iodo-derivatives, the reaction is complicated by competing processes of dehalogenation, followed by the halogenation of the substrate, leading to 3,6-dihalo derivatives.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1492–1495, November, 1987.     

Different approaches to research into the aging process and their implementation in the framework of the “science against aging” complex interdisciplinary program

We presume that extending lifespan and particularly its healthy period is absolutely beneficial for human being. However, the existing views and approaches did not result in a significant extension of human lifespan.     

Unprecedented intermolecular aldol-type condensation involving CH-acid and the nitro group

The first evidence that α-acylnitrone is an intermediate in the base-promoted reaction of 4-nitro-N,N-diethylaniline with aceptophenome to give an enaminoketone was obtained. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1645–1647, August, 1998.     

Synthesis of 4- and 6-substituted nitroindoles

Enolizable ketones react with m-nitroaniline in the presence of strong base such as t-BuOK to give 4- and 6-substituted nitroindoles. The reaction proceeds via oxidative nucleophilic substitution of hydrogen in m-nitroaniline with enolate anions in positions ortho to the amino group giving anionic σ^H adducts that are additionally stabilized by intramolecular interaction between the amino and the carbonyl group. Spontaneous oxidation of the σ^H adducts followed by the Bayer type condensation of the produced ortho-aminonitrobenzyl ketones gives 4- and 6-substituted nitroindoles. The scope of this reaction and its basic mechanistic features are discussed.     

Hydroamination of alkynes with aromatic amines catalyzed by digallane (dpp-bian)Ga—Ga(dpp-bian)

Digallane (dpp-bian)Ga—Ga(dpp-bian) (1) (dpp-bian is the 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) catalyzes the addition of 4-chloroaniline to some terminal alkynes RC≡CH (R = Buⁿ, Ph, 4-MeC₆H₄). The reaction orders in each of the substrates were found for the reaction of phenylacetylene with 4-chloroaniline catalyzed by compound 1. The reaction of compound 1 with phenylacetylene in a molar ratio of 1: 10 led to 1-[N-(2,6-diisopropylphenyl)imino]-2-(1-phenylethylidene)acenaphthene (5) and the compound [C₁₂H₆(NC₆H₃Pr₂ ⁱ)(PhC=CH₂)(PhC=CH)]Ga(C≡CPh)₂ (6). The reaction of digallane 1 with phenylacetylene and aniline in a stoichiometric ratio of 1: 2: 2 gave bis-anilide (dpp-bian)-Ga[N(H)Ph]₂ (7) in 40% yield. The compound (PhC≡C)₃Ga·THF (9) was obtained by the reaction of three equivalents of sodium phenylacetylide (prepared in situ from phenylacetylene and sodium) with one equivalent of GaCl₃ in tetrahydrofuran. Compounds 5—7 and 9 were characterized by IR spectroscopy, ¹H NMR spectroscopy was used to characterize products 5, 6, and 9, whereas EPR spectroscopy was used for amide 7. The structures of compounds 5—7 and 9 were determined by single crystal X-ray diffraction analysis.     

New reaction of mononitroarenes: Condensation with two acetophenone moleculesvia the nitro group

Nitrobenzene,p-bromonitrobenzene,N,N-diethyl-p-nitroaniline, and 9-methyl-3nitrocarbazole undergo condensation with two moles of acetophenone in a DMSO-KOH system to form the corresponding (Z)-1,4-diphenyl-2-arylamino-2-butene-1,4-diones.Translated from Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 480–482, February, 1996     

Vortex motion of a disperse mixture

A study is made of the motion of fine spherical particles in a given steady vortex flow of an incompressible fluid. The results are given of an investigation into the Lyapunov stability of a particle trajectory coincident with the vortex axis, and of trajectories from which the distance to the vortex axis is determined by the condition of equality of the radial components of the force of the phase interaction and of the centrifugal force which acts on the particle.Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 6, pp. 167–169, November–December, 1984.