Addition of Bromotrichloromethane and Tetrachloromethane to cis-Cyclooctene,Cyclohexene, and Norbornadiene in the Presence of Palladium(II) Complexes

Addition of bromotrichloromethane and tetrachloromethane to alkenes in the presence of palladium(II) complexes begins with single-electron transfer from the palladium atom to polyhalomethane molecule, followed by fragmentation of the radical anion thus formed and generation of trichloromethyl radical. Halogen transfer to a carbon-centered radical arising from addition of trichloromethyl radical at the double bond occurs both from the polyhalomethane molecule and from halide palladium complex.     

Mechanism of the catalytic carbonylation of aryl halides with a modified cobalt carbonyl

Investigation of the mechanism of the carbonylation of aryl halides in a catalytic system consisting of cobalt carbonyl, terminal olefin oxide, and base showed that this catalytic system activates aryl halides via a radical anion mechanism. The kinetic regularities of the process together with IR spectral data suggest reversible formation of the active catalytic complex under the reaction condition. The complex is a cyclic metal lactone, and it can form not only from olefin oxide but also from its methanolysis product, the corresponding glycol monomethyl ether.     

Regioselectivity of the methanolysis of polychlorinated biphenyls

Regioselectivity of the methanolysis of lower polychlorinated biphenyls with sodium methoxide in a mixture of methanol and DMSO at 100–130°С was studied. It was found that 2,4,4'-tricholobiphenyl is much more reactive than 2,4-dichlorobiphenyl. This results in different mechanisms of substitution. 2,4-Dichlorobiphenyl reacts with sodium methoxide by the elimination–addition mechanism to form four monosubstitution products in comparable quantities. 2,4,4'-Trichlorobiphenyl reacts with the methodixe ion by the classical SNAr mechanism, with preferential substitution of the 2-chlorine atom.     

Reduction of mono- and dichlorobiphenyls with sodium-naphthalene complex

Reactivity of low-chlorinated congeners of polychlorinated biphenyls in relation to sodiumnaphthalene complex in THF was studied. It was shown that the rate of reduction of these substrates weakly depended on their structure. The regioselectivity of the first stage of reduction of dichlorobiphenyls may be caused by relative stability of the intermediately formed aryl radicals. Kinetic analysis of the processes taking place in the system showed that sodium-naphthalene complex alongside with one-electron reduction of dichlorobiphenyls is involved also in the multi-electron reduction leading directly to biphenyl avoiding the stage of formation of monochlorobiphenyl.     

Sonogashira reaction catalyzed by palladium isocyanide complex modified <Emphasis Type="Italic">in situ</Emphasis>

Palladium isocyanide complex modified in situ by addition of benzohydrazide as nucleophile was shown to catalyze Sonogashira reactions of phenylacetylene with iodobenzenes in refluxing ethanol in the presence of potassium carbonate. The reactions were complete in 2 h, and neither preliminary degassing nor protection from atmospheric moisture and oxygen was necessary. The yields of the cross-coupling products, unsymmetrical diarylacetylenes were only slightly lower than those obtained with the preliminarily prepared catalyst. The proposed procedure was used to synthesize a series of diarylacetylenes containing both electrondonating and electron-withdrawing substituents in the benzene rings.     

A versatile procedure for synthesis of organic acids by cobalt carbonyl catalyzed carbonylation of organic halides

A versatile procedure for synthesis of a broad range of fatty-aromatic and aromatic acids by carbonylation of the corresponding halides under very mild conditions in the presence of cobalt carbonyl as a catalyst was suggested. The main principles of a flexible process for production of practically significant acids and their derivatives were developed.     

Modeling VHF emissivity of snow cover with account of its stratigraphy

In this paper, we discuss a model of emissivity of snow cover taking into account its structure. We assume that upward and downward radiation inside a snow layer are diffuse and apply the two-flux theory of Kubelka and Munk. Snow cover is modelled by a medium comprising discrete scatterers. In the case of dry snow, the scatterers are ice grains. Wet snow is modelled by a mixture of ice grains (with or without water envelopes) and water drops. We assume that the scatterers are spherical particles that have lognormal distribution over size. The brightness temperature of radio emission from snow cover on the soil is calculated using the data of glaciological measurements of physical parameters and microstructure of snow. Results of calculations are compared to measurements of the brightness temperature of radio emission from various types of snow covers. Space Research Institute of Russian Academy of Sciences, Moscow, Russia. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 42, No. 9, pp. 845–857, August 1999.     

Electrochemical Reduction of Trichlorobiphenyls: Mechanism and Regioselectivity

The regioselectivity of electrochemical reduction of four trichlorobiphenyls (PCB 28–30 and PCB 37) was studied by cyclic voltammetry and bulk electrolysis. The number of stages and mechanism of electrochemical reduction of each of the examined substrate were inferred on the basis of the experimental electron transfer coefficients and calculated (DFT) bond lengths and potential energy surface sections. GC/MS analysis of the controlled potential electrolysis products showed that chlorine atom in the disubstituted ring of trichlorobiphenyls is reduced more readily than in the monosubstituted ring and that the rate of chlorine reduction changes in the series o-Cl > p-Cl > m-Cl.     

Coupling of Bis(xylylisocyanide) Palladium(II) Complex with 1,2,4-Thiadiazole-5-amines

The coupling of bis(xylylisocyanide) complex of Pd(II) with 1,2,4-thiadiazole-5-amines leads to the formation of an equilibrium mixture of the binuclear complexes. In each of the studied cases, one of the formed complexes is the kinetic product, and the other one is the thermodynamic product. The complexes which are thermodynamic products have been isolated in the pure form and characterized by means of high-resolution mass spectrometry, IR and NMR spectroscopy, and X-ray diffraction analysis. NMR study of the regioisomerization in a solution has revealed that the relative stability of the thermodynamic products in comparison with the kinetic ones is higher than for the corresponding regioisomers containing 1,3-thiazole or 1,3,4- thiadiazole fragment.