Reaction of allylamine with hexylsilane

The reaction of hexylsilane with allylamine is accompanied by the liberation of hydrogen and formation of allylaminosilanes and compounds with the Si-Si bond. The hydrosilylation pathway virtually is not realized. The B3LYP/6-311G** calculations show that all the considered reactions are thermodynamically allowed.     

Reaction of allylamine with tetraalkyldiboranes

Summary On reacting tetraalkyldiboranenes with allylamine, depending on the order of mixing of the reactants, either allylaminodialkylboron or (3-aminopropyl)-dialkylboron, possessing an inner complex structure, was formed predominately.The authors thank I. P. Yakovleva for obtaining the IR spectra.     

Catalytic reactions of hydrosiloxanes with allyl chloride

Catalytic reactivity of Si-H bond of di-, trisiloxanes with allyl chloride in the presence of platinum catalyst has been examined. Hydrosilylation process competes with hydrogen substitution by chlorine and/or propenyl group. The effect of the reaction conditions as well as structure of siloxane on the yield and selectivity of the number of products has been discussed. Several consecutive-competitive processes have been identified. The results obtained can be helpful in the study of the catalytic hydropolysiloxanes reactions with allyl derivatives-systems of great practical importance, to produce commercial functionalized silicones.     

Kinetics of allyl chloride epoxidation with hydrogen peroxide

The kinetics of allyl chloride oxidation to epichlorohydrin in the presence of titanium-containing zeolite was studied. The influence of the concentrations of the initial substances, reaction products, and temperature on the rate of the process was considered. The mathematical model of the process was constructed on the basis of the experimental data obtained. The rate constants, adsorption equilibrium constants, and activation energies of the reactions were calculated.     

Reaction of N-substituted N′-trifluoromethylcarbodiimides with ammonia

Conclusions N-substituted N-trifluoromethylcarbodiimides react exothermally with ammonia to give N-substituted N-cyanoguanidines.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2399–2400, October, 1988.     

The photooxidation of allyl chloride

The photooxidation of allyl chloride was studied by irradiation either in 100-L Teflon bags or in a 22.7-m³ Teflon smog chamber in the presence of added NO_x. In the absence of added hydrocarbons, the reaction involves a Cl atom chain, which leads to a highly reactive system. A reaction mechanism is presented to account for the following photooxidation products: chloroacetaldehyde, formaldehyde, 1,3-dichloroacetone, 3-chloroacrolein, acrolein, glyoxal, chloroperoxyacetyl nitrate, and peroxypropenyl nitrate. The rate constant for OH reaction with allyl chloride at 298 K was measured by a relative rate method under conditions where the Cl atom chain length was small and was found to be k_OH = 1.7 × 10^?11 cm³ molecule^?1 s^?1. The rate constant for O₃ reaction with allylchloride at 298 K was found to be k_O3 = 1.5 × 10^?18 cm³ molecule^?1 s^?1.     

Reaction of polyfluoroarenesulfonyl bromides with allyl bromide. Synthesis of allyl polyfluoroaryl sulfones

Reactions of polyfluoroarenesulfonyl bromides 4-XC₆F₄SO₂Br (X = F, H, Cl, Br, CF₃) with allyl bromide gave 84–94% of the corresponding allyl polyfluoroaryl sulfones.     

Interaction of fullerene C60 with allylbenzene and allyl chloride

The reaction between allyl compounds and fullerene C₆₀ has been investigated via dilatometry under the conditions of free-radical polymerization. It has been shown that the rate of a variation in the volume of the reaction mixture plotted versus the concentration of fullerene C₆₀ is described by a curve with a minimum. It has been established that, in the presence of fullerene and the allyl monomer, the polymerization of methyl methacrylate proceeds without any induction period. It has been concluded that allyl radicals interact with fullerene C₆₀.     

Complexes of dichlorosilylene with allyl chloride and allyl bromide: matrix IR spectroscopy and quantum chemical studies

Formation of donor-acceptor complexes between dichlorosilylene, SiCl₂, and allyl halides, AllHal(Hal= Cl, Br) was detected in Ar matrixes using matrix IR spectroscopy. In agreement with the predictions of the performed quantum chemical calculations, only broad unstructured absorption bands contributed by different conformers of the 1 : 1 complexes between SiCl₂ and AllHal were observed in IR spectra of matrixes after deposition in the regions of characteristic vibrations of starting reactants. Annealing of matrixes resulted in strong narrowing the bands due to conversions of different conformers into the most stable structures. The predominantly formed conformers in both the reaction systems were those of complexes with SiCl₂ coordinated to the Hal atoms of AllHal in the gauche conformations. At the same time, according to the calculations, the complexes with SiCl₂ coordination to the double bonds of AllHal can be only slightly less stable than the complexes with coordination to the Hal atoms, and all these basic centers can be considered as comparable in their activity in the complexation. The only products revealed upon photolysis of complexes were the products of silylene insertion into the C–Hal bonds, viz., AllSiCl₃ and AllSiCl₂Br. Theoretical study of thermal transformations in the SiCl₂ + AllHal systems showed that formal insertion of SiCl₂ in the C–Hal bonds and its addition to the double bonds of AllHal have low activation barriers of 3–8 kcal mol^–1. However, these barriers are too high for these reactions to occur under the matrix isolation conditions.     

Copolymerization of 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride with N-substituted maleimides

The free-radical copolymerization of 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride with N-phenyl- and N-p-carboxyphenylmaleimide is studied in bulk and in organic solvents. It is shown that copolymerization proceeds to form copolymers with a high tendency toward alternation of monomer units. The kinetic laws of the reaction are investigated, and the relative activities of the monomers are determined. It is found that 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride is involved in copolymerization with N-substituted maleimides to give rise to pyrrolidinium structures. This work was supported by the Russian Foundation for Basic Research (project no. 09-03-00220) and the by the Presidium of the Russian Academy of Sciences through the program Development of Methods of Synthesis of Chemical Substances and the Creation of Novel Materials.