Химические свойства силилхлорзамещенных этилена и ацетилена

Systematic studies on the chemical properties of a new class of compounds – silylchloro derivatives of ethylene and acetylene – and on regularities of their behavior in hydrosilylation, chlorination, and hydroclorination were reviewed. Quite different behavior of the monomers under study in these reactions was found depending on the amount of chlorine atoms and silyl groups and their positions in the molecule, as well as on the nature of substituents at the silicon atom was found.Проведен обзор работ по систематическому изучению химических свойств нового класса соединений – силилхлорзамещенных производных этилена и ацетилена, закономерности их поведения в реакциях гидросилилирования, хлорирования и гидрохлорирования. Выявлен совершенно различный характер поведения изучаемых мономеров в данных реакциях в зависимости от количества и положения в молекуле атомов хлора и силильных групп, а также от характера заместителей у атома кремния

Газофазное взаимодействие тетрахлоргермана с дихлорпроизводными бензола и тиофена в присутствии гексахлордисилана

Gas-phase interaction of dichlorogermylenes formed in GeCl<sub>4</sub>–Si<sub>2</sub>Cl<sub>6</sub> system with o- and p-dichlorobenzene (Ia, Ib), 2,5-dichlorothiophen (V) was studied. :GeCl<sub>2</sub> was shown to insert by (Ia, (Ib), (V) C-Cl bond and form their derivatives with one or two trichlorogemylene groups. Reactions proceeding in organochlorogermanes synthesis are discussed.редставлены результаты синтезов с участием п- и о-дихлорбензолов, 2,5-дихлортиофена, GeCl<sub>4</sub> и Si<sub>2</sub>Cl<sub>6</sub>. Определены основные соединения, образующиеся в процессе синтеза. Для синтезов с о-дихлорбензолом выявлено тормозящее влияние заместителей в орто-положении на внедрение :GeCl<sub>2</sub> в связь C–Cl

Некоторые закономерности жидкофазного каталитического диспропорционирования g-трифторпропилметилдихлорсилана в присутствии этил- и фенилхлорсиланов

γ-Trifluoropropylmethyldichlorosilane interaction with ethyl- and phenylchlorosilanes in aluminum chloride presence was studied. It is demonstrated that besides expected exchange reactions of Cl↔F at silicon, exchange reactions proceed with the participation of γ-trifluoropropyl substituent resulting in the formation of a few new unsaturated allyl-type compounds. There is no intermolecular exchange of organic substituents. It is found that chlorine atoms, which are in γ-position towards silicon in a hydrocarbon chain, are active in dehydrochlorination reactions in aluminum chloride presence in contrast to chlorine atoms in α- and β-positions.Tetraethylsilane has been found to be passive in the studied reactions in contrast to ethylchlorosilanes. A scheme explaining the obtained results is proposed, and quantum-chemical calculations of the basic reactions have been made.Исследовано взаимодействие g-трифторпропилметилдихлорсилана с этил- и фенилхлорсиланами в присутствии хлорида алюминия. Показано, что, помимо ожидаемых реакций обмена Cl«F у атомов кремния, протекают обменные реакции с участием g-трифто-рпропильного заместителя, приводящие к образованию ряда новых непредельных соединений аллильного типа. Проведены квантово-химические расчеты основных стадий протекающих реакций

Chemical properties of silylchloro derivatives of ethylene and acetylene

Systematic studies on the chemical properties of a new class of compounds – silylchloro derivatives of ethylene and acetylene – and on regularities of their behavior in hydrosilylation, chlorination, and hydroclorination were reviewed. Quite different behavior of the monomers under study in these reactions was found depending on the amount of chlorine atoms and silyl groups and their positions in the molecule, as well as on the nature of substituents at the silicon atom was found

Tetrachlorogermane gas-phase interaction with benzene and thiophene dichloroderivatives in hexachlorodisilane presence.

Gas-phase interaction of dichlorogermylenes formed in GeCl<sub>4</sub>–Si<sub>2</sub>Cl<sub>6</sub> system with o- and p-dichlorobenzene (Ia, Ib), 2,5-dichlorothiophen (V) was studied. :GeCl<sub>2</sub> was shown to insert by (Ia, (Ib), (V) C-Cl bond and form their derivatives with one or two trichlorogemylene groups. Reactions proceeding in organochlorogermanes synthesis are discussed

Some regularities of liquid-phase catalytic disproportionation of γ-trifluoropropylmethyldichlorosilane in ethyland phenylchlorosilanes presence

γ-Trifluoropropylmethyldichlorosilane interaction with ethyl- and phenylchlorosilanes in aluminum chloride presence was studied. It is demonstrated that besides expected exchange reactions of Cl↔F at silicon, exchange reactions proceed with the participation of γ-trifluoropropyl substituent resulting in the formation of a few new unsaturated allyl-type compounds. There is no intermolecular exchange of organic substituents. It is found that chlorine atoms, which are in γ-position towards silicon in a hydrocarbon chain, are active in dehydrochlorination reactions in aluminum chloride presence in contrast to chlorine atoms in α- and β-positions.Tetraethylsilane has been found to be passive in the studied reactions in contrast to ethylchlorosilanes. A scheme explaining the obtained results is proposed, and quantum-chemical calculations of the basic reactions have been made