98-12-4Relevant academic research and scientific papers
Thermal reaction of cyclic alkadiene with trichlorosilane. Preparative and mechanistic aspects
Jung, Dong Eui,Han, Joon Soo,Yoo, Bok Ryul
, p. 40 - 44 (2013/03/13)
The thermal reactions of trichlorosilane (1a) with cyclic alkadienes such as cyclopentadiene (2a), 1,3-cyclohexadiene (2b), and 1,4-cyclohexadiene (2c) were studied at temperatures ranging from 170 °C to 250 °C. In this reaction, the hydrosilylation rate increased as the reaction temperature was raised using an equimolar ratio of 1a to 2a. The reaction of 2a with 1a at 250 °C afforded 2-cyclopentenyltrichlorosilane (3a) as the major hydrosilylation product within 1 h in good yield (82%). This reaction also works when dicyclopentadiene (2a′) was used as a reactant instead of 2a. In a large scale preparation under the same conditions, 3a was obtained in 82% isolated yield. It is significant to note that 2a′ can be used for the hydrosilylation, with no requirement of a cracking step under our thermal conditions. While the reaction of cyclohexadienes with 1a under the same conditions gave a mixture of three hydrosilylation products such as 2-cyclohexenyltrichlorosilane (3b), 3-cyclohexenyltrichlorosilane (3c) and cyclohexyltrichlorosilane (5) in moderate yields, along with other unsaturated C6 components, such as benzene and cyclohexene. In the thermal reaction of cycloalkadienes with 1a, the five-membered-ring diene 2a undergoes both a hydrosilylation reaction with 1a as well as a [4 + 2] cycloaddition reaction, leading to the hydrosilylation product 3a in good yield. While the six-membered ring dienes, 2b and 2c, undergo four different types of reactions, including hydrosilylation, [4 + 2] cycloaddition, dehydrogenation, and hydrogenation in competition to give the hydrosilylation products, hexane, and benzene, respectively. The reaction rates of cyclic alkadienes under our thermal conditions increase in the following order: 2c 2b 2a.
Thermal hydrosilylation of olefin with hydrosilane. Preparative and mechanistic aspects
Jung, Dong Euy,Han, Joon Soo,Yoo, Bok Ryul
experimental part, p. 3687 - 3692 (2011/11/29)
The reaction of trichlorosilane (1a) at 250 °C with cycloalkenes, such as cyclopentene (2a), cyclohexene (2b), cycloheptene (2c), and cyclooctene (2d), gave cycloalkyltrichlorosilanes [CnH2n-1SiCl3: n = 5 (3a), 6 (3b), 7 (3c), 8 (3d)] within 6 h in excellent yields (97-98%), but the similar reactions using methyldichlorosilane (1b) instead of 1a required a longer reaction time of 40 h and afforded cycloalkyl(methyl)dichlorosilanes [CnH2n-1SiMeCl2: n = 5 (3e), 6 (3f), 7 (3g), 8 (3h)] in 88-92% yields with 4-8% recovery of reactant 2. In large (2, 0.29 mol)-scale preparations, the reactions of 2a and 2b with 1a (0.58 mol) under the same condition gave 3a and 3b in 95% and 94% isolated yields, respectively. The relative reactivity of four hydrosilanes [HSiCl3-mMem: m = 0-3] in the reaction with 2a indicates that as the number of chlorine-substituent(s) on the silicon increases the rate of the reaction decreases in the following order: n = 3 > 2 > 1 ? 0. In the reaction with 1a, the relative reactivity of four cycloalkenes (ring size = 5-8) decreases in the following order: 2d > 2a > 2c > 2b. Meanwhile linear alkenes like 1-hexene undergo two reactions of self-isomerization and hydrosilylation with hydrosilane to give a mixture of the three isomers (1-, 2-, and 3-silylated hexanes). In this reaction, the reactivity of the terminal 1-hexene is higher than the internal 2- and 3-hexene. The redistribution of hydrosilane 1 and the polymerization of olefin 2 occurred rarely under the thermal reaction condition.
Hydrosilylation of cyclohexene and allyl chloride with trichloro-, dichloro(methyl)-, and chlorodimethylsilanes in the presence of Pt(0) complexes
Belyakova,Chernyshev,Storozhenko,Knyazev,Turkel'taub,Parshina,Kisin
, p. 925 - 930 (2008/02/03)
Hydrosilylation of cyclohexene and allyl chloride in the presence of Pt(0) complexes with tetramethyldivinyldisiloxane (Karstedt catalyst) and hexavinyldisiloxane was studied. It was shown that these catalysts are much more active in the hydrosilylation of cyclohexene with trichloro-, dichloro(methyl)-, and chlorodimethylsilane than the Pt(II)-containing Speier catalyst. In the hydrosilylation of allyl chloride in the presence of Pt(0) complexes, the ratio of the fraction of addition products to the fraction of reduction products increases from 5.7 (Speier catalyst) to 10-16. Quantum-chemical calculations showed that Pt(0) complexes are more active than Pt(II) complexes on the stage of formation of platinum silicon hydride complexes. Pleiades Publishing, Inc., 2006.
Hydrosilylation of cyclohexene, 1-methylcyclohexene, and isopropylidenecyclohexane
Yarosh,Zhilitskaya,Yarosh,Albanov,Voronkov
, p. 1895 - 1899 (2007/10/03)
Hydrosilylation of cyclohexene and isopropylidenecyclohexane with chloro(methyl)silanes Me3-n SiHCln (n = 1-3) gives rise to cyclohexyl- and chloro(2-cyclohexylpropyl)methylsilanes. Hydrosilylation of 1-methylcyclohexene with chlorodimethylsilane (n = 1) occurs anomalously and involves double-bond migration to form a mixture of seven compounds: the cis and trans isomers of 2-, 3-, 4-chlorodimethyl(methylcyclohexyl)silanes and chlorodimethyl(cyclohexylmethyl)silane. Chlorodimethylsilane (n = 2) adds to 1-methylcyclohexene to form a mixture of the cis and trans isomers of dichloro(methyl)(2-methylcyclohexyl)silane and dichloro(cyclohexylmethyl) methylsilane. With trichlorosilane (n = 3), no other products than trichloro(cyclohexylmethyl)silane are formed. The hydrosilylation products were reacted with ethynylmagnesium bromide to synthesize the corresponding ethynyl derivatives. 2004 MAIK "Nauka/Interperiodica".
Chlorohydrosilane derivatives and their preparation method
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, (2008/06/13)
New chlorohydrosilane derivatives having the general formula (I) and preparation method thereof. The chlorohydrosilane derivatives (I) of the present invention which have both Si--Cl and Si--H bonds are prepared by partially reducing chlorosilane of the formula (II) which have at least two Si--Cl bonds with lithiumaluminum hydride. The chlorohydrosilane derivatives (I) of the present invention, which have both Si--H and Si--Cl bonds in a molecule can be advantageously used in preparing various compounds because a Si--H bond enables the hydrosilylation with unsaturated organic compounds, while a Si--Cl bond can participate in hydrolysis or in a reaction with a nucleophilic compound such as Grignard reatent: STR1 wherein R1 is straight, branched, or cyclic alkyl group having 1 to 30 carbon atoms, which can include an aromatic group or heterocyclic group, and R2 represents chloro group, or straight, branched, or cyclic alkyl group having 1 to 30 carbon atoms, which can include an aromatic group or heterocyclic group.
Silsesquioxanes as Models for Silica Surfaces
Feher, Frank J.,Newman, David A.,Walzer, John F.
, p. 1741 - 1748 (2007/10/02)
The hydrolytic condensation of cyclohexyltrichlorosilane (CySiCl3) affords (1), (2), and (3a).Trisilanol 1 and 3b, the bis(triphenyltin) derivative of 3a, have been structurally characterized by single-crystal X-ray diffraction studies.Trisilanol 1 undergoes corner-capping reactions with trifunctional monomers (e.g., R'SiCl3, MeGeCl3, MeSnCl3), is selectively monosilylated to (6a) with chlorotrimethylsilane, and can be dehydrated to (7a).Comparison of the molecular structure of 1 with (111) β-cristobalite and (0001)β-tridymite reveals many structural similarities.Silsesquioxanes 1, 6a, and 7a are discussed as models for silica surfaces.
