78-07-9Relevant articles and documents
Hydrosilylation reaction of ethylene with triethoxysilane catalyzed by ruthenium halides and promoted by cuprous halides
Liu, Ling,Li, Xiaonian,Dong, Hong,Wu, Chuan
, p. 454 - 459 (2013)
The hydrosilylation reaction of ethylene with triethoxysilane catalyzed by ruthenium halides and promoted by cuprous halides, iodine or ferrous chloride tetrahydrates was conducted at temperatures ranging from 30 to 80 C under a mild pressure of ethylene gas. Ruthenium chloride trihydrates and cuprous chloride are proved to be the best catalyst and promoter for this reaction. With the addition of 6.8 × 10-5 mol ruthenium chloride trihydrates per mole of triethoxysilane together with over 3 times of cuprous chloride per mole of ruthenium chloride trihydrates, the reaction can conduct rapidly at temperatures ranging from 40 to 60 C under a pressure of ethylene gas lower than 0.35 MPa with over 96% yield of ethyltriethoxysilane within 6 h.
Sustainable Catalytic Synthesis of Diethyl Carbonate
Putro, Wahyu S.,Ikeda, Akira,Shigeyasu, Shinji,Hamura, Satoshi,Matsumoto, Seiji,Lee, Vladimir Ya.,Choi, Jun-Chul,Fukaya, Norihisa
, p. 842 - 846 (2020/12/07)
New sustainable approaches should be developed to overcome equilibrium limitation of dialkyl carbonate synthesis from CO2 and alcohols. Using tetraethyl orthosilicate (TEOS) and CO2 with Zr catalysts, we report the first example of sustainable catalytic synthesis of diethyl carbonate (DEC). The disiloxane byproduct can be reverted to TEOS. Under the same conditions, DEC can be synthesized using a wide range of alkoxysilane substrates by investigating the effects of the number of ethoxy substituent in alkoxysilane substrates, alkyl chain, and unsaturated moiety on the fundamental property of this reaction. Mechanistic insights obtained by kinetic studies, labeling experiments, and spectroscopic investigations reveal that DEC is generated via nucleophilic ethoxylation of a CO2-inserted Zr catalyst and catalyst regeneration by TEOS. The unprecedented transformation offers a new approach toward a cleaner route for DEC synthesis using recyclable alkoxysilane.
CATALYST AND RELATED METHODS INVOLVING HYDROSILYLATION AND DEHYDROGENATIVE SILYLATION
-
Paragraph 00152-00154; 00157; 00160; 00155, (2019/02/06)
A catalyst having a specific structure and a method fop rearing the catalyst is disclosed. A composition is also disclosed, which comprises: (A) an unsaturated compound including at least one aliphatically unsaturated group per molecule, subject to at least one of the following two provisos: (1) the (A) unsaturated compound also includes at least one silicon-bonded hydrogen atom per molecule; and/or (2) the composition further comprises (B) a silicon hydride compound including at least one silicon-bonded hydrogen atom per molecule. The composition further comprises (C) the catalyst. A method of preparing a hydrosilylation reaction product and a dehydrogenative silylation reaction product are also disclosed.
Fe and Co Complexes of Rigidly Planar Phosphino-Quinoline-Pyridine Ligands for Catalytic Hydrosilylation and Dehydrogenative Silylation
Basu, Debashis,Gilbert-Wilson, Ryan,Gray, Danielle L.,Rauchfuss, Thomas B.,Dash, Aswini K.
, p. 2760 - 2768 (2018/09/10)
Co and Fe dihalide complexes of a new rigidly planar PNN ligand platform are prepared and examined as precatalysts for hydrosilylation of alkenes. Lithiation of Thummel's 8-bromo-2-(pyrid-2′-yl)quinoline followed by treatment with (i-Pr)2PCl and (C6F5)2PCl afforded the phosphine-quinoline-pyridine ligands, abbreviated RPQpy for R = i-Pr and C6F5, respectively. These ligands form 1:1 adducts with the dichlorides and dibromides of iron and cobalt. Crystallographic characterization of FeBr2(iPrPQpy), FeBr2(ArFPQpy), CoCl2(iPrPQpy), CoBr2(iPrPQpy), and CoCl2(ArFPQpy) confirmed that the M-P-C-C-N-C-C-N portion of these complexes is planar within 0.078 ? unlike previous generations of PNN complexes where deviations from planarity were ～0.35 ?. Bond distances as well as magnetism indicate that the Fe complexes are high spin and the cobalt complexes are high spin or participate in spin equilibria. Also investigated were the NNN analogues of the RPQpy ligands, wherein the phosphine group was replaced by the mesityl ketimine. The complexes FeBr2(MesNQpy) and CoCl2(MesNQpy) were characterized crystallographically. Reduction of MX2(RPQpy) complexes with NaBHEt3 generates catalysts active for anti-Markovnikov silylation of simple and complex 1-alkenes with a variety of hydrosilanes. Catalysts derived from MesNQpy exhibited low activity. Fe-RPQpy derived catalysts favor hydrosilylation, whereas Co-RPQpy based catalysts favor dehydrogenative silylation. Catalysts derived from CoX2(iPrPQpy) convert hydrosilanes and ethylene to vinylsilanes. Related experiments were conducted on propylene to give propenylsilanes.
MONONUCLEAR IRON COMPLEX AND ORGANIC SYNTHESIS REACTION USING SAME
-
Paragraph 0215-0217, (2016/12/01)
Provided is a mononuclear iron complex that comprises an iron-silicon bond that is represented by formula (1) and that exhibits excellent catalyst activity in each of a hydrosilylation reaction, a hydrogenation reaction, and reduction of a carbonyl compound. In formula (1), R 1 -R 6 either independently represent an alkyl group, an aryl group, an aralkyl group or the like that may be substituted with a hydrogen atom or X, or represent a crosslinking substituent in which at least one pair comprising one of R 1 -R 3 and one of R 4 -R 6 is combined. X represents a halogen atom, an organoxy group, or the like. L represents a two-electron ligand other than CO. When a plurality of L are present, the plurality of L may be the same as or different from each other. When two L are present, the two L may be bonded to each other. n and m independently represent an integer of 1 to 3 with the stipulation that n+m equals 3 or 4.
COSMETIC TREATMENT METHOD COMPRISING THE APPLICATION OF A COATING BASED ON AN AEROGEL COMPOSITION OF LOW BULK DENSITY
-
Paragraph 0067, (2014/02/15)
The present invention relates to a cosmetic treatment method comprising the formation of a coating on keratin fibres characterized in that it comprises: 1) the preparation of an aerogel precursor composition comprising:—at least one organic solvent chosen from acetone, C1-C4 alcohols, C1-C6 alkanes, C1-C4 ethers, which may or may not be perfluorinated, and mixtures thereof and at least one precursor compound that contains:—at least one atom chosen from silicon, titanium, aluminium and zirconium,—at least one hydroxyl or alkoxy function directly attached to the atom chosen from silicon, titanium, aluminium and zirconium by an oxygen atom, and,—optionally an organic group directly attached to the atom chosen from silicon, titanium, aluminium and zirconium by a carbon atom, 2) the removal of the solvent or solvents resulting in the formation of an aerogel composition having a bulk density less than or equal to 0.35 g/cm3, 3) the application to the keratin fibres of the aerogel composition resulting from step 2) or of the aerogel precursor composition resulting from step 1). Advantageously, the molar ratio between the precursor compounds and the solvent is at most 1/20.
Catalyst design for iron-promoted reductions: An iron disilyl-dicarbonyl complex bearing weakly coordinating η2-(H-Si) moieties
Sunada, Yusuke,Tsutsumi, Hironori,Shigeta, Keisuke,Yoshida, Ryota,Hashimoto, Toru,Nagashima, Hideo
supporting information, p. 16687 - 16692 (2013/12/04)
Iron disilyl dicarbonyl complex 1, in which two H-Si moieties of the 1,2-bis(dimethylsilyl)benzene ligand were coordinated to the iron center in an η2-(H-Si) fashion, was synthesized by the reaction of (η4-C6H8)Fe(CO)3 with 2 equiv. of 1,2-bis(dimethylsilyl)benzene under photo-irradiation. Complex 1 demonstrated high catalytic activity toward the hydrogenation of alkenes, the hydrosilylation of alkenes and the reduction of carbonyl compounds.
Stereoselective synthesis of (E)- and (Z)-triethoxy(vinyl-d 2)silanes by hydrosilylation of acetylene-d 2
Gordillo, Alvaro,Forigua, Johan,Lopez-Mardomingo, Carmen,De Jesus, Ernesto
experimental part, p. 352 - 355 (2011/03/21)
The hydrosilylation of deuterated acetylene with triethoxysilane can be directed to the synthesis of either cis or trans triethoxy(vinyl-d 2)silanes by an appropriate choice of metal catalyst. In addition, we have demonstrated the viability of designing hydrosilylation-arylation sequential processes in which acetylene can be converted into styrenes or stilbenes using the same Pd catalyst for both reactions.
Facile synthetic access to rhenium(II) complexes: Activation of carbonbromine bonds by single-electron transfer
Jiang, Yanfeng,Blacque, Olivier,Fox, Thomas,Freeh, Christian M.,Berke, Heinz
scheme or table, p. 2240 - 2249 (2010/07/05)
The five-coordinated Re1 hydride complexes [Re(Br)(H)(NO) (PR3)2] (R = Cy la, iPr lb) were reacted with benzylbromide, thereby affording the 17-electron mononuclear ReII hydride complexes [Re(Br)2(H)(NO)(PR3)2] (R = Cy 3a, iPr 3b), which were characterized by EPR, cyclic voltammetry, and magnetic susceptibility measurements. In the case of dibromomethane or bromoform, the reaction of 1 afforded ReII hydrides 3 in addition to Re1 carbene hydrides [Re(= CHR1)(Br)(H)(NO)(PR3)2,] (R 1 = H 4, Br 5; R = Cy a, iPr b) in which the hydride ligand is positioned cis to the carbene ligand. For comparison, the dihydrogen Re 1 dibromide complexes [Re(Br)2(NO)(PR3MIf- H2)] (R = Cy 2 a, iPr 2 b) were reacted with allyl- or benzylbromide, thereby affording the monophosphine ReII complex salts [R 3PCH2R'][Re(Br)4(NO)(PR3)] (R' = -CH=CH2 6, Ph 7). The reduction of ReII complexes has also been examined. Complex 3 a or 3 b can be reduced by zinc to afford la or lb in high yield. Under catalytic conditions, this reaction enables homocoupling of benzylbromide (turnover frequency (TOF): 3a 150, 3b 134 h-1) or allylbromide (TOF: 3a 150, 3b 562 h-1). The reaction of 6 a and 6 b with zinc in acetonitrile affords in good yields the monophosphine Re 1 complexes [Re(Br)2(NO)(MeCN)2(PR 3)] (R = Cy 8a, iPr 8b), which showed high catalytic activity toward highly selective dehydrogenative silylation of styrenes (maximum TOF of 61 h-1). Single-electron transfer (SET) mechanisms were proposed for all these transformations. The molecular structures of 3 a, 6 a, 6 b, 7 a, 7 b, and 8 a were established by single-crystal X-ray diffraction studies.
Process for the direct synthesis of trialkoxysilane
-
Page/Page column 17, (2008/06/13)
This invention discloses a process to improve reaction stability in the Direct Synthesis of trialkoxysilanes. The process is particularly effective in the Direct Synthesis of triethoxysilane and its higher alkyl cognates providing improved triethoxysilane yields.
