- Dendritic polarizing agents for DNP SENS
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Dynamic Nuclear Polarization Surface Enhanced NMR Spectroscopy (DNP SENS) is an effective method to significantly improve solid-state NMR investigation of solid surfaces. The presence of unpaired electrons (polarizing agents) is crucial for DNP, but it has drawbacks such as leading to faster nuclear spin relaxation, or even reaction with the substrate under investigation. The latter can be a particular problem for heterogeneous catalysts. Here, we present a series of carbosilane-based dendritic polarizing agents, in which the bulky dendrimer can reduce the interaction between the solid surface and the free radical. We thereby preserve long nuclear T′2 of the surface species, and even successfully enhance a reactive heterogeneous metathesis catalyst.
- Liao, Wei-Chih,Ong, Ta-Chung,Gajan, David,Bernada, Florian,Sauvée, Claire,Yulikov, Maxim,Pucino, Margherita,Schowner, Roman,Schwarzw?lder, Martin,Buchmeiser, Michael R.,Jeschke, Gunnar,Tordo, Paul,Ouari, Olivier,Lesage, Anne,Emsley, Lyndon,Copéret, Christophe
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Read Online
- METHOD FOR THE DEHYDROGENATION OF DICHLOROSILANE
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Dichlorosilane and trichlorosilane are dehydrogenated at elevated temperature in the presence of an ammonium or phosphonium salt as a catalyst, and a halogenated hydrocarbon or hydrogen halide. The method may be used to synthesize organochlorosilane.
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Paragraph 0094
(2021/06/22)
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- Preparation method of 3-chloropropyltrichlorosilane
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The invention relates to a preparation method of 3-chloropropyl trichlorosilane, and belongs to the field of synthesis of silane coupling agents. According to the invention, by taking chloropropene and trichlorosilane raw materials, biopolymer wool as a ligand to synthesize a Wool-Pt catalyst and organic amines as an auxiliary agent, 3-chloropropyltrichlorosilane is prepared under normal pressure. The preparation method provided by the invention has the advantages of simple operation, high reaction activity, good selectivity, high product yield, low catalyst use cost, low energy consumption, safety, environmental protection and the like, and accords with industrial production.
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Paragraph 0003; 0024-0028
(2021/07/14)
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- Continuous production process and device for γ - chloropropyltrichlorosilane
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The invention provides a continuous production process and device for γ -chloropropyltrichlorosilane, which comprises the following steps: respectively metering trichlorosilane and chloropropene into a reactor after being metered, and adding a catalyst. The first Crude products generated in the reactor are processed by a catalyst recovery device to obtain second crude products and a catalyst, the catalyst is returned to the reactor, second crude products are conveyed to first separation units. The second Crude product was separated by first separation units to give γ - chloropropyltrichlorosilane and propyltrichlorosilane. To the method and the device, trichlorosilane and chloropropene are continuously conveyed to the reactor for reaction, unreacted raw materials and the catalyst are returned to the reactor, and products and byproducts are separated and taken out. γ.
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Paragraph 0060-0091
(2021/09/29)
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- Method for producing chloropropyltrichlorosilane
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The invention provides an industrial production method of trichloro(3-chloropropyl)silane. A trichloro(3-chloropropyl)silane addition reaction coarse product is used as reaction substrates; the raw material reactants of chloropropene and trichlorosilane a
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Paragraph 0038-0049; 0053-0059
(2020/03/14)
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- The ligand bidentate phosphine rhodium complex and its manufacturing method, and a hydrosilylation of allyl halide using a rhodium complex compound having a bidentate phosphine (by machine translation)
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In the manufacture of a catalyst can be used as a complex 3 - [be] halo propyl silane and manufacturing method, a method for manufacturing 3 - halo propyl silane efficiently. [Solution] a rhodium complex catalyst or the like is used as a specific formula is obtained. [Drawing] no (by machine translation)
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Paragraph 0047-0048
(2020/09/16)
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- Gamma-chloropropyltrichlorosilane production method and system
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The invention provides a gamma-chloropropyltrichlorosilane production method and system. The production system comprises a tubular reactor, a tank reactor of which an inlet is communicated with an outlet of the tubular reactor and a first outlet is communicated with a first inlet of the tubular reactor, and a rectification device of which an inlet is communicated with a second outlet of the tank reactor. Compared with the existing production system, the production system provided by the invention returns a part of a crude product in the tank reactor to the tubular reactor and an activated catalyst starts a reaction so that a catalyst starting process is avoided, reaction time is shortened and a catalyst use amount is reduced. A part of the crude product in the tank reactor is returned to the tubular reactor and a temperature in the tubular reactor is kept by heat so that energy consumption is reduced. Through control of a reaction temperature in the tubular reactor, reaction selectivity is improved. A reaction temperature in the tank reactor is improved so that the reaction is full.
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Paragraph 0045; 0046; 0047; 0048; 0049; 0050; 0051; 0052
(2016/10/10)
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- Method for preparing organic silicon by passage reaction device
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The invention provides a method for preparing organic silicon by a passage reaction device. Under the condition of main catalysts Z, hydrogen-containing silane X and an unsaturated compound Y are introduced into the passage reaction device; hydrosilylation reaction is performed to prepare the organic silicon, wherein the hydrogen-containing silane X has the structure being HSiRR'Cl, in the formula, R and R' are independently C1 to C16 alkyl or alkoxy; a=1, 2 or 3; b, c and d are respectively and independently 0, 1, 2 or 3; the unsaturated compound Y is a monoene compound or single-alkyne compound; the main catalysts Z are one or several mixed ones of single-component complexes or multi-component complexes of Pt, Pd, Rh, Ru, Cu, Ag, Au or Ir; the passage surface in which reaction flow contacts is subjected to inactivation treatment by an activating agent Z. The problems of long reaction period, poor stability and the like of large-sized reaction equipment are solved; the problem that mixing, pre-reaction and afterreaction are separated and are performed in multi-unit equipment is solved.
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Paragraph 0048
(2016/10/17)
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- A γ-chloro propyl trichlorosilane synthesis method
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The invention discloses a synthesis method of gamma-chloropropyltrichlorosilane. In the method, trichlorosilane and chloropropene are used as raw materials, and a chloroplatinic acid-phenothiazine-organic amine complex is used as a catalyst. The method comprises the synthesis steps of firstly, adding the chloroplatinic acid-phenothiazine-organic amine complex as a catalyst into a pressure reaction kettle, dropwise adding two reaction materials, namely trichlorosilane and chloropropene, into the pressure reaction kettle at the reaction temperature of 100-180 DEG C through an overhead tank, and finishing the synthesis of the gamma-chloropropyltrichlorosilane after reacting at the temperature of 100-180 DEG C for 10-60min, wherein the dropwise adding time of the trichlorosilane and the chloropropene is 1.5-2.5h, and the inner pressure of the reaction kettle is 0.3-1.1MPa. The synthesis method of the gamma-chloropropyltrichlorosilane, disclosed by the invention, has the characteristics of short reaction time, high production efficiency, low material loss, high product yield and the like.
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Paragraph 0025; 0026
(2017/05/12)
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- N-heterocyclic cabeen platinum a carboxylic acid metal salt complex integrated catalyst and preparation method thereof
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The invention relates to the field of organic high-molecular chemistry and discloses an N-heterocyclic carbene platinum complex metal carboxylate integrated catalyst and a preparation method thereof. The preparation method includes following steps: (1) carrying out a reaction between alkyl imidazole and halogenated carboxylic acid to obtain a carboxylic acid functionalized imidazolium salt; (2) carrying out a reaction with chlorides of ferrous, copper, zinc, calcium or magnesium to obtain a imidazole-based ionic liquid containing carboxylates containing the ferrous, the copper, the zinc, the calcium or the magnesium; (3) preparing an N-heterocyclic carbene ligand from the ionic liquid under effect of potassium tert-butyl alcohol; and (4) carrying out a reaction with a Karstedt catalyst to prepare the N-heterocyclic carbene platinum complex metal carboxylate integrated catalyst. The catalyst is high in selectivity, is free of generation of platinum black precipitation, is easy to separate and can be recycled.
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Paragraph 0102; 0103
(2017/08/15)
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- A one-step co-condensation method for the synthesis of well-defined functionalized mesoporous SBA-15 using trimethallylsilanes as organosilane sources
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A new method for the preparation of well-defined functionalized mesoporous SBA-15 has been developed by a one-step co-condensation method using trimethallylsilanes as organosilane sources. This new method enables the incorporation of various bulky organic functional groups with long alkyl chain tethers into the mesoporous silica network.
- Han, Ye Ri,Park, Jung-Woo,Kim, Hanil,Ji, Hyejeong,Lim, Soo Hyun,Jun, Chul-Ho
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supporting information
p. 17084 - 17087
(2015/12/01)
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- Mechanistic insights into the hydrosilylation of allyl compounds - Evidence for different coexisting reaction pathways
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The hydrosilylation of allyl compounds is often accompanied by the formation of high amounts of byproducts. The formation processes have not been fully understood so far. In this work, the allyl hydrosilylation mechanism is investigated in detail and experimental and theoretical evidence for multiple, coexisting reaction pathways is provided. Based on earlier reports and the observations during an extensive catalytic study, different pathways, leading to the observed byproducts, were identified and proven by labeling experiments and DFT calculations. Oxidative addition of the silane and the insertion of the allyl compound into the Pt-H bond turned out to be the crucial, selectivity-determining steps within the catalytic cycle. Based on these findings, it should be possible to systematically influence these steps and pave the way to a rational and straightforward design of more selective catalysts.
- Gigler, Peter,Drees, Markus,Riener, Korbinian,Bechlars, Bettina,Herrmann, Wolfgang A.,Kuehn, Fritz E.
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- PRODUCTION METHOD FOR LINEAR AND CYCLIC TRISILAALKANE
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The present invention relates to a preparation method for a linear or cyclic trisilaalkane which is a substance useful in the preparation of polycarbosilane and silicon carbide precursors. Linear or cyclic trisilaalkane and organic trichlorosilane derivatives can be synthesized simultaneously and in high yield by reacting bis(chlorosily)methane having a Si—H bond, either alone or together with an organic chloride, using a quaternary organic phosphonium salt compound as a catalyst. Further, since the catalyst can be recovered after use, the present invention is very economical and is thus effective for mass-producing precursors for organic/inorganic hybrid substances.
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Page/Page column 6
(2011/04/19)
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- METHOD FOR PRODUCTION OF ORGANOSILICON COMPOUNDS BY HYDROSILYLATION IN IONIC LIQUIDS
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Organosilanes are prepared by hydrosilylation of unsaturated organic compounds by monomeric silanes containing at least one silicon bonded hydrogen, in a process wherein an ionic liquid containing a hydrosilylation catalyst is present as one phase, and the reactants are present in at least a second phase.
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Page/Page column 4; 5
(2010/11/03)
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- Effect of catalysts on the reaction of allyl esters with hydrosilanes
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The reaction of hydrosilylation of allyl esters XOCH 2CH=CH 2 (X = MeCO, CF 3CO, C 3F 7CO) and PhOCH 2CH=CH 2 with hydrosilanes HSiY 3 (Y = Cl, OEt) in the presence of the Speier catalyst, the Speier catalyst with additives, and of various nickel complexes was studied. The catalytic hydrosilylation reaction in the presence of the Speier catalyst is accompanied by the reduction. Additives to the Speier catalyst (vinyltriethoxysilane and some ethers) allow to suppress considerably the reduction reaction. In the presence of the studied nickel complexes mainly reduction and isomerization reactions occurred. The best nickel catalysts of hydrosilylation were the mixtures of NiCl 2 or Ni(acac) 2 with phosphine oxides. In contrast to allyl esters, the hydrosilylation of simple olefins proceeds easier, the content of the product of hydrosilylation in the reaction mixture reaches 94.3%. Pleiades Publishing, Ltd., 2010.
- Belyakova,Pomerantseva,Efimova,Chernyshev,Storozhenko
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experimental part
p. 728 - 733
(2011/01/05)
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- Continuous Preparation of Organosilanes
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The invention relates to a process for the continuous preparation of organosilanes in a reactive distillation column, wherein a homogenous hydrosilylation catalyst is introduced into the column.
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Page/Page column 4-5
(2008/06/13)
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- Liquid-liquid biphasic, platinum-catalyzed hydrosilylation of allyl chloride with trichlorosilane using an ionic liquid catalyst phase in a continuous loop reactor
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The platinum-catalyzed hydrosilylation of allyl chloride with trichlorosilane was investigated in an ionic liquid-organic biphasic reaction mode. After an ionic liquid screening and repetitive batch mode experiments, the process was realized in a continuous mode using a loop reactor concept with integrated continuous separation and recycling of the ionic liquid catalyst phase. The continuous reactor could be operated for 48 h at constant activity and selectivity without addition of platinum indicating that platinum leaching into the product phase was far below 1 ppm. Enhanced selectivity for the product trichloro(3-chloropropyl)silane (compared to the state-of-the art) and the possibility to use simple platinum tetrachloride (PtCl4) as platinum source are further attractive features of this new ionic liquid-based process concept.
- Hofmann, Norbert,Bauer, Andreas,Frey, Thomas,Auer, Marco,Stanjek, Volker,Schulz, Peter S.,Taccardi, Nicola,Wasserscheid, Peter
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experimental part
p. 2599 - 2609
(2009/09/07)
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- Carbosilane dendrimeric carbodiimides: Site isolation as a lactamization tool
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The convergent syntheses of three generations of carbosilane dendrimeric carbodiimides are described. The wedge-type building blocks were synthesized in a divergent way, starting from allyl chloride and a repetitive sequence of hydrosilylation with HSiCl3 and a Grignard reaction with allylmagnesium bromide. Hydrogenation of the terminal double bonds led to inert and stable wedges. The chloride substitutent at the focal point was transformed into several functional groups that eventually led to dendrimeric structures with a carbodiimide core. The extent of the site isolation effect of the dendrimers was studied with dilution experiments monitored by FT-IR spectroscopy on the corresponding dendrimeric ureas. These studies showed that only the first generation self-aggregates via hydrogen bonding, while the second and the third do not, implying isolation of core-bound moieties. The dendrimeric carbodiimides mediated lactamization reactions to obtain homodiketopiperazines.
- Amore, Alessia,Van Heerbeek, Rieko,Zeep, Niek,Van Esch, Jan,Reek, Joost N. H.,Hiemstra, Henk,Van Maarseveen, Jan H.
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p. 1851 - 1860
(2007/10/03)
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- Hydrosilylation of cyclohexene and allyl chloride with trichloro-, dichloro(methyl)-, and chlorodimethylsilanes in the presence of Pt(0) complexes
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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.
- Belyakova,Chernyshev,Storozhenko,Knyazev,Turkel'taub,Parshina,Kisin
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p. 925 - 930
(2008/02/03)
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- Continuous hydrosilylation process
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Continuous hydrosilylation of compounds (A) bearing C—C multiple bonds by means of silicon compounds (B) having Si—H groups, in which the reaction components (A) and (B) are reacted continuously in an integrated loop-tube reactor, with reaction mixture being conveyed from the tube into the loop and back again so that a section of the tube is part of the loop circuit, provides a highly controllable reaction process with high product yields.
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Page/Page column 4-5
(2008/06/13)
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- Processes for manufacturing organochlorosilanes and dipodal silanes and silanes made thereby
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Processes are provided for producing organchlorosilanes and dipodal silanes in which an organic halide or alkene or chloralkene is reacted with a hydridochlorosilane in the presence of a quarternary phosphonium salt catalyst by providing sufficient heat to effect a dehydrohalogenative coupling reaction and/or a hydrosilylation reaction and venting the reaction to control reaction pressure and to remove gaseous byproducts from the reaction. The processes are preferably continuous using a catalyst in fluid form at reaction pressures not exceeding about 600 psi. The reactions may be carried out substantially isothermally and/or isobarically, for example in a plug flow reactor or continuous stirred tank reactor. The processes may produce novel silylated compounds including 1,2-bis(trichlorosilyl)decane or 1,2-bis(trimethoxysilyl)decane.
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Page/Page column 3; 6
(2010/02/10)
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- Process for the production of propyl silanes functionalized in 3-position
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Propyl silanes functionalized in 3-position are produced by catalytically reacting allyl compounds of the formula H2C═CH—CH2X with silanes of the formula R2R3R4SiH and using a 3- to 100-fold excess of silane.
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- Process for the continuous preparation of 3-halopropylorganosilanes
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A process for the continuous preparation of 3-halopropylorganosilanes of the general structure RbH3-a-bXaSiCH2CH2CH2Y??(III), where: R is CH3, C2H5, C3H7, OCH3, OC2H5or OC3H7, X is F, Cl, Br or I, Y is F, Cl, Br or I, and a and b are each one of the numbers 0, 1, 2 or 3 and the sum a+b is 1, 2 or 3, comprising reacting, as starting materials, an allyl halide with a silane carrying at least one H atom, wherein the starting materials are present in stoichiometric amounts or one of the starting materials is present in substoichiometric amounts, wherein the reaction carried out is a partial reaction of from 10% to 80%, on a molar basis, of the starting materials, based on either material, when both are present in stoichiometric amounts, or based on the substoichiometric material.
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- (1,3-Propanediyl)silylene-bis(1-indenyl)dichlorozirconium. Synthesis and polymerization catalysis
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Reaction of indenyllithium with 1,1-dichlorosilacyclobutane gave a mixture of diastereomeric isomers of 1,1-bis(1-indenyl)-1-silacyclobutane (1), and the product was in turn converted into diastereomeric (1,3-propanediyl)silylene-bis(1-indenyl)dichlorozirconium complexes (2) in a 5:2 racemic:meso ratio.Complex 2 was activated with either methyl aluminoxane (MAO) or Ph3CB(C6F5)4 to perform ethylene and propylene polymerizations over a very broad range of temperature of polymerization (-55 deg C Tp 85 deg C).Variations of the polymerization activity (A) and molecular weight (MW) with Tp were investigated as well as the isotactic yield (IY) in the case of propylene polymerizations.Comparisons of those results with other closely related ansa-zirconocene precursors were also made. Keywords: Zirconocene; Homogeneous polymerization; α-olefin; Isospecific polymerization
- Chen, You-Xian,Rausch, Marvin D.,Chien, James C. W.
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- Packing for use in resolution
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The packing for use in resolution proposed for the liquid chromatography for particularly the opti-cal resolution of racemic compounds is prepared by reacting a silica gel carrier with a so-called silane treating agent to introduce a spacer part therein and chemically bonding it with a copper salt of a carboxylic or thiocarboxylic acid selected from the group consisting of optically active D- and L-2--acetizinecaroxylic acid, proline, hydroxyproline and allohydroxyproline. The steric bulkiness, the distance between the silica gel and the optically active group and the degree of hydrophobicity are specified so as to obtain an excellent resolving power.
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- Silaheterocyclen II. Erzeugung und Cycloadditionsreaktionen der Neopentylsilaethene (R = H, Me)
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The monosilacyclobutanes (3) and (4) react with LiBut in pentane to yield the neopentylsilaethenes (1) and (2), respectively.Without suitable reactants, 1 and 2 undergo cyclodimerization to 2,4-dineopentyl-1,3-disilacyclobutanes; in the presence of organic dienes they form cycloaddition compounds: with cyclopentadiene only products are obtained, with cyclohexa-1,3-diene - and -cycloaddition reactions occur at comparable rates; in the reaction with norbornadiene the - is favoured over the -cycloaddition, whereas with 2,3-dimethyl-1,3-butadiene the -process together with the ene-reaction predominate.The -cycloadducts indicate a multistep-pathway, probably with participation of lithiated species, whereas the - and -cycloaddition reactions confirm that the silaethenes 1 and 2 are formed as reactive intermediates.
- Auner, N.
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- Hydrosilylation method, catalyst and method for making
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A hydrosilation catalyst is provided having platinum atoms anchored onto a hydroxylated oxide of silicon or aluminum by Pt-S linkages through sulfur organo siloxy groups. A hydrosilation method and a method for making such platinum catalyst is also provided.
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- Process for the production of alkylsilanes
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An improved process for the preparation of alkylsilanes and/or alkylsilanes substituted at the alkyl group by an addition reaction in the presence of a platinum or palladium supported catalyst wherein the reaction mixture is heated to its boiling point, condensed and the condensate contacts the catalyst, the improvement residing in vaporizing the reaction mixture and maintaining the vapors in out of contact relationship with respect to the platinum or palladium supported catalyst and contacting the reaction mixture only after it has condensed with the platinum or palladium supported catalyst and recovering the condensed reaction product.
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- SILAETHENE I. DARSTELLUNG UND CHARAKTERISIERUNG VON MONOSILACYCLOBUTANEN
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Monosilacyclobutanes of the type RR' are prepared by ring closure reactions of 3-halopropylhalosilanes and by substitution of SiCl containing silacyclobutane rings with organometallic reagents (RMgX, LiR, NaCp).Under optimal experimental conditions yields between 50 and 95percent can be obtained by both procedures.Characterization of the compounds is accomplished by analytical (C, H, N) and NMR, IR and mass spectroscopic investigations.
- Auner, N.,Grobe, J.
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