- Low-valent iron(I) amido olefin complexes as promotors for dehydrogenation reactions
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FeI compounds including hydrogenases show remarkable properties and reactivities. Several iron(I) complexes have been established in stoichiometric reactions as model compounds for N2 or CO2 activation. The development of well-defined iron(I) complexes for catalytic transformations remains a challenge. The few examples include cross-coupling reactions, hydrogenations of terminal olefins, and azide functionalizations. Here the syntheses and properties of bimetallic complexes [MFeI(trop2dae)(solv)] (M=Na, solv=3-thf; M=Li, solv=2-Et2O; trop=5H-dibenzo[a,d]cyclo-hepten-5-yl, dae=(N-CH2-CH2-N) with a d7 Fe low-spin valence-electron configuration are reported. Both compounds promote the dehydrogenation of N,N-dimethylaminoborane, and the former is a precatalyst for the dehydrogenative alcoholysis of silanes. No indications for heterogeneous catalyses were found. High activities and complete conversions were observed particularly with [NaFeI(trop2dae)(thf)3]. Square-planar FeI: A low-valent iron center has been stabilized in a distorted square-planar coordination geometry by using a diamido-diolefin ligand and an alkali metal counterion (see scheme). The heterobimetallic compounds of this type initiate the dehydrogenation of N,N-dimethylaminoborane and the dehydrogenative alcoholysis of silanes. The counterion [Li(OEt2)2]+ or [Na(thf)3]+ affects the catalytic performance.
- Lichtenberg, Crispin,Viciu, Liliana,Grützmacher, Hansj?rg,De Bruin, Bas,Adelhardt, Mario,Sutter, J?rg,Meyer, Karsten
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Read Online
- A triazine-based covalent organic framework/palladium hybrid for one-pot silicon-based cross-coupling of silanes and aryl iodides
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A triazine-based covalent organic framework (COF-SDU1) was synthesized through facile solvothermal conditions and characterized by IR, solid state 13C NMR, XRD, elemental analysis and BET. By a simple solution infiltration method, Pd(ii) species were successfully immobilized into COF-SDU1 due to its two-dimensional eclipsed layer-sheet structure and nitrogen-rich content. High-resolution TEM images showed the uniform loading of the Pd species into the COF-SDU1 matrix. By using this hybrid material, Pd(ii)/COF-SDU1, as a sustainable and green catalyst, one-pot cross-coupling of silanes and aryl iodides was realized with high selectivity. The catalyst can be easily recovered by a simple separation process and recycled several times without obvious loss of activity and selectivity.
- Lin, Sha,Hou, Yuxia,Deng, Xiao,Wang, Haoliang,Sun, Shuzhuang,Zhang, Xiaomei
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Read Online
- Hydrosilane σ-Adduct Intermediates in an Adaptive Zinc-Catalyzed Cross-dehydrocoupling of Si?H and O?H Bonds
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Three-coordinate PhBOX (Formula presented.) ZnR (PhBOX (Formula presented.) =phenyl-(4,4-dimethyl-oxazolinato; R=Me: 2 a, Et: 2 b) catalyzes the dehydrocoupling of primary or secondary silanes and alcohols to give silyl ethers and hydrogen, with high turnover numbers (TON; up to 107) under solvent-free conditions. Primary and secondary silanes react with small, medium, and large alcohols to give various degrees of substitution, from mono- to tri-alkoxylation, whereas tri-substituted silanes do not react with MeOH under these conditions. The effect of coordinative unsaturation on the behavior of the Zn catalyst is revealed through a dramatic variation of both rate law and experimental rate constants, which depend on the concentrations of both the alcohol and hydrosilane reactants. That is, the catalyst adapts its mechanism to access the most facile and efficient conversion. In particular, either alcohol or hydrosilane binds to the open coordination site on the PhBOX (Formula presented.) ZnOR catalyst to form a PhBOX (Formula presented.) ZnOR(HOR) complex under one set of conditions or an unprecedented σ-adduct PhBOX (Formula presented.) ZnOR(H?SiR′3) under other conditions. Saturation kinetics provide evidence for the latter species, in support of the hypothesis that σ-bond metathesis reactions involving four-centered electrocyclic 2σ–2σ transition states are preceded by σ-adducts.
- Patnaik, Smita,Kanbur, Uddhav,Ellern, Arkady,Sadow, Aaron D.
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supporting information
p. 10428 - 10436
(2021/05/27)
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- Charge Modified Porous Organic Polymer Stabilized Ultrasmall Platinum Nanoparticles for the Catalytic Dehydrogenative Coupling of Silanes with Alcohols
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Developing an ideal stabilizer to prevent the aggregation of nanoparticles is still a big challenge for the practical application of noble metal nanocatalysts. Herein, we develop a charge (NTf2?) modified porous organic polymer (POP-NTf2) to stabilize ultrasmall platinum nanoparticles. The catalyst is characterized and applied in the catalytic dehydrogenative coupling of silanes with alcohols. The catalyst exhibits excellent catalytic performance with highly dispersed ultrasmall platinum nanoparticles (ca. 2.22?nm). Moreover, the catalyst can be reused at least five times without any performance significant loss and Pt NPs aggregation. Graphic Abstract: [Figure not available: see fulltext.]
- Chen, Chao,Cheng, Dan,Ding, Shunmin,Liang, Sanqi,Liu, Senqun,Ma, Xiaohua,Su, Tongtong,Wu, Shaohua,Zeng, Rong
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- N-Heterocyclic Carbene Complexes of Nickel, Palladium, and Iridium Derived from Nitron: Synthesis, Structures, and Catalytic Properties
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The mesoionic compound (1,4-diphenyl-1,2,4-triazol-4-ium-3-yl)phenylazanide, commonly referred to as Nitron, has been employed as a "crypto-NHC"to afford 1,2,4-triazolylidene compounds of nickel, palladium, and iridium. Specifically, Nitron reacts with NiBr2, PdCl2, and [Ir(COD)Cl]2 to afford the N-heterocyclic carbene complexes (NitronNHC)2NiBr2, (NitronNHC)2PdCl2, and (NitronNHC)Ir(COD)Cl, respectively. The lattermost compound reacts with (i) CO to afford the dicarbonyl compound (NitronNHC)Ir(CO)2Cl and (ii) CO, in the presence of PPh3, to afford the monocarbonyl compound (NitronNHC)Ir(PPh3)(CO)Cl. Structural studies on (NitronNHC)Ir(COD)Cl and (NitronNHC)Ir(CO)2Cl indicate that NitronNHC has a stronger trans influence than does Cl; furthermore, IR spectroscopic studies on (NitronNHC)Ir(CO)2Cl indicate that NitronNHC is electronically similar to the structurally related Enders carbene but is less electron donating than imidazol-2-ylidenes with aryl substituents. Significantly, the NitronNHC ligand affords catalytic systems, as illustrated by the ability of (NitronNHC)Ir(CO)2Cl to effect (i) the dehydrogenation of formic acid, (ii) aldehyde hydrosilylation, (iii) dehydrocoupling of hydrosilanes and alcohols, and (iv) ketone reduction via transfer hydrogenation.
- Quinlivan, Patrick J.,Loo, Aaron,Shlian, Daniel G.,Martinez, Joan,Parkin, Gerard
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p. 166 - 183
(2021/02/05)
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- Environment-friendly preparation method of diphenyldimethoxysilane
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The invention relates to a preparation method of phenyl alkoxysilane, which includes: dissolving phenyl chlorosilane in an organic solvent, adding alcohol-alkoxide solution and performing a reaction in an inert atmosphere; when the reaction is carried out to a certain degree, adding a sodium alkoxide solution, continuously carrying out the reaction; when the reaction is finished, distilling the reaction product to form the phenyl alkoxysilane.
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Paragraph 0020; 0021; 0038; 0039
(2019/01/08)
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- Pollution-free method for preparing diphenyldiethoxysilane
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The invention relates to a synthetic method of phenyl alkoxysilane, which includes: dissolving phenyl chlorosilane in an organic solvent, and adding an alcohol-alkoxide solution, performing a reactionin an inert atmosphere; when the reaction is carried out to a certain degree, adding a sodium alkoxide solution, continuously carrying out the reaction; when the reaction is finished, distilling thereaction product to form the phenyl alkoxysilane.
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Paragraph 0020-0021; 0023; 0025; 0027; 0029; 0031; 0033
(2019/01/08)
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- High Production of Hydrogen on Demand from Silanes Catalyzed by Iridium Complexes as a Versatile Hydrogen Storage System
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The catalytic dehydrogenative coupling of silanes and alcohols represents a convenient process to produce hydrogen on demand. The catalyst, an iridium complex of the formula [IrCp?(Cl)2(NHC)] containing an N-heterocyclic carbene (NHC) ligand functionalized with a pyrene tag, catalyzes efficiently the reaction at room temperature producing H2 quantitatively within a few minutes. As a result, the dehydrogenative coupling of 1,4-disilabutane and methanol enables an effective hydrogen storage capacity of 4.3 wt % that is as high as the hydrogen contained in the dehydrogenation of formic acid, positioning the silane/alcohol pair as a potential liquid organic hydrogen carrier for energy storage. In addition, the heterogenization of the iridium complex on graphene presents a recyclable catalyst that retains its activity for at least 10 additional runs. The homogeneous distribution of catalytic active sites on the basal plane of graphene prevents diffusion problems, and the reaction kinetics are maintained after immobilization.
- Ventura-Espinosa, David,Sabater, Sara,Carretero-Cerdán, Alba,Baya, Miguel,Mata, Jose A.
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p. 2558 - 2566
(2018/03/13)
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- Dehydrogenative Coupling of Hydrosilanes and Alcohols by Alkali Metal Catalysts for Facile Synthesis of Silyl Ethers
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Cross-dehydrogenative coupling (CDC) of hydrosilanes with hydroxyl groups, using alkali metal hexamethyldisilazide as a single-component catalyst for the formation of Si-O bonds under mild condition, is reported. The potassium salt [KN(SiMe3)2] is highly efficient and chemoselective for a wide range of functionalized alcohols (99% conversion) under solvent-free conditions. The CDC reaction of alcohols with silanes exhibits first-order kinetics with respect to both catalyst and substrate concentrations. The most plausible mechanism for this reaction suggests that the initial step most likely involves the formation of an alkoxide followed by the formation of metal hydride as active species.
- Harinath, Adimulam,Bhattacharjee, Jayeeta,Anga, Srinivas,Panda, Tarun K.
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p. 724 - 730
(2017/05/31)
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- Catalytic Dehydrogenative Coupling of Hydrosilanes with Alcohols for the Production of Hydrogen On-demand: Application of a Silane/Alcohol Pair as a Liquid Organic Hydrogen Carrier
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The compound [Ru(p-cym)(Cl)2(NHC)] is an effective catalyst for the room-temperature coupling of silanes and alcohols with the concomitant formation of molecular hydrogen. High catalyst activity is observed for a variety of substrates affording quantitative yields in minutes at room temperature and with a catalyst loading as low as 0.1 mol %. The coupling reaction is thermodynamically and, in the presence of a Ru complex, kinetically favourable and allows rapid molecular hydrogen generation on-demand at room temperature, under air, and without any additive. The pair silane/alcohol is a potential liquid organic hydrogen carrier (LOHC) for energy storage over long periods in a safe and secure way. Silanes and alcohols are non-toxic compounds and do not require special handling precautions such as high pressure or an inert atmosphere. These properties enhance the practical applications of the pair silane/alcohol as a good LOHC in the automotive industry. The variety and availability of silanes and alcohols permits a pair combination that fulfils the requirements for developing an efficient LOHC.
- Ventura-Espinosa, David,Carretero-Cerdán, Alba,Baya, Miguel,García, Hermenegildo,Mata, Jose A.
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supporting information
p. 10815 - 10821
(2017/08/18)
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- METHOD FOR PRODUCING ORGANOXYSILANE
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PROBLEM TO BE SOLVED: To provide a method for easily producing high quality alkoxysilane without sublimating contaminant urea and urea hydroxide in the distillation of an alkoxysilane layer after separating an alcohol solution layer with urea and urea hydroxide dissolved therein when chlorosilane is reacted with alcohol in a presence of urea. SOLUTION: The method for producing organoxysilane represented by formula (3) comprises: reacting chlorosilane represented by formula (1) with alcohol represented by formula (2) in a presence of urea; removing hydrogen chloride generated by the above reaction, urea hydroxide produced by reaction of urea, and urea in a reaction system as an alcohol solution dissolved in alcohol in the reaction system from the system; and thereafter distilling an obtained organoxysilane layer with metal alkoxide added to the layer, where R1 and R2 are monovalent hydrocarbon groups, a is an integer of 1-3, b is an integer of 0-2, a+b is an integer of 1-3, and R3 is a monovalent hydrocarbon group. SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT
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Paragraph 0039-0040
(2017/04/11)
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- Synthesis of dimethylmanganese(II) complexes bearing N-heterocyclic carbenes and nucleophilic substitution reaction of tetraalkoxysilanes by diorganomanganese(II) complexes
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Reactions of manganese(II) dichlorides bearing a N-heterocyclic carbene ligand (L), [MnCl(μ-Cl)(L)]2(1a, L?=?1,3-diisopropyl-4,5-dimethylimidazole-2-ylidene (IiPr); 1b, L?=?1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene (IMes); 1c, L?=?1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene (IPr)) with MeLi afford the dinuclear dimethylmanganese(II) complexes, [MnMe(μ-Me)(L)]2(2a, L?=?IiPr; 2b, L?=?IMes; 2c, L?=?IPr). Complexes 2a-c achieve nucleophilic substitution of Si(OEt)4to selectively form MeSi(OEt)3. Related arylmanganese(II) complexes analogously react with Si(OEt)4to afford ArSi(OEt)3and Ar2Si(OEt)2(Ar?= Ph, 2,6-Me2(C6H3)). Kinetic studies support an associative mechanism for the observed transformation of Si(OEt)4, in which both the manganese species and Si(OEt)4are involved in the rate-limiting step.
- Hashimoto, Takayoshi,Kawato, Yuko,Nakajima, Yumiko,Ohki, Yasuhiro,Tatsumi, Kazuyuki,Ando, Wataru,Sato, Kazuhiko,Shimada, Shigeru
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- ORGANOPOLYSILOXANE AND METHOD FOR PREPARING THE SAME
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An organopolysiloxane is prepared by hydrolysis and polycondensation of an organosilicon compound in the presence of a liquid hydrolytic condensation catalyst which is separable. The organopolysiloxane contains a high proportion of cyclic polysiloxanes and has a sharp molecular weight distribution due to minimized monomer and polymer contents.
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Paragraph 0075; 0076; 0091; 0092; 0095; 0096
(2020/12/16)
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- Alkyl silane compound (or arylsilanes compd.) manufacturing method (by machine translation)
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PROBLEM TO BE SOLVED: alkyl silane compound (or arylsilanes compd.) in order to obtain an effective compd. perfluoroalkylated (or aryl-) is found, novel alkyl silane compound (or aryl compound) and to provide a method of manufacturing. SOLUTION: the following eq. (A-1), (A-2), (A-3), or (A-4) alkylalkoxysilane compd. represented by, alkyl (or aryl demanganese compd.) demanganese compd. reacting and, by perfluoroalkylated (or aryl-), alkyl silane compound (or arylsilanes compd.) can be efficiently manufactured. ( Eq. (A-1), (A-2), (A-3), during and (A-4), R 1 to 1-20 hydrocarbon groups, R 2 silicon atoms and oxygen atoms are each independently selected from the group consisting of at least 1 may also include a kind of carbon number 1-20 hydrocarbon group. ) Selected drawing: no (by machine translation)
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Paragraph 0031
(2016/10/08)
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- Highly selective oxidation of organosilanes with a reusable nanoporous silver catalyst
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Room temperature highly selective oxidation of organosilanes to organosilanols and organosilyl ethers is achieved in liquid-phase with dealloyed nanoporous silver catalysts. In both cases, aromatic and aliphatic silanes can be effectively converted into the corresponding silanols and silyl ethers by using water and alcohols as oxidant, respectively. Moreover, hydrogen gas is the only by-product and the catalyst can be recycled for several times without evident loss of activity and selectivity.
- Li, Zhiwen,Zhang, Congcong,Tian, Jing,Zhang, Zhonghua,Zhang, Xiaomei,Ding, Yi
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- Nanoporous palladium catalyzed silicon-based one-pot cross-coupling reaction of aryl iodides with organosilanes
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One-pot cross-coupling of aryl iodides with organosilanes is realized in excellent yield by utilizing dealloyed nanoporous palladium as a sustainable and heterogeneous catalyst. The reaction is completed under mild conditions and the catalyst can be reused several times without evident loss of its catalytic activity. This journal is the Partner Organisations 2014.
- Li, Zhiwen,Lin, Sha,Ji, Lisha,Zhang, Zhonghua,Zhang, Xiaomei,Ding, Yi
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p. 1734 - 1737
(2014/06/09)
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- Dinuclear zinc hydride supported by an anionic bis(N-heterocyclic carbene) ligand
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Methylene-linked bis(N,N′-di-tert-butylimidazol-2-ylidene) 1 reacted with diethylzinc to give dinuclear zinc ethyl compound 2, which contains a formally anionic bis(carbene) ligand as a result of deprotonation of the methylene bridge. The reaction of 2 with PhSiH3 gave the phenylsilyl compound 3. The zinc hydride 4 was obtained by the reaction of 2 with LiAlH 4 or Ph3SiOH followed by treatment with PhSiH3. X-ray diffraction studies show that compounds 2, 3, and 4 all have a similar dimeric structure with D2h symmetry. The reaction of hydride 4 with carbon dioxide and N,N′-diisopropylcarbodiimide gave formato (5) and formamidinato (7) derivatives as a result of the insertion of the heterocumulene into both Zn-H bonds. Reaction with Ph2CO gave the diphenylmethoxy compound 6. Hydride 4 shows catalytic activity in the hydrosilylation of 1,1-diphenylethylene and methanolysis of silanes. Copyright
- Rit, Arnab,Spaniol, Thomas P.,Okuda, Jun
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p. 612 - 619
(2014/02/14)
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- Copper nanoparticles supported on doped graphenes as catalyst for the dehydrogenative coupling of silanes and alcohols
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Copper nanoparticles (NPs) supported on a series of undoped and doped graphene materials (Gs) have been obtained by pyrolysis of alginate or chitosan biopolymers, modified or not with boric acid, containing Cu2+ ions at 900 °C under inert atmosphere. The resulting Cu-G materials containing about 17 wt% Cu NPs (from 10 to 200 nm) exhibit high catalytic activity for the dehydrogenative coupling of silanes with alcohols. The optimal material consisting on Cu-(B)G is more efficient than Cu NPs on other carbon supports.
- Blez, Juan F.,Primo, Ana,Asiri, Abdullah M.,lvaro, Mercedes,Garc, Hermenegildo
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supporting information
p. 12581 - 12586
(2015/04/16)
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- A highly active manganese precatalyst for the hydrosilylation of ketones and esters
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The reduction of (Ph2 PPrPDI)MnCl2 allowed the preparation of the formally zerovalent complex, (Ph2 PPrPDI)Mn, which features a pentadentate bis(imino)pyridine chelate. This complex is a highly active precatalyst for the hydrosilylation of ketones, exhibiting TOFs of up to 76,800 h-1 in the absence of solvent. Loadings as low as 0.01 mol % were employed, and (Ph2 PPrPDI)Mn was found to mediate the atom-efficient utilization of Si-H bonds to form quaternary silane products. (Ph2PPrPDI)Mn was also shown to catalyze the dihydrosilylation of esters following cleavage of the substrate acyl C-O bond. Electronic structure investigation of (Ph 2PPrPDI)Mn revealed that this complex possesses an unpaired electron on the metal center, rendering it likely that catalysis takes place following electron transfer to the incoming carbonyl substituent.
- Mukhopadhyay, Tufan K.,Flores, Marco,Groy, Thomas L.,Trovitch, Ryan J.
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supporting information
p. 882 - 885
(2014/02/14)
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- COSMETIC TREATMENT METHOD COMPRISING THE APPLICATION OF A COATING BASED ON AN AEROGEL COMPOSITION OF LOW BULK DENSITY
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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.
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Paragraph 0067
(2014/02/15)
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- METHOD OF PRODUCING A HYDROLYZABLE SILICON-CONTAINING COMPOUND
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The present invention provides a safe, inexpensive, and high yield means of producing a hydrolyzable silicon-containing compound, e.g., an organooxysilane and the like. A compound (A) represented by the general formula R1-O-R2 wherein R1 represents a C4-30, substituted or unsubstituted, tertiary alkyl group or aralkyl group and R2 represents a C1-30, substituted or unsubstituted, monovalent hydrocarbyl group or acyl group, is reacted in the presence of a Lewis acid catalyst with a halosilane (B) represented by the general formula R3mSiX4-m wherein R3 represents the hydrogen atom or a C1-30 substituted or unsubstituted monovalent hydrocarbyl group, X is independently bromine or chlorine, and m represents an integer from 0 to 3.
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Page/Page column 16; 20
(2012/07/14)
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- Practical conversion of chlorosilanes into alkoxysilanes without generating HCl
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Alcohol-free: A versatile, efficient, and practical synthesis of alkoxysilanes without generation of HCl involves the reaction of chlorosilanes with unsymmetrical ethers in the presence of a Lewis acid (see scheme). The reaction proceeds through selective cleavage of C-O bonds and is superior to conventional processes. Industrially feasible reagents are used and only one by-product results. Copyright
- Wakabayashi, Ryutaro,Sugiura, Yasushi,Shibue, Toshimichi,Kuroda, Kazuyuki
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supporting information; experimental part
p. 10708 - 10711
(2011/12/05)
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- Convenient synthesis of alkoxyhalosilanes from hydrosilanes
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Selective dehydrogenative coupling of di- and trihydrosilanes with alcohols catalyzed by PdCl2 or NiCl2 afforded alkoxyhydro- and dialkoxyhydrosilanes in good yield. Further treatment of the resulting alkoxyhydrosilanes with carbon tetrachloride or allyl bromide in the presence of the same catalyst led to the formation of alkoxychloro- and alkoxybromosilanes, respectively. Similar reactions of dialkoxyhydrosilanes with carbon tetrachloride afforded dialkoxychlorosilanes in good yield, although contamination of small amounts of trialkoxysilanes and alkoxydichlorosilanes was detected in the products. Selective substitution of the alkoxyhalosilanes with nucleophiles is also reported.
- Ohshita, Joji,Taketsugu, Ryosuke,Nakahara, Yuki,Kunai, Atsutaka
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p. 3258 - 3264
(2007/10/03)
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- Process for preparing low-chloride or chloride-free alkoxysilanes
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A process for preparing an alkoxysilane with an acidic chloride content of less than 10 ppm by weight, comprising: reacting a chlorosilane with an alcohol in a water-free and solvent-free phase to form a product mixture containing alkoxysilane and residual acidic chloride, with removal of resultant hydrogen chloride from the product mixture, then adding liquid or gaseous ammonia, in an amount corresponding to a stoichiometric excess, based on the content of acidic chloride, to form an ammonia-containing product mixture, treating the ammonia-containing product mixture at a temperature between 10 and 50 DEG C., wherein the ammonia and acidic chloride undergo neutralization, to form a crude product, and optionally, then separating off a salt formed in the course of neutralization, from the crude product, and recovering the alkoxysilane by distilling the crude product.
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- Hydrolytic Etherification of Phenyltrichlorosilane and Structure of Reaction Products
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Hydrolytic etherification of phenyltrichlorosilane by C1-C4 primary alcohols was studied. The effect of the concentration and nature of alcohol on the structure and properties of oligomeric polyphenyl-alkoxysilanes were examined.
- Kuz'menko, N. Ya.
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p. 516 - 522
(2007/10/03)
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- Method for decomposing polysiloxane
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When a polysiloxane or siloxane is contacted with a mixture which comprises an orthoester, a compound having an active hydrogen-containing group and an acid catalyst, it is easily decomposed even at room temperature to provide a silicon compound having a lower molecular weight such as an alkoxysilane.
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- Reaction of Tetraalkoxysilanes with Alkyl(aryl)chlorosilanes
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Alkyl(aryl)trichloro- or dialkyl(diaryl)dichlorosilanes react with tetraalkoxysilanes Si(OMe)4, Si(OEt)4, and Si(OBu)4 to give partially etherfied alkyl(aryl)chlorosilanes RSiCl2(OAlk), RSiCl(OAlk)2, and R2SiCl(OAlk).
- Chernyshev, E. A.,Komalenkova, N. G.,Tagachenkov, A. A.,Bykovchenko, V. G.
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p. 241 - 243
(2007/10/03)
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Phenylmagnesium bromide reacts with triphenylsilyl azide (in contrast to organyl azides) in two parallel reactions. One type of reaction is the substitution of the azide group by the magnesium-bound organyl residue. The other is the formation of the adduct, (C6H5)3SiN3·C6H5MgBr, containing an N-diazonium group. At higher temperatures the adduct decomposes by elimination of N2 to give (C6H5)3SiN(C6H5)MgBr. The same type of reaction generally occurs when silyl azicles R3SiN3 react with arylmagnesium halides R′MgHal. The hydrolysis of the silyl amide leads to amines R′NH2. In connection with this the formation of R3SiNR′(MgHal) by the reaction of R3SiN3 with R′MgHal (=R′Hal + Mg) provides a simple procedure to prepare aromatic amines from aromatic halides.
- Wiberg, Nils,Joo, Wan-Chul
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p. 333 - 340
(2007/10/05)
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