- Kinetic and Theoretical Investigation of Iron(III)-Catalyzed Silane Chlorination
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A highly versatile, robust, and efficient methodology for chlorination of silanes, methoxysilanes and silanols using low loadings of FeCl3 or Fe(acac)3 as the catalyst in the presence of 1-1.5?equivalents of acetyl chloride as the chlorine source was recently developed. The aim of the present paper is to evaluate and derive the reaction mechanisms involved in this reaction by calculating substrates, intermediates, products, and selected transition states, as well as by employing mathematical modeling of the reaction kinetics. The results obtained required reconsideration of the originally proposed overall reaction mechanism. Based on the kinetic and molecular modeling, a new revised reaction mechanism was developed giving a very good correspondence between the experimental data and calculations.
- Savela, Risto,Grnman, Henrik,Sundelin, Heidi,Norrby, Per-Ola,Yu. Murzin, Dmitry,Leino, Reko
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- Hexachloroethane: a highly efficient reagent for the synthesis of chlorosilanes from hydrosilanes
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A new and efficient chlorination protocol is presented for the preparation of chlorosilanes from hydrosilanes. A variety of chlorinating agents in combination with palladium(II) chloride as the catalyst are examined. Among them, hexachloroethane is found to be the best choice, furnishing the desired product in good to quantitative yields under mild conditions. Various hydrosilanes are used as starting materials to explore the scope of this reaction.
- Pongkittiphan, Veerachai,Theodorakis, Emmanuel A.,Chavasiri, Warinthorn
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- Preparation of 1,1,3,3-tetraisopropyl-1,3-dichlorodisiloxane and triisopropylchlorosilane
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A facile, hydrochloric acid-free chlorination of silanes was developed. This allows for the elimination of siloxane bond cleavage and chlorination of carbon-hydrogen bonds during the chlorination of the Si-H bond.
- Chawla, Ram,Larson, Gerald L.
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- Neutral-Eosin-Y-Photocatalyzed Silane Chlorination Using Dichloromethane
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Chlorosilanes are versatile reagents in organic synthesis and material science. A mild pathway is now reported for the quantitative conversion of hydrosilanes to silyl chlorides under visible-light irradiation using neutral eosin Y as a hydrogen-atom-transfer photocatalyst and dichloromethane as a chlorinating agent. Stepwise chlorination of di- and trihydrosilanes was achieved in a highly selective fashion assisted by continuous-flow micro-tubing reactors. The ability to access silyl radicals using photocatalytic Si?H activation promoted by eosin Y offers new perspectives for the synthesis of valuable silicon reagents in a convenient and green manner.
- Fan, Xuanzi,Xiao, Pin,Jiao, Zeqing,Yang, Tingting,Dai, Xiaojuan,Xu, Wengang,Tan, Jin Da,Cui, Ganglong,Su, Hongmei,Fang, Weihai,Wu, Jie
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supporting information
p. 12580 - 12584
(2019/08/16)
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- A method for synthesizing three silane isopropyl chloride
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The invention relates to a high-strength triisopropyl chlorosilane synthesis method, and relates to the technical field of triisopropyl chlorosilane chemical synthesis. According to the invention, triisopropyl silane is subjected to a reaction with an oxidant, such that triisopropyl silanol is prepared, wherein the oxidant is at least any one selected from hydrogen peroxide, peracetic acid, potassium ferrate, potassium chlorate, sodium chlorate, sodium hypochlorite or potassium permanganate; triisopropyl silanol and hydrogen chloride gas are adopted as raw materials, and triisopropyl chlorosilane is prepared under a temperature condition of -5 DEG C to 5 DEG C. According to the invention, triisopropyl silanol is prepared by using triisopropyl silane and the oxidant. Triisopropyl silane can be quantitatively oxidized, no side reaction is caused, and the yield can reach 100%. The chlorination process is carried out under low temperature. Once hydrogen chloride delivery amount is controlled, triisopropyl chlorosilane hydrolysis can be effectively inhibited, and a yield can be higher than 99%.
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Paragraph 0028; 0029
(2017/01/12)
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- Synthesis and reactions of donor cyclopropanes: efficient routes to cis- and trans-tetrahydrofurans
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Abstract A detailed study on the synthesis and reactions of silylmethylcyclopropanes is reported. In their simplest form, these donor-only cyclopropanes undergo Lewis acid promoted reaction to give either cis- or trans-tetrahydrofurans, with the selectivity being reaction condition-dependant. The adducts themselves are demonstrated to be an important scaffold for structural diversification. The combination of a silyl-donor group in a donor-acceptor cyclopropane with novel acceptor groups is also discussed.
- Dunn, Jonathan,Dobbs, Adrian P.
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p. 7386 - 7414
(2015/08/24)
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- Iron-catalyzed chlorination of silanes
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A simple and highly efficient iron-catalyzed method for the chlorination of silanes has been developed. By use of 0.5-2% of the Fe(III)-based catalyst FeCl3 or Fe(acac)3 in the presence of 1-1.5 equiv of acetyl chloride as the chlorine donor, a large number of silanes, alkoxysilanes, and silanols were converted to the corresponding chlorosilanes in 50-93% yields. In contrast to earlier reported methods often suffering from expensive catalysts or use of stoichiometric metal salts, hazardous reagents, and reaction conditions, the presently described methodology allows benign reaction conditions and simple workup while using only catalytic amounts of a readily available and economically viable iron catalyst.
- Savela, Risto,Zawartka, Wojciech,Leino, Reko
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experimental part
p. 3199 - 3206
(2012/06/04)
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- The synthesis of chlorosilanes from alkoxysilanes, silanols, and hydrosilanes with bulky substituents
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We have found that commercially important trialkylchlorosilanes can readily be synthesized by the reaction of alkoxysilanes, silanols, and hydrosilanes with aqueous concentrated hydorochloric acid. Treatment of trialkylalkoxysilanes bearing the bulky alkyl substituents, such as the i-Pr, sec-Bu, tert-Bu, and cyclo-Hex group, with 35% aqueous hydrochloric acid afforded the corresponding trialkylchlorosilanes in excellent yields. Similar treatment of trialkylsilanols with 35% aqueous hydrochloric acid also gave trialkylchlorosilanes in almost quantitative yields. The reaction of methyltrichlorosilane and dimethyldichlorosilane with alkyl-Grignard reagents bearing a bulky alkyl group, followed by treatment of the resulting mixtures with aqueous concentrated hydrochloric acid, produced the respective dialkylmethyl- and alkyldimethylchlorosilanes in high yields. Treatment of trialkylhydrosilanes with concentrated hydrochloric acid in the presence of a palladium catalyst afforded trialkylchlorosilanes in high yields.
- Masaoka, Shin,Banno, Tadashi,Ishikawa, Mitsuo
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p. 174 - 181
(2007/10/03)
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- Production processes for triorganomonoalkoxysilanes and triorganomonochlorosilanes
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A silane containing a bulky hydrocarbon group or groups R therein and having the formula (III) [in-line-formulae]R3-(x+y)(R1)x(R2)ySi(OR3) [/in-line-formulae] can be produced by reacting a silane of the formula (I) [in-line-formulae](R1)x(R2) ySiCl3-(x+y)(OR3) [/in-line-formulae] with a Grignard reagent of the formula (II) [in-line-formulae]RMgX [/in-line-formulae] Further, a tri-organo-chlorosilane of the formula (XIIa) [in-line-formulae](R1)(R2)(R3)SiCl [/in-line-formulae] can be produced by reacting a tri-organo-silane of the formula (XIa) [in-line-formulae](R1)(R2)(R3)SiZ1 [/in-line-formulae] with hydrochloric acid. Furthermore, a tri-organo-monoalkoxysilane of the formula (XXIII) [in-line-formulae]R3-(x+y)(R1)x(R2)ySi(OR3) [/in-line-formulae] can be produced when a silane of the formula (XXI) [in-line-formulae](R1)x(R2)ySiCl4-(x+y) [/in-line-formulae] is reacted with a Grignard reagent of the formula (XXII) [in-line-formulae]RMgX [/in-line-formulae] with addition of and reaction with an alcohol or an epoxy compound during the reaction.
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Page/Page column 23
(2008/06/13)
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- Fluorescein-based metal sensors, and methods of making and using the same
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The present invention is directed, in part, to fluorescein-based ligands for detection of metal ions, and methods of making and using the same.
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- Silylation and germylation of trialkylsilyl(germyl)ethoxyacetylenes containing bulky substituents at the silicon or germanium atom
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Silylation and germylation of trialkylsilyl(germyl)ethoxyacetylenes containing bulky substituents at the silicon or germanium atom were performed. In all cases, the corresponding bis-organoelement-containing ketenes were obtained as the only reaction products. No intermediate isomeric ynol ethers were detected by spectroscopy.
- Ponomarev,Zolotareva,Leont'ev,Kuznetsov,Petrosyan
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p. 1088 - 1092
(2007/10/03)
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- 2-PIPERIDINO-1-ALKANOL DERIVATIVES AS NEUROPROTECTIVE AGENTS
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A method of blocking N-methyl-D-aspartic acid (NMDA) receptor sites in a mammal in need thereof with an effective NMDA blocking (neuroprotective and antiischemic) amount of 2-piperidino-1-alkanol derivatives and 2-azabicyclo-1-alkanol derivatives and analogs and pharmaceutically acceptable salts thereof; methods of using these compounds in the treatment of stroke, spinal cord trauma, traumatic brain injury, multiinfarct dementia, CNS degenerative diseases such as Alzheimer's disease, senile dementia of the Alzheimer's type, Huntington's disease, Parkinson's disease, epilepsy, amyotrophic lateral sclerosis, pain, AIDS dementia, psychotic conditions, drug addictions, migraine, hypoglycemia, anxiolytic conditions, urinary incontinence and an ischemic event arising from CNS surgery, open heart surgery or any procedure during which the function of the cardiovascular system is compromised.
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- Nortropyl-1-alkanol derivatives as antiischemic agents
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2-(8-Azabicyclo[3.2.1]oct-8-yl)alkanols of the formula STR1 wherein Q is S or CH=CH; X is H, OH or another aromatic substituent; R is hydrogen, alkyl, alkenyl or alkynyl; Y and Y1 are taken together and are arylmethylene or aralkylmethylene (or a corresponding epoxy derivative) or Y and Y1 are taken separately and Y is hydrogen or OH, and Y1 is aryl, aralkyl, arylthio, or aryloxy; and structurally related 2-(piperidino)alkanols; pharmaceutical compositions thereof; methods of treating CNS disorders therewith; and intermediates useful in the preparation of said compounds.
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