107-46-0Relevant articles and documents
Baay,MacDiarmid
, p. 159 (1967)
Wannagat et al.
, p. 62,69 (1964)
Siloxane derivatives of 2-mercaptobenzothiazole
Zhilitskaya, Larisa V.,Yarosh, Nina O.,Shagun, Lyudmila G.,Dorofeev, Ivan A.,Larina, Lyudmila I.
, p. 352 - 354 (2017)
First organosilicon captax derivatives were obtained from 2-mercaptobenzothiazole and 1-(iodomethyl)-1,1,3,3,3-pentamethyl-or 1,3-bis(iodomethyl)-1,1,3,3-tetramethyldisiloxanes in the absence or in the presence of bases.
First Ionization Band of 1,1-Dimethylsilaethylene by Transient Photoelectron Spectroscopy
Koenig, T.,McKenna, William
, p. 1212 - 1213 (1981)
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Whitmore et al.
, p. 1551 (1947)
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Mechanistic insights on azide-nitrile cycloadditions: On the dialkyltin oxide-trimethylsilyl azide route and a new vilsmeier-haack-type organocatalyst
Cantillo, David,Gutmann, Bernhard,Kappe, C. Oliver
, p. 4465 - 4475 (2011)
The mechanism of the azide-nitrile cycloaddition mediated by the known dialkylltin oxide-trimethylsilyl azide catalyst system has been addressed through DFT calculations. The catalytic cycle for this tin/silicon complex-based mechanism has been thoroughly examined, disclosing the most plausible intermediates and the energetics involved in the rate enhancement. In addition, a new catalyst, 5-azido-1-methyl-3,4-dihydro-2H-pyrrolium azide, is presented for the formation of tetrazoles by cycloaddition of sodium azide with organic nitriles under neutral conditions. The efficiency of this organocatalyst, generated in situ from N-methyl-2-pyrrolidone (NMP), sodium azide, and trimethylsilyl chloride under reaction conditions, has been examined by preparation of a series of 5-substituted-1H-tetrazoles. The desired target structures were obtained in high yields within 15-25 min employing controlled microwave heating. An in depth computational analysis of the proposed catalytic cycle has also been addressed to understand the nature of the rate acceleration. The computed energy barriers have been compared to the dialkylltin oxide-trimethylsilyl azide metal-based catalyst system. Both the tin/silicon species and the new organocatalyst accelerate the azide-nitrile coupling by activating the nitrile substrate. As compared to the dialkylltin oxide-trimethylsilyl azide method, the organocatalytic system presented herein has the advantage of higher reactivity, in situ generation from inexpensive materials, and low toxicity.
Emeleus, H. J.,Miller, N.
, p. 996 - 997 (1938)
Hunter, M. J.,Warrick, E. L.,Hyde, J. F.,Currie, C. C.
, p. 2284 - 2290 (1946)
REACTION OF BIS(TRIMETHYLSILYL) SULFATE WITH HYDROGEN HALIDES AND WITH PHOSPHORUS AND SULFUR HALIDES AND OXYHALIDES
Voronkov, M. G.,Roman, V. K.,Maletina, E. A.,Korotaeva, I. M.
, p. 621 - 623 (1982)
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Catalytic Metal-Free Deoxygenation of Nitrous Oxide with Disilanes
Anthore-Dalion, Lucile,Nicolas, Emmanuel,Cantat, Thibault
, p. 11563 - 11567 (2019)
Because of its high kinetic stability, conditions to reduce the greenhouse gas N2O are limited; therefore, a better understanding of N2O chemistry and N-O bond cleavage is required. In this work, N2O was deoxygenated under metal-free conditions. Using disilanes as reducing agents and a catalytic amount of fluoride anions or alkoxides allowed a mild reduction at ambient pressure and temperature. DFT calculations unveiled the mechanism, which shows a nucleophilic addition of a silyl anion to the central N atom of N2O and release of N2 from a pseudo-Brook rearrangement.
Persson, Christina,Andersson, Carlaxel
, p. 847 - 850 (1992)
Trimethylethoxysilane Liquid-Phase Hydrolysis Equilibrium and Dimerization Kinetics: Catalyst, Nonideal Mixing, and the Condensation Route
Rankin, Stephen E.,Sefcik, Jan,McCormick, Alon V.
, p. 4233 - 4241 (1999)
Although the kinetics of organoethoxysilane hydrolytic (poly)condensation have been studied under kinetically simplified conditions, materials are actually synthesized from nonideal mixtures with high monomer and catalyst concentrations. Using 29Si nuclear magnetic resonance, we study the hydrolysis of trimethylethoxysilane and the dimerization of the resulting silanol in aqueous ethanol at monomer and catalyst concentrations typical of organically modified silicate synthesis. Under acidic conditions, we find that when (and only when) the effects of solvent composition on catalyst activity are considered, it becomes clear that water-producing condensation is the dominant dimerization route. Under basic conditions, the extent of deprotonation of the weakly acidic silanol passes through a minimum during reaction, thereby producing an anomolous trend in reaction rate. This necessitates a kinetic model which is first order in both silanol and deprotonated silanol and which accounts for changing deprotonation.
Stationary and Pulsed Photolysis and Pyrolysis of 1,1-Dimethylsilacyclobutane
Brix, Th.,Arthur, N. L.,Potzinger, P.
, p. 8193 - 8197 (1989)
A study of the photolysis of 1,1-dimethylsilacyclobutane at 147 - 214 nm shows that of the four primary processes identified the predominant mode of decomposition is to C2H4 and dimethylsilaethene.Evidence from experiments in the presence of SF6 suggests that the dimethylsilaethene is formed initially in a vibrationally excited state: +hν -> Me2SiCH2v + CH2=CH2.Laser pulsed photolysis experiments at 193 nm have been carried out to measure tha absorption spectrum of Me2SiCH2, its absorption cross section, and the rate constant for Me2SCH2 combination: 2Me2SiCH2 -> (Me2SiCH2)2.The values obtained are ? (240 nm, base e) = (1.0 +/- 0.2)E-17 cm2 and k7 = (3.3 +/- 0.8)E-11 cm3 s-1.The kinetics of the pyrolysis of have also been reexamined, yielding the following rate constant expressions: k1/(s-1) = E(15.46 +/- 0.13) exp(-(31043 +/- 218)/T) and k-1/k71/2/(cm3/2s-1/2) = E(-7.0 +/- 0.3) exp(-(7850 +/- 300)/T).From these results, the heat of formation, ?-bond energy, and entropy of Me2SiCH2, have been deduced: ΔHfθ (g, 298 K) = 36 +/- 7 kJ mol-1, B? = 157 +/- 11 kJ mol-1, and Sθ(g, 298 K) = 332 +/- 8 J mol-1 K-1.
Catalytic Iodination of the Aliphatic C-F Bond by YbI3(THF)3: Mechanistic Insight and Synthetic Utility
Janjetovic, Mario,Ekebergh, Andreas,Tr?ff, Annika M.,Hilmersson, G?ran
, p. 2804 - 2807 (2016)
A facile iodination protocol of unactivated alkyl fluorides using catalytic amounts of YbI3(THF)3 in the presence of iodotrimethylsilane as a stoichiometric fluoride trapping agent is presented. 1H NMR spectroscopy demonstrates a two-step catalytic cycle where TMSI regenerates active YbI3(THF)3. Finally, the catalytic reaction is extended into a one-pot procedure to demonstrate a potential application of the method. Overall, the findings present a distinct strategy for C-F bond transformations in the presence of catalytic YbI3(THF)3.
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Pearlson, W. H.,Brice, T. J.,Simons, J. H.
, p. 1769 - 1770 (1945)
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The pentamethylcyclopentadienylsilicon(II) cation as a catalyst for the specific degradation of oligo(ethyleneglycol) diethers
Leszczynska, Kinga,Mix, Andreas,Berger, Raphael J. F.,Rummel, Britta,Neumann, Beate,Stammler, Hans-Georg,Jutzi, Peter
, p. 6843 - 6846 (2011)
Catalytic open sandwiches: Oligo(ethyleneglycol) diethers RO(CH 2CH2O)nR are degraded by the unusual catalyst Cp Si+ (see scheme). The open coordination sphere at silicon allows up to four Si-O contacts; crystal structure data of the reactive compounds [Cp Si(dme)]+BR4- and [Cp Si([12]crown-4)] +BR4- (R=C6F5) show weakly bound ether molecules. Copyright
Unusual desilanolysis of 1,1-Dimethyl-1-(trimethylsiloxy)-3-phenylpropyne
Boyarkina,Mirskov,Voronkov,Rakhlin
, p. 316 - 316 (2001)
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Reactions of trimethyliodosilane with mono-, di-, and trioxacycloalkanes
Voronkov, M. G.,Dubinskaya, E. I.
, p. 13 - 32 (1991)
The reactions of Me3SiI with mono-, di-, and trioxacycloalkanes have been studied first.Preparative methods for the synthesis of some promising synthones, namely α,ω-diiodoalkanes, α,ω-alkanediols, and iodomethyl ω-iodoalkyl ethers, have been developed based on these reactions.The effect of the cycle size and the nature of the substituent on the course of the reactions is demonstrated.Schemes for the mechanism of the reactions are suggested.
Reaction of Trimethylsilyl Benzhydryl Ethers with Methyl N-(Trimethylsilyl)pyroglutamate: An Easy and Rapid N-Alkylation
Rigo, Beno?t,Gautret, Philippe,Legrand, Anne,Hénichart, Jean-Pierre,Couturier, Daniel
, p. 998 - 1000 (1997)
In the presence of a small amount of catalyst (mainly triflic acid), methyl N-(trimethylsilyl)pyroglutamate quickly reacts with benzhydryl chlorides or preferentially with trimethylsilyl benzhydryl ethers to give methyl N-(benzhydryl)pyroglutamates in nearly quantitative isolated yields.
Fessenden,Freenor
, p. 1681 (1961)
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Seyferth,D. et al.
, p. 1080 - 1082 (1968)
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Metathesis of silicon-containing olefins. X. Metathesis of vinyltrimethylsilane catalyzed by ruthenium complexes
Marciniec, Bogdan,Pietraszuk, Cezary,Foltynowicz, Zenon
, p. 83 - 88 (1994)
Self metathesis of vinyltrimethylsilane in the presence of an oxygenated benzene solution of RuCl2(PPh3)3 and RuH2(PPh3)4 follows an unusual course and yields two products, 1,2-bis(silyl)ethene (E) and 1,1-bis(silyl)ethene, with products of dimerization, namely 1,4-bis(silyl)butenes-2 (E + Z) and butenylsilanes as well as hexamethyldisiloxane.Gaseous ethylene and traces of ethane were also detected.It is proposed that vinylsilane is inserted into the Ru-Si bond (via ortho-metallation of the ruthenium triphenylphosphine complex) in competition with pathways involving metal-carbene species.Complexes of ruthenium containing no phenylphosphine give stereoselectively only the (E)-product of metathesis (even in the absence of oxygen and hydrosilane co-catalysts) accompanied by traces of the same by-products. Key words: Silicon; Ruthenium; Metathesis; Olefin
THE SEARCH FOR THE ETHYNYL CATION: NITROSATION OF N,N-BIS(TRIMETHYLSILYL)YNAMINES
Alvarez, Roberto Martinez,Hanack, Michael,Schmid, Thomas,Subramanian, L. R.
, p. 191 - 194 (1995)
The reaction of bis-silylated ynamines with different nitrosyl reagents affords products derived from an electrophilic attack at the β-carbon atom and not the expected alkynyldiazonium salts.
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Sommer et al.
, p. 156 (1946)
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CO2 conversion to isocyanate via multiple N-Si bond cleavage at a bulky uranium(III) complex
Camp, Clément,Chatelain, Lucile,Kefalidis, Christos E.,Pécaut, Jacques,Maron, Laurent,Mazzanti, Marinella
, p. 15454 - 15457 (2015)
The reaction of the sterically saturated uranium(iii) tetrasilylamido complex [K(18c6)][U(N(SiMe3)2)4] with CO2 leads to CO2 insertion into the U-N bond affording the stable U(iv) isocyanate complex [K(18c6)][U(N(SiMe3)2)3(NCO)2]n that was crystallographically characterized. DFT studies indicate that the reaction involves the [2+2] cyclo-addition of a double bond of OCO to the U-N(SiMe3)2 bond and proceeds to the final product through multiple silyl migration steps.
Facile Synthesis of the Dicyanophosphide Anion via Electrochemical Activation of White Phosphorus: An Avenue to Organophosphorus Compounds
Liu, Liu Leo,Mei, Yanbo,Yan, Zeen
supporting information, p. 1517 - 1522 (2022/02/01)
Organophosphorus compounds (OPCs) have gained tremendous interest in the past decades due to their wide applications ranging from synthetic chemistry to materials and biological sciences. We describe herein a practical and versatile approach for the trans
Dimensional Reduction of Lewis Acidic Metal-Organic Frameworks for Multicomponent Reactions
Feng, Xuanyu,Song, Yang,Lin, Wenbin
supporting information, p. 8184 - 8192 (2021/06/27)
Owing to hindered diffusions, the application of porous catalytic materials has been limited to relatively simple organic transformations with small substrates. Herein we report a dimensional reduction strategy to construct a two-dimensional metal-organic framework (MOF), Zr6OTf-BTB, with 96% accessible Lewis acidic sites as probed by the bulky Lewis base pivalonitrile. With nearly free substrate accessibility, Zr6OTf-BTB outperformed two three-dimensional MOF counterparts of similar Lewis acidity (Zr6OTf-BPDC and Zr6OTf-BTC) in catalyzing sterically hindered multicomponent reactions (MCRs) for the construction of tetrahydroquinoline and aziridine carboxylate derivatives with high turnover numbers (TONs). Zr6OTf-BTB was also superior to the homogeneous benchmark Sc(OTf)3 with nearly 14 times higher TON and 9 times longer catalyst lifetime. Furthermore, the topology-activity relationships in these Zr-based Lewis acidic MOFs were rationalized by comparing their Lewis acidity, numbers of Lewis acidic sites, and sterically accessible Lewis acidic sites. Zr6OTf-BTB was successfully used to construct several bioactive molecules via MCRs with excellent efficiency. This dimensional reduction strategy should allow the development of other MOF catalysts for synthetically useful and complicated organic transformations.
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.
