- Application of silicon-based cross-coupling technology to triflates
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Aryl silatranes undergo fluoride-induced cross-coupling with aryl triflates to provide unsymmetrical biaryl derivatives in good to excellent yields. Silatranes also couple with aryl iodides and bromides, although the yields of adduct are lower than with the corresponding siloxane derivates. Aryl siloxanes (which had previously failed to couple with triflates) can be employed for triflate couplings using the Denmark modification, although the yields are lower than the corresponding silatrane reactions.
- Riggleman, Shaundra,DeShong, Philip
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- Reaction of phenyltrifluorosilane and phenyl(hydrocarbyl)difluorosilanes with bis(2-hydroxyethyl)- and tris(2-hydroxyethyl)amine and their N-methyl and O-trimethylsilyl derivatives. A novel route to quasisilatranes
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Reaction of phenyltrifluorosilane, diphenyldifluorosilane, and methylphenyldifluorosilane with bis(2-hydroxyethyl)amine, methyl-bis(2- hydroxyethyl)amine, methyl-bis(2-trimethylsiloxyethyl)amine, leads to 1,3-dioxa-6-aza-2-silacyclooctane derivatives, (N → Si) quasisilatranes: 1,1-difluoroquasisilatrane, 1-phenyl-1-fluoro-5-methylquasisilatrane, or 1-methyl-1-fluoroquasisilatrane, containing the donor-acceptor bond N → Si and pentacoordinate silicon atom. 1-Phenylsilatrane was found to be the product of the reaction of phenyltrifluorosilane with tris(2-trimethylsiloxyethyl)amine, whereas with tris(2-hydroxyethyl)amine 1-phenylsilatrane and 1-fluorosilatrane were formed in the molar ratio of 3:1. The structure of the synthesized compounds was proved by 1H, 13C, 15N, 19F, 29Si NMR and IR spectroscopy.
- Voronkov,Albanov,Grebneva,Trofimova,Chernov,Chipanina
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- Organylsilatranes from the reaction of tetraorganylsilanes with triethanolamine
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Triethanolamine selectively cleaves Si-C bonds in heterylsilanes (3) under basic/nucleophilic catalysis, leading to organylsilatranes (4) with good to excellent yields.
- Gevorgyan, Vladimir,Borisova, Larisa,Lukevics, Edmunds
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- ETCHANT COMPOSITION, METHOD OF ETCHING INSULATING FILM, METHOD OF MANUFACTURING SEMICONDUCTOR DEVICE, AND SILANE COMPOUND
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An etchant composition includes a silane compound represented by the following Chemical Formula 1: wherein R1 to R6 are independently hydrogen, halogen, a substituted or unsubstituted C1-C20 hydrocarbyl group, a phenyl group, a C1-C20 alkoxy group, a carboxy group, a carbonyl group, a nitro group, a tri (C1-C20) alkylsilyl group, a phosphoryl group, or a cyano group, L is a direct bond or C1-C3 hydrocarbylene, A is an n-valent radical, and n is an integer of 1 to 4.
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Paragraph 0089-0093
(2019/12/06)
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- Palladium-catalyzed cross-coupling of aryl chlorides with arylsilatranes
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The cross-coupling reactions of arylsilatranes with readily available and inexpensive aryl chlorides were carried out in toluene/THF at 100 °C for 3 h in the presence of tetrabutylammonium fluoride as an activator for smooth transmetalation and catalytic amounts of palladium(II) acetate and XPhos.
- Yamamoto, Yutaro,Baralle, Alexandre,Godefroy, Ana?s,Murakami, Kei,Yorimitsu, Hideki,Osuka, Atsuhiro
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p. 568 - 574
(2019/05/21)
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- Direct synthesis of 1-organylsilatranes from organyltrichlorosilanes and tris(2-hydroxyethyl)amine
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A direct method of synthesis of 1-organylsilatranes by the reaction of organyltrichlorosilanes with tris(2-hydroxyethyl)amine was developed. 1-Organylsilatranes RSi(OCH2CH2)3N with R = Me, Et, Ph, ClCH2, ICH2, Cl(CH2)3 were prepared by this method in up to 72% yield.
- Voronkov,Kuznetsova
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experimental part
p. 925 - 927
(2011/04/16)
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- A novel route to pentacoordinated organylsilanes and -germanes
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New convenient methods of sila- and germatranes synthesis from ethoxy- and tetraorganylsilanes and -germanes have been elaborated. The reaction of ethoxysilanes with boratrane in the presence of catalytic amounts of metal alcoholates has been investigated. Dimethylformamide (DMF) as a solvent and NaOEt as a catalyst used instead of xylene and Al(Oi-Pr)3 were found to give better yields. The possibility of using alkoxy-, aminosilanes, tetraethoxygermane and even tetraorganylsilanes in this reaction leading to the corresponding atranes with good yields has been demonstrated. Triethanolamine in the presence of catalytic amounts of base or CsF easily substitutes furyl-, dihydrofuryl-, dihydropyranyl- and thienyl groups in tris- and tetraheterylsilanes, leading to organylsilatranes with good to excellent yields.
- Gevorgyan, Vladimir,Borisova, Larisa,Vyater, Armand,Ryabova, Victoria,Lukevics, Edmunds
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p. 149 - 155
(2007/10/03)
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- MEDIUM-SIZED SILICON-CONTAINING RINGS. IV. SILOCANE-SILATRANE TRANSFORMATIONS
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We have discovered an intramolecular condensation of trimethylsilyl ethers of silocines with a phenyl substituent on the silicon atom that leads to the corresponding silatranes.For the preparation of N-(hydroxyethy) derivatives of silocines we have, for the first time, used the cyclosilylation of triethanolamine with a bis(dialkylamino)silane.It was found that in the exothermic reaction of trialkoxyalkylsilanes with N-(hydroxyethyl) derivatives of silocines and their trimethylsilyl ethers the yield of silatranes is only slighthly dependent on the nature of the substituent both in the silocines and in the alkoxysilanes.
- D'yakov, V. M.,Makarov, A. F.
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p. 291 - 294
(2007/10/02)
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- Conversion of hydrosilanes to alkoxysilanes catalyzed by Cp2TiCl2/nBuLi
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The combination of Cp2TiCl2 and nBuLi provides an effective catalyst for alcoholysis of the model silanes n-HexSiH3, PhMeSiH2, Ph2SiH2 and PhMe2SiH by ethanol, isopropanol, t-butyl alcohol and phenol.Increasing the steric bulk of the substituents on either the alcohol or the silane generally requires longer reaction periods and/or increasing temperature.All SiH bonds are converted to SiOEt groups by ethanol and a single SiH bond in secondary silanes and two SiH bonds in tertiary silanes are replaced by t-butyl alcohol.Diols including pinacol, 2,4-pentanediol and 2,5-hexanediol react with PhRSiH2 (R = Me, Ph) to give 1,3-dioxa-2-silacyclopentanes, -hexanes and -heptanes, respectively.Attempts to form caged structures by condensation of primary silanes and triols was unsuccessful.Hydrolysis of PhRSiH2 is promoted by Cp2TiCl2/n-BuLi and the siloxane is produced in quantitative yield when R = Ph and a mixture of linear disiloxanes and trisiloxanes in addition to cyclopolysilanes are produced when R = Me.Other protic reagents including acids, mercaptans, amines and enolizable ketones did not react.The effects of reaction parameters such as temperature, silane to catalyst ratio, solvent, transition metal and replacements for nBuLi were also determined.
- Bedard, Thomas C.,Corey, Joyce Y.
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p. 315 - 333
(2007/10/02)
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- 1-Halosilatranes
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The electronic structure of 1-halosilatranes is discussed.Some new preparative methods based on hetero- and homo-lytic reactions of the silatrane and the Si- and C-substituted silatranes with halogenating reagents are described and also synthetic routes to 1-halosilatranes from certain organotrialkoxy- and organotrichlorosilanes.The electrophilic reactions of 1-iodosilatrane with ethers and esters, carbonyl compounds, alkoxysilanes and siloxanes, terminal alkynes and organomercurials have been studied
- Voronkov, M. G.,Baryshok, V. P.,Petukhov, L. P.,Rakhlin, V. I.,Mirskov, R. G.,Pestunovich, V. A.
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- Atrane Analogous Compounds of the Type (I)
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Heterocyclic cage compounds of type I (compounds 8 - 10) have been prepared by condensation reactions of 1,2,2-trifunctional disilanes Me(R)XSiSiMeX2 (R = Me, Ph, OEt; X = NMe2, OEt) with triethanolamine using the "Dilution Principle".The starting compounds are obtained by Si - Me cleavage of Si2Me6 with acetylchloride/AlCl3 followed by either aminolysis with HNMe2 or alcoholysis with EtOH. 1H NMR spectra indicate N -> Si(1) intraction with the more acidic Si atom in 8 and 9.This result is proved by the X-ray structure analysis of 8 (monoclinic, P 21/c; a = 7.088(2), b = 15.070(4), c = 12.701(4) Angstroem, β = 104.96(2) at -130 deg C, Z = 4); the Si(1) *** N distance is found to be 2.768 Angstroem, connected with a significant angular distortion of the tetrahedral coordination around Si(1) towards a trigonal bipyramid.In compound 10, too, N -> Si(1) coordination is observed at room temperature in spite of almost equal acidity for both Si atoms.This can be explained by the preference of 5- over 6-membered chelating ring systems.At higher temperatures the 1H NMR spectra show a fluctuation of the N-donor between the two Si centres. - Key words: Silatranes, Transanular N -> Si-Interactions, NMR Spectra, X-Ray
- Grobe, Joseph,Henkel, Gerald,Krebs, Bernt,Voulgarakis, Nikolaos
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p. 341 - 351
(2007/10/02)
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- CARBON-SILICON BOND CLEAVAGE OF ORGANOTRIALKOXYSILANES AND ORGANOSILATRANES WITH m-CHLOROPERBENZOIC ACID AND N-BROMOSUCCINIMIDE. NEW ROUTE TO PHENOLS, PRIMARY ALCOHOLS AND BROMIDES
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Alkyl- and aryltriethoxysilanes undergo oxidative carbon-silicon bond cleavage smoothly with m-chloroperbenzoic acid (MCPBA) to afford the corresponding alcohols.Silatranes similarly gave alcohols and bromides with MCPBA and N-bromosuccinimide, respectively.
- Hosomi, Akira,Iijima, Susumu,Sakurai, Hideki
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p. 243 - 246
(2007/10/02)
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