Utility of trichloroisocyanuric acid in the efficient chlorination of silicon hydrides

Alkoxychlorosilanes are scientifically and industrially important toward preparing silicone and silica as well as preparation of siloxane-based nanomaterials by stepwise reactions of Si-OR (R=alkyl) and Si-Cl groups. Intermolecular exchange of alkoxy and chloro groups between alkoxysilanes and chlorosilanes (functional group exchange reaction) provides an efficient and environmentally benign route to alkoxychlorosilanes. BiCl as a Lewis acid catalyst can promote the functional group exchange reactions more efficiently than conventional acid catalysts. Higher reactivity has been observed for chlorosilanes with smaller numbers of Si-CH groups and for alkoxysilanes with larger numbers of Si-CH groups. The reaction mechanism is proposed and selective syntheses of alkoxychlorosilanes are demonstrated. These findings also enable us to synthesize an organotrialkoxysilane with four different substituents.

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“…(6)] or trichloroisocyanuric acid (TCCA) [Eq. (7)] and partial chlorination of Si(OEt) 4 with thionyl chloride [Eq. (8)] .…”

Section: Introductionmentioning

confidence: 99%

Selective Formation of Alkoxychlorosilanes and Organotrialkoxysilane with Four Different Substituents by Intermolecular Exchange Reaction

Komata

Yoshikawa

Tamura

et al. 2016

Chemistry An Asian Journal

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“…After several attempts using possible halogenation reagents, we have finally succeeded in the synthesis of monochlorosilanes, (Rind)SiH 2 Cl (2), by the action of trichloroisocyanuric acid (TCCA). 11 After centrifugation to remove any insoluble materials, monochlorosilanes 2 were isolated as air-and moisture-sensitive colorless crystals in 84% (2a) and 91% (2b) yields. We have found that the use of hexane as a reaction solvent is crucial for the effective control of the monochlorination of 1 to prevent the over-chlorination; the reactions of 1 with TCCA in CH 2 Cl 2 afforded a mixture of monochloro and dichloro compounds.…”

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confidence: 99%

Synthesis and Structures of Sterically Congested Diarylsilanes Bearing Two Bulky Rind Groups

et al. 2016

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The sterically overcrowded diarylsilanes, (Rind) 2 SiH 2 and (Rind) 2 SiBr 2 , with the two bulky Rind groups (Rind: 1,1,3,3,5,5,7,7-octa-R-substituted s-hydrindacen-4-yl) have been synthesized by the coupling reaction of the Rind-substituted monochlorosilanes, (Rind)SiH 2 Cl, with (Rind)Li followed by bromination of the SiH bonds. The key intermediates, (Rind)SiH 2 Cl, have been obtained by the reactions of the trihydrosilanes, (Rind)SiH 3 , with trichloroisocyanuric acid. The structural features of (Rind) 2 SiH 2 and (Rind) 2 SiBr 2 have been fully characterized by NMR spectroscopy and X-ray diffraction studies.

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“…Elemental analysis was performed with an Elemental vario EL analyzer. (EtO) 3 SiCl was prepared according to literature procedure …”

Section: Methodsmentioning

confidence: 99%

Selectively Tunable Domino Reaction of 1,3‐Diphenylpropane‐1,3‐dione on the Ethoxy‐Silicon Core

et al. 2020

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The reaction of (EtO)3SiCl with 1,3‐diphenylpropane‐1,3‐dione in dichloromethane yields an ionic hexacoordinate compound featuring three chelating 1,3‐diphenylpropane‐1,3‐dionato ligands as proven by its X‐ray structure and multinuclear NMR studies in a fast domino reaction. With a proper selection of the solvent (toluene) and the reaction time, the intermediates of the reaction sequence can be selectively obtained. With an excess of the starting chlorosilane and short reaction times, the tetracoordinate silane can be obtained by the replacement of the chloro substituent. This compound shows a dynamic behavior according to its 13C NMR spectrum, involving its pentacoordinate isomer, which is only slightly less stable according to DFT calculations. The hemilabile ethoxy group can easily be replaced by a further 1,3‐diphenylpropane‐1,3‐dionato ligand, yielding the neutral hexacoordinate silane with two chelators and two ethoxy groups, as characterized by X‐ray crystallography and multinuclear NMR studies.

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Utility of trichloroisocyanuric acid in the efficient chlorination of silicon hydrides

Cited by 37 publications

References 28 publications

Selective Formation of Alkoxychlorosilanes and Organotrialkoxysilane with Four Different Substituents by Intermolecular Exchange Reaction

Selective Formation of Alkoxychlorosilanes and Organotrialkoxysilane with Four Different Substituents by Intermolecular Exchange Reaction

Synthesis and Structures of Sterically Congested Diarylsilanes Bearing Two Bulky Rind Groups

Selectively Tunable Domino Reaction of 1,3‐Diphenylpropane‐1,3‐dione on the Ethoxy‐Silicon Core

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