1066-54-2Relevant articles and documents
Silylation of Alcohols, Phenols, and Silanols with Alkynylsilanes – an Efficient Route to Silyl Ethers and Unsymmetrical Siloxanes
Kuciński, Krzysztof,Stachowiak, Hanna,Hreczycho, Grzegorz
, p. 4042 - 4049 (2020)
The formation of several silyl ethers (alkoxysilanes, R3Si-OR') and unsymmetrical siloxanes (R3Si-O-SiR'3) can be catalyzed by the commercially available potassium bis(trimethylsilyl)amide (KHMDS). The reaction proceeds via direct dealkynative coupling between various alcohols or silanols and alkynylsilanes, with a simultaneous formation of gaseous acetylene as the sole by-product. The dehydrogenative and dealkenative coupling of alcohols or silanols are well-investigated, whilst the utilization of alkynylsilanes as silylating agents has never been comprehensively studied in this context. Overall, the presented system allows the synthesis of various attractive organosilicon compounds under mild conditions, making this approach an atom-efficient, environmentally benign, and sustainable alternative to existing synthetic solutions.
Unique σ-bond metathesis of silylalkynes promoted by an ansa-dimethylsilyl and oxo-bridged uranium metallocene
Wang, Jiaxi,Gurevich, Ylia,Botoshansky, Mark,Eisen, Moris S.
, p. 9350 - 9351 (2006)
The tetrachloride salt of uranium reacts with 1 equiv of the lithium ligand Li2[(C5Me4)2SiMe2] in DME to form the complex [η5-(C5Me4)2SiMe2]UCl2·2LiCl·2DME (1), which undergoes a rapid hydrolysis in toluene to yield the dimeric bridged monochloride, monooxide complex [{[η5-(C5Me4)2SiMe2]UCl}2(μ-O)(μ-Cl)?Li?1/2DME]2 (2). Metathesis of 2 with BuLi in DME gives the mono-bridged dibutyl complex {[η5-(C5Me4)2SiMe2]UBu}2(μ-O) (3). Complex 2 was characterized by solid-state X-ray analysis. Complex 3 was found to be an active catalyst for the disproportionation metathesis of TMSC≡CH (TMS = SiMe3) and the cross-metathesis of TMSC≡CH or TMSC≡CTMS with various terminal alkynes. The metathesis of TMSC≡CH gives TMSC≡CTMS and HC≡CH, whereas the cross-metathesis of TMSC≡CH or TMSC≡CTMS with terminal alkynes (RC≡CH) yields TMSC≡CTMS, TMSC≡CR, and HC≡CH. In addition, TMSC≡CCH3 also was found to react with tBuC≡CH, yielding TMSC≡CBut and CH3C≡CH. A plausible mechanism for the catalytic process is presented. Copyright
REACTION OF DIALKYLAMIDES OF TRIMETHYLSILYLPROPIOLIC ACID WITH TRIETHYLGERMYLLITHIUM
Bravo-Zhivotovskii, D. A.,Pigarev, S. D.,Vyazankina, O. A.,Medvedeva, A. S.,Safronova, L. P.,Vyazankin, N. S.
, p. 1733 - 1734 (1984)
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Shell,Owen
, p. 1578,1581 (1972)
McLean,Sacher
, p. 197,201 (1974)
REACTION OF VINYLTRIMETHYLSILANE WITH LITHIUM IN A HYDROCARBON MEDIUM
Khotimskii, V. S.,Bryantseva, I. S.,Durgar'yan, S. G.,Petrovskii, P. V.
, p. 434 (1984)
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Preparation of a Diethynyl Hypervalent Silicon Monomer by Coordination-selective Cleavage: Structure and Polymerization to give Novel Polycarbosilanes containing Main-chain Hexacoordinate Silicon
Boyer-Elma, Karine,Carre, Francis H.,Corriu, Robert J.-P.,Douglas, William E.
, p. 725 - 726 (1995)
The hexacoordinate monomer R2Si(CCH)2 , formed from R2Si(CCSiMe3)2 by coordination-selective cleavage of the trimethylsilyl-acetylene bonds in the presence of Bun4NF, undergoes palladium-catalysed cross-coupling polymerization with dihaloarenes to afford novel polycarbosilanes n (Ar = 1,4-phenylene, 4,4'-biphenylene, 9,10-anthrylene) containing hexacoordinate silicon.
Trimethylsilylacetylene synthesis process
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Paragraph 0024; 0025, (2021/01/11)
The invention discloses a process route for synthesizing trimethylsilylacetylene, which comprises the following steps of: generating trimethylchlorosilylethylene by taking ethylene bromide and trimethylchlorosilane as initial raw materials through a Grignard method, and forming 1-bromo trimethylchlorosilylethylene under the action of alkali through a bromination reagent; and removing monomolecularhydrogen bromide under the action of strong alkali to generate trimethylsilylacetylene. Compared with the traditional process, the process route has the advantages that the use of gas acetylene is avoided, the risk is reduced, the safety is improved, the used raw materials are easily available, the operation is easy, the safety and the environmental protection are realized, and the industrial production can be realized.
Preparation technology of trimethylsilylacetylene
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Paragraph 0001; 0002, (2017/07/19)
Trimethylsilylacetylene is an important chemical product. The technological process comprises steps as follows: (1) preparation of an n-butyl magnesium chloride Grignard reagent; (2) preparation of a unilateral ethynylmagnesium chloride Grignard reagent; (3) preparation of trimethylsilylacetylene; (4) distillation; (5) washing; (6) removal of calcium chloride by suction filtration; (7) atmospheric distillation.
