3027-21-2Relevant articles and documents
Hydrosilane σ-Adduct Intermediates in an Adaptive Zinc-Catalyzed Cross-dehydrocoupling of Si?H and O?H Bonds
Patnaik, Smita,Kanbur, Uddhav,Ellern, Arkady,Sadow, Aaron D.
supporting information, p. 10428 - 10436 (2021/05/27)
Three-coordinate PhBOX (Formula presented.) ZnR (PhBOX (Formula presented.) =phenyl-(4,4-dimethyl-oxazolinato; R=Me: 2 a, Et: 2 b) catalyzes the dehydrocoupling of primary or secondary silanes and alcohols to give silyl ethers and hydrogen, with high turnover numbers (TON; up to 107) under solvent-free conditions. Primary and secondary silanes react with small, medium, and large alcohols to give various degrees of substitution, from mono- to tri-alkoxylation, whereas tri-substituted silanes do not react with MeOH under these conditions. The effect of coordinative unsaturation on the behavior of the Zn catalyst is revealed through a dramatic variation of both rate law and experimental rate constants, which depend on the concentrations of both the alcohol and hydrosilane reactants. That is, the catalyst adapts its mechanism to access the most facile and efficient conversion. In particular, either alcohol or hydrosilane binds to the open coordination site on the PhBOX (Formula presented.) ZnOR catalyst to form a PhBOX (Formula presented.) ZnOR(HOR) complex under one set of conditions or an unprecedented σ-adduct PhBOX (Formula presented.) ZnOR(H?SiR′3) under other conditions. Saturation kinetics provide evidence for the latter species, in support of the hypothesis that σ-bond metathesis reactions involving four-centered electrocyclic 2σ–2σ transition states are preceded by σ-adducts.
Method for industrially producing dialkyl dialkoxy silane
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Paragraph 0058-0060, (2020/04/17)
The invention discloses a method for industrially producing dialkyl dialkoxy silane, which comprises the following steps: in the presence of a catalyst and a solvent A, heating brominated hydrocarbonA and metal magnesium to reflux, and initiating reaction to obtain a first reaction solution; synchronously and dropwise adding chlorinated hydrocarbon and brominated hydrocarbon B which are diluted by a solvent B into the first reaction solution, and continuing reaction to obtain a second reaction solution; dropwise adding the second reaction solution into alkyl trialkoxy silane, and carrying outreflux reaction to obtain a third reaction solution; and cooling the third reaction solution, carrying out solid-liquid separation, and finally, carrying out washing and rectifying to obtain the dialkyl dialkoxy silane. The Grignard reaction of the chlorinated hydrocarbon is promoted by utilizing the high activity of the brominated hydrocarbon, so that on one hand, the overall conversion rate ofthe Grignard reaction can be remarkably improved, byproducts are reduced, the yield of a final product is improved, and on the other hand, the production cost can be reduced.
Platinum-Catalyzed Multicomponent Alcoholysis/Hydrosilylation and Bis-hydrosilylation of Alkynes with Dihydrosilanes
Xu, Jian-Xing,Chen, Mu-Yi,Zheng, Zhan-Jiang,Cao, Jian,Xu, Zheng,Cui, Yu-Ming,Xu, Li-Wen
, p. 3111 - 3116 (2017/08/29)
A new method for the hydrosilylation of alkynes controlled by a platinum catalyst with a monophosphine ligand (called TBSO-MOP) was explored. The platinum-catalyzed multicomponent and sequential silylation reaction involving alkynes, alcohols, and dihydrosilanes resulted in the highly stereoselective and high-yielding construction of functional (E)-vinylsilyl ethers. Moreover, the one-pot bis-hydrosilylation of terminal alkynes with dihydrosilanes was also achieved with the same platinum catalyst system.