- Ir-catalyzed hydrosilylation reaction of allyl acetate with octakis(dimethylsiloxy)octasilsesquioxane and related hydrosilanes
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Hydrosilylation reaction of allyl acetate (AA) with octakis(dimethylsiloxy) octasilsesquioxane [(HSiMe2O)8(SiO1.5) 8] was efficiently catalyzed by chloro(1,5-cyclooctadiene)iridium(I) dimer [Ir(μ-Cl)(COD)]2
- Igarashi, Masayasu,Matsumoto, Tomohiro,Kobayashi, Toshiaki,Sato, Kazuhiko,Ando, Wataru,Shimada, Shigeru,Hara, Masanao,Uchida, Hiroshi
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p. 141 - 146
(2014/01/17)
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- Acyl iodides in organic synthesis: IX. Cleavage of the Si-O-C and Si-O-Si moieties
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Reactions of acyl iodides RCOI (R = Me, Ph) with organosilicon compounds involve cleavage of the Si-O-C and Si-O-Si fragments. Acetyl iodide reacts with alkyl(alkoxy)silanes with evolution of heat, and cleavage of the Si-O bond results in the formation of oligo-or polysiloxanes, alkyl iodides, and alkyl acetates. 1,3-Diacetoxytetramethyldisiloxane is formed in the reaction of acetyl iodide with dimethoxy(dimethyl)silane. Acyl iodides readily react with 1-ethoxysilatrane to give 1-acyloxysilatranes as a result of cleavage of the C-O bond. The reaction of acetyl iodide with hexaethyldisiloxane yields triethylsilyl acetate and triethyliodosilane, while in the reaction with octamethyltrisiloxane iodo(trimethyl)silane and dimethyl(trimethylsiloxy)silyl acetate are obtained. Nauka/Interperiodica 2007.
- Voronkov,Trukhina,Belousova,Kuznetsova,Vlasova
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p. 501 - 506
(2008/02/02)
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- REACTIONS IN THE CHLOROSILANE-SILANOL-SILOXANE SYSTEM
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We obtained the first ?*-values and ES-values for siloxy groups by spectroscopic and kinetic methods.Detailed mechanistic investigations are performed on the hydrolysis of chlorosilanes, the cleavage of Si-O-Si bonds by HCl, and the substituent exchange reaction between silanols and chlorosilanes.
- Ruehlmann, K.
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p. 139 - 152
(2007/10/02)
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- ZUR SYNTHESE VON SILOXANEN. II, STERISCHE SUBSTITUENTENKONSTANTEN FUER SILOXYRESTE
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The acetolysis reactions of compounds of the type XSiMe2Cl (I) with acetic acid in the presence of acetic anhydride were studied kinetically by means of 1H NMR spectroscopy.We found these reactions exclusively influenced by steric effects (ρ=0).The steric susceptibility constant (δ) of the acetolysis reaction, using alkylchlorodimethylsilanes was found to be 1.3.In this investigation the Taft Es nvalues showed a better correlation than the Es(Si) values of Cartledge.From the rate constants of the acetolysis reactions with I (X=Cl, acetoxy or siloxy) we could then obtain for the first time Es values for Cl, acetoxy and a series of siloxy groups at silicon.
- Scheim, U.,Grosse-Ruyken, H.,Ruehlmann, K.,Porzel, A.
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