92992-67-1Relevant articles and documents
Method of manufacturing Organoxysilane compd.
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Paragraph 0042; 0043, (2017/01/05)
PROBLEM TO BE SOLVED: To provide a method for producing an organoxysilane compound efficiently by improving catalyst activity and regioselectivity, when an addition reaction is generated between an unsaturated bond-containing compound and a hydrogen organoxysilane compound by using a platinum compound-containing catalyst. SOLUTION: In this method for producing an organoxysilane compound, an unsaturated bond-containing compound represented by general formula (1): CH2=CH-R1(1) (In the formula, R1is a 1-18C unsubstituted or substituted monovalent hydrocarbon group excluding a norbornenyl group, a monovalent heterocyclic ring-containing group, an organoxysilyl group or an organosiloxanyl group.) and a hydrogen organoxysilane compound represented by general formula (2): HSiR2n(OR3)3-n(2) (In the formula, R2is a 1-10C unsubstituted or substituted monovalent hydrocarbon group. R3is a 1-10C unsubstituted or substituted monovalent hydrocarbon group, and n is an integer of 0-2.) are hydrosilylated by using a platinum compound-containing catalyst in the presence of an ammonium salt of an inorganic acid. The objective organoxysilane compound can be produced efficiently at high reactivity and regioselectivity by this production method. COPYRIGHT: (C)2013,JPOandINPIT
HOMOGENEOUS CATALYSIS. IX. HYDROSILYLATION USING TRIS(PENTANEDIONATO)RHODIUM(III)-TRIALKYLALUMINIUM AS CATALYST
Cornish, Andrew J.,Lappert, Michael F.
, p. 153 - 168 (2007/10/02)
The two component (Ziegler) catalyst -AlEt3 (or an analogue with an alternative cocatalyst) has been investigated for the hydrosilylation by SiHX3 of alkynes, dienes, alkenes, styrene, or allylbenzene at 60 deg C.Terminal alkynes did not yield adducts, but internal alkynes RCCR' gave products of cis-addition with SiHEt3 or SiHEt2Me (but not SiH(OEt)3), without regiospecificity for the case of R R'.Acyclic dienes gave 1/1 adducts with SiHX3 (X = Me, Et, OEt or OSiMe3; but not X = Ph), predominantly (or, for penta-1,3-diene, exclusively) the products of 1,4-addition.Among cyclic dienes, only cyclohexa-1,3- (or -1,4)-diene was hydrosilylated with SiHEt3 to yield cyclohex-2-enyltriethylsilane; cycloocta-1,3-diene was merely rearranged to the 1,5-isomer, norbornadiene was polymerised, and no reaction was observed with 2,5-dimethylhexa-2,4-diene.Internal straight-chain alkenes RR'C=CHR'', RR'C=CR''R''', or cyclohexene proved unreactive; however disubstituted olefins RCH=CHR' gave the terminal (isomerised) 1/1-adducts, e.g., n-C5H11SiEt3 from MeCH=CHEt and SiHEt3.Likewise terminal alkenes RCH=CH2 gave RCH2CH2SiX3 (X = Ph or OEt) or (X = Et) a mixture of isomeric 1/1 adducts.With styrene and SiHEt3, or to a lesser extent SiH(OR)3 (R = Me or Et), the dehydrogenative hydrosilylated material, the vinylsilane PhCH=CHSiX3, was the principial product with isomeric 1/1 adduct byproducts; with allylbenzene, likewise, PhCH2CH=CHSiX3 was a significant, but less important, component of the reaction mixture.Mechanistic pathways are proposed; for the dehydrogenative hydrosilylation of styrene, crucial steps are styrene insertion into a RhIII-SiX3 bond and a subsequent intramolecular hydrogen transfer, which are consistent with both a labelling experiment using SiDEt3 and the lack of dehydrogenation (under the reaction conditions) of PhCH2CH2SiEt3.
