CYCLO-HYDROSILYLATION - NOVEL ROUTE TO SILOXETANES AND SILANONES

被引:22
作者
LANE, TH [1 ]
FRYE, CL [1 ]
机构
[1] DOW CORNING CORP,CORP RES LAB,MIDLAND,MI 48640
关键词
D O I
10.1016/S0022-328X(00)81049-9
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
A novel and convenient method for the apparent liquid phase generation of dimethylsilanone, Me2SiO (D1), based on readily obtainable reactants and employing conventional temperatures (50-150°) is reported herein. Platinum catalyzed hydrosilylation of vinyldimethylcaarbinoxydimethylsilane (I) appears to proceed by an exclusively intramolecular path to produce not only the expected 5-membered heterocyclic, 1,1,3,3-tetramethyl-2-oxa-1 silacyclopentane (V), but also the isomeric and highly unstable 4-membered siloxetane, 1,1,3,3,4-pentamethyl-2-oxa-1-silacyclobutane (IV). The intermediacy of IV is suggested by the products: i.e., 2-methyl-2-butene which is believed to arise along with Me2SiO from fragmentation of IV; D3 and D4 from D1 self-coupling; a 6-membered cyclic derived from insertion of D1 into the Si-O bond of IV, i.e., 1,1,3,3,5,5,6-heptamethyl-2,4-dioxa-1,3-disilacyclohexane (VI); a polymer which upon alkaline cracking produces more 6-ring (VI) but little or no 5-ring (V) suggesting that the polymer arose from copolymerization of D1, D2, and siloxetane (IV). Compound I is also an excellent thermolytic source of D1 as evidenced by the formation of the expected derivatives upon heating in the presence of known silanone traps. © 1979.
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页码:213 / 221
页数:9
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