K. Andrianov, V. I. Sidorov, L. Khananashvili
Nov 1, 1965
Citations
0
Influential Citations
0
Citations
Journal
Journal of Organometallic Chemistry
Abstract
Abstract The reactions of organosiloxanes containing the vinyl group in the α- and β-positions, with diazomethane and phenyl azide have been studied. It is concluded that siloxanes containing the vinyl group in the α-position react with diazomethane and phenyl azide but not siloxanes with the vinyl group in the β-position. The 1-pyrazolin-3-yl derivatives of organosiloxanes formed decompose when heated yielding the corresponding allyl derivatives. The diene synthesis reaction of 3-vinylheptamethyltrisiloxane with 1,3-butadiene leads to the formation of the corresponding cyclohexenyl derivative. The co-hydrolysis reaction of methylallyldichlorosilane with dimethyldichlorosilane (molar ratio, 1:1) gives allylheptamethylcyclotetrasiloxane and 1,5-diallylhexamethylcyclotetrasiloxane; the co-hydrolysis reaction of methylvinyldichlorosilane with dimethylchlorosilane produces 1,1,3,5,5-pentamethyl-3-vinyltrisiloxane; the co-hydrolysis reaction of methylallyldichlorosilane with dimethylchlorosilane gives 1,1,3,5,5-pentamethyl-3-allyltrisiloxane. The addition reactions of acrylonitrile, dicyanoethylene, styrene, indene, 1-heptyne, 2,5-dimethyl-3-hexyne-2,5-diol, 2-vinyl-pyridine, cyclopentadiene; 1,4-dichloro-2-butyne and methylvinyldichlorosilane with pentamethyldisiloxane and 3- H -heptamethyltrisiloxane have been studied. It is concluded that the addition reactions of the above-mentioned compounds give satisfactory yields with the exception of acrylonitrile and dicyanoethylene which do not enter into the addition reaction.