PLATINUM-CATALYZED REACTIONS OF 3,4-BENZO-1,1,2,2-TETRAETHYL-1,2-DISILACYCLOBUT-3-ENE

PLATINUM-CATALYZED REACTIONS OF 3,4-BENZO-1,1,2,2-TETRAETHYL-1,2-DISILACYCLOBUT-3-ENE
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DOI:
10.1021/om00036a044
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发表时间:
1993-12-01
期刊:
影响因子:
2.8
通讯作者:
OHSHITA, J
OHSHITA, J
中科院分区:
化学2区
文献类型:
--
作者:
ISHIKAWA, M;NAKA, A;OHSHITA, J

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3,4-苯并-1,1,2,2-四乙基-1,2-二硅杂环丁烯(1)与催化量的(η ~ 2-亚乙基)双(三苯基膦)铂(0)在乙苯中反应,得到1-(二乙基苯基硅基)-2-(二乙基硅基)苯(2)和顺式-4,5-苯并-1,1,3-三乙基-2-甲基-1,3-二硅杂环丁烯-4-烯(3),产率分别为10%和67%。化合物1在铂催化下与乙烯反应生成5,6-苯并-1,1,4,4-四乙基-1,4-二硅杂环己-5-烯,与苯乙烯和1-己烯反应生成4,5-苯并-1,3-二硅杂环己-4-烯衍生物。1与α-甲基苯乙烯的类似反应产生由3氢化硅烷化成α-甲基苯乙烯产生的加合物。1与苯乙炔、二苯基乙炔、苯基(三甲基硅基)乙炔和3-己炔在铂催化剂存在下反应,得到相应的5,6-苯并-1,4-。二硅杂环己-2,5-二烯。1与苯甲醛反应得到5,6-苯并-2-氧杂-1,4-二硅杂环己-5-烯衍生物。
Treatment of 3,4-benzo-1,1,2,2-tetraethyl-1,2-disilacyclobutene (1) with a catalytic amount of (eta2-ethylene)bis(triphenylphosphine)platinum(0) in refluxing benzene gave 1-(diethylphe-nylsilyl)-2-(diethylsilyl)benzene (2) and cis-4,5-benzo-1,1,3-triethyl-2-methyl-1,3-disilacyclopent-4-ene (3) in 10 % and 67 % yields. The platinum-catalyzed reaction of 1 with ethylene produced 5,6-benzo-1,1,4,4-tetraethyl-1,4-disilacyclohex-5-ene, while with styrene and 1-hexene, compound 1 afforded 4,5-benzo-1,3-disilacyclopent-4-ene derivatives. A similar reaction of 1 with a-methylstyrene produced an adduct arising from hydrosilylation of 3 to alpha-methylstyrene. The reaction of 1 with phenylacetylene, diphenylacetylene, phenyl(trimethylsilyl)acetylene, and 3-hexyne in the presence of a platinum catalyst yielded the respective 5,6-benzo-1,4-. disilacyclohexa-2,5-dienes. With benzaldehyde, 1 gave a 5,6-benzo-2-oxa-1,4-disilacyclohex-5-ene derivative.