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硅烯是有机硅化学中一类基本的反应活性中间体.在研究硅烯与烯烃加成反应的立体化学过程中,我们曾研究了二苯基硅烯、苯基环丙基硅烯与烯加成反应的立体化学.近年来,Gaspar和Boudjouk分别报道了含大体积取代基的硅烯,如二金刚烷基硅烯、二叔丁基硅烯与烯烃的加成反应.我们从取代基的电子效应考虑曾研究了2-苯基-2-(a-噻吩基)六甲基三硅烷的光解,发现反应是自由基机理.氧和硫同属第Ⅵ主族,与噻吩相对应的含呋喃环三硅烷的光解又如何呢?因此,我们又设计并合成了二(α-呋喃基)硅烯的前体,2,2-二(α-呋喃基)六甲基三硅烷(1),并研究了这种硅烯与烯烃加成的立体化学.当1在光照下与trans-2-丁烯或cis-2-丁烯反应,所得硅杂环丙烷衍生物用甲醇开环时,得到了相同的2-丁基-二(α-呋喃基)甲氧基硅烷(3).
Silicone is a kind of basic reactive intermediate in organosilicon chemistry.In the study of the stereochemistry of the addition reaction between silylene and olefin, we have studied the synthesis of diphenylsilyl, phenylcyclopropylsilylene and alkene In recent years, Gaspar and Boudjouk reported the addition reaction of silylens containing bulky substituents, such as diadamantylsiloxane, di-tert-butylsilylene and alkene respectively, The photolysis of 2-phenyl-2- (a-thienyl) hexamethyltrisilane has been studied considering the electron effect. The reaction was found to be a radical mechanism. Oxygen and sulfur belong to the main group VI, corresponding to thiophene What about the photodegradation of furancyclotrisilane? Therefore, we have designed and synthesized the precursor of bis (α-furyl) silylene, 2,2-bis (α-furyl) hexamethyltrisilane 1) and studied the stereochemistry of this addition of silylenes to olefins.When 1 is reacted with trans-2-butene or cis-2-butene in the presence of light, the resulting silacyclopropene derivative is ring opened with methanol , The same 2-butyl-di (α-furyl) methoxysilane (3) was obtained.