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近年来,有机硅化合物在有机合成中的应用日趋广泛,开发了许多颇有意义的有机硅试剂。其中,三甲基碘硅烷是极为有效的试剂。硅-氧键的键能很高(90～110千卡/克分子),从热力学方面考虑,具有弱键能(Si—X)的有机硅试剂与含氧化合物反应,易生成Si—O键的中间体,然后被转化成各种产物。利用有机硅试剂进行反应,往往能在极温和的条件下发生C—O键的断裂、还原脱氧、去卤化及卤化等反应。三甲基碘硅烷的反应性强,极不稳定,遇光、湿气易分解,必须在无水的条件下操作,十分麻烦,而且价格昂贵,目前国内尚未有商品供应。 Olah等发现,用三甲基碘硅烷(Me_3SiI)所进行的反应,几乎都可由廉价的三甲基氯硅烷(Me_3SiCl)和碘化钠(NaI)组成的混合试剂代替,而且某些反应的收率还有所提高。下面简单作一介绍。
In recent years, organic silicon compounds in the increasingly widespread use of organic synthesis, the development of many meaningful silicone reagents. Among them, trimethylsilyl iodide is a very effective reagent. Silicon-oxygen bond can be very high (90 ~ 110 kcal / mole), from a thermodynamic point of view, with a weak bond energy (Si-X) of the organic silicon reagent and oxygen compounds, easy to generate Si-O bond The intermediates are then converted into various products. Reactions with organosilicon reagents often lead to the cleavage of C-O bonds, reductive deoxygenation, dehalogenation and halogenation under very mild conditions. Methyl iodosilane reactivity is very strong, very unstable, the case of light, moisture easily decomposed, must be operated under anhydrous conditions, very troublesome, but also expensive, there is no domestic supply of goods. Olah et al. Found that the reaction with trimethylsilyl iodide (Me_3SiI) can be almost always replaced by a mixture of cheap trimethylchlorosilane (Me_3SiCl) and sodium iodide (NaI), and the reaction of some reactions Rate has improved. Here’s a brief introduction.