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化学学报
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化学学报 ›› 1957, Vol. 23 ›› Issue (2): 124-129. 上一篇    下一篇

论文

甲基矽烷的氣相氯化

陳耀祖1, 陳珊妹1, 王葆仁2   

  1. 1. 复旦大学化学系;
    2. 中国科学院化学研究所
  • 投稿日期:1956-11-30 发布日期:2013-06-03

THE VAPOR PHASE CHLORINATION OF METHYL SILANES

CHEN YAO-TSO1, CHEN SAN-MEI1, WANG PAO-JEN 2   

  1. 1. Institute of Chemistry, Academia Sinica;
    2. Chemistry Department, Futan University
  • Received:1956-11-30 Published:2013-06-03

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839

被引次数

5

作者将下列两类矽烷以及两种氯代异丁烷进行气相(光照)氯化,找出二氯取代的产物,其两个氯原子的相互位置和原来矽烷裹有无矽氯键有很大关系。
(CH3)nSiCl4-n (CH3)mSi(CH2Cl)Cl3-m
n=2,3,4 m=1,2,3
在没有矽氯键的矽烷,两个氯原子取代在不同甲基上的产物比较取代在同一甲基上的为多,这和碳化氢的取代相同。在具有矽氯键的矽烷,二个氯原子取代在同一甲基上的产物比较取代在不同甲基上的为多,这和碳化氢的取代不同。作者认为矽氯键之所以有这种影响是因为它一方面阻尼α-位甲基氯化,另一方面还促进α-位氯甲基的继续氯化。

Methyl silanes of the types (CH3)nSiCl4-n and (CH3)mSi(CH2Cl)Cl3-m have been photochemically chlorinated in the vapor phase.It was found that the structure of the dichlorinated silanes formed was greatly influenced by the presence of Si}CI bond.Silanes with no Si-Cl bond behaved similarly as the hydrocarbons,i.e., the substitution of two Cl-atoms for hydrogen occurred on different C-atoms in preference to the same C-atom, while the presence of the SiCl bond made the reverse to.be true, the gem-dichloro-compound predominated.According to the authors' opinion, this discrepency is due to the fact that the Si-Cl bond exerts an inhibitive effect on the a-methyl group in the event of chlorination, and, at the same time, a promotive effect on the a-chloromethyl group so as to make it easier to be further chlorinated.