CHLORINATION OF AROMATIC COMPOUNDS WITH METAL CHLORIDES
CHLORINATION OF AROMATIC COMPOUNDS WITH METAL CHLORIDES
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DOI：
10.1021/ja01650a069
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发表时间：
1954-01-01
影响因子：
15
通讯作者：
BRACE, NO
中科院分区：
文献类型：
--
作者：
KOVACIC, P;BRACE, NO
研究了无水氯化铁与简单芳香族化合物的反应。以氯苯为催化剂，生成二氯苯（p/o= 88/11）、氯化氢和氯化亚铁。芳香族化合物的反应性，取向，溶剂和催化效应的顺序是一致的极性机制，至少在速率决定步骤。低的Meta取代是由氯化铁的弱”活性”来解释的，而与通常的氯化方法相比，高的对位-邻位比可以在空间基础上合理化。某些其他金属卤化物，如五氧化二锑，也可用作芳香族化合物的卤化剂。金属卤化物的卤化能力被解释为其Friedel-Crafts催化活性和其氧化还原电位的组合。芳香族化合物与氯化铁反应产生自偶联、重排或焦油的例子。
A study has been made of the reaction of anhydrous ferric chloride with simple aromatic compounds. With chloroben-zene, the products were dichlorobenzene (p/o= 88/11), hydrogen chloride and ferrous chloride. The order of reactivity of aromatic compounds, orientation, and solvent and catalytic effects are consistent with a polar mechanism, at leastin the rate-determining step. Low meta substitution is explained by the weak" activity” of ferric chloride, while the high para-ortho ratio, in comparison with the usual method of chlorination, can be rationalized on a steric basis. Certain other metal halides, eg, antimony pentachloride, also function as halogenating agents for aromatic compounds. The halogenating ability of a metal halide is interpreted as a combination of its Friedel-Crafts catalytic activity and its oxidation-reduction potential. Examples are given of aromatic compounds which react with ferric chloride to produce self-coupling, rearrangement or tars.