METHYLENE DERIVATIVES AS INTERMEDIATES IN POLAR REACTIONS .17. THE MECHANISM OF THE REIMER-TIEMANN REACTION
METHYLENE DERIVATIVES AS INTERMEDIATES IN POLAR REACTIONS .17. THE MECHANISM OF THE REIMER-TIEMANN REACTION
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DOI：
10.1021/ja01533a028
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发表时间：
1959-01-01
影响因子：
15
通讯作者：
VANDERVEEN, JM
中科院分区：
文献类型：
--
作者：
HINE, J;VANDERVEEN, JM
氯仿在35℃时与苯氧化钠水溶液反应很慢，但在氢氧化钠的存在下，它迅速反应生成o-羟基苯甲醛和£-羟基苯甲醛（Reimer-Tiemanu反应）。这一观察结果表明，Reimer-Tiemann反应不是由苯氧离子对氯仿的亲核攻击引起的。相反，这个反应似乎是氯仿与氢氧化物离子反应生成二氯甲烷，二氯甲烷再与苯氧离子反应。从苯氧化钠浓度对醛的产率的影响，可以计算出二氯乙烯与氧原子以及苯氧化离子的o和^-碳原子化合的相对速率常数（相对于与水化合的速率常数）。
Chloroform reacts with aqueous sodium phenoxide only very slowly at 35, but in the presence of sodium hydroxide it reacts rapidly to give o-and£-hydroxybenzaldehydes (the Reimer-Tiemanu reaction). This observation shows thatthe Reimer-Tiemann reaction is not initiated by the nucleophilic attack of phenoxide ion on chloroform. The reaction instead appears to involve the reaction of chloroform with hydroxide ion to give dichloromethylene which then reacts with phenoxide ion. From the effect of sodium phenoxide concentration on the yields of aldehydes, the relative rate constant for the com-bination of dichloromethylene with theoxygen atom as well as the o-and^-carbon atoms of the phenoxide ion may be calculated (relative to the rate constant for combination with water).