ELECTROPHILIC DISPLACEMENT REACTIONS .16. METAL ION CATALYSIS IN PROTODEBORONATION OF ARENEBORONIC ACIDS
ELECTROPHILIC DISPLACEMENT REACTIONS .16. METAL ION CATALYSIS IN PROTODEBORONATION OF ARENEBORONIC ACIDS
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DOI：
10.1021/ja01067a031
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发表时间：
1964-01-01
影响因子：
15
通讯作者：
REUWER, JF
中科院分区：
文献类型：
--
作者：
KUIVILA, HG;MANGRAVI.JA;REUWER, JF
本文研究了苯硼酸的脱硼反应动力学，以及pH值和邻、间、对位取代基对脱硼反应速率的影响。pH-速率曲线显示了一个碱催化反应和一个”非催化”反应，这两个反应依次被镉离子催化。邻-对位比一般平行的情况下，镉离子的反应中观察到的，但间和对位取代的酸显示出不同的线性自由能关系的两种反应。镁、锌、铜（II）、铅（II）、镍（II）、钴（II）和银的盐也催化脱硼反应。根据实验结果讨论了金属离子催化脱硼的机理。
A kinetic investigation has been made of the protodeboronation of benzeneboronic acids, and the effects of pH andof substituents in the o-, m-, and^-positions on rate. The pH-rate profile shows a base-catalyzed and an" uncatalyzed" reaction, each of which is catalyzed by cadmium ion in turn. The ortho-para ratios generally parallel those observed earlier for the reaction in the absence of cadmium ion, but the meta-and para-sub-stituted acids show different linear free energy relationships for the two kinds of reaction. Salts of magnesium, zinc, copper (II), lead (II), nickel (II), cobalt (II), and silver also catalyze the protodeboronation. The mechanism of the metal ion catalyzed protodeboronation is discussed in the light of the experimental results.