THE OXIDATION OF ARYLMAGNESIUM HALIDES
THE OXIDATION OF ARYLMAGNESIUM HALIDES
复制标题
芳基卤化镁的氧化
DOI：
10.1021/ja01414a047
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发表时间：
1926
影响因子：
15
通讯作者：
Agnes Wood
中科院分区：
文献类型：
--
作者：
H. Gilman;Agnes Wood
为了研究防腐作用与化学结构之间的关系，有必要制备一些新的酚类化合物。芳基卤化镁的氧化作为几种可能的方法之一进行了尝试。人们早就知道，当格氏试剂用空气或氧气处理时，会发生以下一般反应：RMgX+（O）-> ROMgX。在水解时，ROMgX化合物得到相应的羟基化合物。该反应具有广泛的应用前景。特别地，通过烷基卤化镁的氧化可获得优异的醇产率。[2]用硫、硒和碲处理烷基卤化镁和芳基卤化镁时，类似化合物的产率同样很高。3然而，Bodroux 4在氧化芳基卤化镁时得到的苯酚产率很低。即使尝试了各种条件，他也不能使苯酚5的产率超过18%。对8种芳基卤化镁进行了氧化，以1，4-二溴萘单镁衍生物为原料，酚类化合物的产率最高，为22%。Wuyts在一项仔细的研究中发现，过氧化物很可能是作为中间化合物形成的。除了苯酚之外，他还从苯基溴化镁的氧化中得到苯、二苯基、^-二苯基苯、C6 H5 OH以外的苯酚、苯甲基甲醇和乙醇。Porter和Steele在研究反应机理时，确定了温度对苯酚和主要副产物产率的影响。
In connection with studies involving some relationships between anti-septic action and chemical constitution, it was necessary to prepare a number of new phenols. The oxidation of arylmagnesium halides was tried as one of several possible methods. It has long been known that the following general reaction occurs when Grignard reagents are treated with air or oxygen: RMgX+(O)—> ROMgX. On hydrolysis, the ROMgX compound gives the corresponding hydroxyl compound. The reaction is capable of wide application. In particular, excellent yields of alcohols are obtainable by the oxidation of alkylmagnesium halides. 2 Equally good yields of the analogous com-pounds are obtained when both alkyl-and arylmagnesium halides are treated with sulfur, selenium and tellurium. 3 However, Bodroux4 got very low yields of phenols when he oxidized arylmagnesium halides. Even after trying a variety of conditions he could not get the yield ofphenol5 to exceed 18%. Eight arylmagnesium halides were oxidized and the highest yield of phenolic compound, 22%, was obtained from the monomagnesium derivative of 1, 4-dibromonaph-thalene. Wuyts, 6 in a careful study, showed that peroxides were very probably formed as intermediate compounds. In addition to phenol, from the oxidation of phenylmagnesium bromide, he obtained benzene, diphenyl,^-diphenylbenzene, phenols other than C6H5OH, phenylmethyl carbinol and ethyl alcohol. Porter and Steele, 7 in a study of the mechan-ism of the reaction, determined the influence of temperature upon the yield of phenol and chief by-products.