Oxidation of phenylhydrazine with polyhalomethanes
Oxidation of phenylhydrazine with polyhalomethanes
复制标题
DOI：
10.1021/jo01274a045
复制
发表时间：
1968-10
影响因子：
3.6
通讯作者：
E. S. Huyser;Richard H. S. Wang
中科院分区：
文献类型：
--
作者：
E. S. Huyser;Richard H. S. Wang
溴三氯甲烷和四氯化碳与苯肼反应生成氮、氯仿、苯、卤代苯和卤化氢。虽然这些反应在黑暗中是自发的，但它们会被光和过氧化物加速。这些反应的机理包括在自由基链反应中形成作为中间体的苯二酰亚胺，然后苯二酰亚胺反应生成苯和卤代苯。动力学研究支持一种假定的反应物的双分子反应，导致自由基的形成，从而在暗反应中引发链序列。据报道苯肼被氧化成苯和氮，反应可能涉及形成苯二酰亚胺，在碱性溶液中，被Fehling溶液氧化，3被氧化汞氧化，4被氧气、金属氧化物、高锰酸盐和铬酸盐氧化，5的铁氰化物6和硫酸铜的乙酸溶液。[7]苯肼的其他氧化反应生成氮和苯酚，这些反应可能涉及苯重氮阳离子作为中间氧化产物，已经在酸性介质中用金属氧化物、高锰酸盐和铬酸盐完成，也可以在酸性溶液中用碘和碘酸钾完成。[8] Hardie和Thomson研究了苯二酰亚胺的化学，他们在芳香族溶剂中用苯肼和金属氧化物生成了这种物质。联苯和其它混合二芳基化合物的形成表明在苯二酰亚胺的反应中有自由苯基自由基的中间作用。Cohen和Nicholson提出，N-苯基-N ′-苯甲酰基二酰亚胺（C_8H_8CON = NC_6H_8）与酸、碱或铁离子反应生成的苯二酰亚胺，在均相介质中可直接分解为苯和硝基。
Bromotrichloromethane and carbon tetrachloride undergo reaction with phenylhydrazine yielding nitrogen, chloroform, benzene, a halobenzene, and a hydrogen halide. Although these reactions are spontaneous in the dark, they are accelerated both by light and by peroxides. Evidencefor a mechanism of these reactions involv-ing formation of phenyldiimide as an intermediate produced in a free-radical chain reaction followed by reactions of phenyldiimide yielding benzene and a halobenzene is presented. Kinetic studies support a postulated bimolecular reaction of the reactants resulting in formation of free radicals to initiate the chain sequence in the dark reaction.Phenylhydrazine has been reported to be oxidized to benzene and nitrogen, reactions presumably involving formation of phenyldiimide, by Fehling’s solution, 3 by mercuric oxide, 4 by oxygen, metallic oxides, and permanganates and chromates in alkaline solution, 5 by ferricyanide6 and by copper sulfate in acetic acid. 7 Other oxidations of phenylhydrazine yielding nitrogen and phenol, reactions presumably involving theben-zene diazonium cation as an intermediate oxidation product, havebeen accomplished usingmetallic oxides, permanganate, and chromate in acidic media5 and also by iodine and by potassium iodate in acidic solutions. 8 The chemistry of phenyldiimide was investigated by Hardie and Thomson who generated this species from phenylhydrazine with metallic oxides in aromatic solvents. 9 The formation of biphenyl as well as other mixed diaryls suggested the'intermediacy of free phenyl radicals in the reactions of phenyldiimide. Cohen and Nicholson suggested that phenyldiimide, formed by reaction of N-phenyl-N'-benzoyldiimide (C8H8CON= NC6H8) with acid, base, or ferric ion, could decompose in homogeneous medium directly to benzene and nitro-