金属离子配合物与碳氢化合物的反应。第三部分。醋酸溶液中环己烯、环己-1,3-二烯和环己-1,4-二烯氧化和自氧化反应中的醋酸钯

R. G. Brown, J. M. Davidson
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引用次数: 16

摘要

环己烯、环己-1,3-二烯和环己-1,4-二烯在乙酸溶液中与醋酸钯快速反应生成苯。该反应具有非均相催化步骤,因为它依赖于系统中形成的钯金属。金属微氢化,是一种非常有效的歧化催化剂。HClO4和NaOAc都以歧化为代价促进氧化。环己酮或羟基环己烯类似的氧化反应生成苯酚,而乙酰氧基环己烯则生成乙酸苯和苯的混合物。在0.5 m - hclo4中,环己烯发生竞争性的快速氧化反应,生成环己酮、乙酸环己烯-1-烯-1-酯和乙酸环己烯-3-烯-1-酯。在氧的存在下,环己烯经历缓慢的醋酸钯催化均相氧化生成环己烯-2-烯-1-乙酸酯。同时自由基反应生成环己烯-2-烯-1-醇和环己烯-2-烯-1- 1。环己-1,3-二烯在Pd(OAc)2的存在下被氧迅速氧化,生成复杂的混合物,主要产物是环己-2-烯-1,4-二醇二乙酸酯。在相似的均相条件下,环己-1,4-二烯生成苯、环己-4-烯-1,3-二醇二乙酸酯和副产物Pd2(C6H8)(OAc)2。用苯醌催化醋酸钯氧化环己烯、环己-1,3-二烯和环己-1,4-二烯,分别得到环己-2-烯-1-乙酸酯、环己-2-烯-1,4-二醇二乙酸酯和环己-4-烯-1,3-二醇二乙酸酯。讨论了氧化加合物和π-环己烯钯配合物在这些反应中的作用。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Reaction of metal-ion complexes with hydrocarbons. Part III. Palladium acetate in the oxidation and autoxidation reactions of cyclohexene, cyclohexa-1,3-diene, and cyclohexa-1,4-diene in acetic acid solution
Cyclohexene, cyclohexa-1,3-diene, and cyclohexa-1,4-diene react rapidly with palladium acetate in acetic acid solution to yield benzene. The reaction has a heterogeneous catalytic step since it depends on palladium metal formed in the system. The metal is slightly hydrided and is a very efficient disproportionation catalyst. Both HClO4 and NaOAc promote oxidation at the expense of disproportionation. Similar oxidations of cyclohexanone or hydroxy-cyclohexenes give phenol while acetoxy-cyclohexenes yield mixtures of phenyl acetate and benzene. In 0·5M-HClO4 there is a competing very fast oxidation that yields cyclohexanone, cyclohex-1-en-1-yl acetate, and cyclohex-3-en-1-yl acetate from cyclohexene. In the presence of oxygen, cyclohexene undergoes a slow palladdium acetate-catalysed homogeneous oxidation to yield cyclohex-2-en-1-yl acetate. A concurrent free-radical process yields cyclohex-2-en-1-ol and cyclohex-2-en-1-one. Cyclohexa-1,3-diene is oxidised rapidly by oxygen in the presence of Pd(OAc)2 giving a complex mixture of products, the main one being cyclohex-2-ene-1,4-diol diacetate. Under similar homogeneous conditions, cyclohexa-1,4-diene gives benzene, cyclohex-4-ene-1,3-diol diacetate, and Pd2(C6H8)(OAc)2 as a by-product. The palladium acetate-catalysed oxidation of cyclohexene, cyclohexa-1,3-diene, and cyclohexa-1,4-diene by benzoquinone yields cyclohex-2-en-1-yl acetate, cyclohex-2-ene-1,4-diol diacetate, and cyclohex-4-ene-1,3-diol diacetate respectively with benzene, also, from cyclohexa-1,4-diene. The roles of oxypalladation adducts and π-cyclohexenylpalladium complexes in these reactions are discussed.
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