THE ORTHO-PARA RATIO AND THE INTERMEDIATE IN THE PERSULFATE OXIDATION OF AROMATIC-AMINES (THE BOYLAND-SIMS OXIDATION)
THE ORTHO-PARA RATIO AND THE INTERMEDIATE IN THE PERSULFATE OXIDATION OF AROMATIC-AMINES (THE BOYLAND-SIMS OXIDATION)
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DOI：
10.1021/jo00034a016
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发表时间：
1992-04-10
影响因子：
3.6
通讯作者：
BEHRMAN, EJ
中科院分区：
文献类型：
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作者：
BEHRMAN, EJ
以前认为芳香胺的过硫酸盐氧化只产生邻硫酸盐是不正确的;产生了大量的帕拉异构体。 对2，4-和2，6-二取代芳胺的动力学研究表明，两种异构体与过硫酸盐的反应速率几乎相同。 该反应中可能的中间体是芳基羟胺-O-磺酸盐。 这通过显示N，N-二甲基苯胺N-氧化物与三氧化硫-吡啶络合物之间的反应得到重排为N，N-二甲基苯胺邻硫酸盐和对硫酸盐的混合物的材料来证明，所述混合物的比例与N，N-二甲基苯胺的过硫酸盐氧化所得到的比例相同。 邻位-对位比不受稀释影响。 这导致的结论，重排的分子内的程度是相同的邻位和帕拉异构体的形成。
The previous belief that the persulfate oxidation of aromatic amines gives the o-sulfate exclusively is untrue; substantial quantities of the para isomer are produced. Kinetic studies on 2,4- and 2,6-disubstituted aromatic amines show that the rate of reaction with persulfate is nearly the same for both isomers. The probable intermediate in this reaction is the arylhydroxylamine-O-sulfonate. This was demonstrated by showing that the reaction between N,N-dimethylaniline N-oxide and the sulfur trioxide-pyridine complex gives material which rearranges to a mixture of N,N-dimethylaniline o- and p-sulfates in the same ratio as is given by the persulfate oxidation of N,N-dimethylaniline. The ortho-para ratio is unaffected by dilution. This leads to the conclusion that the degree of intramolecularity of the rearrangement is the same for the formation of both the ortho and para isomers.