AMINE AUTOXIDATION IN AQUEOUS-SOLUTION
AMINE AUTOXIDATION IN AQUEOUS-SOLUTION
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DOI：
10.1071/ch9830719
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发表时间：
1983-01-01
影响因子：
1.1
通讯作者：
PRAGER, RH
中科院分区：
文献类型：
--
作者：
BECKWITH, ALJ;EICHINGER, PH;PRAGER, RH
本文研究了叔脂肪胺水溶液的非催化自氧化反应，以获得Sirotherm树脂氧化机理的相关信息。氧化在游离碱中发生得最快，速率与pK或电离电位的一般相关性表明，形成氨基阳离子的电子转移是速率决定的。该反应不是由自由基引发的，也不是由自由基陷阱抑制的。它被强电子受体和光显著催化，被电子供体n -苯基氨基苯甲酸适度抑制。吡咯烷类和六氢氮卓类化合物的氧化速度比哌啶类化合物快，β-碳上的羟基加快了氧化速度，而γ-碳上的羟基减慢了氧化速度。烷基吡咯烷在水中自氧化的主要产物是n -氧化物。以较小的收率分离出多种吡咯烷酮。
The uncatalysed autoxidation of aqueous solutions of tertiary aliphatic amines has been studied in order to obtain information concerning the mechanism of oxidation of Sirotherm resins. Oxidation occurs most rapidly in the free base, and the general correlation of rate with pK, or ionization potential suggests that electron transfer to form an aminium radical cation is rate-determining. The reaction is not initiated by free radical initiators, nor inhibited by radical traps. It is significantly catalysed by strong electron acceptors and by light and is moderately inhibited by the electron donor N-phenylanthranilic acid. Pyrrolidines and hexahydroazepines are oxidized faster than piperidines, and hydroxyl groups on β-carbons increase the rate of oxidation, while those on γ-carbons decrease it. The major products of autoxidation of alkyl pyrrolidines in water were found to be N-oxides. Various pyrrolidinones were isolated in smaller yield.