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Degradation of 2-deoxyaldoses by alkaline hydrogen peroxide
Carbohydrate Research Pub Date : 1981-03-01 , DOI: 10.1016/s0008-6215(00)85617-7
Horace S. Isbell , Harriet L. Frush , Renee Naves , Preeda Soontracharoen

Abstract Reaction of 2-deoxy- D - arabino -hexose, 2-deoxy- D - lyxo -hexose, and 2-deoxy- D - erythro -pentose with alkaline hydrogen peroxide in the presence of magnesium hydroxide afforded the corresponding 2-deoxyaldonic acid, the 1,4-lactone, and the 1- O -formyl derivative of the next lower alditol. The 2-deoxyaldonic acids were separated in 60–80% yields, as new, crystalline lithium salts. The 1,4-lactones were obtained under conditions that precluded intermidiate formation of the free acids: presumably, the reaction proceeded by way of an intermediate, furanosyl hydroperoxide, which was converted into the lactone by elimination of water. With an excess of alkaline hydrogen peroxide, in the absence of magnesium hydroxide, the substrates were degraded to formic acid, with concurrent decomposition of hydrogen peroxide. It is shown that decomposition of hydrogen peroxide is catalyzed by hydroperoxide anion, and that it takes place by both a chain, and a non-chain, process. The decomposition reactions afford an abundant source of hydroxyl radical capable of oxidizing a wide variety of compounds.

中文翻译:

碱性过氧化氢降解2-脱氧醛糖

摘要在氢氧化镁的存在下,将2-脱氧-D-阿拉伯糖己糖,2-脱氧-D-lyxo-己糖和2-脱氧-D-赤藓糖与碱性过氧化氢反应,得到相应的2-脱氧醛糖酸,下一个低级糖醇的1,4-内酯和1-O-甲酰基衍生物。作为新的结晶锂盐,2-脱氧醛糖酸的分离产率为60-80%。1,4-内酯是在无法中等程度地形成游离酸的条件下获得的:推测,反应是通过中间体呋喃糖基氢过氧化物进行的,通过消除水将其转化为内酯。在氢氧化镁不存在的情况下,使用过量的碱性过氧化氢,将底物降解为甲酸,同时过氧化氢分解。结果表明,过氧化氢的分解是由氢过氧化物阴离子催化的,并且它是通过链状和非链状的过程发生的。分解反应提供了丰富的羟基自由基来源,能够氧化多种化合物。
更新日期:1981-03-01
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