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mnbbv123

金虫 (小有名气)

[求助] 求翻译下下面几段话

标题:Cobalt−Salen Complex-Catalyzed Oxidative Generation of Alkyl Radicals from Aldehydes for the Preparation of Hydroperoxides

摘要:ABSTRACT: Catalytic generation of alkyl radicals from aldehydes via oxidative deformylation was realized using a cobalt-salen complex with H2O2. The deformylation was thought to proceed through homolytic cleavage of peroxohemiacetal intermediates to provide even primary alkyl radicals under mild conditions. Variously substituted and functionalized hydroperoxides were obtained from corresponding aldehydes in good yield.


还有这段:The final stage of the reaction was examined by employing 18O2 to confirm the source of the O atoms in the hydroperoxide product (Scheme 8). When 1 was reacted with H216O2 under an 18O2 atmosphere with otherwise similar conditions, the product in which both of the peroxy O atoms were labeled with 18O was
obtained with about 70% 18O incorporation. This result strongly supports the proposal that O2 generated by the reaction of Co(III) with H2O2, or its cobalt complex Co(III)OO·, traps the alkyl radical generated from peroxohemiacetal intermediate 6.
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yanniige

新虫 (初入文坛)

【答案】应助回帖

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mnbbv123: 金币+5, 翻译EPI+1, ★★★★★最佳答案, 很好,谢谢!!! 2013-11-26 15:23:07
标题: 以钴配体复合物为催化剂催化氧化乙醛制备烷基自由基和氢过氧化物
摘要: 实现了以钴配体复合物为催化剂催化甲醛的氧化去甲酰化反应以制备烷基自由基和双氧水。去甲酰化过程被认为是过氧化半缩醛分子在温和的反应条件下发生均裂,生成两分子的烷基自由基。被不同取代基和官能团修饰的乙醛分子生成与其对应的的取代或官能化的氢过氧化物,产率很高。
同位素(氧18)标记的氧气被用来研究反应的最后一步,以确定氢过氧化物中氧原子的来源(图8)。当图8中标记为1的化合物在同位素氧18标记的氧气氛中与水(其中绝大多数O是同位素氧16)反应,保持其他条件不变,产物过氧化物中的两个氧原子都是氧18标记的占了70%。这一结果强烈证实了三价钴与双氧水反应生成的,或者过氧化三价钴释放出的氧气,捕获了由过氧化半缩醛(图中标记为6的物质)生成的烷基自由基。
2楼2013-11-26 11:54:47
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