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| 本帖產(chǎn)生 1 個 翻譯EPI ，點擊這里進行查看 | |||
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標題：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. 還有這段：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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【答案】應(yīng)助回帖
★ ★ ★ ★ ★
mnbbv123: 金幣+5, 翻譯EPI+1, ★★★★★最佳答案, 很好，謝謝�。。� 2013-11-26 15:23:07
mnbbv123: 金幣+5, 翻譯EPI+1, ★★★★★最佳答案, 很好，謝謝�。。� 2013-11-26 15:23:07
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標題: 以鈷配體復(fù)合物為催化劑催化氧化乙醛制備烷基自由基和氫過氧化物 摘要: 實現(xiàn)了以鈷配體復(fù)合物為催化劑催化甲醛的氧化去甲�；磻�(yīng)以制備烷基自由基和雙氧水。去甲�；^程被認為是過氧化半縮醛分子在溫和的反應(yīng)條件下發(fā)生均裂，生成兩分子的烷基自由基。被不同取代基和官能團修飾的乙醛分子生成與其對應(yīng)的的取代或官能化的氫過氧化物，產(chǎn)率很高。 同位素（氧18）標記的氧氣被用來研究反應(yīng)的最后一步，以確定氫過氧化物中氧原子的來源（圖8）。當圖8中標記為1的化合物在同位素氧18標記的氧氣氛中與水（其中絕大多數(shù)O是同位素氧16）反應(yīng)，保持其他條件不變，產(chǎn)物過氧化物中的兩個氧原子都是氧18標記的占了70%。這一結(jié)果強烈證實了三價鈷與雙氧水反應(yīng)生成的，或者過氧化三價鈷釋放出的氧氣，捕獲了由過氧化半縮醛（圖中標記為6的物質(zhì)）生成的烷基自由基。 |
2樓2013-11-26 11:54:47
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