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'Green' Halogenation Reactions: Oxidative Aerobic Halogenation and 'On Water' Bromination with Hydrobromic Acid and Hydrogen Peroxide

机译:“绿色”卤化反应:氧化有氧卤化和“水”溴化与氢溴酸和过氧化氢

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@@1.Introduction Halogenation of organic compounds is one of the most important transformations in organic synthesis. Molecular bromine, as the classical reagent for achieving this conversion, is both toxic and corrosive and its high reactivity resulting in highly exothermic reactions makes performing bromination in a selective manner difficult. Furthermore, by using molecular bromine only half of the bromine atoms are utilized while the other half ends up as HBr -a potentially hazardous pollutant. Alternative brominating agents, such as tetraikylammonium tribromides[1] and N-bromosuccinimide[2], have been used increasingly for bromination of organic compounds resulting in an easier handling and higher selectivity of reaction. Nevertheless, the use of these brominating agents has some limitations including low atom efficiency, need for removal of the reagent residue and finally, molecular bromine is needed for their preparation. On the other hand, nature has developed a molecular halogen-free strategy for halogenation using hydrogen peroxide (haloperoxidase) or oxygen (flavin dependent halogenase) and X-to produce "X+" in the enzymes active site[3].
机译:@@有机化合物的卤化1.介绍在有机合成中最重要的变换之一。分子溴,作为用于实现该转化的经典试剂,既有毒和腐蚀性和其导致高度放热反应的高反应性使得难以在以选择性方式进行溴化。此外,通过使用分子溴只有一半的溴原子的,而另一半为HBr的-a潜在危险的污染物最终被使用。替代的溴化剂,如三溴化tetraikylammonium [1]和N-溴代琥珀酰亚胺[2],已越来越多地用于产生在更容易处理的有机化合物的溴化和反应的选择性更高。然而,使用这些溴化剂的有一定的局限性包括低效率原子,需要用于去除试剂的残余物,最后,需要用于它们的制备的分子溴。在另一方面,自然界已经开发了使用过氧化氢(卤过氧化物酶)或氧卤化分子不含卤素的策略(黄素依赖性halogenase)和X在酶的活性位点[3]产生“X +”。

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