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经 S_(RN)1历程的光诱导卤代芳烃亲核取代反应有时获得高产率的产物。我们曾将其用于抗炎药物萘普生的合成。但是,photo—S_(RN)1反应通常在钾/液氨中进行。低温操作限制了它在工业上的应用。为此,我们寻求在室温下进行 photo—S_(RN)1反应的体系。Semmelhack和Bunnett都曾报道过在DMF,DMSO和THF中的Photo—S_(RN)。THF完全阻止了光反应,其他溶剂都程度不同地延缓Photo—S_(RN)反1应。并有大量脱卤副产物(芳烃)生成。DMF和DMSO的高沸点也给反应的后处理增加麻烦。我们仍倾向于使用类似于液氨的质子溶剂。而且沸点又不宜太高。乙二胺似乎是较好的选择,本文报道在钾/乙二胺中的Photo—S_(RN)1。
Photoinduced halogenated aromatics nucleophilic substitution reaction via S RN 1 course sometimes yields high yields of product. We have used it for the synthesis of the anti-inflammatory drug naproxen. However, the photo-S_ (RN) 1 reaction is usually carried out in potassium / liquid ammonia. Low temperature operation limits its industrial application. To this end, we sought a system for photo-S_ (RN) 1 reaction at room temperature. Photo-S_ (RN) in DMF, DMSO and THF has been reported by both Semmelhack and Bunnett. THF completely blocked the photoreaction, and the other solvents delayed Photo-S_ (RN) trans-1 to varying degrees. And a large number of dehalogenation by-products (aromatic) generation. The high boiling points of DMF and DMSO also add trouble to the work-up of the reaction. We still tend to use protic solvents similar to liquid ammonia. And the boiling point should not be too high. Ethylenediamine appears to be the better choice, Photo-S_ (RN) 1 in potassium / ethylenediamine reported here.