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在铝粉催化下,以对甲苯磺酰胺(TsNH2)和N-溴代丁二酰亚胺(NBS)为氮源和卤素源,二氯甲烷作溶剂,建立了肉桂酸酯双键上的高度区域选择和立体选择性氨卤加成反应新体系.该法在室温下,无需惰性气体保护可高产率的给出邻位氨基、卤素的加成产物,最高收率可达97%.实验证明,当肉桂酸酯中与双键直接相连苯环上对位具有强给电子基团时(如CH3O),该反应的产率高,同时得到唯一的α-溴-β-氨基肉桂酸酯加成产物;当肉桂酸酯中与双键直接相连苯环对位不具有强给电子基团(如CH3O)时,该反应的产率较低,同时得到唯一的α-氨基-β-溴的肉桂酸酯加成产物.这一实验结果证明了肉桂酸酯衍生物(缺电子烯键)的氨溴加成反应是一个亲电加成反应.共考察了20种不同结构的肉桂酸酯的氨溴加成反应情况,其产物结构经核磁共振氢谱、碳谱、质谱及元素分析方法进行了确证,并对该反应的机理进行了探讨.
Under the aluminum powder catalysis, p-toluenesulfonamide (TsNH2) and N-bromosuccinimide (NBS) were used as nitrogen source and halogen source, and methylene chloride was used as the solvent to establish the height of cinnamate double bond Regioselective and stereoselective amine-halogenated addition reaction.The new method can give a high yield of ortho-amino and halogen addition products with high yield up to 97% without inert gas protection at room temperature.Experimental evidence , When cinnamate is directly linked to the double bond with a strong electron donating group on the para-position of the benzene ring (eg, CH3O), the yield of the reaction is high and the only alpha-bromo-beta-aminocinnamate ; When the cinnamate ester is directly linked to the double bond and the para-position of the benzene ring does not have a strong electron-donating group (such as CH3O), the yield of the reaction is lower and the only α-amino-β-bromo Cinnamic acid ester addition product.This experimental result proves that the bromine addition reaction of the cinnamate derivative (electron-deficient ethylenic bond) is an electrophilic addition reaction.A total of 20 different structures of cinnamate Ammonia bromine addition reaction, the product structure was confirmed by 1H nuclear magnetic resonance, carbon, mass spectrometry and elemental analysis were confirmed, and the anti The mechanism should be discussed.