取代邻羟基苯乙酮的简便绿色合成  

Green and convenient synthesis of substituted 1-(2-hydroxyphenyl) ethanone

作　　者：高文涛[1] 兰帅[1] 李阳[1] 吕明月[1] 邢学达 郑宏梅 

机构地区：[1]渤海大学超精细化学品研究所,辽宁锦州121000

出　　处：《化学研究与应用》2014年第7期1148-1154,共7页Chemical Research and Application

基　　金：辽宁省自然科学基金项目(2012S001)资助;辽宁省教育厅科学研究一般项目(L2013428)资助

摘　　要：以对甲(氯、溴)苯酚(1a-c)为起始原料经酰化得对甲(氯、溴)苯酚乙酯,再以BF3·2HAc为催化剂无溶剂条件下实现Fries重排,以77.3%-80.4%的收率分别得到了5-甲基(氯、溴)邻羟基苯乙酮(2a-c);应用环境友好的聚乙二醇-400为溶剂,N-氯(溴、碘)代丁二酰亚胺为卤代试剂对邻羟基苯乙酮进行卤代反应,以61.8%-92.4%的收率制备3,5-二氯(溴、碘)邻羟基苯乙酮(4a-c);以邻羟基苯乙酮为原料,硝酸铈铵(CAN)为绿色硝化试剂,分别以29.8%和63.9%的收率得到了3位和5位硝化产物1-(2-羟基-3-硝基苯基)乙酮、1-(2-羟基-5-硝基苯基)乙酮(5a-b)。以上制备过程具有反应条件温和、后处理简单、环境友好等优点,为制备取代邻羟基苯乙酮提供了简单且绿色的新方法。5-Methyl-,chloro,and bromo-substituted 2-hydroxy-acetophenones（2a-c） were synthesized in good yields of 77. 3%-80. 4%,involving the acetylation reaction of the respective 4-methyl-,chloro,and bromo-phenols（1a-c） with acetic anhydride fol-lowed by Fries rearrangement in the presence of BF3·2HAc as catalyst under solvent-free condition. 3,5-Dihalo-substituted 2-hy-droxy-acetophenones（4a-c）were obtained in the yields of 61. 8-92. 4%by the halogenation reaction of 2-hydroxy-acetophenone（3） with N-halosuccinimide using PEG-400 as solvent at room temperature. The nitration of 2-hydroxy-acetophenone（3）with a green ni-trating agent of cerium ammonium nitrate（ CAN） was also investigated,affording two products 3-nitro-and 5-nitro-substituted 2-hy-droxy-acetophenones（5a,b）in 29. 8% and 63. 9%yield,respectively. Our developed experimental procedures for the preparation of the 2-hydroxy-acetophenone derivatives 2a-c,4a-c,and 5a,b are characterized by mild conditions,simple work-up,and environmen-tal benefits of the reaction medium,and thus could be used as a useful and green alternative approach to previously reported meth-ods.

关 键 词：邻羟基苯乙酮 绿色 合成 FRIES重排 卤代 硝化 

分 类 号：O625[理学—有机化学]