取代邻羟基苯乙酮的简便绿色合成.pdf

第26卷第7期
化学研究与应用
Vol 26 No. 7
2014年7月
Chemical Research and Application
July, 2014
文章编号:1004-1656(2014)07-148-0
取代邻羟基苯乙酮的筒便绿色合成
高文涛“,兰帅,李阳,吕明月,那学达,郑宏梅
渤海大学超精细化学品研究所,辽宁锦州121000
摘要:以对甲(氯、溴)苯酚(1ac)为起始原料经酰化得对甲(氯、溴)苯酚乙酯,再以BF32HAc为催化剂无溶
剂条件下实现ies重排,以73%-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)代丁二酰亚胺为鹵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(4ac);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
(2-羟基-5-硝基苯基)乙開(5a-)。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。
关键词:邻羟基苯乙酮;绿色;合成;Fies重排;鹵代;确化
中分类号:0625文献标志码;A
Green and convenient synthesis of substituted 1-(2-hydroxyphenyl )ethanone
GAO Wen-tao", LAN Shuai, LI Yang, LV Ming-yue, XING Xue-da, ZHENG Hong-mei
Institute of Superfine Chemicals, Bohai University, Jinzhou, Liaoning 121000, China)
Abstrac: 5-methyl-, chior, and romo-substitmue 2 rxy-acetoenones(2- 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 BF 2 HAC 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 Nhalosuccinim e using PG4 a ent a room emea Te i ation of 2-h rox -acetophenone(3 )with a green ni
trating agent of cer um ammonium nitrate(CAN )was also investiga e a oring two products 3-nitro-and 5-nitr-substituted 2-hy
droxy-acetophenones(5a, b)in 29. 8% and 63.9% yield, respectively. ur developed experimental procedures for the preparation of
the 2-hydroxy-acetophenone derivatives 2a-c Aa-c, and Sa, 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.
Key words: 1-(2-hydroxyphenyl )ethanone; green; synthesis Fries rearrangement; halogenated; nitrification
邻羟基苯乙酮是合成抗肿瘤病毒生物活性物罗帕酮( Propafenone hydrochloride)的重要中间
质查尔酮( chalcone)和IA类抗心律失常药盐酸普体い),同样取代邻羟基苯乙酮在药物合成中也有
收稿日期:2014-01-14;修回日期:201404-06
基金项目:冠宁省自然科学基金项目(20125001)资助;辽宁省教育厅科学研究一般项目(I2013428)资助
联系人简介:高文涛(1962-),男,教授,主要从事有机合成研究。E-mail:isfc@bhu.edu,cn