第 45 卷第 6 期 Vol. 45 No. 6 2015 年 12 月 Dec 2015

所属栏目：农药及中间体 钯炭催化制备4′-氯-2-氨基联苯

张慧丽，康永利，张 文，王 轩，栗晓东，姚晓龙 （天津市均凯化工科技有限公司，天津 300384）

摘　要：以对氯苯硼酸和邻氯硝基苯为原料，在N，N-二甲基乙酰胺和水的溶液中以钯炭为催化剂、碳酸钾为助催化剂经Suzuki反应得4′-氯-2-硝基联苯；在乙醇溶液中然后以锌粉或铁粉为还原剂回流下还原得到新型杀菌剂啶酰菌胺的关键中间体4′-氯-2-氨基联苯。考察了钯碳用量、温度、溶剂配比、碱、反应时间对反应的影响，优化的反应条件为：n（邻氯硝基苯）∶n（对氯苯硼酸）∶n（钯碳）∶n（碳酸钾）=1.00∶1.50∶0.03∶3.00，反应溶剂m（DMAC）∶m（水）=30∶1；反应温度为130℃，碳酸钾为弱碱，反应时间为12 h。优化条件下反应收率69.43%，该路线具有原材料易得、成本低、催化剂可回收套用等优点。

关键词：啶酰菌胺；4′-氯-2-氨基联苯；对氯苯硼酸；邻氯硝基苯

中图分类号：TQ2　　文献标识码：A　　文章编号：1009-9212（2015）05-0010-04

Preparation of 4′-Chloro-2-aminobiphenyl Using Palladium Carbon as Catalyst

ZHANG Hui-li, KANG Yong-li, ZHANG Wen, WANG Xuan, LI Xiao-dong, YAO Xiao-long (Tianjin Junkai Chemical Co., Ltd., Tianjin 300384,China)

Abstract：Using 4-chlorophenylboronic acid and 2-nitrochlorobenzene as raw materials, palladium carbon and alkali as catalyst in N,N-dimethylacetamide and water, the reaction mixture was heated to 130℃ for 12 hours by Suzuki reaction to give 4′-chloro-2-nitro-biphenyl. Then, 4′-chloro-2-nitro-biphenyl was reduced by zinc powder or iron powder in ethanol at reflux to give 4′-chloro-2-aminobipheny, a key intermediate of the new fungicide Boscalid. The amount of palladium carbon, temperature of the reaction, the ratio of solvent, alkali and reaction time was evaluated. The optimum reaction conditions were as following: n(2-nitrochlorobenzene):n(4-chlorophenylboronic acid):n(palladium carbon):n(potassium carbonate)=1.00:1.50:0.03:3.00; the weight ratio of DMAC to water was 30:1; reaction temperature was 130℃; potassium carbonate was used as the alkali; the reaction time was 12 h. The route had advantages of low cost, no phosphours ligands, easy to obtain raw materials, the catalyst recycling, environment friendly, etc.

Key words：boscalid; 4′-chloro-2-aminobiphenyl; 4-chlorophenylboronic acid; 2-nitrochlorobenzene

基金项目：天津市科技支撑计划重点项目（15ZCZDNC00100）。

作者简介：张慧丽（1983-），女，河北石家庄人，硕士，研究方向：农药医药中间体合成。

收稿日期： 2015-09-1