铜催化的二氟甲基化反应研究
毕业论文关键词：铜；二氟甲基；偶联反应；一溴二氟苯乙酮；一溴二氟甲苯
Studies on the Copper Catalyzed Difluoromethylation Reaction
Abstract: In recent years, the synthesis of difluoromethyl-containing compounds has attracted considerable attention among chemists. The introduction of difluoromethyl group into some organic molecules can significantly change their physiological activities. This thesis focuses on the studies of copper catalyzed difluoromethylation reaction of aromatic halides withbromodifluoroacetophenone and bromodifluoromethyl benzene. And the results showed that without any copper catalyst, bromodifluoromethyl benzene can smoothly react with alkenes only under the initiation of sodium dithionite, giving the difluoromethylating products in moderate to good yields. After screening the solvents, temperature, and the reaction time etc., an optimal reaction condition for the addition of bromodifluoromethyl benzene and alkenes was given: moderate to good yields of the difluoromethylating products can be obtained when the reaction was performed under the initiation of sodium dithionite in DMF at 50-60 oC for 13 h.
Keywords: Copper; Difluoromethyl; Coupling reaction; Bromodifluoroacetophenone; Bromodifluoromethyl benzene
目 录
1 前言 1
1.1 开题依据 1
1.2 文献综述 4
1.2.1 含氟材料 4
1.2.2 含氟有机生理活性物质 4
1.2.3 茶碱二氟甲基化的研究[9] 6
1.2.4 Kobayashi小组[10]的偶联反应 6
1.2.5 铜参与的一卤二氟磷酸酯和芳基、烯基卤化物的偶联反应 7
1.2.6 铜参与的二氟甲基苯基砜反应研究 7
1.3 工艺路线的确定 9
1.3.1 溴二氟苯乙酮的制备 9
1.3.2 铜催化下溴二氟苯乙酮和碘苯的偶联反应 9
1.3.3 铜催化下一溴二氟甲苯和烯烃类化合物的加成反应 9
1.4 方案论证 10
2 实验部分 11
2.1 主要实验仪器 11
2.2 试剂与原料 11
2.2.1 主要试剂名称及物性常数 11
2.2.2 原料名称及物性常数 12
2.3 实验步骤 13
2.3.1 铜催化的溴二氟苯乙酮和碘苯的偶联反应 14
2.3.2 铜催化下一溴二氟甲苯和烯烃类化合物的加成反应研究 15
2.3.2.1 一溴二氟甲苯和1-己烯不同条件下的反应研究 15
2.3.2.2 一溴二氟甲苯和乙酸烯丙酯的反应研究 17
2.3.2.3 一溴二氟甲苯和丙烯酸乙酯的反应研究 18
2.3.2.4 一溴二氟甲苯和环己烯的反应研究 19