采用一价铜盐为催化剂、二甲基甲酰胺为溶剂,在均相体系中催化3-氯-1-丁烯异构化生成1-氯-2-丁烯.考察了溶剂、反应温度、催化剂种类和加入量对反应的影响,研究发现反应温度和催化剂的加入量对异构化反应有较大影响.在最优条件3-氯-1-丁烯1 mL,二甲基甲酰胺9 mL,CuCl 0.10 g,60℃反应5 h,产物和原料的浓度比为3.88 mmol L-1.采用在线红外光谱对反应过程进行监测,检测到有红外吸收峰在反应过程中先增加后减少的变化过程,提出了可能的反应机理.
The isomerization of 3-chloro-1-butene to crotyl chloride was carried out in the homogeneous catalytic system containing cuprous salt and dimethylformamide.Factors such as solvent,temperature,and content of catalyst that influence the reaction were investigated.The type of solvent and content of catalyst had great effect on the isomerization.Equilibrium constant of the title reaction reached 3.88,which was kept for 5 h at 60 ℃ under the optimal condition.The process of isomerization was monitored with in-situ FTIR-ATR and the possible reaction mechanism was suggested in this paper.