摘要
实验以硝基苯为溶剂,在四苯基溴化磷和呋喃-丙酮冠醚为相转移催化剂作用下,研究了氯苯甲醛(2a)、邻氯苯甲醛(2b)、3,4-二氯苯甲醛(2c)、2,3-二氯苯甲醛(2d)卤素交换氟化反应动力学和热力学。在n(氟化钾):n(氯代苯甲醛):n(四苯基溴化磷):n(丙酮-呋喃冠醚)=4:1:0.1:0.05的条件下,通过对433～473 K的实验数据分析,得出各温度的反应速率常数,并求得其反应活化能、指前因子和活化自由能。结果表明:反应为一级反应。在453,463 K时,k_(2a)>k_(2b)、k_(2c)>k_(2d);在473 K时,k_(2a)<k_(2b)。
With Ph4 PBr and acetone-furan crown ether as phase transfer catalysts, nitrobenzene as solvent, the halogen-exchange fluorination of chlorobenzaldehyde using KF as the fluorination agent was studied. The kinetics were investigated and the reaction rate constants, activition energy, pre-exponential factor and Gibbs free energy of activation were obtained under the optimum conditions of n （KF）：n（chlorobenzaldehyde）：n（Ph4PBr）：n（acetone-furan crown ether）=4：1：0.1：0.05 in the temperature range of 433 K to 473 K. The results showed that the reaction is first order, the reaction rate increases sharply with increasing temperature k2a〉k2b、k2c〉k2d;at 453 K and 463 K and k2a〈k2b at 473 K.
出处
《精细石油化工》
CAS
CSCD
北大核心
2009年第5期31-34,共4页
Speciality Petrochemicals
基金
江苏省科技攻关项目(BE2004045)
关键词
氯代苯甲醛
卤素交换氟化
相转移催化
动力学
chlorobenzaldehyde
halogen-exchange fluorination
phase transfer catalysis
kinetics
