超声辐射碳酸钾催化Knoevenagel反应及4H-色烯的合成  

Knoevenagel condensation and the synthesis of 4H-chromene derivatives catalyzed by K_2CO_3 under ultrasound irradiation

作　　者：曾育才[1] 刘小玲[1] 杨素珍 郭丽曼 ZENG Yu-cai;LIU Xiao-ling;YANG Su-zhen;GUO Li-man(College of Chemistry and Environment, Jiaying College, Meizhou, Guangdong 514015, China)

机构地区：[1]嘉应学院化学与环境学院,广东梅州514015

出　　处：《日用化学工业》2019年第1期34-39,共6页China Surfactant Detergent & Cosmetics

基　　金：嘉应学院自然科研基金资助项目(No.2014KJY04)

摘　　要：在超声辐射下,无溶剂K_2CO_3催化芳醛与氰基乙酸酯发生Knoevenagel反应合成4种2-氰基肉桂酸酯和6种4H-色烯衍生物。实验结果表明:当苯甲醛与氰基乙酸甲酯用量各为10 mmol,无水碳酸钾用量为1 mmol,超声功率为150 W,室温下反应30 min以94.6%高产率得到2-氰基肉桂酸甲酯;推电子基的4-取代苯甲醛与氰基乙酸酯的缩合产率明显下降。当水杨醛用量为10 mmol,氰基乙酸乙酯用量为22.5 mmol,无水碳酸钾用量为0.1 mmol,超声功率为250 W,30℃下反应20 min以91%产率得到4H-色烯衍生物;推电子基的5-取代水杨醛则不能反应。产物结构通过熔点测定、IR和1H NMR进行表征。Four 2-cyano-cinnamates and six 4H-chromene derivatives were synthesized from aromatic aldehydes with cyanoacetates via solvent-free Knoevenagel condensation using K2CO3 as catalyst under ultrasound irradiation. The experimental results indicate that the yield of methyl 2-cyano-cinnamate is up to 94.6% after reaction for 30 min at room temperature under ultrasonic power of 150 W when the dosages of benzaldehyde, methyl cyanoacetate and K2CO3 are 10, 10 and 1 mmol, respectively. However, for the 4-substituted benzaldehyde with electron-donating groups, the yields of condensation with cyanoacetate significantly decrease in the same condition. In contrast, the yield of 4H-chromene derivative is up to 91% after reaction for 20 min at 30 ℃ under ultrasonic power of 250 W when the amounts of salicylaldehyde, ethyl cyanoacetate and K2CO3 are 10, 22.5 and 0.1 mmol, respectively. However, 5-substituted salicylaldehyde with electron-donating groups can’t react with cyanoacetate. The products were characterized by mp, IR and ^1H NMR.

关 键 词：个人护理用品添加剂 超声辐射 KNOEVENAGEL反应 2-氰基肉桂酸酯 4H-色烯衍生物 

分 类 号：TQ658[化学工程—精细化工]