脯氨酸类催化剂催化2-庚基环戊酮的Baeyer-Villiger氧化反应  

Baeyer-Villiger Oxidation of 2-Heptylcyclopentanone Catalyzed by Proline-based Catalysts

作　　者：陈蕊蕊 于凤丽[2] 于世涛[1] CHEN Ruirui;YU Fengli;YU Shitao(College of Chemical Engineering,Qingdao University of Science and Technology,Qingdao 266042,China;College of Chemistry and Molecular Engineering,Qingdao University of Science and Technology,Qingdao 266042,China)

机构地区：[1]青岛科技大学化工学院,山东青岛266042 [2]青岛科技大学化学与分子工程学院,山东青岛266042

出　　处：《青岛科技大学学报（自然科学版）》2021年第1期14-19,共6页Journal of Qingdao University of Science and Technology:Natural Science Edition

基　　金：国家自然科学基金项目(21878166);山东省重点研发计划项目(2017GGX70102)。

摘　　要：以L-脯氨酸和不同BrΦnsted酸为原料,通过一步法合成出一系列脯氨酸类催化剂,用于催化2-庚基环戊酮的Baeyer-Villiger氧化反应。筛选出具有适宜酸度和氧化性的[ProH]H2PW12O40表现出最佳的催化活性。优化出[ProH]H2PW12O40催化的最佳反应条件:n(2-庚基环戊酮)=0.1 mmol,n([ProH]H2PW12O40)=0.004 mmol,n(30%H2O2)=0.35 mmol,T=50℃,t=6 h。在最佳条件下,2-庚基环戊酮的转化率为97.22%,δ-十二内酯的选择性是82.33%。反应结束后,用水萃取催化剂并除水干燥,便可实现重复利用。经过4次循环后,其催化活性没有明显下降。[ProH]H2PW12O40可用于催化多种环酮的Baeyer-Villiger氧化,结果表明[ProH]H2PW12O40具有良好的底物普适性。By using L-proline and different BrΦnsted acids as raw materials,a series of proline-based catalysts are synthesized by one-step synthesis,and used for catalyzing Baeyer-Villiger oxidation of 2-heptylcyclopentanone.The catalyst of[ProH]H2PW12O40 owing to its suitable acidity and oxidizability exhibits the best catalytic activity.The optimization is carried out to obtain the optimum reaction conditions:n(2-heptylcyclopentanone)=0.1 mmol,n([ProH]H2PW12O40)=0.004 mmol,n(30%H2O2)=0.35 mmol,T=50℃,t=6 h.Under the optimal conditions,the conversion of 2-heptylcyclopentanone is 97.22%,and the selectivity ofδ-dodecarolactone is up to 82.33%.After the reaction,the catalyst[ProH]H2PW12-O40can be extracted by water,dried,and reused.After four cycles,there is no significant decrease in catalytic activity.[ProH]H2PW12O40 is also used to catalyze the Baeyer-Villiger oxidation of various cyclic ketones,and the results show that[ProH]H2PW12O40 has a general applicability for substrates.

关 键 词：脯氨酸 BAEYER-VILLIGER氧化 2-庚基环戊酮 δ-十二内酯 

分 类 号：O624.4[理学—有机化学]