离子液体促进的萘并[1,2,3-de]苯并吡喃-2,7-二酮的合成  

Synthesis of Naphtho[1,2,3-de]benzopyran-2,7-dione Promoted by Ionic Liquids

作　　者：郑纪芳 谭伟强[1] 吕丽莉[1] 杨启鹏[1] ZHENG Ji-fang;TAN Wei-qiang;LV Li-li;YANG Qi-peng(Research Center of Environmental Biology and Green Chemistry,School of Environmental and Municipal Engineering,Qingdao University of Technology,Qingdao 266033,China)

机构地区：[1]青岛理工大学环境与市政工程学院生物环保与绿色化工研究中心,山东青岛266033

出　　处：《化学试剂》2020年第4期445-449,共5页Chemical Reagents

基　　金：国家自然科学基金资助项目(21506109);教育部海洋药物重点实验室(中国海洋大学)开放课题项目((KLMD)(OUC)201301)。

摘　　要：以1-乙酰氧基-4-甲氧基-9,10-蒽醌和β-酮酸酯(丙二酸二乙酯、乙酰乙酸乙酯和苯甲酰乙酸乙酯)为主要原料,碳酸钾为碱,经离子液体促进的Knoevenagel缩环反应合成了标题类化合物。合成条件为n(1-乙酰氧基-4-甲氧基-9,10-蒽醌)∶n(β-酮酸酯)∶n(碳酸钾)=1∶1.5∶5,反应温度为40℃,离子液体为[Mmim][DMP],所得产物收率分别为85.0%、50.0%、65.0%。产物及中间体经1HNMR、13CNMR、LC-MS和HRMS方法进行确证。比较了离子液体相对于有机溶剂对反应的影响,考察了离子液体类型、反应温度、碱及用量对反应收率的影响。实验结果表明,离子液体中反应收率优于常规有机溶剂,对反应有促进作用,离子液体[Mmim][DMP]中产物收率最高,反应温度适中,较高会导致原料分解,无机碱更适合β-酮酸酯为底物的反应。The title compounds were synthesized via Knoevenagel condensation reaction promoted by ionic liquids from 1-acetoxy-4-methoxy-9,10-anthraquinone andβ-keto esters(diethyl malonate,ethyl acetoacetate and ethyl benzoyl acetate)as the main raw materials,potassium carbonate as base.The synthesis conditions were n(1-acetoxy-4-methoxy-9,10-anthraquinone)∶n(β-keto esters)∶n(K2CO3)=1∶1.5∶5,reaction temperature 40℃,ionic liquid[Mmim][DMP].The product yields achieved 85.0%,50.0%,65.0%,respectively.The structure of products and intermediate were confirmed by 1HNMR,13CNMR,LC-MS and HRMS.The effects of ionic liquids on the reaction were compared with those of organic solvents.The effects of ionic liquids type,reaction temperature,base and its amount on the yield were investigated.The experimental results show that the ionic liquids as solvent can promote the reaction,which is better than organic solvent.Ionic liquids[Mmim][DMP]as solvent achieved the highest yield.The reaction temperature is moderate,and higher will lead to the decomposition of raw materials.Inorganic bases are more suitable for the reaction ofβ-keto esters as substrates.

关 键 词：蒽醌类化合物 离子液体 Β-酮酸酯 Knoevenagel缩环反应 合成 

分 类 号：O626.2[理学—有机化学]