摘要
分别以麦芽酚和乙基麦芽酚为起始原料,经乙酰化、钯碳氢化、羰基α位乙酰氧化和脱乙酰基4步反应,合成了双羟基吡喃酮化合物2,3-二氢-3,5-二羟基-6-甲基-4H-吡喃-4-酮(Ⅴa)和2,3-二氢-3,5-二羟基-6-乙基-4H-吡喃-4-酮(Ⅴb)。利用^(1)HNMR、^(13)CNMR和HRMS对每步反应的产物进行了结构表征,优化了合成反应工艺,通过清除自由基实验对化合物的抗氧化活性进行了测试。结果表明,双羟基吡喃酮化合物表现出优异的抗氧化活性,其中Ⅴb对2,2′-偶氮-双-(3-乙基苯并噻唑啉-6-磺酸)二铵盐自由基(ABTS^(+)·)、2,2-二(4-叔辛基苯基)-1-苦肼基自由基(DPPH·)和Galvinoxyl自由基(Galvinoxyl·)的清除率分别为88.9%、83.8%和68.4%,明显高于维生素E(V_(E))和2,6-二叔丁基对甲酚(BHT)。构效关系表明,在吡喃酮结构中引入羟基或增强侧链取代基的给电子能力均能提高化合物清除自由基的能力。
2,3-Dihydro-3,5-dihydroxyl-6-methyl-4H-pyran-4-one(Ⅴa)and 2,3-dihydro-3,5-dihydroxyl-6-ethyl-4H-pyran-4-one(Ⅴb),two types of dihydroxypyranones,were synthesized respectively by a four-step reaction of acetylation,palladium hydrogenation,carbonylα-acetoxylation and deacetylation using maltol and ethyl maltol as raw materials.The structure of each product was then characterized by~1HNMR,^(13)CNMR and HRMS followed by optimization of the synthesis process.Furthermore,the two dihydroxypyranones exhibited excellent antioxidant activity demonstrated by free radical scavenging assay.The scavenging rates against diammonium 2,2’-azino-bis(3-ethylbenzothiazoline-6-sulfonate)free radical(ABTS^(+)·),2,2-di(4-tert-octylphenyl)-1-picrylhydrazyl free radical(DPPH·)and Galvinoxyl free radical(Galvinoxyl·)ofⅤb were 88.9%,83.8%and 68.4%respectively,obviously higher in comparison to vitamin E and2,6-di-tert-butyl-4-methylphenol.The structure-activity relationship revealed that introduction of hydroxyl groups into the structure of pyranone or enhancement of electron donating ability of side chain substituents contributed to the free radical scavenging capability improvement.
作者
王清福
蔡莉莉
刘前进
杜佳
万帅
白冰
席高磊
陈芝飞
WANG Qingfu;CAI Lili;LIU Qianjin;DU Jia;WAN Shuai;BAI Bing;XI Gaolei;CHEN Zhifei(Technology Center,China Tobacco Henan Industrial Co.,Ltd.,Zhengzhou 450000,Henan,China;College of Food and Bioengineering,Zhengzhou University of Light Industry,Zhengzhou 450000,Henan,China)
出处
《精细化工》
EI
CAS
CSCD
北大核心
2022年第6期1205-1211,共7页
Fine Chemicals
关键词
双羟基吡喃酮
合成
工艺优化
自由基
抗氧化活性
医药原料
dihydroxypyranones
synthesis
process optimization
free radicals
antioxidant activity
drug materials
作者简介
王清福(1990-),男,博士,E-mail:wqfhust@163.com;联系人:席高磊(1987-),男,博士,E-mail:xigaoleijida@126.com;联系人:陈芝飞(1979-),男,研究员,E-mail:chenzhifei@126.com。
