槲皮素五乙酸酯的合成及表征
|
摘要
以槲皮素为原料,浓硫酸作催化剂,65℃与乙酸酐反应,TLC板监测反应完毕,过滤、氯仿/甲醇重结晶合成了槲皮素乙酸酯。UV显示槲皮素的两个特征吸收峰均发生蓝移,这是形成新化合物共轭体系变化引起的。IR中ν-OH峰明显减弱,说明槲皮素的五个羟基发生了反应,νc=o位于1776.0cm~(-1),酯羰基峰明显增强,νc-o位于1199.18cm~(-1),变宽增强。~1H-NMR中3-OH、5-OH、7-OH、3′-OH、4′-OH上面的氢全部消失,说明与乙酸酐发生了酯化反应,同时,出现五组乙酰基的甲基峰。MS中513.1为槲皮素五乙酸酯的分子离子峰。槲皮素与乙酸酐反应可以得到槲皮素五乙酸酯。
The quercetin and concentrated sulfuric acid is used as the raw material and catalyst respectively,and reacts with acetic anhydride at65℃; the TLC plate is used to monitor the completion of reaction; after the filtration,chloroform/methanol recrystallization,the quercetin acetate is prepared.The UV shows that two characteristic absorption peaks of quercetin have a blue shift,which is caused by the change of conjugated system by the formation of new compounds.The ν-OHpeak in IR spectrum weakens significantly,which indicates that the five hydroxyl groups of quercetin has reacted,the νc=ois located in 1776.0 cm~(-1),the ester carbonyl group peak has enhanced obviously,the νc-ois located in 1199.18 cm~(-1),has widened and enhanced.The hydrogen of 3-OH,5-OH,7-OH,3'-OH,4'-OH in ~1H-NMR spectrum has disappeared,which indicates the esterification reaction with acetic anhydride has taken place,meantime there are 5 methyl group peaks of acetyl groups has appeared.In the MS spectrum,the quercetin pentaacetate molecular ion peak appears at 513.1.It is concluded that the quercetin pentaacetate can be prepared by the reaction of quercetin with acetic anhydride.
The quercetin and concentrated sulfuric acid is used as the raw material and catalyst respectively,and reacts with acetic anhydride at65℃; the TLC plate is used to monitor the completion of reaction; after the filtration,chloroform/methanol recrystallization,the quercetin acetate is prepared.The UV shows that two characteristic absorption peaks of quercetin have a blue shift,which is caused by the change of conjugated system by the formation of new compounds.The ν-OHpeak in IR spectrum weakens significantly,which indicates that the five hydroxyl groups of quercetin has reacted,the νc=ois located in 1776.0 cm~(-1),the ester carbonyl group peak has enhanced obviously,the νc-ois located in 1199.18 cm~(-1),has widened and enhanced.The hydrogen of 3-OH,5-OH,7-OH,3'-OH,4'-OH in ~1H-NMR spectrum has disappeared,which indicates the esterification reaction with acetic anhydride has taken place,meantime there are 5 methyl group peaks of acetyl groups has appeared.In the MS spectrum,the quercetin pentaacetate molecular ion peak appears at 513.1.It is concluded that the quercetin pentaacetate can be prepared by the reaction of quercetin with acetic anhydride.
引文
[1]ALKA GUPTA,KAVITA BIRHMAN,INDIRA RAHEJA,et al.Quercetin:A wonder bioflavonoid with therapeutic potential in disease management[J].Asian Pacific Journal of Tropical Disease,2016,6(3):248~252
[2]JAN A T,KAMLI M R,MURTAZA I,et al.Dietary flavonoid quercetin and associated health benefits an overview[J].Food Rev Int,2010:26:302~317.
[3]AKIRA MURAKAMI,HITOSHI ASHIDA,JUNJI TERAO.Multitargeted cancer prevention by quercetin[J].Cancer Letters,2008,269(2):315~325.
[4]FEDERICO DAJA.Life Or Death:Neuroprotective And Anticancer Effects Of Quercetin[J].Journal of Ethnopharmacology,2012,143(2):383~396.
[5]EDWARDS R L,LYON T,LITWIN S E,et al.Quercetin reduces blood pressure in hypertensive subjects[J].J Nutr,2007,137(11):2405~2411.
[6]FRANCISCO PEREZ-VIZCAINO,JUAN DUARTE,ROSARIO JIMENEZ,et al.Antihypertensive effects of the flavonoid quercetin[J].Pharmacological Reports,2009,61(1):67~75.
[7]FEDORA GRANDE,ORTENSIA I PARISI,ROBERTA A Mordocco,et al.Quercetin derivatives as novel antihypertensive agents:Synthesis and physiological characterization[J].European Journal of Pharmaceutical Sciences,2016,82:161~170.
[8]SHYAMALA GANESAN,ANDREA N FARIS,ADAM T COMSTOCK,et al.Quercetin Inhibits Rhinovirus Replication In Vitro And In Vivo[J].Antiviral Research,2012,94(3):258~271.
[9]AGNES W BOOTS,GUIDO R.M M HAENEN,AALT BAST.Health effects of quercetin:From antioxidant to nutraceutical[J].European Journal of Pharmacology,2008,585(2~3):325~337.
[10]VENGADESHPRABHU KARUPPAGOUNDER,SOMASUNDARAM ARUMUGAM,RAJARAJAN A THANDAVARAYAN,et al.Molecular targets of quercetin with anti-inflammatory properties in atopic dermatitis[J].Discovery Tod Drugay,2016,21(4):632~639.
[11]EDISON OSORIO,EDWIN G P魪REZ,CARLOS ARECHE,et al.Why is quercetin a better antioxidant than taxifolin Theoretical study of mechanisms involving activated forms[J].J Mol Model,2013,19:2165~2172.
[12]VANESA A MUNOZ,GABRIELA V FERRARI,MARTIAS I SANCHO,et al.Spectroscopic and Thermodynamic Study of Chrysin and Quercetin Complexes with Cu(II)[J].J.Chem.Eng.Data,2016,61(2):987~995.
[13]WANG WEIYOU,SUN CUIXIA,MAO LIKE,et al.The biological activities,chemical stability,metabolism and delivery systems of quercetin:A review[J].Trends in Food Science&Technology,2016,56:21~38.
[14]FRANCESCA MAININI,ALESSANDRO CONTINI,DONATELLA NAVA,et al.Synthesis,Molecular Characterization and Preliminary Antioxidant Activity Evaluation of Quercetin Fatty Esters[J].J Am Oil Chem Soc,2013,90:1751~1759.
[15]ALEXANDRA PRIMIKYRI,GLORIA MAZZONE,CHRISTINA LEKKA,et al.Understanding Zinc(II)Chelation with Quercetin and Luteolin:A Combined NMR and Theoretical Study[J].J.Phys.Chem.B,2015,119(1):83~95.
[16]AGATA ZDYB,STANISLAW KRAWCZYK.Characterization of adsorption and electronic excited states of quercetin on titanium dioxide nanoparticles[J].Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,2016,157:197~203.
[17]TORU SAITO,TAKASHI KAWAKAMI,SHUSUKE YAMANAKA,et al.Computational Study of Catalytic Reaction of Quercetin2,4-Dioxygenase[J].J.Phys.Chem.B,2015,119(23):6952~6962.
[18]RON SIMKOVITCH,DAN HUPPERT.Excited-State Intramolecular Proton Transfer of the Natural Product Quercetin[J].J.Phys.Chem.B,2015,119(32):10244~10251.
[19]GHOLAMREZA DEHGHAN,ZAHRA KHOSHKAM.Tin(II)-Quercetin Complex:Synthesis,Spectral Characterisation And Antioxidant Activity[J].Food Chemistry,2012,131(2):422~426.
[20]RAVICHANDRAN R,RAJENDRAN M,DEVAPIRIAM D.Structural Characterization And Physicochemical Properties Of Quercetin-Pb Complex[J].Journal of Coordination Chemistry,2014,67(8):1449~1462.
[21]ANIFE AHMEDOVA,KATARZYNA PARADOWSKA,IWONA WAWER.1H,13C MAS NMR And DFT GIAO Study Of Quercetin And Its Complex With Al(III)In Solid State[J].J Inorg Biochem.,2012,110:27~35.
[22]KIM MIHYANG,PARK YOUNGRONG,CHO SOOYOUNG,et al.Synthesis of alkyl quercetin derivatives[J].J Korean Soc Appl Biol Chem,2015,58(3):343~348.
[23]KARIMOVA E R,BALTINA L A,SPIRIKHIN L V,et al.Synthesis and antioxidant activity of quercetin ethers[J].Chemistry of Natural Compounds,2015,51(5):851~855.
[2]JAN A T,KAMLI M R,MURTAZA I,et al.Dietary flavonoid quercetin and associated health benefits an overview[J].Food Rev Int,2010:26:302~317.
[3]AKIRA MURAKAMI,HITOSHI ASHIDA,JUNJI TERAO.Multitargeted cancer prevention by quercetin[J].Cancer Letters,2008,269(2):315~325.
[4]FEDERICO DAJA.Life Or Death:Neuroprotective And Anticancer Effects Of Quercetin[J].Journal of Ethnopharmacology,2012,143(2):383~396.
[5]EDWARDS R L,LYON T,LITWIN S E,et al.Quercetin reduces blood pressure in hypertensive subjects[J].J Nutr,2007,137(11):2405~2411.
[6]FRANCISCO PEREZ-VIZCAINO,JUAN DUARTE,ROSARIO JIMENEZ,et al.Antihypertensive effects of the flavonoid quercetin[J].Pharmacological Reports,2009,61(1):67~75.
[7]FEDORA GRANDE,ORTENSIA I PARISI,ROBERTA A Mordocco,et al.Quercetin derivatives as novel antihypertensive agents:Synthesis and physiological characterization[J].European Journal of Pharmaceutical Sciences,2016,82:161~170.
[8]SHYAMALA GANESAN,ANDREA N FARIS,ADAM T COMSTOCK,et al.Quercetin Inhibits Rhinovirus Replication In Vitro And In Vivo[J].Antiviral Research,2012,94(3):258~271.
[9]AGNES W BOOTS,GUIDO R.M M HAENEN,AALT BAST.Health effects of quercetin:From antioxidant to nutraceutical[J].European Journal of Pharmacology,2008,585(2~3):325~337.
[10]VENGADESHPRABHU KARUPPAGOUNDER,SOMASUNDARAM ARUMUGAM,RAJARAJAN A THANDAVARAYAN,et al.Molecular targets of quercetin with anti-inflammatory properties in atopic dermatitis[J].Discovery Tod Drugay,2016,21(4):632~639.
[11]EDISON OSORIO,EDWIN G P魪REZ,CARLOS ARECHE,et al.Why is quercetin a better antioxidant than taxifolin Theoretical study of mechanisms involving activated forms[J].J Mol Model,2013,19:2165~2172.
[12]VANESA A MUNOZ,GABRIELA V FERRARI,MARTIAS I SANCHO,et al.Spectroscopic and Thermodynamic Study of Chrysin and Quercetin Complexes with Cu(II)[J].J.Chem.Eng.Data,2016,61(2):987~995.
[13]WANG WEIYOU,SUN CUIXIA,MAO LIKE,et al.The biological activities,chemical stability,metabolism and delivery systems of quercetin:A review[J].Trends in Food Science&Technology,2016,56:21~38.
[14]FRANCESCA MAININI,ALESSANDRO CONTINI,DONATELLA NAVA,et al.Synthesis,Molecular Characterization and Preliminary Antioxidant Activity Evaluation of Quercetin Fatty Esters[J].J Am Oil Chem Soc,2013,90:1751~1759.
[15]ALEXANDRA PRIMIKYRI,GLORIA MAZZONE,CHRISTINA LEKKA,et al.Understanding Zinc(II)Chelation with Quercetin and Luteolin:A Combined NMR and Theoretical Study[J].J.Phys.Chem.B,2015,119(1):83~95.
[16]AGATA ZDYB,STANISLAW KRAWCZYK.Characterization of adsorption and electronic excited states of quercetin on titanium dioxide nanoparticles[J].Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,2016,157:197~203.
[17]TORU SAITO,TAKASHI KAWAKAMI,SHUSUKE YAMANAKA,et al.Computational Study of Catalytic Reaction of Quercetin2,4-Dioxygenase[J].J.Phys.Chem.B,2015,119(23):6952~6962.
[18]RON SIMKOVITCH,DAN HUPPERT.Excited-State Intramolecular Proton Transfer of the Natural Product Quercetin[J].J.Phys.Chem.B,2015,119(32):10244~10251.
[19]GHOLAMREZA DEHGHAN,ZAHRA KHOSHKAM.Tin(II)-Quercetin Complex:Synthesis,Spectral Characterisation And Antioxidant Activity[J].Food Chemistry,2012,131(2):422~426.
[20]RAVICHANDRAN R,RAJENDRAN M,DEVAPIRIAM D.Structural Characterization And Physicochemical Properties Of Quercetin-Pb Complex[J].Journal of Coordination Chemistry,2014,67(8):1449~1462.
[21]ANIFE AHMEDOVA,KATARZYNA PARADOWSKA,IWONA WAWER.1H,13C MAS NMR And DFT GIAO Study Of Quercetin And Its Complex With Al(III)In Solid State[J].J Inorg Biochem.,2012,110:27~35.
[22]KIM MIHYANG,PARK YOUNGRONG,CHO SOOYOUNG,et al.Synthesis of alkyl quercetin derivatives[J].J Korean Soc Appl Biol Chem,2015,58(3):343~348.
[23]KARIMOVA E R,BALTINA L A,SPIRIKHIN L V,et al.Synthesis and antioxidant activity of quercetin ethers[J].Chemistry of Natural Compounds,2015,51(5):851~855.