槲皮素苯甲酸酯的合成与表征
|
摘要
以槲皮素为原料、浓硫酸作催化剂,85℃与苯甲酰氯反应,TLC板监测反应完毕,过滤、氯仿/甲醇重结晶合成标题化合物。UV表征显示,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引起的。IR中ν—OH峰明显减弱,说明槲皮素的5个羟基中有的羟基发生了反应;νCO位于1 745.32 cm-1,酯羰基峰明显增强;νC—O位于1 259.66cm-1,峰变宽增强。1HNMR中3-OH、3'-OH、4'-OH上面的氢消失,说明与苯甲酰氯发生了酯化反应;同时,在δ6.7~8.4处有苯甲酰基的多重峰。MS中m/z 615.2为槲皮素三苯甲酸酯的分子离子峰。因此,槲皮素与苯甲酰氯反应可以得到标题化合物。
The quercetin benzoic acid esters were synthesized by filtration and recrystallization of chloroform/methanol after the reaction of quercetin,as raw material,with benzoyl chloride at 85 ℃ with the concentrated sulfuric acid as catalyst and the TLC plate as monitor.The UV shows that the two characteristic absorption peaks of quercetin both were blue-shifted,which was caused by the formation of a new conjugate system. The obviously decreased ν—OHpeaks in IR indicate the reaction of some hydroxyl groups of the 5 hydroxyl groups of quercetin.The ester carbonyl peak was significantly enhanced as the νCOat 1 745. 32 cm-1.The peak width was enhanced as the νC—Oat 1 259. 66 cm-1. The disappearance of the hydrogen on 3-OH,3'-OH and 4'-OH in1 HNMR indicates that the esterification with benzoyl chloride occurred.At the same time,there were peaks of benzoyl groups at δ6. 7 ~ 8. 4.The molecular ion peak of quercetin tribenzoate is m/z 615. 2(MS).Therefore,quercetin tribenzoate can be obtained by reaction of quercetin with benzoyl chloride.
The quercetin benzoic acid esters were synthesized by filtration and recrystallization of chloroform/methanol after the reaction of quercetin,as raw material,with benzoyl chloride at 85 ℃ with the concentrated sulfuric acid as catalyst and the TLC plate as monitor.The UV shows that the two characteristic absorption peaks of quercetin both were blue-shifted,which was caused by the formation of a new conjugate system. The obviously decreased ν—OHpeaks in IR indicate the reaction of some hydroxyl groups of the 5 hydroxyl groups of quercetin.The ester carbonyl peak was significantly enhanced as the νCOat 1 745. 32 cm-1.The peak width was enhanced as the νC—Oat 1 259. 66 cm-1. The disappearance of the hydrogen on 3-OH,3'-OH and 4'-OH in1 HNMR indicates that the esterification with benzoyl chloride occurred.At the same time,there were peaks of benzoyl groups at δ6. 7 ~ 8. 4.The molecular ion peak of quercetin tribenzoate is m/z 615. 2(MS).Therefore,quercetin tribenzoate can be obtained by reaction of quercetin with benzoyl chloride.
引文
[1]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(2):302-307.
[2]MURAKAMI A,ASHIDA H,TERAO J,et al.Multitargeted cancer prevention by quercetin[J].Cancer Lett.,2008,269(2):315-325.
[3]DAJA F.Life or death:neuroprotective and anticancer effects of quercetin[J].J.Ethnopharmacol.,2012,143(2):383-396.
[4]EDWARDS R L,LYON T,LITWIN S E,et al.Quercetin reduces blood pressure in hypertensive subjects[J].J.Nutr.,2007,137(11):2 405-2 411.
[5]PEREZ-VIZCAINO F,DUARTE J,JIMENEZ R,et al.Antihypertensive effects of the flavonoid quercetin[J].Pharmacol.Rep.,2009,61(1):67-75.
[6]GRANDE F,PARISI O I,MORDOCCO R A,et al.Quercetin derivatives as novel antihypertensive agents:synthesis and physiological characterization[J].Eur.J.Pharm.Sci.,2016,82(2):161-170.
[7]GANESAN S,FARIS A N,COMSTOCK A T,et al.Quercetin inhibits rhinovirus replication in vitro and in vivo[J].Antivir.Res.,2012,94(3):258-271.
[8]BOOTS A W,HAENEN G R M M,BAST A.Health effects of quercetin:from antioxidant to nutraceutical[J].Eur.J.Pharmacol.,2008,585(2/3):325-337.
[9]VENGADESHPRABHU K,SOMASUNDARAM A,RAJARAJAN A T,et al.Molecular targets of quercetin with anti-inflammatory properties in atopic dermatitis[J].Drug Discov.Today,2016,21(4):632-639.
[10]OSORIO E,PREZ E G,ARECHE C,et al.Why is quercetin a better antioxidant than taxifolin?Theoretical study of mechanisms involving activated forms[J].J.Mol.Model,2013,19(9):2 165-2 172.
[11]GUPTA A,BIRHMAN K,RAHEJA I,et al.Quercetin:a wonder bioflavonoid with therapeutic potential in disease management[J].Asian Pac.J.Trop.Med.,2016,6(3):248-252.
[12]MUOZ V A,FERRARI G V,SANCHO M I,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 Wei-you,SUN Cui-xia,MAO Li-ke,et al.The biological activities,chemical stability,metabolism and delivery systems of quercetin:a review[J].Trends.Food Sci.Tech.,2016,56(1):21-38.
[14]MAININI F,CONTINI A,NAVA D,et al.Synthesis,molecular characterization and preliminary antioxidant activity evaluation of quercetin fatty esters[J].J.Am.Chem.Soc.,2013,90(10):1 751-1 759.
[15]PRIMIKYRI A,MAZZONE G,LEKKA C,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]ZDYB A,KRAWCZYK S.Characterization of adsorption and electronic excited states of quercetin on titanium dioxide nanoparticles[J].Spectrochim.Acta A,2016,157(2):197-203.
[17]SAITO T,KAWAKAMI T,YAMANAKA S,et al.Computational study of catalytic reaction of quercetin 2,4-dioxygenase[J].J.Phys.Chem.B,2015,119(23):6 952-6 962.
[18]SIMKOVITCH R,HUPPERT D.Excited-state intra molecular proton transfer of the natural product quercetin[J].J.Phys.Chem.B,2015,119(12):10 244-10 251.
[19]DEHGHAN G,KHOSHKAM Z.Tin(Ⅱ)-quercetin complex:synthesis,spectral characterisation and antioxidant activity[J].Food Chem.,2012,131(2):422-426.
[20]RAVICHANDRAN R,RAJENDRAN M,DEVAPIRIAM D.Structural characterization and physicochemical properties of quercetin-Pb complex[J].J.Coord.Chem.,2014,67(8):1449-1462.
[21]AHMEDOVA A,PARADOWSKA K,WAWER I.1HNMR,13CNMR and dft giao study of quercetin and its complex with Al(Ⅲ)in solid state[J].J.Inorg.Biochem.,2012,110(1):27-35.
[22]KIM M,PARK Y,CHO S,et al.Synthesis of alkyl quercetin derivatives[J].J.Korean Soc.Appl.Bi.,2015,58(3):1-6.
[23]KARIMOVA E R,BALTINA L A,SPIRIKHIN L V,et al.Synthesis and antioxidant activity of quercetin ethers[J].Chem.Nat.Compd.,2015,51(5):851-855.
[2]MURAKAMI A,ASHIDA H,TERAO J,et al.Multitargeted cancer prevention by quercetin[J].Cancer Lett.,2008,269(2):315-325.
[3]DAJA F.Life or death:neuroprotective and anticancer effects of quercetin[J].J.Ethnopharmacol.,2012,143(2):383-396.
[4]EDWARDS R L,LYON T,LITWIN S E,et al.Quercetin reduces blood pressure in hypertensive subjects[J].J.Nutr.,2007,137(11):2 405-2 411.
[5]PEREZ-VIZCAINO F,DUARTE J,JIMENEZ R,et al.Antihypertensive effects of the flavonoid quercetin[J].Pharmacol.Rep.,2009,61(1):67-75.
[6]GRANDE F,PARISI O I,MORDOCCO R A,et al.Quercetin derivatives as novel antihypertensive agents:synthesis and physiological characterization[J].Eur.J.Pharm.Sci.,2016,82(2):161-170.
[7]GANESAN S,FARIS A N,COMSTOCK A T,et al.Quercetin inhibits rhinovirus replication in vitro and in vivo[J].Antivir.Res.,2012,94(3):258-271.
[8]BOOTS A W,HAENEN G R M M,BAST A.Health effects of quercetin:from antioxidant to nutraceutical[J].Eur.J.Pharmacol.,2008,585(2/3):325-337.
[9]VENGADESHPRABHU K,SOMASUNDARAM A,RAJARAJAN A T,et al.Molecular targets of quercetin with anti-inflammatory properties in atopic dermatitis[J].Drug Discov.Today,2016,21(4):632-639.
[10]OSORIO E,PREZ E G,ARECHE C,et al.Why is quercetin a better antioxidant than taxifolin?Theoretical study of mechanisms involving activated forms[J].J.Mol.Model,2013,19(9):2 165-2 172.
[11]GUPTA A,BIRHMAN K,RAHEJA I,et al.Quercetin:a wonder bioflavonoid with therapeutic potential in disease management[J].Asian Pac.J.Trop.Med.,2016,6(3):248-252.
[12]MUOZ V A,FERRARI G V,SANCHO M I,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 Wei-you,SUN Cui-xia,MAO Li-ke,et al.The biological activities,chemical stability,metabolism and delivery systems of quercetin:a review[J].Trends.Food Sci.Tech.,2016,56(1):21-38.
[14]MAININI F,CONTINI A,NAVA D,et al.Synthesis,molecular characterization and preliminary antioxidant activity evaluation of quercetin fatty esters[J].J.Am.Chem.Soc.,2013,90(10):1 751-1 759.
[15]PRIMIKYRI A,MAZZONE G,LEKKA C,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]ZDYB A,KRAWCZYK S.Characterization of adsorption and electronic excited states of quercetin on titanium dioxide nanoparticles[J].Spectrochim.Acta A,2016,157(2):197-203.
[17]SAITO T,KAWAKAMI T,YAMANAKA S,et al.Computational study of catalytic reaction of quercetin 2,4-dioxygenase[J].J.Phys.Chem.B,2015,119(23):6 952-6 962.
[18]SIMKOVITCH R,HUPPERT D.Excited-state intra molecular proton transfer of the natural product quercetin[J].J.Phys.Chem.B,2015,119(12):10 244-10 251.
[19]DEHGHAN G,KHOSHKAM Z.Tin(Ⅱ)-quercetin complex:synthesis,spectral characterisation and antioxidant activity[J].Food Chem.,2012,131(2):422-426.
[20]RAVICHANDRAN R,RAJENDRAN M,DEVAPIRIAM D.Structural characterization and physicochemical properties of quercetin-Pb complex[J].J.Coord.Chem.,2014,67(8):1449-1462.
[21]AHMEDOVA A,PARADOWSKA K,WAWER I.1HNMR,13CNMR and dft giao study of quercetin and its complex with Al(Ⅲ)in solid state[J].J.Inorg.Biochem.,2012,110(1):27-35.
[22]KIM M,PARK Y,CHO S,et al.Synthesis of alkyl quercetin derivatives[J].J.Korean Soc.Appl.Bi.,2015,58(3):1-6.
[23]KARIMOVA E R,BALTINA L A,SPIRIKHIN L V,et al.Synthesis and antioxidant activity of quercetin ethers[J].Chem.Nat.Compd.,2015,51(5):851-855.