芦丁一锅煮合成槲皮素五乙酸酯
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摘要
以芦丁为原料,浓硫酸作为催化剂,65℃与乙酸酐反应,薄层色谱法(TLC)板监测反应完毕,过滤,氯仿/甲醇重结晶,可以得到槲皮素五乙酸酯。结果显示: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1 776.0cm~(-1),酯羰基峰明显增强,νC—O位于1 199.0cm~(-1)、变宽增强;1 H 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m/z:513.1为槲皮素五乙酸酯的分子离子峰。
Quercetin pentaacetat was synthesized at 65 ℃ with rutin and acetic anhydride as raw materials and concentrated sulfuric acid as catalyst.The reaction was detected by thin layer chromatography(TLC)and the filtered product was recrystallized from the mixture of chloroform and methanol.The results showed that five hydroxyls of quercetin had been exchanged because the strength of the peak of ν—OHin IR spectrum decreased significantly.It also can be found that the strength of the peak of νC=O at 1 776 cm~(-1) increased obviously.For the peak of νC—Oat 1 199.0 cm~(-1),its width broaden and its strength increased.The hydrogen of hydroxyls(3-OH,5-OH,7-OH,3′-OH and 4′-OH)all disappeared in 1 H NMR spectrum,indicating the complete esterification with acetic anhydride.At the same time,five peaks of methyls of acetyl appeared,and the peaks of m/z:513.1 in MS is the molecular ion peak of quercetin pentaacetate.
Quercetin pentaacetat was synthesized at 65 ℃ with rutin and acetic anhydride as raw materials and concentrated sulfuric acid as catalyst.The reaction was detected by thin layer chromatography(TLC)and the filtered product was recrystallized from the mixture of chloroform and methanol.The results showed that five hydroxyls of quercetin had been exchanged because the strength of the peak of ν—OHin IR spectrum decreased significantly.It also can be found that the strength of the peak of νC=O at 1 776 cm~(-1) increased obviously.For the peak of νC—Oat 1 199.0 cm~(-1),its width broaden and its strength increased.The hydrogen of hydroxyls(3-OH,5-OH,7-OH,3′-OH and 4′-OH)all disappeared in 1 H NMR spectrum,indicating the complete esterification with acetic anhydride.At the same time,five peaks of methyls of acetyl appeared,and the peaks of m/z:513.1 in MS is the molecular ion peak of quercetin pentaacetate.
引文
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[20]Marion P,Bernela B,Piccirilli A,et al.Sustainable Chemistry:How to Produce Better and More From less?[J]Green Chem,2017,19(21):4 973-4 989.
[21]Elisavet D B,Heiko L,Pasquale M,et al.Synthesis of Nano-and Microstructures from Proanthocyanidins,Tannic Acid and Epigallocatechin-3-O-gallate for Active Delivery[J].Green Chem,2017,19(21):5 074-5 091.
[22]Francesca M,Alessandro C,Donatella N,et al.Synthesis,Molecular Characterization and Preliminary Antioxidant Activity Evaluation of Quercetin Fatty Esters[J].J Am Oil Chem Soc,2013,90:1 751-1 759.
[23]Paola D A,Barbara D M,Sonia G,et al.Quercetin Derivatives as Potent Inducers of Selective Cytotoxicity in Glioma Cells[J].Eur J Pharm Sci,2017,101:56-65.
[24]Ron S,Dan H.Excited-state Intramolecular Proton Transfer of the Natural Product Quercetin[J].JPhys Chem B,2015,119(32):10 244-10 251.
[25]Gholamreza D,Zahra K.Tin(Ⅱ)-quercetin Complex:Synthesis,Spectral Characterisation and Antioxidant Activity[J].Food Chem,2012,131(2):422-426.
[26]Ravichandran R,Rajendran M,Devapiriam D.Structural Characterization And Physicochemical Properties of Quercetin-Pb Complex[J].J Coord Chem,2014,67(8):1 449-1 462.
[27]Anife A,Katarzyna P,Iwona W.1 H,13 C MASNMR and DFT GIAO Study of Quercetin and Its Complex with Al(Ⅲ)in Solid State[J].J Inorg Biochem,2012,110:27-35.
[28]Mihyang K,Youngrong P,Sooyoung C,et al.Synthesis of Alkyl Quercetin Derivatives[J].J Korean Soc Appl Biol Chem,2015,58(3):343-348.
[29]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]Jan A T,Mli K,Murtaza I,et al.Dietary Avonoid Quercetin and Associated Health Benefits an Overview[J].Food Rev Int,2010,26:302-317.
[3]Akira M,Hitoshi A,Junji T.Multitargeted Cancer Prevention by Quercetin[J].Cancer Lett,2008,269(2):315-325.
[4]Federico D,Or D L.Neuroprotective and Anticancer Effects of Quercetin[J].J Ethnopharmacology,2012,143(2):383-396.
[5]Dharambir K,Sonam M,Katrin S,et al.Molecular Mechanisms of Action of Quercetin in Cancer:Recent Advances[J].Tumor Biol,2016,37:12 927-12 939.
[6]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.
[7]Shyamala G,Andrea N F,Adam T C,et al.Quercetin Inhibits Rhinovirus Replication In vitro and In vivo[J].Antiviral Res,2012,94(3):258-271.
[8]Agnes W B,Guido R M,Alt B.Health Effects of Quercetin:From Antioxidant to Nutraceutical[J].Eur J Pharmacol,2008,585(2-3):325-337.
[9]Vengadeshprabhu K,Somasundaram A,Rajarajan AT,et al.Molecular Targets of Quercetin with Antiinflammatory Properties in Atopic Dermatitis[J].Drug Discovery Today,2016,21(4):632-639.
[10]Edison O,Edwin P G,Carlos A,et al.Why is Quercetin a Better Antioxidant than Taxifolin?Theoretical Study of Mechanisms Involving Activated Forms[J].J Mol Model,2013,19:2 165-2 172.
[11]Alka G,Kavita B,Indira R,et al.Quercetin:AWonder Bioflavonoid with Therapeutic Potential in Disease Management[J].Asian Pac J Trop Dis,2016,6(3):248-252.
[12]Vanesa A M,Gabriela V F,Matias I S,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]Huang H E,Jia Q I,Jingui M,et al.Discovering Novel Quercetin-3-O-amino Acid-esters as a New Class of Src Tyrosine Kinase Inhibitors[J].Eur JMed Chem,2009,44:1 982-1 988.
[14]Wang X L,Duan Y.Anti-platelet Aggregation Mechanisms of Quercetin Fatty Acid Ester[J].JChem Pharm Res,2014,6(6):599-602.
[15]Natasa M,Martin S,Marcela K,et al.Modulation of BV-2Microglia Functions by Novel Quercetin Pivaloyl Ester[J].Neurochem Int,2015,90:246-254.
[16]Satvir S L,Ziaullah Z,Vasantha H P,et al.Novel Quercetin-3-O-glucoside Eicosapentaenoic Acid Ester,Ameliorates Inflammation and Hyperlipidemia[J].Inflammopharmacology,2015,23:173-185.
[17]Panagiotis T N,Paraskevi T,Anastasios P,et al.Novel Polyfunctional Esters of Ibuprofen and Ketoprofen with Hypolipidemic,Lipoxygenase Inhibitory and Enhanced Anti-inflammatory Activity[J].Med Chem Res 2017,26:461-472.
[18]Kellica T F,Chatziathanasiadou M V,Lee M S,et al.Rational Design and Structure-activity Relationship Studies of Quercetin-amino Acid Hybrids Targeting the Anti-apoptotic Protein Bcl-xL[J].Org Biomol Chem,2017,15:7 956-7 976.
[19]Zhuang S K,He Y,Zhang C J,et al.One-pot Synthesis of Phenyl-benzylketone Thiosemicarbazone[J].Chin J Org Chem,2010,30(2):299-302(in Chinese).(庄肃凯,贺云,张创军等,一锅煮法合成苯基苄基酮缩氨基硫脲[J].有机化学,2010,30(2):299-302.)
[20]Marion P,Bernela B,Piccirilli A,et al.Sustainable Chemistry:How to Produce Better and More From less?[J]Green Chem,2017,19(21):4 973-4 989.
[21]Elisavet D B,Heiko L,Pasquale M,et al.Synthesis of Nano-and Microstructures from Proanthocyanidins,Tannic Acid and Epigallocatechin-3-O-gallate for Active Delivery[J].Green Chem,2017,19(21):5 074-5 091.
[22]Francesca M,Alessandro C,Donatella N,et al.Synthesis,Molecular Characterization and Preliminary Antioxidant Activity Evaluation of Quercetin Fatty Esters[J].J Am Oil Chem Soc,2013,90:1 751-1 759.
[23]Paola D A,Barbara D M,Sonia G,et al.Quercetin Derivatives as Potent Inducers of Selective Cytotoxicity in Glioma Cells[J].Eur J Pharm Sci,2017,101:56-65.
[24]Ron S,Dan H.Excited-state Intramolecular Proton Transfer of the Natural Product Quercetin[J].JPhys Chem B,2015,119(32):10 244-10 251.
[25]Gholamreza D,Zahra K.Tin(Ⅱ)-quercetin Complex:Synthesis,Spectral Characterisation and Antioxidant Activity[J].Food Chem,2012,131(2):422-426.
[26]Ravichandran R,Rajendran M,Devapiriam D.Structural Characterization And Physicochemical Properties of Quercetin-Pb Complex[J].J Coord Chem,2014,67(8):1 449-1 462.
[27]Anife A,Katarzyna P,Iwona W.1 H,13 C MASNMR and DFT GIAO Study of Quercetin and Its Complex with Al(Ⅲ)in Solid State[J].J Inorg Biochem,2012,110:27-35.
[28]Mihyang K,Youngrong P,Sooyoung C,et al.Synthesis of Alkyl Quercetin Derivatives[J].J Korean Soc Appl Biol Chem,2015,58(3):343-348.
[29]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.