一锅煮法由芦丁合成槲皮素五丙酸酯
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摘要
采用一锅煮法由芦丁直接合成槲皮素酯。以芦丁为原料,浓硫酸作催化剂,65℃与丙酸酐反应,TLC板监测反应完毕,过滤、氯仿/甲醇重结晶。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1760.0cm~(-1),酯羰基峰明显增强,νc-o位于1240.0cm~(-1)、变宽增强;~1H-NMR中槲皮素的3-OH、5-OH、7-OH、3′-OH、4′-OH上面的氢全部消失,说明与丙酸酐发生了酯化反应,同时,出现五组丙酰基的甲基峰和亚甲基峰;MS中583.1为槲皮素五丙酸酯的分子离子峰。芦丁与丙酸酐反应可以得到槲皮素五丙酸酯。
The one-pot procedure was use to prepare the quercetin ester from rutin directly. The product was synthesized at 65 °C with rutin and propionic anhydride as raw materials and the concentrated sulfuric acid as catalyst. During the process, the reaction was monitored by TLC plate and the filtered products was recrystallized from the mixture of chloroform and methanol. The strength of the peak of ν-OHin IR decreased significantly which indicated that the five hydroxyl groups of quercetin had reacted. In addition, the strength of the peak of the νc=olocated at 1760.0cm~(-1)increased obviously. The width of peak of νc-olocated at 1240.0cm~(-1)was wider and the strength increased. Besides, all the hydrogens of 3-OH, 5-OH, 7-OH,3'-OH, 4'-OH of quercetin in ~1H-NMR disappeared which indicated that the propionic anhydride had reacted with quercetin by esterification reac-tion. Meanwhile, the five groups of methyl and methylene peaks of propionyl appeared. Moreover, the molecular ion peak located at 583.1 of quercetin penta-acrylate was found in MS. The quercetin penta-acrylate could be synthesized by the reaction between rutin with propionic anhydride.
The one-pot procedure was use to prepare the quercetin ester from rutin directly. The product was synthesized at 65 °C with rutin and propionic anhydride as raw materials and the concentrated sulfuric acid as catalyst. During the process, the reaction was monitored by TLC plate and the filtered products was recrystallized from the mixture of chloroform and methanol. The strength of the peak of ν-OHin IR decreased significantly which indicated that the five hydroxyl groups of quercetin had reacted. In addition, the strength of the peak of the νc=olocated at 1760.0cm~(-1)increased obviously. The width of peak of νc-olocated at 1240.0cm~(-1)was wider and the strength increased. Besides, all the hydrogens of 3-OH, 5-OH, 7-OH,3'-OH, 4'-OH of quercetin in ~1H-NMR disappeared which indicated that the propionic anhydride had reacted with quercetin by esterification reac-tion. Meanwhile, the five groups of methyl and methylene peaks of propionyl appeared. Moreover, the molecular ion peak located at 583.1 of quercetin penta-acrylate was found in MS. The quercetin penta-acrylate could be synthesized by the reaction between rutin with propionic anhydride.
引文
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[19]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] P MARION, B BERNELA, A PICCIRILLI, et al. Sustainable chemistry:how to produce better and more from less[J]. Green Chemistry, 2017, 19(21):4973~4989.
[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):5074~5091.
[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,2013,90:1751~1759.
[23] PAOLA D A, BARBARA D M, SONIA G, et al. Quercetin derivatives as potent inducers of selective cytotoxicity in glioma cells[J]. European Journal of Pharmaceutical Sciences,2017,101:56~65.
[24] RON SIMKOVITCH, DAN HUPPERT. Excited-State Intramolecular Proton Transfer of the Natural Product Quercetin[J].J.Phys. Chem. B,2015,119(32):10244~10251.
[25] GHOLAMREZA D, ZAHRA K. Tin(II)-Quercetin Complex:Synthesis, Spectral Characterisation And Antioxidant Activity[J].Food Chemistry,2012,131(2):422-~426.
[26] AVICHANDRAN R, RAJENDRAN M, DEVAPIRIAM D. Structural Characterization And Physicochemical Properties Of Quercetin-Pb Complex[J]. Journal of Coordination Chemistry,2014,67(8):1449~1462.
[27] ANIFE A, KATARZYNA P, IWONA W. 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.
[28] KIM MIHYANG,PARK YOUNGRONG,CHO SOOYOUNG, et al.Synthesis of alkyl quercetin derivatives[J].Journal of the Korean Society for Applied Biological Chemistry,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].Chemistry of Natural Compounds, 2015,51(5):851~855.
[2] JAN A T, KAMLI M R, MURTAZA I, et al.Dietary覲avonoid quercetin and associated health bene覱ts an overview[J]. Food Rev Int.,2010,26:302~317.
[3] AKIRA M, HITOSHI A, JUNJI T. 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] DHARAMBIR K, SONAM M, KATRIN S, et al. Molecular mechanisms of action of quercetin in cancer:recent advances[J]. Tumor Biol,2016,37:12927~12939.
[6] EDWARDS RL, LYON T, LITWIN SE, et al. Quercetin reduces blood pressure in hypertensive subjects[J].J Nutr,2007,137(11):2405~2411.
[7] SHYAMALA G, ANDREA N F, ADAM T C, et al. Quercetin Inhibits Rhinovirus Replication In Vitro And InVivo[J]. Antiviral Research, 2012, 94(3):258~271.
[8] AGNES W B, GUIDO R M, ALT BAST. Health effects of quercetin:From antioxidant to nutraceutical[J].European Journal of Pharmacology, 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]. Discovery, Tod, Drugay, 2016,21(4):632~639.
[10] EDISON OSORIO, EDWIN G. PREZ, 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.
[11] ALKA G, KAVITA B, INDIRA R, et al. Quercetin:A wonder bioflavonoid with therapeutic potential in disease management[J].Asian Pacific Journal of Tropical Disease, 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] HE HUANG,QI JIA,JINGUI MA, et al. Discovering novel quercetin-3-O-amino acid-esters as a new class of Src tyrosine kinase inhibitors[J].European Journal of Medicinal Chemistry, 2009, 44:1982~1988.
[14] WANG XIAO LAN, DUAN YU, Anti-platelet aggregation mechanisms of quercetin fatty acid ester[J].Journal of Chemical and Pharmaceutical Research,2014,6(6):599~602.
[15] NATASA M, MARTIN S, MARCELA K, et al. Modulation of BV-2 microglia functions by novel quercetin pivaloyl ester[J].Neurochemistry International, 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]. MEDICINAL,CHEMISTRY,RESEARCH,(Med Chem Res).2017, 26:461~472.
[18] TAHSIN F K, MARIA V C, MIN-SUNG L E, et al. Rational design and structure-activity relationship studies of quercetinamino acid hybrids targeting the anti-apoptotic protein Bcl-xL[J].Organic Biomolecular Chemistry,(Org. Biomol. Chem.),2017, 15:7956~7976.
[19]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] P MARION, B BERNELA, A PICCIRILLI, et al. Sustainable chemistry:how to produce better and more from less[J]. Green Chemistry, 2017, 19(21):4973~4989.
[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):5074~5091.
[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,2013,90:1751~1759.
[23] PAOLA D A, BARBARA D M, SONIA G, et al. Quercetin derivatives as potent inducers of selective cytotoxicity in glioma cells[J]. European Journal of Pharmaceutical Sciences,2017,101:56~65.
[24] RON SIMKOVITCH, DAN HUPPERT. Excited-State Intramolecular Proton Transfer of the Natural Product Quercetin[J].J.Phys. Chem. B,2015,119(32):10244~10251.
[25] GHOLAMREZA D, ZAHRA K. Tin(II)-Quercetin Complex:Synthesis, Spectral Characterisation And Antioxidant Activity[J].Food Chemistry,2012,131(2):422-~426.
[26] AVICHANDRAN R, RAJENDRAN M, DEVAPIRIAM D. Structural Characterization And Physicochemical Properties Of Quercetin-Pb Complex[J]. Journal of Coordination Chemistry,2014,67(8):1449~1462.
[27] ANIFE A, KATARZYNA P, IWONA W. 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.
[28] KIM MIHYANG,PARK YOUNGRONG,CHO SOOYOUNG, et al.Synthesis of alkyl quercetin derivatives[J].Journal of the Korean Society for Applied Biological Chemistry,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].Chemistry of Natural Compounds, 2015,51(5):851~855.