典型黄烷酮、黄酮的绿色合成新方法研究
摘要
本文以2'-羟基查耳酮为原料,分别以吡啶-水和吡啶-水-I2为催化环化体系,在加热或光照条件下合成了典型的黄烷酮和黄酮。
在吡啶-水体系的加热反应中,研究了加热时间、温度、溶剂比等因素对黄烷酮产率的影响,通过单因素实验和正交实验得出了在此反应体系下的最佳反应条件为:时间为1小时,温度为90℃,吡啶-水体积百分比为40:60。推测了反应历程,并对比了其它溶剂体系对黄烷酮产率的影响。
在吡啶-水体系的光照反应中,研究了光照时间、溶剂比、光照强度对合成黄烷酮产率的影响,得出了光照时间为8小时、吡啶:水体积百分为40:60、产率与光照强度无关等的最佳反应条件。
在吡啶-水体系加热一段时间后加入I2合成黄酮的实验中,考察了反应时间、催化剂用量等因素对黄酮产率的影响,反应时间为8小时,催化剂量为I_2:查耳酮摩尔质量比=1:1的单因素试验条件。
本文研究的催化环化体系,具有反应时间短、产率高,无副产物、操作简单、溶剂易于回收等优点。产物结构均经紫外、红外、质谱、核磁验证。
In this paper ,the flavanones have been synthesized from 2'-hydroxychalcone in the prence of mixed solvent pyridine-water by heating or visibal irradiation, and the flavones have also been synthesized from 2'-hydroxychalcone in the prence of pyridine -water-iodin by heating .
In the reaction of pyridine-water phase by heating , the effects of reaction time,reaction temperature and solvent ratio was discussed through single-factor experiment and orthogonal experiment. The optimized reaction were : reactoion temperature 90℃,reaction time 1h and solvent ratio 40%:60%.
In the reaction of pyridine-water phase on visible irradiation, the effects of reaction time, light intensity and solvent ratio was discussed through single-factor experiment. The optimized reaction were : reaction time 8h solvent ratio 40%:60%.The quantum yields of flavanone are of independent of light intensity
In the approach of the synthesis of flavone in pyridine-water-iodine by heating , the effects of reaction time, amount of catalyst was discussed . The optimized reaction were : reaction time 8h , 2'-hydroxychalcone: iodine=1:1(molar ratio).
The synthesis methods of flavanones have adventages of short reaction time ,good yields,no by-product and ease operation .The structures of 2'-hydroxychalcone ,flavanone and flavorne were confirmed by UV, IR, H-NMR and elemental analysis.
在吡啶-水体系的加热反应中,研究了加热时间、温度、溶剂比等因素对黄烷酮产率的影响,通过单因素实验和正交实验得出了在此反应体系下的最佳反应条件为:时间为1小时,温度为90℃,吡啶-水体积百分比为40:60。推测了反应历程,并对比了其它溶剂体系对黄烷酮产率的影响。
在吡啶-水体系的光照反应中,研究了光照时间、溶剂比、光照强度对合成黄烷酮产率的影响,得出了光照时间为8小时、吡啶:水体积百分为40:60、产率与光照强度无关等的最佳反应条件。
在吡啶-水体系加热一段时间后加入I2合成黄酮的实验中,考察了反应时间、催化剂用量等因素对黄酮产率的影响,反应时间为8小时,催化剂量为I_2:查耳酮摩尔质量比=1:1的单因素试验条件。
本文研究的催化环化体系,具有反应时间短、产率高,无副产物、操作简单、溶剂易于回收等优点。产物结构均经紫外、红外、质谱、核磁验证。
In this paper ,the flavanones have been synthesized from 2'-hydroxychalcone in the prence of mixed solvent pyridine-water by heating or visibal irradiation, and the flavones have also been synthesized from 2'-hydroxychalcone in the prence of pyridine -water-iodin by heating .
In the reaction of pyridine-water phase by heating , the effects of reaction time,reaction temperature and solvent ratio was discussed through single-factor experiment and orthogonal experiment. The optimized reaction were : reactoion temperature 90℃,reaction time 1h and solvent ratio 40%:60%.
In the reaction of pyridine-water phase on visible irradiation, the effects of reaction time, light intensity and solvent ratio was discussed through single-factor experiment. The optimized reaction were : reaction time 8h solvent ratio 40%:60%.The quantum yields of flavanone are of independent of light intensity
In the approach of the synthesis of flavone in pyridine-water-iodine by heating , the effects of reaction time, amount of catalyst was discussed . The optimized reaction were : reaction time 8h , 2'-hydroxychalcone: iodine=1:1(molar ratio).
The synthesis methods of flavanones have adventages of short reaction time ,good yields,no by-product and ease operation .The structures of 2'-hydroxychalcone ,flavanone and flavorne were confirmed by UV, IR, H-NMR and elemental analysis.
引文
[1] Hironoric T, Mosaml S. Comparative study on the antibacterial activity of phytochemical flavanones against methicillin resistant Staphylococcus aureus. J. Ethnopharmacol, 1996, 50(1):27~34.
[2] Muthiah N S, Viswanthan S. Anti-inflammatory activity of flavone and its methoxy derivatives-a structive activity study. Indian J. Pharm.Sct., 1993, 55(5):180~183.
[3] Konoshima T, Takasaki M. Antibacterials aids agents, 10. Acacetin-T-O-β-D-galactopyr–anoside, an anti-HIV principle from Chrysanthemum morifolium and a structure activity correlation with some related flavonoids. Shoyakugaku Zasshi, 1989, 43(2):135~141.
[4] Hu C Q, Chenks S Q. Studies on inhibitors of skin tumor promotion (V), Inhibitory effects of flavonoids of Epstein Barrvirus activation II. J. Nat. Prod., 1994, 57(1):42~51.
[5] Cao G H, Sofic E. Antimutagenic effects of flavonoids, chalcones and structurally related compounds on the activity of 2-amino-3-methyimidazol[4,5-f] quinoline (IQ) and other heterocyclic amine mutagehs from cooked food. Ronaldl Free Razdical Biol. Med., 1997, 22(5):749~760.
[6] Edenharder R, Petersodorff V I. Antioxidant and prooxidant behavior of flavonoids: structure- activity relationships. Mutat Res., 1993, 287(2):261~274.
[7] HuiI K M, Wang X H, Xue H. Interaction of flavones from the rodes of scutellaria baicalensis with the benzodiazepine site. Planta Med, 2000,66(1):91~92.
[8] Rammanthan R, Das N P, Tan C H. Inhibitory effect of 2-hydroxy chalone and other flavoids on human cancer cell proliferation. Int J Oncol, 1993,3(1):115~119.
[9] Shahidi F, Wanasandan U. Stablization canola oil by matralantioxidants. 1994,558:301~304.
[10]胡利红,覃章兰,李超.黄烷酮化合物的合成研究进展,化学通报, 2003,1:12~18,32.
[11] Chandrasekhar S, Vijeender K, Venkatram Reddy K. New synthesis of flavanones catalyzed by L-proline. Tetrahedron Letters, 2005, 46:6991~6993
[12] Saravanamurugan S, Palanichamy M. Arabindoo B et al. Solvent free synthesis of chalcone and flavanone overzinc oxide supported metal oxide catalysts. Catalysis Communications, 2005, 6:399~403.
[13] Choudary B M, Ranganath K V S, Yadav J, et al. Synthesis of flavanones using nanocrystalline MgO.Tetrahedron Letters, 2005, 46:1369~1371.
[14] Liu Z, Corte′s-Concepcio′n J A, Mustian M et al.Effect of basic properties of MgO on the heterogeneoussynthesis of flavanone. Applied Catalysis A: General, 2006,302:232~236.
[15]吴君臣.黄酮及噻唑类衍生物的合成研究.中国学位论文数据库硕士论文,苏州大学2005
[16] Wang Xueguang, Cheng Soofin. Solvent-free synthesis of flavanones over aminopropyl -functionalized SBA-15.Catalysis Communications, 2006, 7: 689~695.
[17] Aitmambetov A, Kubzheterova A. An improved method for the synthesis of flavanones. Translated from Bioorganicheskaya Khimiya, 2002,28(2):189~190.
[18] AitmambetovA, Da limov D, Kubzheterova A. Synthetic analogs of natural flavolignans XV Isomerization of 2-hydroxychalcones into flavanones using triethylamine. Chemistry of Natural Compounds, 2001, 37(5):
[19] Almed N, Ansari W H.An improved procedure for the isomerisation of 2-hydroxysubstituted chalcones to flavanones using silica supported-BiCl3 under dry Conditions. J.Chem.Research, 2003, 5:572~573.
[20] Tanaka K, Sugino T. Efficient conversion of 2’-hydroxychalcones intoflavanones and flavanols in a water suspension medium.Green Chemistry, 2001, 3: 133~134.
[21]王灿.黄酮类化合物的合成.中国学位论文数据库硕士论文,苏州大学,2006:21~22.
[22]汤立军,张淑芬.黄酮化合物的合成新方法.有机化学, 2004,24(8):882~889.
[23] Bose G, Mondal E, Khsn A T, et al. An environmentally benign synthesis of aurones and flavones from 2’-acetoxychalcones using n-tetrabutylammonium tribromide.Tetrahedron Lett, 2001,42:8907
[24] Gupta M, Paul A, Gupta R, et al. A rapid method for the cyclization of 2’-hydroxychalcones into flavones organic preparations and procedures. Internation gal., 2000,32(3):280~283.
[25] Alis M, Iqpal J, Hyas M. A convenient synthesis of 5-hydroxyflavones. Chem Ind., 1985,8:2760
[26] Fatma W, Iqbal J, Ismail H, et al. A novel reagent system for dehydrogenation of flavanone to flavone. Chem Ind., 1979, 32(2):315.
[27] Iquaql J, Fatama W, Shaida W A, et al. A one-step synthesis of 3-iodoflavones from 2’-hydroxychalcones. J Chem Res., 1982, 92:
[28]李庚新,吕以仙,刘俊义.科学通报, 1985,30(12):953~955.
[29] Silva A M S, Pinto D C G A, Cavaleiro J A A. Synthesis and reactivity of styrylchromones. Heterocycl Chem., 1996,33:1887.
[30] Lokhande P D, Sakate S S, Tasande K N, et al. Dimethylsulfoxide-iodine catalysed deprotection of 2’-allyloxychalcones synthesis of flavones. Tetrahedron Letters, 2005,46:1573~1574.
[31] Linuma M, Iwashimam K, Mstsura S. Synthetic studies on flavone derivatives.XIV. Synthesis of 2’,4’,5’-trioxygenated flavones. Chem Pharm Bull., 1984,32(12):4935~4941.
[32] Hossia M A. Synthesis of genkwanin. India J Chem., 1997, 36C:00927~00928.
[33] Ahmed N, Ali H, Vanlier J E. Silica gel supported InBr3 and InCl3: new catalysts for the facile and rapid oxidation of 2’-hydroxychalcones and flavanones to their corresponding flavones under solvent freeconditions. Tetrahedron Letters, 2005,46:253~256.
[34] Maki Y, Shimada K, Sako M, et al. Photo-oxidative cyclisation of 2’-hydeoxychalcones leading to flavone induced by heterocycle N-Oxides.Tebrahedron,1988,44(11):3187~3194.
[35] Pandey G, Krishna A, Kumaraseamy G. Photosensitized (set) conversion of 2’-hydroxychalcones to flavonoids a probable biogenetic pathway. Tetrahed lett., 1987,28(39):4615~4616.
[36] Zivko S, Ibro T. Blectrochemical transformations of 2’-hydroxychalcones into flavanoids. Tetrahed Lett., 1986,27(3):407~408.
[2] Muthiah N S, Viswanthan S. Anti-inflammatory activity of flavone and its methoxy derivatives-a structive activity study. Indian J. Pharm.Sct., 1993, 55(5):180~183.
[3] Konoshima T, Takasaki M. Antibacterials aids agents, 10. Acacetin-T-O-β-D-galactopyr–anoside, an anti-HIV principle from Chrysanthemum morifolium and a structure activity correlation with some related flavonoids. Shoyakugaku Zasshi, 1989, 43(2):135~141.
[4] Hu C Q, Chenks S Q. Studies on inhibitors of skin tumor promotion (V), Inhibitory effects of flavonoids of Epstein Barrvirus activation II. J. Nat. Prod., 1994, 57(1):42~51.
[5] Cao G H, Sofic E. Antimutagenic effects of flavonoids, chalcones and structurally related compounds on the activity of 2-amino-3-methyimidazol[4,5-f] quinoline (IQ) and other heterocyclic amine mutagehs from cooked food. Ronaldl Free Razdical Biol. Med., 1997, 22(5):749~760.
[6] Edenharder R, Petersodorff V I. Antioxidant and prooxidant behavior of flavonoids: structure- activity relationships. Mutat Res., 1993, 287(2):261~274.
[7] HuiI K M, Wang X H, Xue H. Interaction of flavones from the rodes of scutellaria baicalensis with the benzodiazepine site. Planta Med, 2000,66(1):91~92.
[8] Rammanthan R, Das N P, Tan C H. Inhibitory effect of 2-hydroxy chalone and other flavoids on human cancer cell proliferation. Int J Oncol, 1993,3(1):115~119.
[9] Shahidi F, Wanasandan U. Stablization canola oil by matralantioxidants. 1994,558:301~304.
[10]胡利红,覃章兰,李超.黄烷酮化合物的合成研究进展,化学通报, 2003,1:12~18,32.
[11] Chandrasekhar S, Vijeender K, Venkatram Reddy K. New synthesis of flavanones catalyzed by L-proline. Tetrahedron Letters, 2005, 46:6991~6993
[12] Saravanamurugan S, Palanichamy M. Arabindoo B et al. Solvent free synthesis of chalcone and flavanone overzinc oxide supported metal oxide catalysts. Catalysis Communications, 2005, 6:399~403.
[13] Choudary B M, Ranganath K V S, Yadav J, et al. Synthesis of flavanones using nanocrystalline MgO.Tetrahedron Letters, 2005, 46:1369~1371.
[14] Liu Z, Corte′s-Concepcio′n J A, Mustian M et al.Effect of basic properties of MgO on the heterogeneoussynthesis of flavanone. Applied Catalysis A: General, 2006,302:232~236.
[15]吴君臣.黄酮及噻唑类衍生物的合成研究.中国学位论文数据库硕士论文,苏州大学2005
[16] Wang Xueguang, Cheng Soofin. Solvent-free synthesis of flavanones over aminopropyl -functionalized SBA-15.Catalysis Communications, 2006, 7: 689~695.
[17] Aitmambetov A, Kubzheterova A. An improved method for the synthesis of flavanones. Translated from Bioorganicheskaya Khimiya, 2002,28(2):189~190.
[18] AitmambetovA, Da limov D, Kubzheterova A. Synthetic analogs of natural flavolignans XV Isomerization of 2-hydroxychalcones into flavanones using triethylamine. Chemistry of Natural Compounds, 2001, 37(5):
[19] Almed N, Ansari W H.An improved procedure for the isomerisation of 2-hydroxysubstituted chalcones to flavanones using silica supported-BiCl3 under dry Conditions. J.Chem.Research, 2003, 5:572~573.
[20] Tanaka K, Sugino T. Efficient conversion of 2’-hydroxychalcones intoflavanones and flavanols in a water suspension medium.Green Chemistry, 2001, 3: 133~134.
[21]王灿.黄酮类化合物的合成.中国学位论文数据库硕士论文,苏州大学,2006:21~22.
[22]汤立军,张淑芬.黄酮化合物的合成新方法.有机化学, 2004,24(8):882~889.
[23] Bose G, Mondal E, Khsn A T, et al. An environmentally benign synthesis of aurones and flavones from 2’-acetoxychalcones using n-tetrabutylammonium tribromide.Tetrahedron Lett, 2001,42:8907
[24] Gupta M, Paul A, Gupta R, et al. A rapid method for the cyclization of 2’-hydroxychalcones into flavones organic preparations and procedures. Internation gal., 2000,32(3):280~283.
[25] Alis M, Iqpal J, Hyas M. A convenient synthesis of 5-hydroxyflavones. Chem Ind., 1985,8:2760
[26] Fatma W, Iqbal J, Ismail H, et al. A novel reagent system for dehydrogenation of flavanone to flavone. Chem Ind., 1979, 32(2):315.
[27] Iquaql J, Fatama W, Shaida W A, et al. A one-step synthesis of 3-iodoflavones from 2’-hydroxychalcones. J Chem Res., 1982, 92:
[28]李庚新,吕以仙,刘俊义.科学通报, 1985,30(12):953~955.
[29] Silva A M S, Pinto D C G A, Cavaleiro J A A. Synthesis and reactivity of styrylchromones. Heterocycl Chem., 1996,33:1887.
[30] Lokhande P D, Sakate S S, Tasande K N, et al. Dimethylsulfoxide-iodine catalysed deprotection of 2’-allyloxychalcones synthesis of flavones. Tetrahedron Letters, 2005,46:1573~1574.
[31] Linuma M, Iwashimam K, Mstsura S. Synthetic studies on flavone derivatives.XIV. Synthesis of 2’,4’,5’-trioxygenated flavones. Chem Pharm Bull., 1984,32(12):4935~4941.
[32] Hossia M A. Synthesis of genkwanin. India J Chem., 1997, 36C:00927~00928.
[33] Ahmed N, Ali H, Vanlier J E. Silica gel supported InBr3 and InCl3: new catalysts for the facile and rapid oxidation of 2’-hydroxychalcones and flavanones to their corresponding flavones under solvent freeconditions. Tetrahedron Letters, 2005,46:253~256.
[34] Maki Y, Shimada K, Sako M, et al. Photo-oxidative cyclisation of 2’-hydeoxychalcones leading to flavone induced by heterocycle N-Oxides.Tebrahedron,1988,44(11):3187~3194.
[35] Pandey G, Krishna A, Kumaraseamy G. Photosensitized (set) conversion of 2’-hydroxychalcones to flavonoids a probable biogenetic pathway. Tetrahed lett., 1987,28(39):4615~4616.
[36] Zivko S, Ibro T. Blectrochemical transformations of 2’-hydroxychalcones into flavanoids. Tetrahed Lett., 1986,27(3):407~408.