黄酮及异黄酮类化合物的合成研究
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摘要
黄酮和异黄酮类化合物具有广泛而重要的生物活性和药理活性,例如抗癌,抗炎,抗肝脏毒性等。其化学合成研究受到普遍重视。近年来,随着铜催化的碳-氮偶联氨基化反应以及串联反应的广泛研究及报道,本课题组也采用铜催化串联缩合-环化反应合成了吡唑并[1, 5-a]喹啉和吡唑并[1, 5-a]吲哚类等化合物。鉴于此,我们探索利用铜催化的碳-氧键分子内环化反应来合成黄酮及异黄酮类化合物。
结果表明,以取代1-(2-卤素苯基)-丙烷-1, 3-二酮为原料,在[DMSO/K2CO3/130℃/8h]无金属催化的条件下,进行分子内环合反应得到17个黄酮类化合物。采用取代3-(2-卤素苯基)-3-氧-丙醛为原料,在[CuI/2-吡啶甲酸/K2CO3/DMF/135-140℃/20h]条件下,进行分子内环合反应得到了13个异黄酮类化合物。
Flavones and isoflavones are a group of naturally occurring compounds that widely distributed in the plant kingdom, and have been associated with a wide variety of biological and pharmaceutical activities, including antitumoral, antiviral, antiin?ammatory, antioxidant, hepatoprotective, and antithrombotic actions. Inspired by reports of Cu(I)-catalyzed intermolecular C-N coupling reaction, we use a novel method of Cu(I)-catalyzed intramolecular amination reaction to synthesize pyrazolo[1, 5-a]indole derivatives and pyrazolo[1, 5-a]quinoline derivatives. Based on the study, we are thinking about using a novel method of Cu(I)-catalyzed intramolecular C-O cyclization reaction to synthesize flavone and isoflavone derivatives.
As a result, we found that flavones were developed by intramolecular C-O cyclization reaction under the condition of [DMSO/K2CO3/130℃/8h] starting from 1-(o-halophenyl)-propane-1, 3-diones. And isoflavones were obtained by using commercially available copper (I) iodide as an effective catalyst under the condition of [CuI/2-picolinic acid/K2CO3/DMF/135-140℃/20h] starting from various 3-(2-halo phenyl)-3-oxopropanals.
结果表明,以取代1-(2-卤素苯基)-丙烷-1, 3-二酮为原料,在[DMSO/K2CO3/130℃/8h]无金属催化的条件下,进行分子内环合反应得到17个黄酮类化合物。采用取代3-(2-卤素苯基)-3-氧-丙醛为原料,在[CuI/2-吡啶甲酸/K2CO3/DMF/135-140℃/20h]条件下,进行分子内环合反应得到了13个异黄酮类化合物。
Flavones and isoflavones are a group of naturally occurring compounds that widely distributed in the plant kingdom, and have been associated with a wide variety of biological and pharmaceutical activities, including antitumoral, antiviral, antiin?ammatory, antioxidant, hepatoprotective, and antithrombotic actions. Inspired by reports of Cu(I)-catalyzed intermolecular C-N coupling reaction, we use a novel method of Cu(I)-catalyzed intramolecular amination reaction to synthesize pyrazolo[1, 5-a]indole derivatives and pyrazolo[1, 5-a]quinoline derivatives. Based on the study, we are thinking about using a novel method of Cu(I)-catalyzed intramolecular C-O cyclization reaction to synthesize flavone and isoflavone derivatives.
As a result, we found that flavones were developed by intramolecular C-O cyclization reaction under the condition of [DMSO/K2CO3/130℃/8h] starting from 1-(o-halophenyl)-propane-1, 3-diones. And isoflavones were obtained by using commercially available copper (I) iodide as an effective catalyst under the condition of [CuI/2-picolinic acid/K2CO3/DMF/135-140℃/20h] starting from various 3-(2-halo phenyl)-3-oxopropanals.
引文
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[2]龚金炎,张英,吴晓琴.黄酮类化合物抗病毒活性的研究进展[J].中草药, 2008, 39(4) : 623-627.
[3]陈丛瑾,黄克瀛,李德良等.植物中黄酮类化合物的提取方法研究概况[J].生物质化学工程, 2007, 41(3): 42-44.
[4]马长雨,杨悦武,郭治昕.微波萃取在中药提取和分析中的应用[J].中草药, 2004, 35(11): 7-10.
[5]张春秀,胡小玲,卢锦花等.双水相萃取法富集分离银杏叶浸取液的探讨[J].化学研究与应用, 2001, 13(6): 686-688.
[6]陈晓娟,周春山.酶法及半仿生法提取杜仲叶中绿原酸和黄酮[J].精细化工, 2006, 23(3): 257-259.
[7]于涛,钱和.膜分离技术在提取银杏叶黄酮类化合物中的应用[J].无锡轻工大学学报,2004, 23(6): 55-58.
[8] Gabor M. Flavonoids and bioflavinoids (ed. by Frakas L. et al). Elsevier, 1981. 363
[9] Haddad A. Q.; Venkateswaran V.; Viswanathan L. et al. Novel antiprolife-rative flavonoids induce cell cycle arrest in human prostate cancer cell lines [J]. Prostate Cancer Prostatic Dis., 2006, 9(1): 68-76.
[10]张延坤,马燕.大豆异黄酮的特性及其特殊生理功能[J].解放军预防医学杂志, 2003, 21(4) : 307-310.
[11] Naim M.; Gestetner B.; Bondi A. et al. Antioxidative and antihemolytic activities of soybean isoflavones [J]. J. Agric. Food Chem., 1976, 24(6): 1174-1177.
[12] Rebai B. A.; Wissem B.; Mohamed B. S. et al. Antioxidant and free radical-scavenging properties of three flavonoids isolated from the leave of Rhamnus alaternus L. (Rhamnaceae): A structure-activity relationship study [J]. Food Chem., 2009, 116, 258-264.
[13] Zielonka J.; Gebicki J.; Grynkiewicz G. Radical scavenging properties of genistein [J]. Free Radic. Biol. Med. 2003, 35(8): 958 - 965.
[14] Wang W.; Higuchi C.; Zhang R. Individual and combinatory effect of soy isolfavones on the in vitro potentiation of lymphocyte activation [J]. Nutr Cancer, 1997, 26(1): 29-34.
[15]宗灿华,马山,于国萍.荷叶黄酮抗衰老作用研究[J].中国食物与营养, 2009, 10, 52-53.
[16] Anthony, M. S.; Clarkson T. B.; Hughes Jr. Cl. Soybean isoflavones improve cardiovascular risk factors without affecting the reproductive system of peripubertal rhesus monkeys [J]. J. Nutr, 1996, 126: 43-50.
[17]杨薇.大豆中植物性雌激素的构效关系及药理作用[J].中国新药杂志, 2001, 10(12): 892-896.
[18]朱大元.中草药, 1982, 13: 43。
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