新型类黄酮杂环类衍生物的合成、反应及其性质研究
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摘要
黄酮类化合物具有广泛的生物活性,许多黄酮类化合物已被应用于医药和农药领域。为了寻找高活性黄酮类化合物,人们在不断从植物体内分离新型黄酮类化合物的同时也对其结构进行改造。二十世纪九十年代以来,农药发展进入了一个新的时代,即以杂环化合物为主的时代。杂环化合物由于其广谱、高效、低毒的生物活性而引起各国化学家的重视。因而,本论文在前人研究基础上将噻唑、吡唑和哒嗪等杂环引入类黄酮骨架中,设计合成了233个新型类黄酮类杂环化合物,同时对黄酮类化合物的合成方法进行了探索。具体内容如下所示:
     (1)基于活性亚结构拼接原理,将噻唑酮引入黄酮骨架结构中,利用微波辅助液相组合平行合成技术,以3-醛基色酮、伯胺和巯基乙酸为原料,合成了一个具有杀虫活性的2-(4-氧代-4H-色烯-3-)噻唑-4-酮类化合物库。与常规加热方法相比,微波辅助液相组合平行合成技术大大缩短反应时间,提高了反应收率。生物活性测试结果显示2-(4-氧代-4H-色烯-3-)噻唑-4-酮类衍生物在杀菌和除草方面表现出较弱的抑制活性,但在杀虫方面表现出良好的抑制活性。在250mg.L~(-1)的浓度下,所测试的化合物当中有5个化合物对朱砂叶螨表现出70%以上的杀虫活性。其中化合物I-2 c对朱砂叶螨的抑制率达到90.5%。同时,对中间体色酮酰腙类化合物也进行了生物活性测试。实验结果显示,这一类化合物在杀菌和杀虫方面表现出一定的抑制活性。(2)基于活性亚结构拼接的原理,将杂环吡唑酮引入苯并吡喃环中,利用微波辅助多步液相组合平行合成手段,以3-羧基色酮为原料,快速产生了一个结构多样性的具有杀虫活性的苯并吡喃[4,3-c]吡唑-3(2H)-酮类化合物库。与常规平行合成相比,微波辅助多步液相组合平行合成将反应时间由16h缩短至13min,并提高了产物收率。生测实验结果显示,在250 mg.L~(-1)的浓度下,这类化合物对朱砂叶螨表现出良好的杀虫活性,即使当浓度降低至100mg.L~(-1)的情况下仍有部分化合物表现出一定的抑制活性。
     (3)以苯并吡喃[4,3-c]吡唑-3(2H)-酮类化合物为先导进行结构修饰,并设计合成了四个系列化合物,并对其进行了生物活性筛选。生测结果显示,仅Ⅳ系列化合物对朱砂叶螨表现出较好的抑制活性。Ⅲ系列化合物和Ⅵ系列化合物虽然杀虫活性较弱,但都表现出一定的杀菌活性。
     (4)建立了3-羟基-2-芳甲酰基苯并呋喃类衍生物的合成新方法:以2-溴苯乙酮与水杨酸酯为原料,在无水碳酸钾作用下,一步关环合成3-羟基-2-芳甲酰基苯并呋喃类衍生物。与以往合成方法相比,此方法缩短了反应步骤,提高了产物收率。
     (5)建立了苯并吡喃4-酮-3-甲酸乙酯类化合物的合成新方法:以邻羟基苯甲酰乙酸乙酯和原甲酸甲酯为原料一步关环以较好的分离收率得3-酯基色酮。
     (6)在苯并吡喃稠杂环系列晶体体系上研究了由分子内氢键所导致的晶体分子构象的变化对固态超分子结构的影响。通过对晶体结构分析,取代基的类型对分子间π-π共轭有较大的影响:当在N上引入吸电子取代基时,分子间π-π共轭相互作用减弱;当N上取代基是推电子取代基时,分子间π-π共轭相互作用增强。同时,晶体分子构型对固态超分子结构也存在很大的影响。当取代基与呋喃环呈反式构型,且取代基为推电子基取代基时,晶体分子间往往形成相互包合的二聚体。这种现象仍需要大量的实验去证实。
     (7)利用微波辅助有机合成技术,首次报道了黄烷酮以N-溴代丁二酰亚胺(NBS)为溴化试剂在偶氮双异丁氰(AIBN)催化下高选择性转化为3-溴黄酮或黄酮。这种方法具有收率高、反应时间短(10min)和适用性强等特点,是合成3-溴黄酮和黄酮类衍生物较为理想的方法。(8)首次报道了微波辅助下以离子液体为反应介质,在噻唑盐和Et_3N催化下的分子内Stetter反应。反应基本在5-20min内结束,并以很好的分离收率得到产物。与常规方法相比,微波辅助下在室温离子液体中进行的分子内Stetter反应缩短了反应时间,提高了反应收率。此外,室温离子液体回收再用的结果显示,室温离子液体连同催化剂完全能够回收再用。并在此基础上,我们发展了一种环境友好的高效的合成苯并二氢吡喃-4-酮类衍生物的新方法。
Flavonoids are widely distributed diverse groups of plant secondary metabolites with widespread biological activities. Many of them have been used as medicine and pesticide. In order to search highly biological activities flavonoids, the reformation of the structure goes on in parallel with the separation of new flavonoids form plants. Since 1990s, pesticide has entered into a new period, heterocyclic compounds era. Heterocyclic compounds attracted significant interest of chemists due to its widespread and highly biological activities. For the low activities of flavonoids, we designed and synthesized six series of 233 novel heterocyclic flavonoids by introduction of thiazole, pyrazole and pyridazine in order to search new lead compounds with highly activities. At the same time, we explored the efficient methods for the preparation of flavonoids. It may be summarized as follows:
     (1) On the basis of the principle of combination of active groups, it is the first report about the application of liquid-phase combinatorial parallel synthesis under microwave irradiation to construct a library of 2-(4-oxo-4H-1-benzopyran-3-yl)-4-thiazolidinones with insecticidal activity by fusing a thiazolidinone to the flavonoid skeleton, using 3-formyl chromone, primary amine and mercaptoacetic acid as reactants. Compared with an identical library generated by conventional parallel synthesis, the microwave-assisted parallel synthesis approach dramatically decreased the reaction time, and substantially increased the product yields.The bioassay showed that they not exhibit obviously herbicidal activity and fungicidal activity but insecticidal activity. Five of them exhibited beyond 70% inhibition of Tetranychus cinnabarnus in 250 mg.L~(-1). The best one was compound 2-9 c which exhibited 90.5 % inhibition of Tetranychus cinnabarnus. At the same time, the biological activities of N'-((4-oxo-4H- chromen-3-yl) methylene) acyl hydrazone derivatives were also studied. The results showed that they exhibited middling fungicidal activity and insecticidal activity.
     (2) On the basis of the principle of combination of active groups, it is the first report that a rapid library-generation via liquid-phase multiple-parallel synthesis of 2-(substituted)benzyl-1-benzopyrano [4,3-c] pyrazol-3-ones with insecticidal activity by fusing a pyrazol-3-one to the flavonoid skeleton under microwave irradiation was successfully performed using chromenone-3-carboxylic acids as starting materials. Compared with an identical library generated by conventional parallel synthesis, microwave-assisted parallel synthesis dramatically decreased reaction time from an average of 16 h to 13 min, and the yields of products and intermediates were improved in most cases. A bioassay indicated that the compounds of the library exhibited excellent insectidal activity aginst T cinnabarinus at the dosage of 250 mg.L~(-1), and some compounds still exhibited insecticidal activity when the dosage was reduced to 50 mg.L~(-1). This showed that 2-(substituted) benzyl-1-benzopyrano [4, 3-c] pyrazol-3-ones might be used as lead structures for further optimization.
     (3) Benzopyrano- [4,3-c] pyrazol-3-ones was identified as lead compounds for further studies. And four series of 115 novel heterocyclic flavonoids was designed and synthesized. But, the bioassay indicated only IV series compounds showed middling insecticidal activity. III and VI series compounds showed feeble insecticidal activity but middling fungicidal activity.
     (4) We developed a new efficient methods for the preparation of (3-hydroxybenzofuran-2-yl) (phenyl) methanone derivatives. (3-Hydroxybenzofuran-2-yl) (Phenyl) methanone derivatives were synthesized in a one step substitution cylization reaction of 2-bromo-1-phenylethanone and methyl 2-hydroxybenzoate in the presence of potassium carbonate. Compared with old methods, it reduces the steps and substantially increased the product yields.
     (5) We developed a new efficient methods for the preparation of methyl 4-oxo-4H-chromene-3-carboxylate derivatives. Methyl 4-oxo-4H-chromene-3- carboxylate derivatives were synthesized in excellent yields via a one step cylization reaction of ethyl 3-(2-hydroxyphenyl)-3- oxopropanoate and triethyl orthoformate.
     (6) On the base of a serier of crystal VI, the effects of substituents on molecule configuration and the structure of solid supermolecule crystals were studied. The properties of substituents have tremendous influence on the aromaticπ-πstacking interactions. The aromaticπ-πstacking interactions was weakened by introducing the electron drawing substituents. However, the aromaticπ-πstacking interactions was strengthened by introducing the donating drawing substituents. At the same time, the molecular configurations also have tremendous influence on the structure of solid supermolecule crystals. When the donating drawing substituents shows trans configurations with furan ring, the molecules generates an dimer embosomed with each other by aromaticπ-πstacking interactions. The phenomena shall be demonstrated later by a mass of experiments.
     (7) We presented the first report of a highly selective transformation of flavanones to 3-bromoflavones or flavones by using N-bromosuccinimide (NBS) as a brominating reagent in the presence of catalytic amount of 2, 2'-azobis (isobutyronitrile) (AIBN) under microwave irradiation. The combination of excellent yields, shorter reaction time (10 min), and high levels of functional group compatibility makes this an attractive synthetic approach to 3-bromoflavones and flavones.
     (8) We presented the first report of microwave-assisted intramolecular Stetter reaction using imidazolium-type room temperature ionic liquids (RTILs) as solvents, with thiazolium salts and Et_3N as catalysts. The features such as excellent yields, shorter reaction time (5 ~ 20 min), and recyclable and reusable ionic liquid and catalyst make this method an environmentally benign and highly efficient procedure for the preparation of chromanone derivatives.
引文
[1] Herman, C.; Adlercereutz, T. Soybean Isoflavones and Cancer Risk Soybean Phytoestrogen Intake and Cancer Risk. J. Nutr. 1995, 125 (3), 757-770
    [2] 颜春洪,韩锐,异黄铜genistein对小鼠恶性黑色瘤转移的实验性治疗.药学学报,999,34(11),814-817.
    [3] Keung, W. M.; Vallee, B. L. Daidzin: a potent and selective inhibitor of human mitochonddal aldehyde dehydrogenase. Proc. Natl. Acad. Sci. USA, 1993, 90, 1247-1251
    [4] Agostino, M.; Brizio-Molteni L.; Persky, V. In vitro hormonal effects of soybean isoflavones. J. Nutr. 1995, 125(3), 751-6.
    [5] Stephen, B. G.; Peterson, C. G. Potential role of dietary isoflavones in the prevention of cancer. Adv. Exp. Med. Biol. 1994, 354, 135-147
    [6] 朱庆磊,吕欣然.葛根素的药理学和临床应用研究进展.中草药,1997,28(11),693-696
    [7] 黄芸、秦民坚,余国奠。异黄酮类化合物在植物界的分布及药理作用。中国野生植物资源,2001,20(1),5-7
    [8] Yamazaki, I.; Kinoshita, M. Calcitonin secreting Property of ipriflavone in the presence of estrogen. Life Sci. 1986, 38(1), 1535-41
    [9] 卢田静,异黄酮对活性氧引起的酯质过氧化的抑制作用。国外医学:中国中药争册,1999,21(3),58-59
    [10] Huh, I. H.; Lee, S. J.; Kim, H. C. Studies on the anti-inflammatory activity of daidzein. Yakhak Hoechi, 1987, 31(3), 154-163
    [11] Wang, W. Q.; Higuchi. C. M.; Zhang, R. Individual and combinatory effects of soy isoflavones on the in vitro potentiation of iymphocyte activation. Nutr. Cancer 1997, 29(1), 29-34
    [12] Hollingworth, R. M.; Ahammadsahib, K. I. Rev. Pestic. Toxicol. 1995, 3, 277-302.
    [13] 王春梅,石志琦.蛇床子素对黄瓜白粉病防治试验.江苏农业科学,2005,(4),57-58.
    [14] Balcells, M.; Avilla, J.; Profitos, J. Synthesis of Phenoxyphenyl Pyridine and Pyrazine Carboxamides: Activity against Cydia Pomonella (L.) Eggs. J. Agric. Food. Chem. 2000, 48(1), 83-87
    [15] Ito, H.; Imai, C. et al., 5-(m-cyanobenzylamino) Pyrazole derivatives. WO Patent 0 208 196, 2002
    [16] Takasugi, J. J.; Buckwalter, B. L. 2-aryl-Delta2-1, 3, 4-(oxa and thia) diazoline insecticidal and acaricidal agents. US Patent 6 235 762, 2001
    [17] Ryu, E. K.; Kim, H. R.; Jeon D. J., et al. Herbicidal 5-benzyloxymethy-1,2- isoxazoline derivatives. WO Patent 0 219 825, 2002
    [18] Okada, I.; Takizawa, E.; Fukuchi, T. Pyridazinones and noxious organism controlling agent containing the compound as active component. JP Patent 2 002 003 479, 2002
    [19] Fujimoto, T. T. Method of producing hybrid cereal grain seeds by application of 1- ary-1, 4-dihydro-4-oxo (thi)-pyridazines. US Patent 4 345 934, 1982
    [20] Wepplo P. J.; Drabb, T. W. Process for the preparation of chiral nicotinic, quinolinic or benzoic acid imidazolinone herbicides. US Patent 6 339 158, 2002
    [21] Hegde, V. B.; Bis, S. J.; Heo. E. C.; et al. Preparation of 1, 2, 4-triazole derivatives as insecticides or acaricides and processes. US Patent 2 002 019 370, 2002
    [22] Herrmann S.; Kotysch, W. R.; Kather, K. Substituted hetericyclyl alkylamino-1, 3, 5-triazines. WO Patent 021 060, 2002
    [23] Pees, K. J.; Pfrengle, W. Heffernan, G. Fungicidal 5-phenyl substituted 2-(cyanoamino) pyrimidines. WO Patent 0 196 314, 2001
    [24] James, A. et al., E. I. du Pont de Nemours and company, Artheropodicidal Anillides. WO Patent 9 220 682, 1992
    [25] Peras, M. S. C.; Khan, A. Q. Biotransfornmation of the phytoalexub canakexin by the phytopathogen Rhizotonia Solani. Phytochemistry 2000, 53, 59-69
    [26] Smith, C. J. Accumulation of phytoalexins: defence mechanism and stimulus response system. New Phytologist 1996, 132, 1-45
    [27] Brooks, C. J. W.; Watson, D. G. Phytoalexins. Nat. Prod. Rep. 1985, 2, 427-459
    [28] Dixon, R. A., Harrison, M. J., Lamb, C. J. Early ecents in the activation of plant defense responses. Annual Rev. Plant Phytopathol. 1994, 32, 479-501
    [29] Muller, K. O.; Borger, H. Experimentelle untercuchunger uber die phytophtora; resistenz der kartoffel, Arb. Biol. Anst. Reichsanst. 1940, 23, 189-231
    [30] Brooks, C. J. W.; Watson, D. G. Phytoalexins. Nat. Prod. Rep. 1985, 2, 427-459
    [31] Hammerschmidt, R.; Dann, E. K. The role of phytoalexins in plant protection. Novartis Foundation Symposium 1999, 223, 175-190
    [32] Enkerli, J.; Bhatt, G.; Covert, S. F. Maackiain detoxinfication contributes to the virulence of Nectria haematococca MP Ⅵ on chickpea. Molecular Plant-Microbe Interactions 1998, 11, 317-326
    [33] Cruikshank, L. A. M.; Perrin, D. R. Isolation of a phytoalexin from Pisum Sativum L. Nature 1960, 187, 779-800
    [34] Ingha, J. L.; Isoflavonoid phytoalexins from yam bean. J. Biosci. 1979, 34C, 683-688
    [35] Ingha, J. L.; Markham, K. R.; Identification of the Erythrina phytoalexin, cristacarpin, and a note on chirality of other 6a-hydroxperocapans. Phytochemistru 1982, 19, 1203-1207
    [36] Denny, T. P.; VanEtten, H. D. Tolerance by Nectria haematococca MO Ⅵ of the Chickpea (Cicer arietinum) Phytoalexins medicarpin and maackiain. Physiol. Plant. Pathol. 1981, 19, 419-437
    [37] Turbek, C. S.; Li, D.; Choi, G. H.; Schardl, C. L.; Smith, D. A. Induction and Purification of kievitone hydratase from Fusarium solani f. sp. Phascoli. Phytochemistry 1990, 29, 2841-2846
    [38] Turbek, C. S.; Smith, D. A.; Schardl, C. L. An extracelluar enzyme from Fusarium solani f. sp. Phaseoli, which catalyes hydration of the isoflavonoid phytaolexin phascollidin. FEMS Microbiol. Lett. 1992, 94, 187-190
    [39] AI-Douri, N. A. Stress metabolites of Phaseolus vulgaris growing in Iraq. A; exandda J. Pharm. Sci. 1997, 11, 125-126
    [40] Edwards, C.; Strange, R. N. Separation and identification of phytoalexins from leaves of groundnut (Arachis hypogaea) and deve; opment of a method for their determination by reversed-phase high performance liquid chromatography. J. Chrom. 1991, 185-193.
    [41] Boue, S. M.; Burrow, M. E.; Carter, C. H.; Ehrlich, K. C.; Clevaland, T. E.; Mclachlan, J. A. Accumulation of soybean phytoalexins with antiestrogcnic activity from cotyledons inoculated with fungi. 18th ACS National Meeting, New Orleans Aug. 1999, 22-26,
    [42] Farooq, A.; Tahara, S. Fungal metabolism of flavonoids and related phytoalexins. Current topics in phytochemistry 1999, 2, 1-33
    [43] Tal, B., Robeson, D. J. The induction, by fungal inoculation, of ayapin and scopoletin biosynthesis in Helianthus annus. Phytochemistry 1986, 25, 77-79
    [44] Kurosaki, E; Nishi, A. Isolation and antifungal activity of the phytoalexin 6-methoxymellein from cultures carrot cells. Phytochemistry 1983, 22, 669-672
    [45] Kuzzel, N. R,; Miller, C. E. A. phytochemical study of Xanthium canadenes. J. Am. Pharm. Assoc. 1952, 39, 202-204
    [46] Cuendet, M.; Potterat, O.; Salvi, A.; Testa, B.; Hostettmann, K. Astibene and dihydrochalcones with radical scavenging activities from Loiseleuria procumbens. Phytochemistry 2000, 54, 871-874
    [47] Wang, J.; Ruan, D.; Cheng, Z.; Zhou, L.; Phytoalexins from Dracaena cochinchinesis resin. Yingyong Shengtai Xueba 1999, 10, 255-256
    [48] Syu, W.; Don, M.; Lee, G.; Sun, C.; Cytotoxic and novel compounds from Solanum indicum. J. Nat. Prod. 2001, 64, 1232-1233
    [49] Repcak, M.; Imrich, J.; Franekova, M. U. A stress metabolite of Chamomilla recutita (L.) Rauschert. J. Plant Physiol. 2001, 158, 1085-1087.
    [50] Urdangarin, C.; Regente, M. C.; Jorrin, J.; Dela Canal. L. Sunflower Coumarin hytoalexin inhibit the growth of the virulent pathogen Sclerotinia sclerotiorum J. Phytopathol. 1999, 147, 441-443
    [51] Hargreaves, J. A.; Mansfield, J. W.; Coxon, D. T.; Proce, K. R. Wyerone epoxide as a phytoalexin in Vicia faba and its metabolism by Botrytis cinerea and B. Fabae in vitro. Phytochemistry 1976, 15, 1119-1121
    [52] Nakada, H.; Kobayashi, A.; Yamashita, K. Sterechemistry and biological activity of phytoalexin "safynol" from safflower. Agric. Biol. Chem. 1977, 41, 1761-1765
    [53] De Wit, P. J. M.; Kodde, E. Induction of polyacetylexins in Lycopersico esculentus after inoculation with Cladosporium fulvum (syn. Fulvia fulva). Physiol. Plant Pathol. 1981, 18, 143-148
    [54] Wakler, R. R.; Wade, G. C.; Resistance of potato tubers (Solanum tuberosum) to Phoma exiqua var. exigua and phoma exigua vau foveata. Aust. J. Bot.1978, 26, 239-251.
    [55] Katsui, N.; Matsunaga, A.; Masamune, T.; Studies on the phytoalexins. Ⅺ. Structure of lubimin and oxylubimin, antifungal metabolites from diseased potato tubers. Tetrahedron Lett. 1974, 51/52, 4483-4486
    [56] Afzal, M.; AI-Oriquant, G. ~(13)C and proton-NMR spectra of sesqioterpenoid and related. Phytoalexins. Heterocycles 1986, 24, 2943-2961.
    [57] Schallenberg, J.; Meyer, E. Simple synthesis of 3-substituted indoles and their application for high yield ~(14)C-labelling. Z. Naturforsch. 1983, 38b, 108-112
    [58] Fujita, M.; Yoshizawa T. Induction of sweet potato phytoalexins by trichothecene mycotoxins. Mycotoxins 1987, 25, 29-30
    [59] Taskasugi, M.; Okinaka S.; Katsui, N.; Masamune, T.; Shirata, A.; Ohuchi, M. Isolation and structure of lettucenin A, A novel guaianolide phytoalexin from Lactuca sativa var. capitata (Compositae). J. Chem. Soc., Chem. Commun. 1985, 10, 621-622.
    [60] Ward, E. W. B.; Stoessl. A. Postinfectiona inhibitors from Plants. Ⅲ. Detoxification of capsidiol, and antifungal compound from peppers. Phytopathol. 1972, 62, 1186-1187
    [61] Akatsuka, T.; Kodama, O.; Sekido, H.; Kono, Y.; Takeuchi, S. Novel phytolaexins (oryzalexins A, B and C) isolation, characterization and biological activities of oryzalexins. Agric. Biol. Chem. 1985, 49, 1689-1694.
    [62] Gross, D. Antimierobial defense compounds in Gramineae. Zeitschrift fuer Pflanzenkrankheiten und Pflanzenschuiz 1989, 96, 535-553
    [63] Mayama, S. The role of avenalumin in the resistance of oats to crown rust. Kagawa Daigaku Nogakubu Kiyo 1983, 42, 1-64
    [64] Yue, Q.; Bacon, C. W.; Richardson, M. D. Biotransfornation of benzoxazolinone and 6-methoxybenzoxazolinone by Fusarium moniliforrme. Phytochemistry 1998, 48, 451-454.
    [65] Takasugi, M.; Katsui, N.; Shirata, A. Isolation of three novel sulfur-containing phytoalexins from the Chinese cabbage Brassica capestris L. ssp. Pekinensis (Crueiferae). J. Chem. Soc., Chem. Commun. 1986, 1077-1078
    [66] Pedras, M. S. C.; Jha, M.; Ahiahonu, P. W. K. The synthesis and biosynthesis of phytoalexins produced by cruciferous plants. Curr. Org. Chem. 2003, 1635-1647
    [67] Pedras, M. S. C.; Okanga, F. I. Probing the phytopathogenic blackleg fungus with a phytoalexin bomolog. J. Org. Chem., 1998, 63, 416-417
    [68] Pedras, M. S. C., Montaut, S. Probing crucial metabolic pathways in fungal pathogens of crucifers: biotransformation of indole-3-acetaldoxime, 4-hydroxyphenylacetald oxime and their metabolites. Bioorg. Med. Chem. 2003, 11, 3115-3120
    [69] Bykova, T. D.; Davydova, M. A.; Ozeretskovskaya, O. L.; Moiseeva, N. A. Antifungal substances in apples. Mikologiyai. Fitopatologiya 1977, 11, 116-122
    [70] Breuil, A.; Adrian, M.; Pirio, N.; Meunier, P.; Bessis, R.; Jeandet, P. Metabolism of Stilbene phytoalexins by Botrytis cinerea. Tetrahedron Lett. 1995, 39, 537-540
    [71] Pezet, R.; Pont, V.; Hoang-Van, K. Evidence for Oxidative detoxification of pterostibene and resveratrol by a laccase-like stilbene oxidase produced by Botrytis cinerea. Physiol. Mol. Plant. Pathol. 1991, 39, 441-450
    [72] Aguamah, G. E.; Langcake, P.; Leworthy, D. P.; Page, J. A.; Pryce, R. J.; Strange, R. N. Two novel stilbene phytoalexins from Arachis hypogaea. Phytochemistry 1981, 20, 1381-1383
    [73] Fagboun, D. E.; Ogundana, S. K.; Adesanya, S, A.; Roberts, M. F. Induction of PAL activity and dihydrostilbene phytoalexins in Dioscorea alata and their plant growth inhibitory properties. Phytochemistry 1987, 26, 3187-3189
    [74] Cline, E. L; Adesanya, S. A.; Ogundana, S. K.; Roberts, M. F. Induction of PAL activity and dihydrostilbene phytoalexins in Dioscorea alata and their plant growth inhibitory properties. Phytochemistry 1989, 28, 2621-2625.
    [75] Yoshihiko I., Yoshiaki K., Mayuri K., Physiological activities of 3, 4, 3', 5'-tetrahydroxystibene isolated from the heartwood of Cassia garrettiana CRAIB. Chem. pharm. Bull. 1984, 32 (1), 213~218
    [76] Mohammad, A. A., Kaoru K., Yoshisuke T., Synthesis and nematocidal activity of hydroxystilbenes. Chem. Pharm. Bull. 1992, 40(5), 1130-1136
    [77] Winkel, S. B. Flavonoid biosynthesis: A colorful model for genetics, biochemistry, cell biology and biotechnology. Plant Physiology 2001,126, 485-493
    [78] Horowitz, R. M.; Gentili, B. Flavonoid constituents of Citrus. In: Nagy, S.; Shaw, P. E.; Veldhuis MK (Ed.) Citrus Science and Technology, 1977, pp 397-426
    [79] Ollis, W. D. In the Chemistry of fiavonoid Compounds, Ed. T. Geissman, Pergamon Press, Oxford, 1962, P396
    [80] Mathieson, R. A.; KiLts, W. D. Binding of Phyto-oestrogan and oestradiol-17 beta by cytoplasmic receptors in the pituitary gland and hypothalamus of the ewe. J. Endocrinol, 1980, 85, 317-25
    [81] 张光成,方思鸣,葛根异黄酮的抗氧化作用.同济医科大学,1997,26(5),340—343
    [82] Jha, H, C, Yon Recklinghuasen, G. Ziliken, F. Inhibition of in vitro microsomal lipid peroxidation by isoflavonoids. Biolchem Pharmacol 1985, 34, 1367-72
    [83] 刘文,宋之娟,梁念慈,金雀异黄素对猪血小板聚集和胞浆游离钙的影响。中国药理学报1998,19(16),540-542
    [84] Hollingworth, R. M.; Ahammadsahib, K. I. Inhibitors of respiratory Complex Ⅰ: mechanisms, pesticidal actions and toxicology Rev. Pestic. Toxicol. 1995, 3, 277-302.
    [85] Fukami, H.; Nakajima, M. Rotenone and the rotenoids. In Naturally Occurring Insecticides; Jacobson, M., Crosby, D. G., (Ed.), New York, 1971; p71-97.
    [86] Negherbon, W. 0. Hanaboak of Toxicology Volume Ⅲ: Insecticides; Saunders, W. B. (Ed. ) Philadelphia, PA, 1959, p 661-673.
    [87] Tomlin, C. D. S., Ed. Rotenone. In The Pesticide Manual, 11th ed.; British Crop Protection Council: Farnham, Surrey, U.K. 1997; pp1097-1099.
    [88] LaForge, F. B.; Hailer, H. L.; Smith, L. E. The Determination of the Structure of Rotenone. Chem. Rev.; 1933, 12(2), 181-213.
    [89] Hailer, H. L.; Goodhur, L. D.; Jones, H. A. The Constituents of Derris and Other Rotenone-bearing Plants. Chem. Rev. 1942, 30 (1); 33-48.
    [90] Oxley, J. Indian Archipelago and East Asia 1848, 2, 641-643.
    [91] Oberholzer, M. E.; Rail, G. J. H.; Roux, D. G. Concurrence of 12a-hydroxy- and 12a-O-methylrotenoids. Isolation of the first natural 12a-O-methylrotenoids. Tetrahedron Lett. 1974, 25, 2211-14.
    [92] Norton, L. B.; Hansberry, R. Constituents of the Insecticidal Resin of the Yam Bean (Pachyrrhizus erosus) J. Am. Chem. Soc. 1945, 67, 1609-1614.
    [93] Cheng, H. M.; Yamamoto, I.; Casida, J. E.; Rotenone photodecomposition. J. Agr. Food Chem. 1972, 20 (4), 850~856
    [94] Li, L.; Wang, H. K.; Chang, J. J.; Mcphall, A. T.; Mcphall, D. R.; Estes, J. R.; Lee, K. H.; et al.; Antitumor Agents, 138. Rotenoids and Isoflavones as Cytotoxic Constituents from Amorpha fruficosa. J. Nat. Prod. 1993, 56 (5), 690-698
    [95] Konoshima, T.; Terada, H.; Kokuma, M.; Kozuk, M.; Tokuda, H.; Estes, J. R.; Li, k; Wang, H. K.; Lee, K. H.; Studies on Inhibitors of Skin Tumor Promotion, Ⅻ. Rotenoids from Amorpha fruticosa. J. Nat Prod. 1993, 56 (5), 843-848
    [96] Fang, N.; Casida, J. E. Novel Bioactive Cube Insecticide Constituents: Isolation and Preparation of 13-horno-13-Oxa-6a, 12a-dehydrorotenoids. J. Org. Chem. 1997, 62, 350-353
    [97] Fang, N.; Rowlands, J. C.; Casida, J. E.; Anomalous Structure-Activity Relationships of 13- homo-13-Oxarotenoids and 13-homo-13-Oxadehydrorotenoids. Chem. Res. Toxicol. 1997, 10, 853-858
    [98] Fang, N.; Casida, J. E. Cube Resin Insecticide: Identification and Biological Activity of 29 Rotenoid Constituents. J. Agric. Food Chem. 1999, 47, 2130-2136
    [99] Wright, G. M. A. Pereliminary examination of rotenone and some of its degradation products. J. Am. Chem. Soc. 1928, 50 (12); 3355-3360.
    [100] Butenandt, A.; McCartney, W. Vegetable, fish and insect poisons. Ⅲ. Rotenone, the physiologically active constituent of Derris elliptica. (3) Constitution of rotenone. Ann, 1932, 494, 17-41.
    [101] Laforg, F. B.; Haller, H. L. Rotenone. ⅩⅨ. The nature of the alkali soluble hydrogenation products of rotenone and its derivaves and their bearing on the structure of rotenone. J. Am. Chem. Soc. 1932, 54, 810-818.
    [102] Takei, S.; Miyajirua, S.; Ono, M., Ber. 1932, 65, 1041-1046
    [103] Buchi, G.; Crombie, L.; Godin, P. J.; Kaltenbronn, J. S.; Siddalingaiah, K. S.; Whiting, D. A. The absolute configuration of rotenone. J. Chem. Soc. 1961, 2843-2860.
    [104] Crombie, L; Lown, J. W. Proton magnetic studies of rotenone and related compounds. J. Chem. Soc. 1962, 775-781
    [105] Carlson, D. G.; Weisieder, D.; Tallent, W. H. NMR investigations of rotenoids. Teterahedron 1973, 29, 2731-41
    [106] Arora, S. K.; Bates, R. B.; Grady, R. A.; Delfel N. E., Dehalogenation of 5-bromouracil by bisulfite buffers. Kinetic evidence for a multistep reaction pathway. J. Am. Chem. Soc. 1975, 5752-5755
    [107] Tomlin, C. D. S. (Ed.) The Pesticide Manual, 11th ed.; BCPC: Farnham, U.K. 1997; pp1097-1099.
    [108] Crombie, L. Natural product chemistry and its part in the defence against insects and fungi in agriculture. Pestic. Sci. 1999, 55, 761-774
    [109] Hoult, J. R. S.; Paya, M. Pharmacological and biochemical actions of simple coumarins, natural products with therapeutic potential [J]. Gen. Pharmacol 1996, 27: 713-722.
    [110] Dixon, R. A.; Palva, N. L. Stress-induced phenylpropanoid metabolism [J]. Plant Cell 1995, (7), 1085-1097.
    [111] Murray, R. D. H.; Mendez, J.; Brown, S. A. The Natural Coumarins: Occurrence, Chemistry and Biochemistry; John Wiley and Sons: Chichester; 1982.
    [112] Murray, R. D. H. Coumarins. Nat. Prod. Rep. 1989, 6, 591-624.
    [113] Murray, R. D. H. Coumarins. Nat. Prod. Rep. 1995, 12, 477-505.
    [114] Estevez-Braun, A.; Gonzalez, A. Coumarins. G. Nat. Prod. Rep. 1997, 14, 465-475.
    [115] 王超,严清平.蛇床子素防治板蓝根霜霉病、黄瓜瓜绢螟的应用效果.江苏农业科学,2003,144-146.
    [116] 石志琦,沈寿国.蛇床子素对植物病原真菌抑制机制的初步研究.农药学学报,2004,6(4):28-32.
    [117] Farbenfabriken Bayre, Synthesis of thiophosphoric acid esters of 3-halohydroxycoumarins for use as insecticides. GB Patent 713 142, 1954.
    [118] Farbenfabdken Bayre, Esters of thiophosphoric. US Patent 2 583 744, 1952.
    [119] Farbenfabriken Bayre, Synthesis of thiophosphofic acid esters of 3-halohydroxy-coumarins for use as insecticides. US Patent 2 748 146, 1956.
    [120] Schrader, G; L. (Walter. Farbenfabriken Bayre), Insecticides. DE Patent 1 016 055, 1957.
    [121] Farbenfabriken Bayre, Insecticidal phenylthionophosphonate esters. DE Patent 1 059 456, 1957
    [122] Farbenfabriken Bayre, Phosphinothioate insecticides. DE Patent 1 099 788, 1958
    [123] Farbenfabriken Bayre Aktiengesellschaft, Phosphonates and thiophosphonates. GB Patent 863 434, 1961
    [124] Farbenfabriken Bayre Aktiengesellschaft, Coumarin phosphonic esters. US Patent 3 067 210, 1962
    [125] Farbenfabriken Bayre Aktiengesellschaft, Phosphonic and thiophosphonic acid esters. US Patent 3 223 754, 1963
    [126] Farbenfabriken Bayre Aktiengesellsehaft, Phosphinic acid esters. US Patent 3 232 830, 1966.
    [127] Farbenfabriken Bayre Aktiengesellschaft, Alkyl or cycloalkylthiophosphonic acid ester amides. US Patent 3 260 712, 1966
    [128] Eddy, G. W.; Knipling, E. F. Synergistic insecticidal compounds with O, O-dialkyl O-(4-methylumbeiliferone) thiophosphate. US Patent 2 826 530, 1958-03-11
    [129] Fusco, R.; Losco, G.; Peri, C. A. Phosphate esters of substituted umbelliferones as insecticides. US Patent 2 860 085, 1958.
    [130] Newallis, P. E.; Baker, J. W.; Chupp, J. P. (Monsanto Chemical Company), O-(Coumarinyl) dialkylphosphinothioates. US Patent 3 061 613, 1962
    [131] Uhlenbroek, J. H.; Van-den-Bos, B. G. (North American Philips Company), Phosphorus-containing heterocyclic compounds. US Patent 3 051 615, 1962
    [132] Suzuci, S., Insecticidal Compositions Containing O, O-Dimethyl-O-(3-methyl-4-Nitrophenyl)-Thionphosphate. US Patent 3 091 515, 1963
    [133] Mcdougall & Robertson Limited Company, Pesticidal coumarinyl thionophosphates. GB Patent 1 041 521, 1963
    [134] Newallis, P. E.; Chupp, J. P.; Baker, J. W. (Monsanto Company), Dialkylphosphinothioate pesticides. US Patent 3 159 534, 1964
    [135] Raetz, R. F. W.; Bliss, A. D. (Olin Mathieson Chemical Corporation), Spiro thiophosphates useful as pesticides. US Patent 3 445 468, 1969
    [136] Stauffer chemical company, Pesticidal phosphorus-containing coumarins. US Patent 3 703 532, 1972
    [137] Gutman, A. D. (Stauffer chemical company), Insecticidal and acaricidal oximino phosphorus-containing pyrimidines or coumarins. US Patent 3 737 528, 1973
    [138] Zumstein, S. F.; Assmm, E.; et al., Phosphinic acid esters. DE Patent 2 304 128, 1972
    [139] McIntyre, J. S.; Knight, A. R. (Dow Chemical Co.), Pesticidal 3-(alkoxyphenyl carbamoyl)-4-hydroxycoumarins. US Patent 3 511 856, 1970
    [140] Hirono, Y.; Ishikawa, H.; Sawaki, M.; Iwataki, I. (Nippon Soda Co., Ltd., Japan), Herbicidal and miticidal 3-(alkoxyaminoalkylidene) chroman-2, 4-diones. JP Patent 50 154 263, 1975.
    [141] Beriger, E. (Ciba-Geigy A.-G., Switz.), Pesticidal composition. DE Patent 2 643 428, 1977.
    [142] Beriger, E. (Ciba-Geigy A.-G., Switz.), Pesticide composition. DE Patent 2 643 476, 1977
    [143] Beriger, E. (Ciba-Geigy Corp., USA). Insecticidally active 3-N-(4-trifluoromethylphenyl) carbamoyl-4-ydroxyoumarin. US Patent 4078075, 1978.
    [144] Franz, E.; Klauke, E.; Hammann, I. (Bayer A.-G., Fed. Rep. Ger.), 3-Carbamoyl-4-hydroxyl-coumarins and their use as pesticides. DE Patent 3 012 642, 1981.
    [145] Liu, C. L.; Guan, A. Y.; Zhang, H.; Zhang, M. G.; Li, Z. G.; Li, M.; Li, L.; Li, Z. N.; Hou, C. G. (Shenyang Research Institute of Chemical Industry, Peop. Rep. China). Preparation of benzopyrone derivatives as pesticides and bactericides. WO Patent 2 005 044 813, 2005.
    [146] Harrison, C. R.; Lahm, G. P.; Shapiro, R. (du Pont de Nemours, E. I., and Co., USA). Preparation of arthropodicidal tetrahydrobenzopyranopyrazoles. EP Patent 386 892, 1990.
    [147] Harrison, C. R.; Lahm, G. P.; Shapiro, R. (du Pont de Nemours, E. I., and Co., USA). Preparation of arthropodicidal tetrahydrobenzopyranopyrazoles. WO Patent 9 010 623, 1990
    [148] Harrison, C. R.; Lahm, G. P. (du Pont de Nemours, E. I., and Co., USA). Preparation of arthropodicidal pyrazolines, pyrazolidines and hydrazines. WO Patent 9 111 438, 1991.
    [149] Harrison, C. R.; Lett, R. M.; Mccann, S. F.; Shapiro, R.; Stevenson, T. M. (du Pont de Nemours, E. I., and Co., USA). Arthropodicidal pyrazolines, pyrazolidines and hydrazines. WO Patent 9 203 421, 1992
    [150] Bamette, W. E.; Harrison, C. R.; Lahm, G. P.; Piotrowski, D. W., Wing, K. D. (du Pont de Nemours, E. I., and Co., USA).Preparation of [1]benzopyrano[4,3-c]pyrazole-3a(4H) carboxylates and analogs as arthropodicides. WO Patent 9 220 682, 1992
    [151] Du Pont de Nemours, E. I., and Co., USA. Arthropodicidal Carboxanilides WO Patent 9 211 249, 1992
    [152] Lowder, P. D. (du Pont de Nemours, E. I., and Co., USA). Agrochemical artlaropodicidal heterocyclic amide derivatives. WO Patent 9 318 038, 1993.
    [153] Harrison, C. R.; Lahm, G. P. (du Pont de Nemours, E. I., and Co., USA), Preparation of arthropodicidal pyrazolines, pyrazolidines and hydrazines. US Patent 5 369 121, 1994.
    [154] Harrison, C. R.; Lett, R. M.; Mccann, S. F.; Shapiro, R.; Stevenson, T. M. (E. I. Du Pont de Nemours & Co., USA). Arthropodicidal pyrazolines, pyrazolidines and hydrazines. US Patent 5 474 998, 1995
    [155] John, P. D.; George P. L. (E. I. Du Pont de Nemours & Co., USA). Substituted Semicarbazone Arthropodicieds. US Patent 5 428 027, 1995
    [156] Howard, M. H. J.; Stevenson, T. M. (Du Pont de Nemours, E. I., and Co., USA).Preparation of arthropodicidal pentafluorothio-substituted anilides. WO Patent 9 516 676, 1995
    [157] Bamette, W. E.; Harrison, C. R.; Lahm, G. P.; Piotrowski, D. W.; Wing, K. D. (E. I. Du Pont de Nemours & CO., USA) Arthropodicidal benzopyranopyrazole- and indenooxadiazine-derived anilides. US Patent 5 500 438, 1996.
    [158] E. I. Du Pont de Nemours & Co., USA, Arthropodicidal Tetrahydropuridazines. US Patent 5 591 729, 1997.
    [159] Du Pont de Nemours, E. I., and Co., USA. Preparation of arthropodicidal oxadiazines. US 6232489, 2001-05-15
    [160] Kumial Chemical Industry Co., Ltd., Japan, Organic phosphoric acid esters. JP Patent 5 600 5492, 1981
    [161] Kumiai Chemical Industry CO., Ltd., Japan, Organic phosphoric acid esters. US Patent 4303653, 1981
    [162] Kumiai Chemical Industry Co., Ltd., Japan, Dihydrobenzopyranyl phosphorothiolates. JP Patent 59 088 495, 1984
    [163] Kumiai Chemical Industry Co., Ltd., Japan, Polyalkylchromenols. JP Patent 57 109 779, 1982.
    [164] Weissmueller, J.; Erdelen, C.; Wachendorff-Neumann, U.; Stendel, W.; Leicht, W. (Bayer A.-G., Germany). Preparation of 5-chromenylpyridazin-3-ones as pesticides. EP Patent 0 453 837,1990
    [165] Weissmueiler, J.; Erdelen, C.; Wachendorff-Neumann, U.; Stendel, W.; Leicht, W. (Bayer A.-G., Germany). Preparation of 5-chromenylpyridazin-3-ones as pesticides. EP Patent 453 837, 1991
    [166] Weissmueller, J.; Erdelen, C.; Wachendorff-Neumann, U.; Stendel, W.; Leicht, W. (Bayer A.-G., Germany). Preparation of 5-chromenylpyridazin-3-ones as pesticides. US Patent 5 141 939, 1992
    [167] Yang, G. H.; Cao, L. H.; Cui, P. Y. The synthesis of 2-(chromon-2/3-yl)-3-(5-thione-4-hydro-1, 3, 4-thiadiazol-2-yl)-4-oxo-thiazolidine. J.Chin.Chem. Soc. (Taipei, Taiwan) 2005, 52(5), 1033-1036.
    [168] Mulwad, V. V.; Shirodkar, J. M. Synthesis and biological activity of some new thiazolidinones & azetidinones of 6-amino coumarin. Indian J. Heterocyclic Chem. 2002, 11(4), 291-294.
    [169] Mulwad, V. V.; Shirodkar, J. M. Synthesis and biological activity of some new Schiff's bases, thiazolidinones and azetidinones of 4-hydroxycoumarin. Indian J. Heterocyclic Chem. 2002, 11 (3), 199-202.
    [170] Abdel H., Omaima M.; Abdel-Alim, M. A.; El-Hamouly, W. S., Tawfeek, H. H.; Dokki, E. Synthesis of some Schiff's bases of naturally occurring chromone and furochromone derivatives and their anti-microbial activity. Sohag Pure & Applied Science Bulletin 1992, 8, 13-20.
    [171] Fitton, A. O.; Humphrey, G. L.; Kosmirak, M.; Suschitzky, H.; Suschitzky, J. L Reactions of formylchromone derivatives. Part 4. Interaction of 3-formyl-chromones with thioglycolic add. J. Chem. Res., Synop. 1984, 8, 248-9.
    [172] Rao, G. V. P.; Rajitha, B.; Reddy, Y. T.; Reddy, P. N.; Kumar, V. N. Synthesis of biologically active chromene benzothiadiazole derivatives. Phosphorus, Sulfur and Silicon and the Relat. Elem. 2005, 180(9), 2119-2126.
    [173] Savitha, G.; Perumai, P. T. An efficient one-pot synthesis of tetrahydro-quinoline derivatives via an aza Diels-Alder reaction mediated by CAN in an aqueous medium and oxidation to heteroaryl quinolines. Tetrahedron Lett. 21106, 47(21), 3589-3593.
    [174] Xie, Z. F.; Liu, F. G.; Hui, Y. H.; Liu, C. H.; Sun, Y. D. Synthesis of new 3-(4-oxo- 4H-chromen-3-yl)-3a,6a-dihydropyrrolo[3,4-d]isoxazole-4,6-dione derivatives by 1,3-dipolar cycloaddition reaction. J. Heterocyclic Chem. 2005, 42(4), 695-697.
    [175] Shokol, T. V.; Semenyuchenko, V. V.; Khilya, V. P. 5-phenyl-2-(pyrazol-4-yl)-l, 3, 4-thiadiazoles. Chem. Heterocyclic Compd. 2005, 41(5), 673-678.
    [176] Shokol, T. V.; Semenyuchenko, V. V.; Khilya, V. P. Synthesis of 2-R-6-ethyl-7- hydroxy-3-(5-phenyl-1, 3, 4-thiadiazolyl-2)chromones. Chem. Heterocyclic Compd. 2004, 40(12), 1588-1594.
    [177] Tsao, L.; Van, V.; Sun, G.; Yu, L. Synthesis of 3-(5-aryl-1, 3, 4-oxadiazol- 2-yl) chromones. Russian J. Gen. Chem. 2001, 71(5), 767-769.
    [178] Wu, P.; Cao, L. H. One step synthesis of new substituted 3-(1H-imidazol-1-yl) flavones with montmorillouiteKSF catalyst and their fungicidal activity. Yingyong Huaxue 2005, 22(8), 848-851.
    [179] Cao, L. H.; Huang, Y.; Liu, Y. T.; Sun, G. Z. Microwave irradiation promoted synthesis of 3-(3'-acetyl-5'- aryl-1', 3', 4'-dihydrooxadiazol-2'-yl)-chromones. Yingyong Huaxue 2001, 18(4), 312-314.
    [180] Cao, L.; Zhang, L.; Liu, J. J., Synthesis of 2-R-6-ethyl-7-hydroxy-3-(5-phenyl-1, 3, 4-thiadiazolyl-2) chromones. Chem. Heterocyclic Comp. 2004, 40(2), 214-218.
    [181] Xie, Z. F.; Liu, F. M.; Mo, X. X.; Hui, Y. H.; Sun, Y. D. Synthesis of new 3a, 6a-dihydro-4, 6-dioxopyrrolo [3, 4-d] pyrazole derivatives by 1, 3-dipolar cycloaddition reaction. Youji Huaxue 2005, 25(6), 696-699.
    [182] Reddy, P. N.; Reddy, Y. T.; Kumar, V. N.; Rajitha, B. Synthesis of new hetero aroyl chromen-4-ones. Heterocyclic Commun. 2005, 11(3-4), 235-240
    [183] Levai, A.; Silva, A. M. S.; Pinto, D. C. G. A.; Cavaleiro, J. A. S.; Alkorta, I.; Elguero, J.; Jekoe, J. Synthesis of pyrazolyl-2-pyrazolines by treatment of 3-(3-aryl-3-oxopropenyl)-chromen-4-ones with hydrazine and their oxidation to bis(pyrazoles). Eur. J. Org. Chem. 2004, 22, 4672-4679
    [184] Abass, M.; Hassan, A. Chemistry of substituted quinolinones Ⅶ. Utility in synthesis and reactions of 3-[4-(chmmen-3-ylmethylene) pyrazolin-3-yl] quinolin-2(1H)-ones with some bidentate nucleophiles. Chem. Papers 2003, 57(4), 267-277;
    [185] Cao, L.; Wang, W. Synthesis of 3-(5-aryl-1, 3, 4-oxadiazol-2-yl) chromones. Chem. Heterocyclic Compd. 2003, 39(8), 1072-1075
    [186] Levai, A.; Jeko, J. Synthesis of 3-aroyl-4-(3-chrtmmnyl)-2-pyrazolines. J. Heterocydic Chem. 2002, 39(6), 1333-1336
    [187] Bandyopadhyay, C.; Nag. P. P.; Sur, K. R.; Patra, R.; Banerjee, S.; Sen, A.; Ghosh, T. Biginelli reaction on 4-oxo-4H-1-benzopyran-3-carboxaldehyde-a search for reaction pathway. J. Indian Chem. Soc. 2004, 81(2), 132-136
    [188] Sharma, V. P. Synthesis of 3-(2-benzimidazolyl) chromones. J. Heterocyclic Chem. 2003, 40(5), 879-883
    [189] Kumar, B.; Kaur, B.; Kaur, J.; Parmar, A.; Anand, R. D.; Kumar, H. Thermal/microwave assisted synthesis of substituted tetrahydropyrimidines as potent calcium channel blockers. Indian J Chem, Section B 2002, 41B (7), 1526-1530.
    [190] Reddy, G. J.; Thimpathaiah, C.; Latha, D.; Rao, K. S.; Khalilullah, M. Synthesis of 2-(coumarin-3-yl)-4-(chromon-3-yl)-benzopyrano[4,3-b]pyridines. Indian J Chem., Section B 2004, 43B (12), 2702-2704;
    [191] Reddy, G. J.; Latha, D.; Sailaja, S.; Rao, K. S.; Khalilullah, M. Synthesis of 7-aryl-/chromonyl-substituted benzopyrano[4,3-d]pyrazolo[1,5-a]pyrimidines by reaction of 5(3)-aminopyrazoles. Heterocyclic Commun. 2003, 9(6), 567-570;
    [192] Ghosh, C. K.; Karak, S. K.; Patra, A. Benzopyrans. Part 43. Reactions of some simple condensates of 4-oxo-4H-1-benzopyran-3-carboxyaldehyde with ethyl β-aminocrotonate. J. Chem. Res., Synop. 2002, (7), 311-313;
    [193] Nikalje, M. A. G.; Ingle, R. D.; Bhingolikar, V. E.; Mane, R. A. Synthesis of new chromonyl/thiochromonyl 1,5-benzothiazepines and their antimicrobial activity. Indian J. Heterocyclic Chem. 2003, 13(1), 37-40;
    [194] Shaumugam, P.; Annie, G.; Perumal, P. T. Synthesis of novel 3, 4-dihydropyrimidinones on water soluble solid support catalyzed by indium triflate. J. Heterocyclic Chem. 2003, 40(5), 879-883;
    [195] Sharma, V. P. Synthesis of 3-(2-benzimidazolyl) chromones Indian J. Heterocyclic Chem. 2003, 13(2), 171-172;
    [196] Abdel-Rahman, A. H.; Hammouda, M. A. A.; El-Desoky, S. I. Synthesis of some new azole, azepine, pyridine, and pyrimidine derivatives using 6-hydroxy-4H-4-oxo[1]-benzopyran-3- carboxaldehyde as a versatile starting material. Heteroatom Chem. 2005, 16(1), 20-27;
    [197] Liu, Y. J.; Chao, H.; Yao, J. H.; Li, Hong; Yuan, Y. X.; Ji, L. N. Synthesis, characterization, and DNA interaction studies of the ruthenium(Ⅱ) complexes [Ru(bpy)2(ipbp)]~(2+) and [Ru(ipbp) (phen)2]~(2+) (ipbp=3-(1H-imidazo[4,5-f] [1,10] phenanthrolin-2-yl)-4H-1-benzopyran-2-one; bpy=2,2'-bipyridine; phen=1,10-phenanthroline). Heiv. Chim. Acta 2004, 87(12), 3119-3130;
    [198] 195、Abdel-Rahman, A. H.; Khalil, A. M.; Keshk, E. M. Synthesis and reactions of some new substituted 6-imidazolyl-4-oxo-4H-1-benzopyran-3- carboxaldehyde and use of DNA in evaluation of their biological activity. Bollettino Chimico Farmaceutico 2001, 140(6), 387-396;
    [199] Sharma, V. P. Synthesis of 3-(2-benzothiazolyl) chromones. Indian J. Heterocyclic Chem. 2003 13(1), 95-96;
    [200] Uchil, Vinod Rama; Joshi, Vidya. One step synthesis of new substituted 3-(1H-imidazol-1-yl) fiavones with montmorillonite-KSF catalyst and their fungicidal activity. Indian J. Heterocyclic Chem. 2001, 10(3), 161-166;
    [201] Tsao, L.; Chzhan, L.; Lyu, Ts. Synthesis of 3-(3-acetyl-5-aroyl-1, 3, 4-oxadiazol-2-yl) chromones. Chem. Nat. Compd. 2002, 37(4), 311-314;
    [202] Shokol, T. V.; Semenyuchenko, V. V.; Khilya, V. P. Synthesis of 2-R-6-ethyl-7-hydroxy-3-(5-phenyl-l,3,4-thiadiazolyl-2)chromones. Chem. Heterocyclic Compd. 2004, 40(12), 1588-1594;
    [203] Shokol, T. V.; Semenyuchenko, V. V.; Khilya, V. P. 5-phenyl-2-(pyrazol-4-yl)-1, 3, 4-thiadiazoles. Chem. Heterocyclic Compd 2005, 41(5), 673-678;
    [204] Lin, G.; Lei, J.. Synthesis of coumafin derivatives and application as antifungal agent. CN 1450062, 2003-06-09
    [205] Aitmambetov, A.; Ismailova, G. O.; Ibragimova, Z. Y. Synthetic and modified isoflavonoids. Part Ⅹ. Reaction of pseudobaptigenin analogs with P_2S_5. Chem. Nat. Compd. 2004, 40(5), 444-446
    [206] Khilya, V. P.; Tkachuk, T. M.; Shevchuk, L. I. Synthesis of thiazole analogs of isofiavoliguans. Chem. Nat. Compd. 2001, 36(6), 574-578;
    [207] Turov, A. V.; Khilya, V. P. Effects of chelation on the interaction of substituted 3-hetaryl-4-thioxochromones with lanthanide shift reagents. Chem. Heterocyclic Compd. 2000, 36(5), 527-531;
    [208] Shaw, S. C.; Kumar, Rajesh; Gupta, Anju Kumari; Dev, Avnisha. Synthesis of 6, 7, 2'-trimethoxy-4', 5'-methylenedioxy-isoflavone-a constituent of Cordyla africana (Leguminosae). Acta Cienc. Indica, Chem. 2001, 27(2), 75-76;
    [209] Emami, Saeed; Kebriaeezadeh, Abbas; Zamani, Mohammad Jafar; Shafiee, Abbas. Azolylchromans as a novel scaffold for anticonvulsant activity. Bioorg. Med. Chem. Lett. 2006, 16(7), 1803-1806;
    [210] Dyck, B.; Zhao, L.; Tamiya, J.; Pontillo, J.; Hudson, S.; Ching, B.; Heise, C. E.; Wen, J.; Norton, C.; Madan, A.; Schwarz, D.; Wade, W.; Goodfellow, V. S. Substituted chromones and quinolones as potent melaninconcentrating hormone receptor 1 antagonists. Bioorg. Med. Chem. Lett. 2006, 16(16), 4237-4242; 2006
    [211] Ding, K.; Wang, S. M. Efficient synthesis of isoflavone analogues via a Suzuki coupling reaction. Tetrahedron Lett. 2005, 46(21), 3707-3709;
    [212] Lei, Jian-Guang; Xu, Ming-Hua; Lin, Guo-Qiang. Nickel-catalyzed cross-coupling reactions of 4-mesylcoumarins with aryl halides: Facile synthesis of 4-substituted coumarins. Synlett 2004, (13), 2364-2368;
    [213] Lin, Chi-Fong; Lu, Wen-Der; Wang, I-Wen; Wu, Ming-Jung. Synthesis of 2-(diarylmethylene)- 3-benzofuranones promoted via palladium-catalyzed reactions of aryl iodides with 3-aryl-1-(2-tert- butyldimethylsilyloxy) phenyl-2-propyn-1-ones. Synlett 2003, (13), 2057-2061;
    [214] Joo, Y. H.; Kim, J. K.; Kang, S. H.; Nob, M. S.; Ha, J. Y.; Choi, J. K.; Lira, K. M.; Lee, C. H.; Chung, S. 2, 3-Diarylbenzopyran derivatives as a novel class of selective cyclooxygenase-2 inhibitors. Bioorg. Med. Chem.Lett. 2003, 13(3), 413-417;
    [215] Venkati, M.; Kmpadanam, G. L. David. A new synthesis of cis-3-substituted chroman-4-ols. Synth. Commun. 2002, 32(14), 2227-2235;
    [216] Hong, R.; Feng, J.; Hoen, R.; Lin, G.-q. Synthesis of (±)-3,3'-bis(3,4-dihydro-4-hydroxy-6-methoxy-2H-1-benzopyran): a literature correction. Tetrahedron 2001, 57(41), 8685-8689;
    [217] Yokoe, I.; Sugita, Y.; Shirataki, Y. Facile synthesis of isoflavones by the cross-coupling reaction of 3-iodochromone with arylboronic acids. Chem.Pharm. Bull 1989, 37(2), 529-30;
    [218] Bhadange, R. E.; Kolhe, S. V.; Doshi, A. G.; Raut, A. W. Synthesis of dimer by using copper metal with and without solvent. Asian J. Chem. 2001,13(3), 1249-1251;
    [219] Lin, G. q; Hong, R. A new reagent system for modified Ullmann-type coupling reactions: NiCl2 (PPh3)2/PPh3/Zn/NaH/toluene. J. Org. Chem. 2001, 66(8), 2877-2880;
    [220] Sharma, Vinay Prabha. Synthesis and bioassay of some 3-(2H-1,4-benzothiazin-3-yl)- 2-methylchromones. Asian J. Chem. 2004, 16(3-4), 1966-1968;
    [221] Ghosh, Chandra Kanta; Ghosh, Chandreyi; Karak, Sumit Kumar; Chakravarty, Ajit Kumar. Benzopyrans. Part 451. Reactions of monobrominated 3-acetyl-2-methyl-1-benzopyran-4-one with some binucleophiles. J. Chem. Res. 2004, (1), 84-86;
    [222] Ghosh, C. K.; Karak, S. K.; Patra, A. Benzopyrans. Part 47. Reactions of 3-[β-(dimethylamino) acryloyl]-1-benzopyran-4-ones with some nitrogen nucleophiles. Indian J. Chem., Section B: 2004, 43B(12), 2666-2669;
    [223] Desai, J.; Nair, K. B.; Misra, A. N. Synthesis and antimicrobial activities of some new pyrazolines, phenylpyrazolines, flavanones and related compounds. Indian J. Heterocyclic Chem. 2001, 10(4), 261-266;
    [224] Luo, S. Z.; Mi, X. 1.; Xu, H.; Wang, P. G.; Cheng, J. P. Efficient Baylis-Hillman Reactions of Cyclic Enones in Methanol As Catalyzed by Methoxide Anion. J. Org. Chem. 2004, 69(24), 8413-8422;
    [225] Basavaiah, Deevi; Rao, Anumolu Jaganmohan. 1-Benzopyran-4(4H)-ones as novel activated alkenes in the Baylis-Hillman reaction: a simple and facile synthesis of indolizine-fused-chromones. Tetrahedron Lett. 2003, 44(23), 4365-4368;
    [226] Risitano, Francesco; Grassi, Giovanni; Foil, Francesco. Risitano, Francesco; Grassi, Giovanni; Foti, Francesco. Reactions of 3-substituted chromones with o-phenylenediamine. J. Heterocyclic Chem. 2001, 38(5), 1083-1086;
    [227] El-Shenawy, A. I. Synthesis and biological activity of 2-[3, 7-diacetyl-8- (2-cyanomethyl) -4, 6-dioxo-4H, 6H-pyrano [3, 2-g] chromen-2-yl] acetonitrile and its derivatives. Egyptian J. Chem. 2002, 45(4), 787-795;
    [228] Kumbhare, R. M.; Chinchkhede, P. W.; Ingle, V. N. Synthesis of benzopyranopyrazoles. Asian J. Chem. 2000, 12(2), 501-505;
    [229] El-Fotooh, G. H, A.; Abd El-Salam, O. I.; Mohamed, A. M.; Abdel H. N. Novel fluoro substituted benzo[b]pyran with anti-lung cancer activity, Indian J. Chem., Section B: 2005, 44B (9), 1887-1893;
    [230] Hammam, A. E. F. G.; Fahmy, A. F. M.; Amr, A. G. I. E.; Mohamed, A. M. Synthesis of novel tricyclic heterocyclic compounds as potential anticancer agents using chromanone and thiochromanone as synthons. Indian J. Chem. Section B. 2003, 42B (8), 1985-1993;
    [231] Rudenko, R. V.; Desenko, S. M.; Chebanov, V. A.; Chemenko, V. N.; Musatov, V. I. Synthesis and rearrangement of benzopyrano[4,3-c]pyrazole derivatives. Mendeleev Commun. 2005, (2), 83-84;
    [232] Levai, A. Fused heterocycles. 8. An efficient procedure for the stereoselective synthesis of trans-2,3,3a,4-tetrahydro-3-aryl-2-phenyl[1]benzopyrano[4,3-c]pyrazoles and their [1]benzothiopyrano analogs. J. Heterocyclic Chem. 1998, 35(1), 13-16;
    [233] Toth, G.; Szollosy, A.; Lorand, T.; Konya, T.r; Szabo, D.; Foldesi, A.; Levai, A. Fused heterocycles. Part 3. Synthesis and stereochemistry of benzopyrano- and benzothiapyrano [4, 3-c] pyrazoles J. Chem. Soc., Perkin Trans. Ⅱ. 1989, (4), 319-23;
    [234] Sangwan, N. K. Use of characteristic proton NMR chemical shifts to differentiate diastereoisomeric [1] benzopyrano [4, 3-c] pyrazoles, pyrazolo [4, 3-c] quinolines, and related compounds. J. Chem. Res., Synop. 1987, (1), 22-3;
    [235] Kamecki, J.; Perka, W.; Pijewska, L. 3-Arylideneflavanones. Part Ⅰ. Reactions with nucleophilic reagents. Pol. J. Chem. 1985, 59(3), 285-92;
    [236] Levai, A.; Szollosy, A.; Toth, G. Fused heterocycles. Part 2. Synthesis and stereochemistry of benzopyrano [4, 3-c] pyrazolines and related compounds. J. Chem. Res. Synop. 1985, (12), 392-3;
    [237] Sangwan, N. K.; Rastogi, S. N. Studies in antifertility agents. Part ⅩⅩⅫ. Synthesis and stereochemistry of 3,3a-trans- and cis-2(H)-acetyl-3-aryl-3,3a-dihydropyrazolo[4,3-c][2H] chromenes, pyrazolo[3,4-a] benzocycloalk-1-enes and 3,3a-trans- and cis- (2H)-acetyl-3-aryl-8-methoxy-5-tosyl-3,3a,4,5-tetrahydro-pyrazolo[4,3-c] quinolines. Indian J. Chem. Section B. 1981, 20B (2), 135-9;
    [238] Breslin, M. J.; Coleman, P. J.; Cox, C. D.; Neilson, L. A.; Whitman, D. B. Preparation of pyrazole derivatives as mitotic kinesin inhibitors for treatment of cellular proliferative diseases. WO Patent 2 006 086 358 A2, 2006
    [239] Collins, Ian James; Leeson, Paul David; Rowley, Michael. Preparation of fused tricyelic heteroaromatic derivatives as dopamine receptor subtype ligands. WO Patent 9 507 262, 1995
    [240] Bellassoued, F. M. C.; Maitte, P. Reactivity of cyclic β-enaminones. Ⅱ. Direct eyclocondensation of amidines, hydrazines, and hydroxylamine with 3-(pyrrolidinomethylene)-4-chromanone. J. Heterocyclic Chem. 1986, 23(6), 1753-6;
    [241] Muthusubramanian, L.; Misra, G. S. Synthesis of bromonaphtho-pyranoisoxazoles and pyrazoles as potential antimicrobial agents. Eur. J. Med. Chem. 1986, 21(2), 163-6;
    [242] Subramanian, L. M.; Misra, G. S. Synthesis of naphthopyranoisoxazoles and naphthapyranopyrazoles via cyanoethylation. Synthesis 1984, (12), 1063-5;
    [243] Di-Parsia, M. T.; Suarez, C.; Vitolo, M. J.; Marquez, V. E.; Beyer, B.; Urbina, C.; Hurtado, I. Synthesis and study of the potential antiallergic activity of some pyrazole derivatives. J. Med Chem 1981, 24(1), 117-19;
    [244] Dean, F. M.; Murray, S. 3-(Hydroxymethylene) chroman-4-one. J. Chem. Soc., Perkin Trans, 1:1975, (17), 1706-11;
    [245] Bedair, A. H.; Ammar, Y. A.; El-Agrody, A. M.; Mohamed, Y. A. Reactions with 5:6-benzo[f] chroman-4-one. Proc. R. Soc. London, Ser. A 1987, 53(2), 308-16;
    [246] Press, J. B.; Bimberg, G. H. Heterocyclic-fused benzopyrans as cannabinoid analogs. J。Heterocyclic Chem. 1985, 22(2), 561-4;
    [247] Chandrasekhar, S.; Rajaiah, G.; Srihari, P. New and practical synthesis of 1, 4-dihydro- benzopyranopyrazoles. Tetrahedron Lett. 2001, 42(37), 6599-6601;
    [248] Lahm, G, P.; Harrison, C. R.; Daub, J. P.; Shapiro, R.; Long, J. K.; Allen, D. E.; March, W. A.; Griswold, S. M.; March, R. W.; Reeves, B. M. Synthesis and biological activity of indazole insecticides. ACS Symp. Ser. 2002, 110-120;
    [249] Bishop, J. E.; Flaxman, K. A.; Orlek, B. S.; Sammes, P. G.; Weller, D. J. Steric acceleration of intramolecular oxime and hydrazone cycloadditions. J. Chem. Soc., Perkin Trans. 1 1995, (20), 2551-5;
    [250] Rai, K. M. Lokanatha; Hassner, A. Synthetic methods. 30. Chloramine-T in heterocyclic synthesis. A simple procedure for the generation of nitrilimines and its application to the synthesis of pyrazolines. Synth. Commun. 1989, 19(16), 2799-807;
    [251] Meier, H.; Heimgartner, H. Intramolecular 1, 3-dipolar cycloadditions of diarylnitrilimines generated from 2, 5-diaryltetrazoles. HeIv Chim. Acta 1985, 68(5), 1283-300;
    [252] Shimizu, T.; Hayashi, Y.i; Nakano, M.; Teramura, K. Intra-and intermolecular [3+2] cycloadditions of aldehyde or ketohydrazones. Bull. Chem. Soc. Jpn. 1984, 57(1), 134-41;
    [253] Janietz, D.; Rudorf, W. D. [1] Benzopyrano [4, 3-c] pyrazoles by intramolecular nitrile imine addition to acetylenes. Tetrahedron 1989, 45(6), 1661-6;
    [254] Tsuge, O.; Ueno, K.; Kanemasa, S. Intramolecular 1, 3-dipolar cydoaddifions to a furan ring, Chem. Lett 1984, (2), 285-8
    [255] Schmitt, G.; Lande, B. Intramolecular cycloadditions of nitrilimines on olefins and acetylenes. Tetrahedron Lett. 1978, (39), 3727-8;
    [256] Padwa, A.; Nahm, S.; Sato, E. Photochemical transformations of small ring heterocyclic compounds. 9. Intramolecular 1, 3-dipolar cycloaddition reactions of alkenyl-subituted nitrile imines. J. Org. Chem. 1978, 43(9), 1664-71;
    [257] Shimizu, T.; Hayashi, Y.; Miki, M.; Teramura, K. Reactions of aldehydes with hydrazine hydrochlorides in the presence of dipolarophiles: intra-and intermolecular [3+2] cycloadditions. J. Org. Chem. 1987, 52(11), 2277-85;
    [258] Janietz, D.; Rudolf, W. D. Benzopyrano [4, 3-c] pyrazoles by intramolecular nitrile imine addition to acetylenes. Tetrahedron 1989, 45(6), 1661-6;
    [259] Fouchet, B.; Joucla, M.; Hamelin, J. (3+2) Intramolecular cationic cycloadditions and 1, 3-dipolar cycloadditions of phenylhydrazones. Tetrahedron Lett. 1981, 22(14), 1333-6;
    [260] Shimizu, T.; Hayashi, Y.; Ishikawa, S.; Teramura, K. Intramolecular 1, 3-dipolar cycloaddition of nitrilimines bearing alkenyl groups. Bull. Chem. Soc. Jpn. 1982, 55(8), 2456-9;
    [261] Shimizu, T.; Hayashi, Y.; Kitora, Y.; Teramura, K. Intramolecular 1, 3-dipolar cycloadditions and intramolecular ene reactions of 2-(alkenyloxy)benzaldehyde arylhydrazones. Bull Chem. Soc. Jpn. 1982, 55(8), 2450-5;
    [262] Shimizu, T.; Hayashi, Y.; Nagano, Y.; Teramura, K. Intramolecular cycloaddition reactions of N-sulfonyl nitrile imides bearing alkenyl groups. Bull Chem. Soc. Jpn. 1980, 53(2), 429-34;
    [263] Meier, H.; Heinzelmann, W.; Heimgartner, H. Inter-and intramolecular trapping reactions of photochemically generated diarylnitrilimines. Chimia 1980, 34(12), 506-8.
    [264] Roberman, A. I.; Madrazo, C.; Odov, V. D. Condensed A2-pyrazolines and hydrazones isomeric to them. Vestn. Khar'kov. Un-ta 1977, 161, 100-4.
    [265] Grigg, R.; Liu, A.; Shaw, D.; Suganthan, S.; Washington, M. L.; Woodall, D. E.; Yoganathan, G. Palladium-catalyzed cascade molecular queuing-cycloaddition, cyclocondensation and Diels-Alder reactions. Tetrahedron Lett. 2000, 41(36), 7129-7133;
    [266] El-Fotooh G Hammam, Abou; Abd El-Salam, Osama I.; Mohamed, Ashraf M.; Abdel Hafez, Nagla. Indian J. Chem. Section B. 2002, 41B (9), 1887-1893;
    [267] Colotta, V.; Cecchi, L.; MeLani, F.; Palazzino, G.; Filacchioni, G. The correct synthesis of 2, 3-dihydro-2-aryl-4-R-[1] benzopyrano [4, 3-c] pyrazole-3-ones. Tetrahedron Lett. 1987, 28 (43), 5165-8;
    [268] Chantegrel, Bernard; Gelin, Suzanne. Synthesis of 3-(2-hydroxyaryl)-1-methyl-2- pyrazolin-5-ones from 4-hydroxycoumarins and their conversion to 2-methyl-1-benzopyrano [4, 3-c] pyrazol-3(2H)-one derivatives. Synthesis 1985, (5), 548-50;
    [269] Frogget, J. A.; Hockley, M. H.; Titman, R. B.;Novel preparation of 1-aryl-3-(2-hydrophenl)-2-pyrazolin-5-ones and their conversion into 2-aryl-4-methyl[1]benzoyrano[4,3-c]pyrazol-3(2H)-ones J. Chart Res. Synop. 1997,1, 30-31;
    [270] Bjoerk, Per Axel; Fex, Tomas; Pettersson, Lars Olof Goeran; Sorensen, Poul; Da Graca, Thrige Dorthe. WO Patent 2 003 004 495, 2003
    [271] Titman, R. B.; Hockley, M. H. Preparation of benzopyrano (4, 3-c) pyrazoles as immuno-modulators. WO Patent 9 303 036, 1993
    [272] Titman, R. B.; Hockley, M. H.; Gill, O. S. Preparation of 2-(2-pyridyl)-3-oxo-benzopyrano [4, 3-c] pyrazole-4-acetates and related compounds as immunomodulators. WO Patent 9 111 448, 1991
    [273] Bowen, J. G.; Hockley, M. H.; Housley, J. R.; Hunneyball, I..; Titman, R. B.; Webber, D. G. Preparation of [1]benzopyrano[4,3-c] pyrazole derivatives as immunomodulators. EP Patent 354 693, 1990
    [274] Ghosh, C. K.; Khan, S. Heterocyclic system. Part Ⅶ. Reactions of 4-oxo-4H-[1] benzopyran-3- carboxaldehyde and -3-carboxylic ester with guanidine. Indian J. Chem. Section B: 1979, 18B (2), 128-30;
    [275] Ghosh, C. K.; Pal, C. Benzopyrans. Part ⅩⅩ. 4-Oxo-4H-[1] benzopyran-3-carbonitrile/carboxylic acid: change of their reaction courses by a methyl substituent at the 2-position. Indian J. Chem. Section B: 1985, 24B (12), 1288-90;
    [276] Ghosh, C. K.., Mukhopadhyay, K. K. Reactions of 4-oxo-4H-1-benzopyran-3- carboxylic acids with phenylhydrazine, guanidine, and hydroxylamine. Synthesis 1978, 779~781
    [277] Loubinoux, B.; Colin, J. L.; Antonot-Colin, B.; Lalloz, L. Synthesis of ethyl 3-alkyl-4-oxochroman-3-carboxylates and their conversion to some derivatives. Tetrahedron 1987, 43(1), 93-100;
    [278] Kastari, T. R.; Arunchalam, T.; Indian J. Chem. 1970, 8, 203-206
    [279] Colotta, V.; Cecchi, L.; Melani, F.; Filacchioni, G.; Martini, C.; Gelli, S.; Lucacchini, A. Tricyclic heteroaromatic systems: [1]benzopyranopyrazol-4-ones as benzodiazepine receptor ligands. J. Pharm. Sci. 1991, 80(3), 276-9;
    [280] Chantegrel, B.; Nadi, A. I.; Gelin, S. 4-Oxo-1H- and -2H-[1] benzopyrano [4, 3-c] pyrazoles. Preparation from 4-hydroxycoumarin or 3-chromonecathoxylic acid derivatives. Tetrahedron Lett. 1983, 24(4), 381-4;
    [281] Eiden, F.; Zimmerman, E. Pyrans and pyridones. Part 61. The reaction of 4-hydroxycoumarin, 4-hydroxy-1-thiocoumarin and 4-mercaptocoumarin with diphenylketene. Arch. Pharm. 1976, 309(8), 619-25;
    [282] Colotta, V.; Cecchi, L; Filacchioni, G.; Melani, F.; Palazzino, G.; Martini, C.; Giannaccini, G.; Lueacchini, A. Synthesis, binding studies, and structure activity relationships of 1-aryl- and 2-aryl[1]benzopyranopyrazol-4-ones, central benzodiazepine receptor ligands. J. Med. Chem. 1988, 31(1), 1-3;
    [283] Mulwad, V. V.; Shirodkar, J. M. Synthesis of antibacterial compounds from 4-hydroxycoumarins. Part Ⅱ. Indian J. Chem. 2002, 41B (6), 1263-1267;
    [284] Checchi, S.; Pecori V. L.; Vincieri, F. 4-Hydroxycoumarins. Ⅷ. Substitution reactions of 4-chloro-3-cyanocoumarins. Gazz. Chim. Ital. 1968, 98(12), 1488-1502;
    [285] Budzisz, E.; Malecka, M.; Nawrot, B. Synthesis and structure of highly substituted pyrazole ligands and their complexes with platinum(Ⅱ) and palladium (Ⅲ) metal ions. Tetrahedron 2004, 60(8), 1749-1759;
    [286] Saloutin, V. I.; Bazyl, I. T.; Skryabina, Z. E.; Kisil, S. P. Reaction of 3-carboxy (ethoxycarbonyl) substituted 5, 6, 7, 8-tetrafluorochromones with N-nucleophiles. Russ. J. Org. Chem. 1997, 33(8), 1167-1175;
    [287] Litkei, G.Y.; Khilya, V. P.; Turov, A. V.; Szilagyi, L; Bokotey, S.; Synthesis of spirocyclopropanecarboxylic acids from flavanones and their transformation into pyridazinones. Khim. Geterotsiklicheskikh Soedinenii 1995, (5), 616-23.
    [288] Cignarella, G.; Barlocco, D. Unexpected behavior of the oxidizing agent sodium m-nitrobenzenesulfonate: synthesis of a new class of 5-hydroxy [1] benzopyrano [4, 3-c] pyridazin-3(2H)-ones. J. Heterocyclic Chem. 1995, 32(1), 79-80.
    [289] Mahmound, M. R. Studies on novel heterocyclic ring systems. Reactions of 2-[p-(N,N1-dimethylaminophenyl)]naphtho[2,1-b]-2,3-dihydropyran-4-one with 2-mercaptoaniline and formation of naphtho[2,1-b]pyrano[4,3-c]pyridazin-3-one derivative. Synthetic Commun. 1994, 24(14), 2057-62.
    [290] Hogale, M. B.; Chavan, P. B.; Kharade, D. R. Synthesis of some new benzopyranpyridazin-3-ones. J. Indian Chem. Soc. 1992, 69(7), 405-6.
    [291] Cignarella, G.; Barlocco, D.; Villa, S.; Curzu, M. M.; Pinna, G. A.; Lavezzo, A.; Tricyclic 3-(2H)-pyridazinone derivatives. Synthesis and evaluation of their antisecretory and antiulcer activity. Eur. J. Med. Chem. 1992, 27(8), 819-23.
    [292] Cignarella, G.; Barlocco, D.; Curzu, M. M.; Pinna, G. A.; Cazzulani, P.; Cassin, M.; Lumachi, B. Synthesis and pharmacological evaluation of 4,4a-dihydro-5H-[1]benzopyrano [4,3-c]pyridazin-3(2H)-one bioisosteres of antihypertensive and antithrombotic benzo[h] cinnolinones. Eur. J. Med. Chem. 1990, 25(9), 749-56.
    [293] Nakao, Tohru; Kawakami, Minoru; Morita, Kenji; Obata, Minoru; Morimoto, Yasuto; Takehara, Shuzo; Studies on the synthesis of condensed pyridazine derivatives. Ⅱ. Synthesis and anxiolytic activities of 2-aryl-4,4a, 5, 6-tetrahydropyridazino [4, 3-c] quinolin- 3(2H)-ones, 2-aryl-4a, 5- dihydro-2H-(1) benzothiopyrano [4, 3-c] pyridazin-3(4H)-ones, and related compounds. Yakugaku Zasshi 1990, 110(8), 573-85
    [294] Cignarella, Giorgio; Barlocco, Daniela; Rossi, Guendalina; Spirocyclopro-panecarboxylic acids derived from 1-tetralone and 4-chromanone and their conversion to the corresponding pyridazinones. Synthesis 1990, (2), 160-2.
    [295] Grigg, R.; Dowling, M.; Jordan, M. W. X: Y-ZH systems as potential 1, 3-dipoles. Part 13. Prototropie generation of azomethine imines from hydra. Tetrahedron 1987, 43(24), 5873-86.
    [296] Shimizu, T.; Hayashi, Y.; Kitora, Y.; Intramolecular 1, 3-dipolar cyeloadditions and intramolecular erie reactions of 2-(alkenyloxy) benzaldehyde arylhydrazones. Bull. Chem. Soc. Jpn. 1982, 55(8), 2450-5.
    [297] Fouchet, B.; Joucla, M.; Hamelin, J. (3+2) Intramolecular cationic cycloadditions and 1, 3-dipolar cycloadditions of phenylhydrazones. Tetrahedron Lett. 1981, 22(14), 1333-6;
    [298] Hajela, Kanchan; Kapil, R. S. Synthesis of substituted benzopyranopyridazinones and pyridazines, Indian J. Chem. 1990, 29B (7), 685-7.
    [299] Shimizu, T.; Hayashi, Y. ; K. Y.; Teramura, K. Intramolecular 1,3-dipolar cycloadditions and intramolecular ene reactions of 2-(alkenyloxy)benzaldehyde arylhydrazones. Bull. Chem. Soc. Jpn, 1982, 55(8), 2450-5;
    [300] 胡利明,李学恕,陈志远,刘钊杰,含1H-吡唑和噻(二)唑的新型双杂环化合物的合成及其生物活性。有机化学,2003,23(10),1131-1134
    [1] Dolle, R. E. Comprehensive Survey of Combinatorial Library Synthesis: 1999. J. Comb. Chem. 2000, 2, 383-433.
    [2] Dolle, R. E. Comprehensive Survey of Combinatorial Library Synthesis: 2000. J. Comb. Chem. 2001, 3, 477-517.
    [3] Dolle, R. E. Comprehensive Survey of Combinatorial Library Synthesis: 2001 J. Comb. Chem. 2002, 4, 369-418.
    [4] Kirschning, A.; Monenschein, H.; Wittenberg, R.: Functionalized polymers—emerging versatile tools for solution-phase chemistry and automated parallel synthesis. Angew. Chem. Int. Ed Engl. 2001, 40: 650-679.
    [5] Santagada, V.; Perissutti, E.; Caliendo, G. The Application of Microwave Irradiation as New Convenient Synthetic Procedure in Drug Discovery. Curr. Med. Chem. 2002, 9. 1251-1283
    [6] Tietze, L. F.; Hippe, T.; Steinmetz, A. Synthesis of Enantiopure Vitamin E via Sharpless Bishydroxylation of an Enyue. Synlett 1996, 11, 1041-1042.
    [7] Swamy, K. M. K.; Yeh, W. B.; Lin, M.J; Sun, C. M. Microwave-Assisted Polymer-Supported Combinatorial Synthesis. Curr. Med. Chem. 2003, 10, 2403-2423
    [8] Nielsen, J.; Hoel, A. M. L. Microwave-assisted solid-phase Ugi four-component condensations. Tetrahedron Lett. 1999, 40, 3941-3944.
    [9] Stadler, A.; Kappe, C. O. Automated Library Generation Using Sequential Microwave-Assisted Chemistry. Application toward the Biginelli Multicomponent Condensation. J. Comb. Chem. 2001, 3, 624-630.
    [10] Brain, C. T.; Branton, S.A. Synthesis of 1, 3, 4-Oxadiazoles Using Polymer-supported Reagents. Synlett, 2001, 3, 382-384.
    [11] Bendale, P. M.; Sun, C. M. Rapid Microwave-Assisted Liquid-Phase Combinatorial Synthesis of 2-(Arylamino) benzimidazoles. J. Comb. Chem. 2002, 4, 359-361.
    [12] Wu, C. Y.; Sun, C. M. Parallel Synthesis of 1, 2, 3, 4-Tetrahydro-β-carbolines Using Microwave Irradiation. Synlett, 2002, 17, 1709-1711.
    [13] Dallinger, D.; Gorobets, N. Y.; Kappe, C. O. Rapid Microwave-Assisted Liquid-Phase Combinatorial Synthesis of 2-(Arylamino) benzimidazoles. Org. Lett. 2003, 5, 1205-1208.
    [14] Chang, W. J.; Yeh, W. B.; Sun, C. M. Microwave-Assisted Soluble Polymer-Supported Synthesis of Benzopiperazinones Synlett 2003, 18, 1688-1692.
    [15] Lin, M. J.; Sun, C. M. Focused Microwave-Assisted Parallel Synthesis of bis-Benzimidazoles. Synlett 2004, 18, 663-666.
    [16] Lee, M. J.; Sun, C. M.; Traceless synthesis of hydantoin by focused microwave irradiation Tetrahedron Lett. 2004, 45,437-440.
    [17] Tung, C. L.; Sun, C. M. Liquid phase synthesis of chiral quinoxalinones by microwave irradiation Tetrahedron Lett. 2004, 45, 1159-1162.
    [18] Nuchter, M.; Ondruschka, B.; Bonrath, W.; Gum, A. Microwave assisted synthesis-a critical technology overview. Green Chem. 2004, 6, 128-131.
    [19] Kappe, C. O. Controlled Microwave Heating in Modern Organic Synthesis. Angew. Chem. Int. Ed. 2004, 43, 6250-84.
    [20] Larhed, M.; Hallberg, A. Microwave-assisted high-speed chemistry: a new technique in drug discovery. Drug Discovery Today 2001, 6, 406-416.
    [21] Lu, Y. M.; Zhang, W. Microwave-assisted Synthesis of a 3-Aminoimidazo [1, 2-a]-pyridine/pyrazine Library by Fluorous Multicomponent Reaefions and Subsequent Cross-coupling Reactions. QsAR & Comb. Sci., 2004, 23 (10), 827-835
    [22] 谢心宏,王福久.噻虫啉——一种新型的叶面施用杀虫剂,农药,2001, 40 (1), 41-42
    [23] Uneme, H.; Iwanaga, K; higuchi, N, Hguchi, N.; Kando, Y.; Okauchi, T.; Akayama, A.; Minamida, I. Synthesis and insexticidal activity of nitroguanidine derivatives. Pestic Sci. 1999, 55(2), 202-205
    [24] 陈立、徐汉虹.新型烟碱型杀虫剂吡虫啉作用机制研究进展.湖北农学院学报,1998,18(1),85-88
    [25] Iwataki, I.; Kaeriyama M.; Matsui, N.; et al., Heterocylic Compounds. US 442116, 1984-04-10
    [26] Maienfisch, P. L.; Huerlimann, H.; Rindlisbacher, A.; Gsell, L.; Dettwiler, H.; Haettenschwiler, J.; Sieger, E.; Walti, M. The discover of thiamethoxam: a second-generation neonicotinoid. Pest. Manag. Sci. 2001, 57(2), 165-176.
    [27] Paul, S.; Gupta, M. Selective Fries rearrangement catalyzed by zinc powder. Synthesis 2004, (11), 1789-1792;
    [28] Nohara, A.; Umetani, T.; Sanno, Y. Antianaphylactic agents. I. Facile synthesis of 4-oxo-4H-1-benzopyran-3-carboxaldehydes by Vilsmeier reagents. Tetrahedron 1974, 30(19), 3553-61.
    [29] 于建新,刘方明,鲁文杰,李燕萍,糟新民,刘育亭,刘从,3-(2-卓二唑啉基)-色酮类化合物的合成研究.有机化学,2000,01,72-80
    [30] Yang, G. H.; Cao, L. H.; Cui, P. Y. The synthesis of 2-(chromon-2/3-yl)-3-(5-thione- 4-hydro-1, 3, 4-thiadiazol-2-yl)-4-oxo-thiazolidine. J. Chin. Chem. Soc. 2005, 52(5), 1033-1036.
    [31] Fitton, A. O.; Humphrey, G. L.; Kosmirak, M.; Suschitzky, H.; Suschitzky, J. L. Reactions of formylchromone derivatives. Part 4. Interaction of 3-formylchromones with thioglycolic acid. J. Chem. Res., Synop. 1984, (8), 248-9
    [32] Gududuru, V.; Nguyen, V.; Dalton, J. T.; Miller, D. D. Efficient Microwave Enhanced Synthesis of 4-Thiazolidinones. Synlett 2004, 13, 2357-2358.
    [33] 李在国,汪清民,黄君珉.有机中间体的制备,化学工业出版社,第二版,1997,pp 67
    [34] Wang, B. D.; Yang, Z. Y.; Li, T.-R. Synthesis, characterization, and DNA-binding properties of the Ln (Ⅲ) complexes with 6-hydroxychromone-3-carbaldehyde 2- hydroxybenzoylhydrazone. Bioorg. Med. Chem. Lett. 2006,14(17), 6011-1021;
    [35] Wu, P.; Cao, L. H. Synthesis of 3-(3-acetyl-5-phenoxymethyl-2, 3-dihydro-1, 3, 4- oxadiazol- 2- yl) chromones. Yingyong Huaxue 2005, 22(8), 848-851;
    [36] Cao, L.; Wang, W.Synthesis of 3-(5-aryl-1, 3, 4-oxadiazol-2-yl) chromones. Chem. Heterocycl. Compd. 2003, 39(8), 1072-1075;
    [37] Chomous, V. A.; Bratenko, M. K.; Vovk, M. V.; Sidorchuk, I. I. Synthesis and antimicrobial activity of pyrazole-4-carboxylic acid hydrazides and N-(pyrazol-4-ylcarbonyl)hydrazones of aromatic and heteroaromatic aldehydes. Pharm. Chem. J. 2001, 35(4), 203-205;
    [38] Tsao, L.; Chzhan, L.; Lyu, T. Synthesis of 3-(3-acetyl-5-aroyl-1, 3, 4-oxadiazol-2-yl) chromones. Chem. Nat. Compd. 2002, 37(4), 311-314;
    [39] Cao, Ling-Hua; Huang, Yan; Liu, Yu-Ting; Sun, Guan-Zhong. Microwave irradiation promoted synthesis of 3-(3'-acetyl-5'-aryl-1',3',4'-dihydrooxadiazol-2'-yl)- chromones. Yingyong Huaxue 2001, 18(4), 312-314;
    [1] 陈文彬,金桂玉,含稠杂环新农药的研究进展,农药学学报 2000,12(4),1~10。
    [2] Ghosh, C. K.; Khan, S. Heterocyclic systems; Defunctionalization of 4-oxo-4H-[1] benzopyran- 3-carboxylic acids and -3-carboxaldehydes. Synthesis 1981, (9), 719-21.
    [3] Jpn. Kokai Tokkyo Koho, Chromone-3-carboxylic acids. JP 57059883A2, 1982-04-10
    [4] Machida, Y.; Nomoto, S.; Negi, S.; Ikuta, H.; Saito, I. Oxidation of 4-oxo-4H-1-benzopyran-3- carboxaldehydes with N-bromosuccinimide. Synth. Commun. 1980, 10(12), 889-95;
    [5] Cao, L. H.; Zhang, L.; Cui, P. Y. Synthesis of 3-(3-alkyl-5-thioxo-1H-4, 5-dihydro-1, 2, 4-triazol-4-yl)-aminocarbonylchromones. Chem. Heterocycl. Compd. 2004, 40 (5), 635-640;
    [6] Ghosh, T.; Patra, R.; Bandyopadhyay, C. Study of differences in the reactivity of alkyl and aryl nitrones derived from 4-oco-4H-1-benzopyran-3- carboxaldehyde. J. Chem. Res. 2004, (1), 47-49;
    [7] Cao, L. H.; Zhang, L.; Gu, J. Synthesis of 3-(3'-aryl-5'-thione-1',2',4'-triazole-4'-yl)- aminocarbonyl chromones. Youji Huaxue 2002, 22(6), 405-410;
    [8] Okumura, K.; Kondo, K.; Oine, T.; Inoue, L Synthesis of chromone- 3-carboxanilides. Chem. Pharm. Bull. 1974, 22(12), 2959-65;
    [9] Al-Houari, Ghali; B.; Bouchra F.; Bennani, B.; Ben-Larbi, N.; Kerbal, A.i; Laude, B.; Vebrel, J. Cycloaddition on some diarylnitrilimines on 3-substituted 4H-1-benzopyran-4-ones regiochemistry of the pyrazolines and pyrazoles obtained. J. Marocain de Chimie Heterocyclique 2002,1(1), 22-30;
    [10] Ghosh, C. K.; Mukhopadhyay, K. K. Reactions of 4-oxo-4H-1-benzopyran-3-carboxylic acids with phenylhydrazine, guanidine, and hydroxylamine. Synthesis 1978, (10), 779-81.
    [11] Gross H.; Butger, W. P-Chlorophnoxymethyl chloride. Organic synthesis 1973, 5, 221-222
    [12] Loubinoux, B.; CoLin, J. L; Antonot-Colin, B.; Lalloz, Lucien. Fac, S., Univ. Nancy I, Vandoeuvre Les Nancy, Fr. Synthesis of ethyl 3-alkyl-4-oxochroman-3-carboxylates and their conversion to some derivatives. Tetrahedron 1987, 43(1), 93-100.
    [13] Ciganek, E. Esters of 2, 3-Dihydro-3-oxobenzofuran-2-acetic Acid and 3, 4-Dihydro- 4-oxo-2H-1-benzopyran-3-acetic Acid by Intramolecular stetter Reactions. Synthesis 1995, 1311-1314
    [14] Enders, D.; Breuer, K.; Runsink, J.; Teles, J. H. The First Asymmetric Intramolecular Stetter Reaction. Helv. Chim. Acta. 1996, 79, 1899-1902.
    [15] Langley, W.D. p-Bromophencyl Bromide, Organic synthesis 1929, 1,127-128
    [16] Mosher, W. R.; Serrdge, P. M.; Lipp, D. W. Reactions of 2-Actl-3(2H)-benfuranones with hydrazines and Diamines. J. Org. Chem. 1975, 37(15), 2402-2404
    [17] Mazumdar, A. K. D.; Karmakar, P. K.; Rangachari, K.; Banerjee, K. R.; BanerJI, K. D. Synthesis of some 2-(2'-methoxybenzoyl)-coumaran-3-ones. J. Indian Chem. Soc. 1990, 61, 911-913.
    [18] Geissman, T. A.; Armen, A. The rearrangement of 2-Acetyl- and 2-benzoylcoumarone Oxime p-Toluenesufonates. J. Am. Chem. Soc. 1955, 77, 1623-1627.
    [19] Bryant, B.; Haslam, D. L. Synthesis of some 2-benzoylcoumaran-3-ones and some related ω-(2-methoxycarbonyl-phenoxy) acetophenones. J. Chem. Soc. 1965, 77, 2361-2364.
    [20] Bryant, B.; Chromono(2',3':3,2)benzofurans, J. Chem. Soc. 1965, 5140-5141
    [21] Oandit, U. K.; Bruicr, T. C. Imidazole Catalysis Ⅶ. The Dependence of Imidazole Catalysis of Ester Hydrolysis on the nature of the Acyl Group. J. Am. Chem. Soc. 1960, 82, 3386-3390;
    [22] Cremins, P. J.; Hayes, R.; Wallace, T. W. Hetrroannulation of 4-OXO-4H-1- benzophyans (chromones) via the conjugate addition of haloalkanols in the presence of base. Tetrahedron 1991, 47, 9431-9438
    [23] Abdallah, H.; Gree, R.; Carrie, R. Reaction of diazoacetaldehyde dimethyl acetal with electrophilic coumarins and a chromone. Bulletin de la Societe Chimique de France 1984, (7-8, Pt. 2), 338-44.
    [24] Al Houari, Ghali; Baba, Bouchra Filali; Bennani, Brahim; Ben Larbi, Najib; Kerbal, Abdelali; Laude, Bernard; Vebrel, Joel. Cycloaddition on some diarylnitrilimines on 3-substituted 4H-1-benzopyran-4-ones regiochemistry of the pyrazolines and pyrazoles obtained. Journal Marocain de Chimie Heterocyclique 2002, 1(1), 22-30;
    [25] Modranka, R.; Ochocki, J. Convenient synthesis of phosphonate derivatives of 4-chloro-2H- chromenes. Pol. J. Chem. 2004, 78 (7), 943-950;
    [26] Kumar, R.; Nath, M.; Tyrrell, D. Lorne J. Design and Synthesis of Novel 5-Substituted Acyclic Pyrimidine Nucleosides as Potent and Selective Inhibitors of Hepatitis B Virus. J. Med. Chem. 2002, 45 (10), 2041-2055
    [27] Machida, Y.; Nomoto, S.; Negi, S.; Ikuta, H.; Saito, I. Oxidation of 4-oxo-4H-1- benzpyran-3-carboxaldehydes with N-bromosuccinimide. Synth. Commun. 1980, 10 (12), 889-895
    [28] Cremins, Peter J.; Saengehantara, Suthiweth T.; Wallace, Timothy W. Cycloadditions of substituted benzopyran-4-ones to electron-rich dienes: a new route to xanthone derivatives. Tetrahedron 1987, 43(13), 3075-82;
    [29] Barili, P. L; Valenti, P.; Artali, R.; Bombieri, G.; Da Re, P. Synthesis and properties of 6-fluoro-7-chloro-4-oxo-4H-chromene 3-carboxylic acid. X-ray structure of achiral heterotopic 3-diethoxymethyl-6- fluoro- 7- chloro-4-oxo-4H-chromene. Zeitschrift fuer Kristallographie 2001, 216(11), 600-603;
    [30] Dugdr, Sundeep; O'Neil, Steven V. Preparation of bicyclic acyl guanidines as sodium/proton exchange inhibitors. WO 2000064445 A1, 2000-11-02
    [31] Hoegberg, T.; Vora, M.; Drake, Steven D.; Mitscher, Lester A.; Chu, D. T. W. Structure-activity relationships among DNA-gyrase inhibitors. Synthesis and antimicrobial evaluation of chromones and coumarins related to oxolinic acid. Acta Chem. Scand. 1984, B38 (5), 359-66;
    [32] Dunn, W. J., Ⅲ; Hopfinger, A. J.; Catana, C.; Duraiswami, C.J. Med. Chem.; 1996; 39(24), 4825-4832.
    [33] Hunter, C. A.; Sanders, J. K. M.The nature of .pi.-.pi. Interactions. J. Am. Chem. Soc. 1990; H2(14); 5525-5534.
    [34] Bernstein, J.; Davis, R. E.; Shimoni, L.; Chang N. L. Patterns in Hydrogen Bonding: Functionality and Graph Set Analysis in Crystals. Angew. Chem. Int. Ed. Engl. 1995, 34 (15), 1555-1573
    [35] Mehta, G.; Sen, S.; Ramesh, S. S.; Crystal Structures of Conformationally Locked Cyclitols: An Analysis of Hydrogen-Bonded Architectures and their Implications in Crystal Engineering. Eur. J. Org. Chem. 2007, 3, 423-436
    [1] Khattab, A. M.; Grace, M. H.; El-Khrisy, E. A. A new flavone derivative from Ehretia ovalifotia leaves. Pharmazie 2001, 56, 661-662;
    [2] Horie, T.; Tominaga, H.; Kawamura, Y.; Hada, T.; Ueda, N.; Amano, Y.; Yamamoto, S. Synthesis of 5, 7, 8- and 5, 6, 7-trioxygenated 3-alkyl-3', 4'-dihydroxyflavones and their inhibitory activities against arachidonate 5-lipoxygenase. J. Med. Chem. 1991, 34, 2169-2176;
    [3] Van Acker, F. A. A.; Hageman, J. A.; Haenen, G. R. M. M.; Van der Vijgh, W. J. E; Bast, A.; Menge, W. M. P. B. Synthesis of Novel 3,7-Substituted-2-(3',4'-dihydroxyphenyl)flavones with Improved Antioxidant Activity. J. Med. Chem. 2000, 43, 3752-3760;
    [4] Nussbaumer, P.; Lehr, P.; Billich, A. 2-Substituted 4-(Thio)chromenone 6-O-Sulfamates: Potent Inhibitors of Human Steroid Sulfatase. J. Med. Chem. 2002, 45, 4310-4320;
    [5] Souza, J.; Molfetta, J. F. A.; Honorio, K. M.; Santos, R. H. A.; Silva, A. B. F. A Study on the Antipicornavirus Activity of Flavonoid Compounds (Flavones) by Using Quantum Chemical and Chemometric Methods. J. Chem. Inf. Comput. Sci. 2004, 44, 1153-1161
    [6] Lokshin, V.; Heynderickx, A.; Samat, A.; Pepe, G.; Guglielmetti, R. New and facile synthesis of 3-styrylflavones. Tetrahedron Lett. 1999, 40, 6761-6764;
    [7] Pinto, D. C. G. A.; Silva, A. M. S.; Almeida, L. M. P. M. J.; Cavaleiro, A. S.; Elguero, J. 3-Aroyl-5- hydroxyflavones: Synthesis and Transformation into Aroylpyrazoles. Eur. J. Org. Chem. 2002, 3807-3815;
    [8] Joo, Y. H.; Kim, J. K.; Kang, S. H.; Nob, M. S.; Hal, J. Y.; Cho, J. K.; Lim, K. M.; Lee, C. H.; Chung, S. 2, 3-Diarylbenzopyran derivatives as a novel class of selective cyclooxygenase-2 inhibitors. Bioorg. Med. Chem. Lett. 2003, 13, 413-417;
    [9] Pal, M.; Subramanian, V.; Parasuraman, K.; Yeleswarapu, K. R. Palladium catalyzed reaction in aqueous DMF: synthesis of 3-alkynyl substituted flavones in the presence of prolinol. Tetrahedron 2003, 59, 9563-9570;
    [10] Pal, M.; Parasuraman, K.; Subramanian, V.; Dakarapu, R.; Yeleswarapu, K. R.; Palladium mediated stereospecific synthesis of 3-enynyl substituted thioflavones/flavones. Tetrahedron Lett. 2004, 45, 2305-2309.
    [11] Sonare, S. S.; Doshi, A. G. A new synthesis of 3-bromoflavones. J. India Chem. Soc. 1992, 69, 875-875;
    [12] Rho, H. S.; Ko, B. S.; Kim, H. K.; Ju, Y. S.; Synthesis of 3-bromo derivatives flavones. Synthetic Communications Synth. Commun. 2002, 32, 1303-1310;
    [13] Joo, Y. H.; Kim, J. K.; Kang, S. H.; A convenient synthesis of 3-bromoflavones. Synth. Commun. 2002, 32, 1653-1658;
    [14] Joo, Y. H.; Kim, J. K.; A facile synthetic method of 3-bromoflavones. Synth. Commun. 1998, 28, 4287-4293.
    [15] Ramanarayanan, G. V.; Shukla, V. G.; Akamanchi, K. G. A Novel and One Step Procedure for Preparation of α-Bromo-α,β-tmsaturated Carbonyl Compounds. Synlett 2002, (12), 2059-2061.
    [16] Mazumdar, A. K. D.; Karmakar, P. K.; Tiwari, S. K.; Banerjee, K. P.; Banerji, K. D. Synthesis of some 2-(2'-methoxyphenyl)chromones. J. Indian Chem. Soc. 1990, 67 (10), 845-847.
    [17] Kalinin, V. N.; Shostakovskii, M. V.; Ponomarev, A. B. Palladium-catalyzed synthesis of flavones and chromones via carbonylative coupling of o-iodophenols with terminal acetylenes.Terahedron Lett. 1990, 31, 4073-4076
    [18] Shankar, Ch. G.; Mallarah, B. Veera.; Srimannarayana, G. Dehydrogenation of Chromanones and Flavanones by 2, 3-Dichloro-5, 6-dicyano-1, 4-benzoquinone (DDQ): A Facile Method for the Synthesis of Chromones and Flavones. Synthesis 1983, 310-314;
    [19] Refat, H. M.; Heterocyelic Synthesis with Nitriles: Synthesis of Some New Claromone and Flavone and Its Utilization for the Synthesis of Potentially Antitumorigenic Polycyclic Chromones and Flavones. Synth. Commun. 1999, 29 (9), 1429-1436.
    [20] Doshi, A. G.; Soni, P. A. B.; Ghiya, J. Oxidation of 2'-hydroxychalcones. Indian J. Chem. 1986, 25B, 759;
    [21] Singh, Om V.; Kapoor, R. P. Dehydrogenation of flavanones to flavones using thallium (Ⅲ) acetate (TTA). Tetrahedron Lett. 1990, 31(10), 1459-62.
    [22] Prakash, O.; Pahuja, S. Synthesis of flavones from the hypervalent iodine oxidation of flavanones using [hydroxy(tosyloxy)iodo]benzene in methanol. Synth. Commun. 1990, 20, 1417-22
    [23] Prakash, O,; Tanwar, M. P. Hypervalent Iodine Oxidation of Flavanones: Convenient and Useful Synthesis of Flavones and Isoflavones. J. Chem. Res. Sypon. 1995, 213;
    [24] Khanna, M. S.; Singh, O. V.; Garg, C. P.; Kapoor, R. P. Oxidation of Flavanones Using Thallium(Ⅲ) Salts: A New Route for the Synthesis of Flavones and Isoflavones. J. Chem. Soc. Perkin Trans.1 1992, 2565-2568;
    [25] Lorette, N.B.; Gage, T. B.; Wender, S. H. The use of N-Bromosuccinimide and pyridinium bromide perbromide in the conversion of flavones into flavones. J. Org. Chem. 1951, 16, 930-933
    [26] Ahmed, N.; Ali, H.; van Lier, J. E. Silica gel-supported InBr3 and InC13: new catalysts for the facile and rapid oxidation of 2'-hydroxychalcones and flavanones to their corresponding flavones under solvent free conditions. Tetrahedron Lett. 2005, 46, 253-256.
    [27] Looker, J. H.; Holm, M. J. Notes- A New Procedure for the Dehydragenation of Flavanones with N-Bromosuccinimide. J. Org. Chem. 1959, 24, 567-568;
    [28] Climent, M. J.; Garcia, H.; Iborra, S.; Miranda, M. A.; Primo, J.; Photosensitised dehydrogenation of flavanones to flavones using TPT. Heterocycles 1989, 29, 115-21.
    [29] Czompa, A.; Dinya, Z.; Antus, S.; Varga, Z.; Synthesis and Antioxidant Activity of Flavanoid Derivatives Containing a 1, 4-Benzodioxane Moiety. Arch. Pharm. 2000, 333 (6), 175~180
    [30] Looker, J. H.; Holm, M. J.; ANew Procedure for the Dehydrogenation of flavones using NBS. J Org Chem. 1959, 24, 567-568.
    [31] Aft, H. Chemistry of Dihydroquercetin. Ⅱ. Reaction of Partially Acetylated Polyhydroxyflavanones with N-Halosuccinimides J. Org. Chem. 1965, 30, 897-901;
    [32] Heasley, V. L.; Louie, T. J.; Luttrull, D. K.; Millar, M. D.; Moore, H. B.; Nogales, D. E; Sauerbrey, A. M.; Shibuya, T. Y.; Stanley, M. S.; Shellhamer, D. E Effect of N-bromosuccinimide (NBS) and other N-brominating agents on the bromination of .alpha.,.beta.-unsaturated ketones in methanol. J. Org. Chem. 1988, 53, 2199-2204.
    [33] Kappe, C. O. Controlled Microwave Heating in Modern Organic SynthesisAngew.. Chem. Int. Ed. 2004, 43, 6250-6284;
    [34] Lead Beater, N. E.; Torenins, H. M.; Tye, H.; Microwave-promoted organic synthesis using ionic liquids: A mini review. Comb. Chem. High Through. Screen 2004, 7, 511-528;
    [35] Wu, C. Y.; Sun, C. M. Parallel Synthesis of 1, 2, 3, 4-Tetrahydro-β-carbolines Using Microwave Irradiation. Synlett 2002, 17, 1709-1711;
    [36] Dallinger, D.; Gorobets, N. Y.; Kappe, High-Throughput Synthesis of N3-Acylated Dihydropyrimidines Combining Microwave-Assisted Synthesis and Scavenging Techniques. C. O. Org. Lett. 2003, 5, 1205-1208;
    [37] Chang, W. J.; Yeh, W. B.; Sun, C. M. Microwave-Assisted Soluble Polymer-Supported Synthesis of Benzopiperazinones. Synlett 2003, 18, 1688-1692;
    [38] Lin, M. J.; Sun, C. M. Focused Microwave-Assisted Parallel Synthesis of bis-Benzimidazoles. Synlett 2004, 18, 663-666;
    [39] Lee, M. J.; Sun, C. M. Traceless synthesis of hydantoin by focused microwave irradiation. Tetrahedron Lett. 2004, 45, 437-440.
    [40] Tung, C. L.; Sun, C. M.; Liquid phase synthesis of chiral quinoxalinones by microwave irradiation Tetrahedron Lett. 2004, 45, 1159-1162;
    [41] Nuchter, M.; Ondruschka, B.; Bonrath, W.; Gum, A. Microwave assisted synthesis-a critical technology overview. Green Chem. 2004, 6, 128-141.
    [42] Mahal, M. S.; Rai, H. S.; Venkataraman, K. Synthetical experiments in the ehromone group. ⅩⅥ. Chalcones and flavanones and their oxidation to flavones by means of selenium dioxide. J Chem. Soc. 1935, 866-8.
    [43] Baker, W.; Harbone, J. B.; Ollis, W. D. Some properties of 4-thionflavone and its methiodide and of 4-thionchromones. Journal of the Chemical Society. J. Chem. Soc. 1952, 1303-9.
    [44] Mallik, U. K.; Saha, M. M.; Mallik, A. K., Cyclodehydrogenation of 2'-hydroxychalcones and dehydrogenation of flavanones using nickel peroxide. Indian J. Chem. Soc. 1989, 20B, 970-2;
    [45] Nishinaga, A.; Ando, H.; Maruyama, K.; Mashino, T. ANew Metal Complex Promoted System for Highly Selective Synthesis of 4H-Chromen-4-ones (Chromones). Synthesis 1992, 9, 839-841.
    [46] Ciattini, P. G.; Morera, E.; Ortar, G.; Rossi, S. S. Preparative and regiochemical aspects of the palladium-catalyzed carbonylative coupling of 2-hydroxyaryl iodides with ethynylareues. Tetrahedron 1991, 47(32), 6449-56
    [47] Muthukrishnan, M.; Patti, P. S.; More, Shivaji V.; Joshi, Ramesh A. Facile oxidation of flavanones to flavones using [hydroxy(tosyloxy)iodo] benzene in an ionic liquid. Mendeleev Commun. 2005, (3), 100-101.
    [48] Hatori, S. SYNTHESE VON 3', 4'-METHYLENDIOXYFLAVON, 3', 4'-METHYLENDIOXYFLAVONOL, 3', 4'-DIMETHOXYFLAVON UND 3', 4'-DIMETHOXYFLAVONOL Bull. Chem. Soc. Jpn. 1927, 2, 171-175.
    [49] D. Bogdal, M. Lukasiewicz, J. Pielichowski, Halogenation of carbazole and other aromatic compounds with hydrohalic acids and hydrogen peroxide under microwave irradiation Green Chem. 2004, 6, 110-113;
    [50] Goswami, S.; Dey, S.; Jana, S.; Adak, A. K. Side Chain Bromination of Mono and Dimethyl Heteroaromatic and Aromatic Compounds by Solid Phase N-Bromosuccinimide Reaction without Radical Initiator under Microwave. Chem. Lett. 2004, 33, 916-917;
    [51] Rodriguez, H.; Reyes, O.; Suarez, M.; Garay, H. E.; Perez, R.; Cruz, L. J.; Verdecia, Y.; Martin, N.; Seoane, C.; Solid-phase synthesis of 4-aryl substituted 5-carboxy-6-methyl-3,4-dihydropyridones. Terahedron Lett. 2002, 43, 439-441;
    [52] Seijas, J. A.; Vazquez-Tato, M. P.; Carballido-Reboredo, R. Solvent-Free Synthesis of Functionalized Flavones under Microwave Irradiation J. Org. Chem. 2005, 70, 2855-2858.
    [53] Stadler, A.; Kappe, C. O. Microwave-assisted Michael reactions of 3-(2'-nitrovinyl) indole with indoles on TLC-grade silica gel. A new facile synthesis of 2, 2-bis (3'-indolyl) nitroethanes. Tetrahedron Lett. 2001, 57, 3915-3920
    [54] Marder, M.; Viola, H.; Wasowski, C.; Wolfman, C.; Waterman, P. G.; Cassels, B. K.; Medina, J. H.; Paladin, A. C.; X6-Bromoflavone, a high affinity ligand for the central benzodiazepine receptors is a member of a family of active flavonoids. Biochem. Biophy. Res. Commun. 1996, 223, 384-389.
    [1] Stetter, H.; Kuhlman H. Addition of Aliphatic Aldehydes to Activated Double Bonds. Angew. Chem., Int. Ed. Engl. 1974, 13, 539-539.
    [2] Stetter, H.; Schreckenberg, M. Fruhgeschichte der quantenmechanischen Behandlung der chemischen Bindung. Angew. Chem. 1973, 85, 89-94.
    [3] Stetter, H.; Kuhlmann, H. The Catalytic Nucleophilic Addition of Aldehydes to Electrophilic Double Bonds. Org. React. 1991, 40, 407-496.
    [4] Nair, V.; Bindu, S.; Sreekumar, V. N-Heterocyclic Carbenes: Reagents, Not Just Ligands! Angew. Chem. Int. Ed. 2004, 43, 5130.
    [5] Cesar, V.; Bellemin-Laponnaz, S.; Gade, L. H. Chiral N-heterocyclic carbenes as stereodirecting ligands in asymmetric catalysis. Chem. Soc. Rev. 2004, 33, 619.
    [6] Enders, D.; Balensiefer, T. Nucleophilic Carbenes in Asymmetric Organocatalysis. Acc. Chem. Res. 2004, 37, 534 -541.
    [7] Raghavan, S.; Anuradha K. Solid-phase synthesis of 1, 4-diketones by thiazolium salt promoted addition of aldehydes to chalcones. Tetrahedron Lett. 2002, 43, 5181-5183.
    [8] Enders, D.; Kallfass, U. An Efficient Nucleophilic Carbene Catalyst for the Asymmetric Benzoin Condensation. Angew. Chem. Int. Ed. 2002, 41, 1743-1445.
    [9] Mattson, A. E.; Bharadwaj, A. R.; Scheidt, K. A. The Thiazolium-Catalyzed Sila-Stetter Reaction: Conjugate Addition of Acylsilanes to Unsaturated Esters and Ketones. J. Am. Chem. Soc. 2004, 126, 2314-2315.
    [10] Nakamura, T.; Hara, O.; Tamura, T.; Makino K.; Hamada, Y. A Facile Synthesis of Chroman-4-ones and 2, 3-Dihydroquinolin-4-ones with Quaternary Carbon Using Intramolecular Stetter Reaction Catalyzed by Thiazolium Salt. Synlett 2005, 155-157.
    [11] Harrington, P. E.; Tius, M. A. A Formal Total Synthesis of Roseophilin: Cyclopentannelation Approach to the Macrocyclic Core. Org. Lett. 1999, 1(4), 649-652
    [12] Galopin, C. C. Ashort and efficient synthesis of (±)-trans-sabinene hydrate. Tetrahedron Lett. 2001, 42, 5589-5591.
    [13] Merrill, B. A.; LeGoff, E. A general synthetic route to 2, 2':5', 2"-terpyrrole, 2, 5-di (2-pyrryl) thiophene, and alkyl-substituted analogs. J. Org. Chem. 1990, 55, 2904-2908.
    [14] Brettle, R.; Dunmur, D. A.; Marson, C. M.; Pinol, M.; Toriyama, K. New Liquid Crystalline Compounds Based on Thiophene. Chem. Lett. 1992, 613-616.
    [15] Jones, R. A.; Karatza, M.; Voro, T. N.; Civcir, E U.; Franck, A.; Ozturk, O.; Seaman, J. P.; Whitmore, A. P.; Williamson, D. J. Tetrahedron 1996, 52, 8707.
    [16] Braun, R. U.; Zeitler, K.; Muller, T. J. J. In Search of Catalytically Active Species in the Surfactant-Mediated Biphasic Alkene Epoxidation with Mimoun-Type Complexes. Org. Lett. 2001, 3, 329-332.
    [17] Anjaiah, S.; Chandrasekhar, S.; Gree, R. Synthesis and preliminary use of novel acrylic ester-derived task-specific ionic liquids. Tetrahedron Lett. 2004, 45, 569-571.
    [18] Enders, D.; Breuer, K.; Runsink, J.; Teles, J. H. The First Asymmetric Intramolecular Stetter Reaction. Helv. Chim. Acta. 1996, 79, 1899-1902.
    [19] Kerr, M. S.; Read de Alaniz, J.; Rovis, T. A Highly Enantioselective Catalytic Intramolecular Stetter Reaction. J. Am. Chem. Soc. 2002,124, 10298-10299.
    [20] Kerr, M. S.; Rovis, T. Effect of the Michael Acceptor in the Asymmetric Intramolecular Stetter Reaction. Synlett 2003, 1934-1936.
    [21] Christmann, M. New Developments in the Asymmetric Stetter Reaction. Angew. Chem. Int. Ed. 2005, 44, 2632-2634
    [22] [Reynolds, N. T.; Rovis, T. The effect of pre-existing stereocenters in the intramolecular asymmetric Stetter reaction. Tetrahedron 2005, 61, 6368.
    [23] Kerr, M. S.; Rovis T. Enantioselective Synthesis of Quaternary Stereocenters via a Catalytic Asymmetric Stetter Reaction. J. Am. Chem. Soc. 2004, 126, 8876-8877.
    [24] Mennen, A. M.; Blank, J. T.; Tran-Dube, M. B.; Imbdglio, J. E.; Miller, S. J. A peptide-catalyzed asymmetric Stetter reaction. Chem. Commun. 2005, 195-197.
    [25] Anjaiah S.; Chandrasekhar S.; Gree R. Stetter Reaction in Room Temperature Ionic Liquids and Application to the Synthesis of Haloperidol. Adv. Synth. Catal. 2004, 346, 1329-1334.
    [26] Kappe, C. O. Controlled Microwave Heating in Modern Organic Synthesis. Angew. Chem. Int. Ed. 2004, 43, 6250-6284;
    [27] Lead Beater, N. E.; Torenius, H. M.; Tye, H.; Microwave-promoted organic synthesis using ionic liquids: A mini review. Comb. Chem. High Through. Screen. 2004. 7, 511-528;
    [28] 张锁江,张香平,李春山,绿色介质:离子液体的合成及规模化制各新技术.精细化工原料及中间体,2006,1,3-4
    [29] Bonhote, P.; Dias, A. P.; Papageorgiou, N.; Kalyanasundaram, K.; Gratzel, M. Hydrophobic highly conductive ambient-temperature molten salts [J]. Inorg. Chem. 1996, 35 (5):1168-21178.
    [30] Ciganek, E. Esters of 2, 3-Dihydro-3-oxobenzofuran-2-acetic Acid and 3,4-Dihydro-4-oxo- 2H-1- benzopyran-3-acetic Acid by Intramolecular Stetter Reactions Synthesis 1995, 1311-1314.
    [31] Old, K. B.; Main, L. The kinetics and mechanism of the cyclization of some 2'-hydroxychalcones to flavanones in basic aqueous solution. J. Chem. Soc., Perkin Trans. 2 1982, 1309-1312.

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