Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/16547
標題: 微波加速之有機反應的研究 (一) N-芳基鄰胺基苯甲酸衍生物之合成 (二) N-取代吡咯-2-羧醛之合成
The Study of Microwave Accelerated Organic Reaction (1) Synthesis of N-Phenylanthranilic Acids (2) Synthesis of N-Substituted Pyrrole-2-carboxaldehyde
作者: 傅凱伶
Fu, Kai-Ling
關鍵字: Microwave
N-芳基鄰胺基苯甲酸衍生物
N-Phenylanthranilic Acids
N-Substituted Pyrrole-2-carboxaldehyde
N-取代吡咯-2-羧醛
出版社: 化學系所
引用: 1.Kwoh, C. K.; Anderson, L. G.; Greene, J. M.; Johnson, D. A.; O''Dell, R.; Robbins, M. L.; Roberts, W. N.; Simms, R. W.; Yood, R. A. "Guidelines for the management of rheumatoid arthritis - 2002 update", Arthritis Rheum. 2002, 46, 328-346. 2.Setter, S. M.; Corbett, C.; Gates, B. J.; Terriff, C.; Johns, C. A.; Sclar, D. A.; Popovian, R. "Nonsteroidal anti-inflammatory drugs: the need for assessment and education." Home Care Provid. 2001, 6, 100-105. 3.(a) Budoff, P. W. "Use of mefenamic acid in the treatment of primary dysmenorrhea." JAMA 1979, 241, 2713-2716. (b) Patrick, E. A.;Iris, F. L., "Current Satus of the Etiology and Mangement of Dysmenorrea in Adolescence", Pediatrics 1982, 70, 516-523. 4.Ullmann, F. "A new path for preparing diphenylamine derivatives", Chem. Ber. 1903, 36, 2382-2384. 5.Carrasco, R.; Pellon, R. F.; Elguero, J.; Goya, P.; Paez, J. A. "The Use of Ultrasound in the Synthesis of N-Arylanthranilic Acids by the Ullmann Goldberg Reaction", Synth. Commun.1989, 19, 2077-2080. 6.Price, C. C.; Roberts, R. M. "4-chloro-2-(3-pyridylamino)benzoic acid and its conversion to 6-chloro-9-hydroxy-pyrido[3,2-b]quinoline", J. Org. Chem 1946, 11, 463-468. 7.Juby, P. F.; Hudyma, T. W.; Brown, M. "Preparation and antiinflammatory properties of some 5-(2-anilinophenyl)tetrazoles." J. Med. Chem. 1968, 11, 111-117. 8.Jonsson, S.; Andersson, G.; Fex, T.; Fristedt, T.; Hedlund, G.; Jansson, K.; Abramo, L.; Fritzson, I.; Pekarski, O.; Runstrom, A.; Sandin, H.; Thuvesson, I.; Bjork, A. "Synthesis and biological evaluation of new 1,2-dihydro-4-hydroxy-2-oxo-3-quinolinecarboxamides for treatment of autoimmune disorders: Structure-activity relationship", J. Med. Chem. 2004, 47, 2075-2088. 9.Dheyongera, J. P.; Geldenhuys, W. J.; Dekker, T. G.; Van der Schyf, C. J. "Synthesis, biological evaluation, and molecular modeling of novel thioacridone derivatives related to the anticancer alkaloid acronycine", Bioorg. Med. Chem. 2005, 13, 689-698. 10.Acheson, R. M. "Preparation of Diphenylamine-2-carboxylic Acid", Acridines 1973, 160-171. 11.Pellon, R. F.; Carrasco, R.; Rodes, L. "Synthesis of N-Phenylanthranilic Acids Using Water as Solvent", Synth. commun. 1993, 23, 1447-1453. 12.Pellon, R. F.; Carrasco, R.; Marquez, T.; Mamposo, T. "Use of N,N-Dimethylformamide as solvent in the synthesis of N-phenylanthranilic acids", Tetrahedron Lett. 1997, 38, 5107-5110. 13.Gorvin, J. H. "The Synthesis of Di-Arylamines and Tri-Arylamines through Halogen Displacement by Base-Activated Arylamines - Comparison with the Ullmann Condensation", Perkin trans., 1. 1988, 1331-1335. 14.Weston, P. E.; Adkins, H. "Catalysis with Copper in the Ullmann Reaction", J. Am. Chem. Soc. 1928, 50, 859-866. 15.Pellon, R. F.; Mamposo, T.; Carrasco, R.; Rodes, L. "Use of pyridine as cocatalyst for the synthesis of N-phenylanthranilic acids", Synth. Commun. 1996, 26, 3877-3883. 16.Palacios, M. L. D.; Comdom, R. F. P. "Synthesis of N-phenylanthranilic acid derivatives using water as solvent in the presence of ultrasound irradiation", Synth. Commun. 2003, 33, 1771-1775. 17.(a) Ma, D.; Cai, Q.; Zhang, H. "Mild method for Ullmann coupling reaction of amines and aryl halides", Org. Lett. 2003, 5, 2453-2455. (b) Zhang, H.; Cai, Q.; Ma, D. "Amino acid promoted CuI-catalyzed C-N bond formation between aryl halides and amines or N-containing heterocycles", J. Org. Chem. 2005, 70, 5164-5173. 18.Henle, T. "Protein-bound advanced glycation endproducts (AGEs) as bioactive amino acid derivatives in foods", Amino Acids 2005, 29, 313–322. 19.Hodge, J. E. "Dehydrated Foods, Chemistry of Browning Reactions in Model Systems", J. Agric. Food Chem. 1953, 1, 928 - 943. 20.Friedman, M. "Food Browning and Its Prevention: An Overview", J. Agric. Food Chem. 1996, 44, 631-653. 21.陳文賢,"水活性控制與食品儲存" 科學發展2004年7月,379期,18~23頁 22.Zamora, R.; Hidalgo, F. J. "Coordinate contribution of lipid oxidation and Maillard reaction to the nonenzymatic food browning", Crit. Rev. Food Sci. Nutr. 2005, 45, 49-59. 23.(a) Reddy, V. P.; Obrenovich, M. E.; Atwood, C. S.; Perry, G.; Smith, M. A. "Involvement of Maillard reactions in Alzheimer disease. "Neurotox. Res. 2002, 4, 191-209. (b) Nagaraj, R. H.; Portero-Otin, M.; Monnier, V. M. "Pyrraline ether crosslinks as a basis for protein crosslinking by the advanced Maillard reaction in aging and diabetes", Archives of Biochemistry and Biophysics 1996, 325, 152-158. (c) Horvat, S.; Jakas, A. "Peptide and amino acid glycation: new insights into the Maillard reaction." J. Pept. Sci. 2004, 10, 119-137. 24.(a) Monnier, V. M.; Wu, X. "Enzymatic deglycation with amadoriase enzymes from Aspergillus sp. as a potential strategy against the complications of diabetes and aging." Biochem. Soc. Trans. 2003, 31, 1349-1353. (b) Lee, K. G.; Shibamoto, T. "Toxicology and antioxidant activities of non-enzymatic browning reaction products: Review", Food Reviews International 2002, 18, 151-175. 25.(a) Tamura, O.; Iyama, N.; Ishibashi, H. "Syntheses of (-)-Funebrine and (-)-Funebral, Using Sequential Transesterification and Intramolecular Cycloaddition of a Chiral Nitrone", J. Org. Chem. 2004, 69, 1475-1480. (b) Yang, Y.-P.; Cheng, M.-J.; Teng, C.-M.; Chang, Y.-L.; Tsai, I.-L.; Chen, I.-S. "Chemical and anti-platelet constituents from Formosan Zanthoxylum simulans", Phytochemistry (Elsevier) 2002, 61, 567-572. 26.(a) Chin, Y.-W.; Lim, S. W.; Kim, S.-H.; Shin, D.-Y.; Suh, Y.-G.; Kim, Y.-B.; Kim, Y. C.; Kim, J. "Hepatoprotective pyrrole derivatives of Lycium chinense fruits", Bioorganic & Medicinal Chemistry Letters 2003, 13, 79-81. (b) Sang, S.; Lao, A.; Wang, Y.; Chin, C.-K.; Rosen, R. T.; Ho, C.-T. "Antifungal constituents from the seeds of Allium fistulosum L", J. Agric. Food Chem.2002, 50, 6318-6321. 27.(a) Miller, R.; Olsson, K.; Pernemalm, P. "Formation of aromatic compounds from carbohydrates. IX. reaction of D-glucose and L-lysine in slightly acidic, aqueous solution", Acta Chem. Scand. Ser. B 1984, 38, 689-694. (b) Ninomiya, M.; Matsuzaki, T.; Shigematsu, H. "Formation of reducing substances in the Maillard reaction between D-glucose and aminobutyric acid", Biosci. Biotech. Biochem. 1992, 56, 806-807. (c) Ruiter, A. "Browning reaction of glycolic aldehyde with aminoethanol. III. Structure of a reaction product and comparison with aldose-aminoethanol browning", Lebensm.-Wiss. Technol. 1973, 6, 142-146. 28.Miller, R.; Olsson, K. "Synthesis of (±)-2-formyl-5-(hydroxymethyl)pyrrole-1-norleucine. A biologically active Maillard reaction product derived from glucose and lysine", Acta Chem. Scand. Ser. B 1985, B39, 717-723. 29.Abu-Samra, A.; Morris, J. S.; Koirtyohann, S. R. "Wet ashing of some biological samples in a microwave oven", Anal. Chem. 1975, 47, 1475-1477. 30.(a) Nuchter, M.; Muller, U.; Ondruschka, B.; Tied, A.; Lautenschlager, W. "Microwave-assisted chemical reactions", Chem. Eng. Technol. 2003, 26, 1207-1216. (b) Kappe, C. O. "Controlled microwave heating in modern organic synthesis", Angewandte Chemie-International Edition 2004, 43, 6250-6284. (c) Nuchter, M.; Ondruschka, B.; Bonrath, W.; Gum, A. "Microwave assisted synthesis - a critical technology overview", Green Chemistry 2004, 6, 128-141. (d) Alupei, V.; Ritter, H. "Microwave syntheses under normal pressure", Nachrichten Aus Der Chemie 2005, 53, 518-522. (e) Gelens, E.; Smeets, L.; Sliedregt, L.; van Steen, B. J.; Kruse, C. G.; Leurs, R.; Orru, R. V. A. "An atom efficient and solvent-free synthesis of structurally diverse amides using microwaves", Tetrahedron Lett. 2005, 46, 3751-3754. (f) Leadbeater, N. E.; Pillsbury, S. J.; Shanahan, E.; Williams, V. A. "An assessment of the technique of simultaneous cooling in conjunction with microwave heating for organic synthesis", Tetrahedron 2005, 61, 3565-3585. (g) 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. 31.Lidstrom, P.; Tinerney, J.; Wathey, B.; Westman, J. "Microwave assisted organic synthesis-a review", Tetrahedron 2001, 57, 9225-9283. 32.Loupy, A. "Microwaves in Organic Synthesis", Wiley-VCH 2004. 33.Santagada, V.; Perissutti, E.; Caliendo, G. "The Application of Microwave Irradiation as New Convenient Synthetic Procedure in Drug Discovery", Current Medicinal Chemistry 2002, 9, 1251-1283. 34.Von-Hippel, A. R. "Dielectric Materials and Applications." John Wiley :New York 1954. 35.Kingston, H. M.; Jassie, L. B. "Microwave energy for acid decomposition at elevated temperatures and pressures using biological and botanical samples", Anal. Chem. 1986, 58, 2534-2541. 36.Giguere, R. J.; Bray, T. L.; Duncan, S. M.; Majetich , G. "Application of commercial microwave ovens to organic synthesis." Tetrahedron Lett. 1986, 27, 4945-4948. 37.Loupy, A.; Petit, A.; Hamelin, J.; Texier-Boullet, F.; Jacquault, P.; Mathe, D. "New solvent free organic synthesis using focused microwaves", Synthesis-Stuttgart 1998, 9, 1213-1234. 38.羅琪興,"微波加速之有機反應的研究 -- (一) 以醇類與異氰酸酯製備胺基甲酸酯 (二) 利用鹼性條件切斷1,3-雙酮化合物"中華民國中興大學化研所,碩士畢業論文,1999年。 39.林雅香,"微波加速有機反應之研究 -- (一) 由酯類與胺類製備醯胺 (二) 由酸類與胺類製備醯胺"中華民國中興大學化研所,碩士畢業論文,2000年。 40.Cai, L.; Liu, X.; Tao, X.; Shen, D. "Efficient Microwave-Assisted Cyanation of Aryl Bromide", Synth. commun. 2004, 34, 1215-1221. 41.王振宏,"微波加速有機反應之研究 -- (一) 聚3-羥丁酯降解反應(二) 合成苯并哌喃衍生物"中華民國中興大學化研所,碩士畢業論文,2005年。
摘要: 本論文報導我們以微波加速N-芳基鄰胺基苯甲酸以及N-取代吡咯-2-羧醛之合成的研究成果。 一. N-芳基鄰胺基苯甲酸 我們發現在微波照射下,N-芳基鄰胺基苯甲酸的產率和傳統加熱的產率相當,但反應時間可從傳統加熱所需的2~ 4小時降至使用家用微波爐以800 W照射10分鐘,聚焦式微波反應裝置以270 W照射10分鐘。 而當不使用任何溶劑,僅以純反應物來進行反應或利用鹼性固態擔體的反應條件下皆無法得到預期產物,故此反應必須在有溶劑與催化劑存在的條件下才會進行。 二. N-取代吡咯-2-羧醛 我們成功地利用田口實驗設計方法快速地尋找微波加速N-取代吡咯-2-羧醛之合成反應條件,而將傳統加熱所需的4~15小時降至使用聚焦式微波反應裝置以270 W照射20分鐘,且其產率較傳統加熱方式提升2~ 14倍。 因此,我們已成功地建立一個手續簡便的合成N-芳基鄰胺基苯甲酸之方式。以及發展出一個有效利用微波照射加速N-取代吡咯-2-羧醛之合成方法。所以,利用微波照射已經被證實可有效加速有機反應的方法,並且對工業具有很大的應用潛力。
We report herein our studies on microwave-assisted N-phenylanthranilic acids formation and the synthesis of N-substituted pyrrole-2-carboxaldehyde. I. Preparation of N-phenylanthranilic acids The reaction times of the formation of N-phenylanthranilic acids, by reacting o-chlorobenzoic acid and substituted aniline, were greatly reduced from 2~4 hours in conventional method to 10 min by using domestic microwave irradiation at 800 W, and focused microwave irradiation at 270 W, while the yields were comparable. The above reaction did not work under neat or solid support conditions. II. Synthesis N-substituted pyrrole-2-carboxaldehyde Taguchi''s method was employed in the experimental conditions to afford highest yield of N-substituted pyrrole-2-carboxaldehyde utilizing microwave irradiation. We have not only decreased the reaction time from 4~15 hours under conventional heating to only 20 min by focused microwave irradiation at 270 W, but also drastically improved the yields 2~14 times. In conclusion, microwave irradiation has been proved to be an effective method in accelerating organic reactions and therefore has an immense potential in industrial applications.
URI: http://hdl.handle.net/11455/16547
其他識別: U0005-2908200615554600
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