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研究生(中)沈世偉
研究生(英)Shen Shih-Wei
論文名稱(中)新非極性-取代吡啶化合物之合成及液晶性質之研究
論文名稱(英)Synthesis and Characterization of New Nonpolar Substituted Pyridine-Containing Liquid Crystal
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指導教授(中)賈文隆
指導教授(英)
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關鍵字(中)液晶 吡 啶 格林納試劑 非極性
關鍵字(英)liquid crystal pyridine Grinard reagent
摘要(中)和商業用的5-CB比較,本研究乃試圖以pyridine取代 benzene位置,並將cyano group 改成其他取代基。首先將1- bromo-4-pentylbenzene或1-bromo-4-butylbenzene與Mg混和,反應得到Grignard試劑。將3-取代吡啶與氯甲酸乙酯混和,反應得到3-取代-碳醯基吡啶鹽。再將3-取代-碳醯基吡啶鹽與Grignard試劑混和,反應得到中間產物二氫吡啶化合物(dihydropyridine)。再將中間產物與氧化劑混和,進行氧化脫氫反應,可以得到3-取代6-aryl吡啶化合物。本次合成的化合物,產率由55%〜88%,其中E及G compound具有液晶特性, 經由POM觀察到mosaic texture,推測應為smectic phase,而我們針對這2種產物分別測定其熱性質及相變化,並以1H NMR、13C NMR、IR測定其結構。
摘要(英)Comparing with 5-CB ,this research has replaced one of benzene by pyridine and changed cyano group to other functional groups. This study describes a novel and efficient synthesis of pyridine-containing liquid crystalline 3-substituted 6-(4-alkylphenyl)pyridines. 4-Alkylphenyl magnesium bromide was reacted with 3-substituted N-ethoxycarbonylpyridinium chloride to give regioselective 1,6-dihydropyridine intermediates, which were subsequently oxidized by o-chloranil. Good yields and high α-regioselectivity on pyridine ring were observed in all cases. Only two of these 3-substituted 6-(4-alkylphenyl)pyridines were found to be liquid crystalline, they were 6-(4-n-butylphenyl)-3-phenylpyridine and 6-(4-n-pentylphenyl)-3-phenylpyridine.
論文目次目 錄 一、緒論……………………………………………………………….….2 1-1 前言………………………………………………………………….2 1-2 液晶簡介………………………………………………………….…3 1-2-1液晶的發現……………………………………………………..….3 1-2-2液晶的分類…………………………………………………..…….5 1-3 文獻回顧…………………………………………………………….7 1-4 研究動機…………………………………………………………...14 二、原理…………………………………………………………………16 2-1 3-取代-N-醯基吡啶鹽類……………………...………………...…16 2-2格林那親核試劑(Grignard reagent)…………………………...….16 2-3 3-取代-N-醯基吡啶鹽與格林那親核試劑的反應……………......17 2-4 中間產物dihydropyridine的芳香化反應…………………………19 三、實驗…………………………………………………………………21 3-1 實驗藥品………………………………………………………….21 3-2 實驗儀器………………………………………………………….22 3-3 實驗步驟及方法……………………………….…………………23 3-3-1典型反應步驟與方法…………………………………………….23 3-3-2氧化步驟………………………………………………………….24 3-3-3 反應步驟………………………………………………………...25 3-4 轉移溫度測驗方法………………………………………………...26 四、結果與討論…………………………………………………………27 4-1 合成部份………………………………………..………………...34 4-2 NMR的部份……………………………………...………………37 4-3 DSC測試方面…………………………………………………….37 4-4 POM方面…………………………………………………………37 4-5 IR圖譜分析………………………………………………………38 4-6 3-鹵素吡啶部份之合成結果…………………………………….39 4-7 EA方面…………………………………………………..……….40 五、結論…………………………………………………………………45 參考文獻………………………………………………………………..47 表目錄 Table 1 6-(4’-n-butylphenyl)pyridine之產物與數據………………...27 Table 2 6-(4’-n-butylphenyl)-3-methylpyridine之產物與數據……....28 Table 3 6-(4’-n-butylphenyl)-3-ethylpyridine之產物與數據………...29 Table 4 6-(4’-n-butylphenyl)-3-butylpyridine之產物與數據………...30 Table 5 6-(4’-n-butylphenyl)-3-phenylpyridine之產物與數據………31 Table 6 6-(4’-n-pentylphenyl)pyridine之產物與數據………………..32 Table 7 6-(4’-n-pentylphenyl)-3-phenylpyridine之產物與數據……..33 Table 8 1H NMR 及 13C NMR 光譜結果與數據………………...…42 Table 9 FT-IR光譜、沸點(熔點)及產率表…………………………...43 Table 10 相轉移溫度………………………..………………………..44 圖目錄 Figure-1 6-(4’-n-butylphenyl)pyridine之1H NMR光譜……………….49 Figure-2 6-(4’-n-butylphenyl)-3-methylpyridine之1H NMR光譜….…50 Figure-3 6-(4’-n-butylphenyl)-3-ethylpyridine之1H NMR光譜…….…51 Figure-4 6-(4’-n-butylphenyl)-3-butylpyridine之1H NMR光譜………52 Figure-5 6-(4’-n-butylphenyl)-3-phenylpyridine之1H NMR光譜……..53 Figure-6 6-(4’-n-pentylphenyl)pyridine之1H NMR光譜……………..54 Figure-7 6-(4’-n-pentylphenyl)-3-phenylpyridine之1H NMR光譜…....55 Figure-8 4-n-Butyl-benzoic acid ethyl ester之1H NMR光譜………….56 Figure-9 6-(4’-n-butylphenyl)pyridine之13C NMR光譜……………...57 Figure-10 6-(4’-n-butylphenyl)-3-methylpyridine之13C NMR光譜...58 Figure-11 6-(4’-n-butylphenyl)-3-ethylpyridine之13C NMR光譜…..59 Figure-12 6-(4’-n-butylphenyl)-3-butylpyridine之13C NMR光譜…..60 Figure-13 6-(4’-n-butylphenyl)-3-phenylpyridine之13C NMR光譜…61 Figure-14 6-(4’-n-pentylphenyl)pyridine之13C NMR光譜………….62 Figure-15 6-(4’-n-pentylphenyl)-3-phenylpyridine之13C NMR光譜..63 Figure-16 6-(4’-n-butylphenyl)pyridine之IR光譜…………………….64 Figure-17 6-(4’-n-butylphenyl)-3-methylpyridine之IR光譜…………..65 Figure-18 6-(4’-n-butylphenyl)-3-ethylpyridine之IR光譜…………….66 Figure-19 6-(4’-n-butylphenyl)-3-butylpyridine之IR光譜……………67 Figure-20 6-(4’-n-butylphenyl)-3-phenylpyridine之IR光譜…………..68 Figure-21 6-(4’-n-pentylphenyl)pyridine之IR光譜……………………69 Figure-22 6-(4’-n-pentylphenyl)-3-phenylpyridine之IR光譜………...70 Figure-23 6-(4’-n-butylphenyl)-3-phenylpyridine之DSC光譜………..71 Figure-24 6-(4’-n-pentylphenyl)-3-phenylpyridine之DSC光譜………72 Figure-25 6-(4’-n-pentylphenyl)-3-phenylpyridine 與6-(4’-n-butylphenyl)-3-phenylpyridine之DSC比較光譜…………..73 Figure-26 6-(4’-butylphenyl)-3-phenylpyridine之POM圖(常溫下 30℃ ╳100)……………………. ………………………..………………..….74 Figure-27 6-(4’-butylphenyl)-3-phenylpyridine之POM圖(heating 30℃ ╳200)……………. …………………………………. …………. …….74 Figure-28 6-(4’-butylphenyl)-3-phenylpyridine之POM圖(heating 35℃ ╳200)…. ……………………………………………………………….75 Figure-29 6-(4’-butylphenyl)-3-phenylpyridine之POM圖(heating 45℃ ╳200)……………. ……………………….…………. …………. ……75 Figure-30 6-(4’-butylphenyl)-3-phenylpyridine之POM圖(heating 55℃ ╳200)……………. …………………………………. …………. …….76 Figure-31 6-(4’-butylphenyl)-3-phenylpyridine之POM圖(heating 65℃ ╳200) …………. …………. …………. …………. …………....……..76 Figure-32 6-(4’-butylphenyl)-3-phenylpyridine之POM圖(heating 75℃ ╳200)…. …………. …………. …………. …………. ………. ...……77 Figure-33 6-(4’-butylphenyl)-3-phenylpyridine之POM圖(heating 85℃ ╳200)……………. …………. …………. …………. ………….... …..77 Figure-34 6-(4’-butylphenyl)-3-phenylpyridine之POM圖(heating 95℃ ╳200)….. ……………. …………. …………. …………. ………...….78 Figure-35 6-(4’-butylphenyl)-3-phenylpyridine之POM圖(heating 105℃ ╳200)……………. …………. …………. …………. ……………...…78 Figure-36 6-(4’-butylphenyl)-3-phenylpyridine之POM圖(cooling 113℃ ╳100)…. …………. …………. …………. …………. …………..…...79 Figure-37 6-(4’-butylphenyl)-3-phenylpyridine之POM圖(cooling 113℃ ╳200)………………. …………. …………. …………. ……..……….79 Figure-38 6-(4’-butylphenyl)-3-phenylpyridine之POM圖(cooling 105℃ ╳200)……………. …………. …………. …………. …………. …….80 Figure-39 6-(4’-butylphenyl)-3-phenylpyridine之POM圖(cooling 95℃ ╳200)……………. …………. …………. …………. ………….. ……80 Figure-40 6-(4’-butylphenyl)-3-phenylpyridine之POM圖(cooling 85℃ ╳200)……………. …………. …………. …………. ………….……..81 Figure-41 6-(4’-butylphenyl)-3-phenylpyridine之POM圖(cooling 75℃ ╳200)……………. …………. …………. …………. …….…….…….81 Figure-42 6-(4’-butylphenyl)-3-phenylpyridine之POM圖(cooling 65℃ ╳200)……………. …………. …………. …………. …………. …….82 Figure-43 6-(4’-butylphenyl)-3-phenylpyridine之POM圖(cooling 55℃ ╳200)……………. …………. …………. …………. ………. ……….82 Figure-44 6-(4’-butylphenyl)-3-phenylpyridine之POM圖(cooling 45℃ ╳200)……………. …………. …………. …………. ………….……..83 Figure-45 6-(4’-butylphenyl)-3-phenylpyridine之POM圖(cooling 35℃ ╳200)……………. …………. …………. …………. .. …………....…83 Figure-46 6-(4’-butylphenyl)-3-phenylpyridine之POM圖(cooling 30℃ ╳100)………………. …………. …………. …………. …………. ….84 Figure-47 6-(4’-pentylphenyl)-3-phenylpyridine之POM圖(未加熱30℃ ╳100)….. …………. …………. …………. …………. ………………85 Figure-48 6-(4’-pentylphenyl)-3-phenylpyridine之POM圖(未加熱 30℃ ╳200)….. …………. …………. …………. …………. …………. 85 Figure-49 6-(4’-pentylphenyl)-3-phenylpyridine之POM圖(heating 35℃ ╳200)………………. …………. …………. …………. ……………...86 Figure-50 6-(4’-pentylphenyl)-3-phenylpyridine之POM圖(heating 45℃ ╳200)…………….……. . . . . . . . . .………. . . . . . . .………. . . . ……86 Figure-51 6-(4’-pentylphenyl)-3-phenylpyridine之POM圖(heating 55℃ ╳200)……. . . . . . . . .………. . . . . . . .………. . . . . . . .………. . . …..87 Figure-52 6-(4’-pentylphenyl)-3-phenylpyridine之POM圖(heating 65℃ ╳200)…. . . . . . . .………. . . . . . . .………. . . . . . . .………. . . . . …....87 Figure-53 6-(4’-pentylphenyl)-3-phenylpyridine之POM圖(heating 75℃ ╳200)…. . . . . . . .………. . . . . . . .………. . . . . . . .………. . . . . ...….88 Figure-54 6-(4’-pentylphenyl)-3-phenylpyridine之POM圖(heating 85℃ ╳200)……. . . . . . . .………. . . . . . . .………. . . . . . . .………. . . …... 88 Figure-55 6-(4’-pentylphenyl)-3-phenylpyridine之POM圖(heating 95℃ ╳200)…. . . . . . . .………. . . . . . . .………. . . . . . . .………. . . . . …....89 Figure-56 6-(4’-pentylphenyl)-3-phenylpyridine之POM圖(heating 105℃ ╳200) . . . . . . . .………. . . . . . . .………. . . . . . . .………. . . . .…..89 Figure-57 6-(4’-pentylphenyl)-3-phenylpyridine之POM圖(cooling 113℃ ╳200)……. . . . . . . .………. . . . . . . .………. . . . . . . .………. . . ..90 Figure-58 6-(4’-pentylphenyl)-3-phenylpyridine之POM圖(cooling 105℃ ╳200)…. . . . . . . .………. . . . . . . .………. . . . . . . .………. . . . . ..90 Figure-59 6-(4’-pentylphenyl)-3-phenylpyridine之POM圖(cooling 95℃ ╳200)…. . . . . . . .………. . . . . . . .………. . . . . . . .………. . . …... . . 91 Figure-60 6-(4’-pentylphenyl)-3-phenylpyridine之POM圖(cooling 85℃ ╳200)…. . . . . . . .………. . . . . . . .………. . . . . . . .………. . . …... . ..91 Figure-61 6-(4’-pentylphenyl)-3-phenylpyridine之POM圖(cooling 75℃ ╳200)…. . . . . . . .………. . . . . . . .………. . . . . . . .………. . . . . ……92 Figure-62 6-(4’-pentylphenyl)-3-phenylpyridine之POM圖(cooling 65℃ ╳200)…. . . . . . . .………. . . . . . . .………. . . . . . . .………. . . …... …92 Figure-63 6-(4’-pentylphenyl)-3-phenylpyridine之POM圖(cooling 55℃ ╳200)……. . . . . . . .………. . . . . . . .………. . . . . . . .………. . …... . 93 Figure-64 6-(4’-pentylphenyl)-3-phenylpyridine之POM圖(cooling 45℃ ╳200)……. . . . . . . .………. . . . . . . .………. . . . . . . .………. . …... . 93 Figure-65 6-(4’-pentylphenyl)-3-phenylpyridine之POM圖(cooling 35℃ ╳200) . . . . . . . .………. . . . . . . .………. . . . . . . .………. . . . . …...…94 Figure-66 6-(4’-pentylphenyl)-3-phenylpyridine之POM圖(cooling 30℃ ╳200)…. . . . . . . .………. . . . . . . .………. . . . . . . .………. . …... . . ..94
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