臺灣博碩士論文加值系統

本篇論文主要包含具有pyrazole結構之有機液晶。所有化合物經由1H-NMR, 13C-NMR, Mass與元素分析以鑑定其結構及純度,液晶相性質則是利用偏光顯微鏡(POM)來觀測相種類及熱微差掃描分析儀(DSC)測量相變化時之溫度與熱焓值，最後以變溫粉末X光繞射儀(XRD)確認其相的種類。
系列化合物Tpz-Cn在n=6時呈現出SmA之液晶相，然後在n=8~16時則展現出SmC之液晶相。化合物Tpz-2Cn在n=6~16時即呈現出Colh的液晶相，然後我們將其配位基與NiCl2進行配位形成錯合物，其錯合物則展現出Colh之液晶。
為了探討pyrazole上的NH對形成液晶是否為ㄧ重要因素，我們將NH取代成O原子合成出具有isoxazole結構之化合物，其相行為在n=12~16時皆為結晶相，因此可之NH對液晶行為有重大的影響。

In this thesis, we report the synthesis, characterization and mesomorphic properties of a series of new mesogenic derivatives based on pyrazole structureies. All compounds were characterized by 1H, 13C-NMR spectroscopy and elemental analysis. The phase behaviors of these mesogenic compounds were characterized and studied by differential scanning calorimeter (DSC) and polarization optical microscope.

In the serie, a new type of mesogenic compounds derived from heterocyclic pyrazoles were prepared and studied. The compounds of Tpz-Cn, exhibited smectic phases, as expected for their rod-like structures, compounds of Tpz-2Cn, exhibited columnar hexagonal phases, as expected for their discotic-like structures. The metal complexes, Tpz-2Cn-Ni, formed by reacting the pyrazoles with NiCl2 are exhibited columnar hexagonal phases too.

謝誌………………………………………………………………………i
摘要……………………………………………………………………ii
英文摘要………………………………………………………………iii
目錄……………………………………………………………………iv
圖目錄…………………………………………………………………ix
表目錄………………………………………………………………xiii
第ㄧ章 緒論………………………………………………1
1-1前言…………………………………………………………………2
1-2液晶之起源與簡介…………………………………………………2
1-3液晶的分類…………………………………………………………2
1-4液晶的基本構造……………………………………………………5
1-5液晶的物理性質…………………………………………………10
1-6研究動機……………………………………………………………13
第二章實驗部分………………………………………………………14
2-1實驗藥品……………………………………………………………15
2-2儀器設備…………………………………………………………17
2-3實驗流程…………………………………………………………22
2-3-1實驗流程(1)……………………………………………………22
2-3-2實驗流程(2)……………………………………………………23
2-4實驗步驟……………………………………………………………24
2-4-1系列Tpz-Cn之合成………………………………………………24
2-4-1-1 Methyl 4-alkoxybenzoates之合成………………………24
2-4-1-2 1,5-bis (4-(alkoxy)phenyl) pentane-1,3,5-trione之合成...24
2-4-1-3 1-(4-alkoxyphenyl)-2-(3-(4-alkoxyphenyl)-1H-pyrazol-5-yl)ethanone之合成………………………………………27
2-4-2系列Tpz-2Cn之合成……………………………………………30
2-4-2-1 Ethyl 3,4-dialkoxybenzoates之合成…………………30
2-4-2-2 1-(3,4-bis(alkoxy)phenyl)-2-(3-(3,4-bis(alkoxy)phenyl)-1H-pyrazol-5-yl)ethanone之合成………………………33
2-4-2-3 Bis[1-(3,4-bis(alkoxy)phenyl)-2-(3-(3,4-bis(alkoxy)phenyl)-1H-pyrazol-5-yl)ethanone] nickel (II) complexes之合成………………………………36
2-4-3系列Tiz-Cn之合成………………………………………………37
2-4-3-1 1-(4-(alkoxy)phenyl)-2-(3-(4-(alkoxy)phenyl)isoxazol-5-yl)ethanone之合成………………………………………………………………………37
第三章結果與討論……………………………………………………40
3-1反應機構之探討……………………………………………………41
3-1-1醚化反應…………………………………………………………41
3-1-2 Triketone之合成反應…………………………………………42
3-1-3 Pyrazole之合成反應…………………………………………42
3-2系列之結果與討論…………………………………………………44
3-2-1系列Tpz-Cn之化合物……………………………………………44
3-2-1-1化合物之結構鑑定……………………………………………44
3-2-1-2 NMR之鑑定……………………………………………………44
3-2-1-3質譜分析………………………………………………………45
3-2-1-4元素分析………………………………………………………45
3-2-1-5化合物液晶相之鑑定…………………………………………46
3-2-1-6熱分析之數據…………………………………………………46
3-2-1-7偏光顯微鏡之觀察……………………………………………49
3-2-1-8系列Tpz-Cn之粉末X-ray繞射………………………………50
3-2-1-9系列化合物Tpz-C3之單晶繞射數據…………………………55
3-2-2系列Tpz-2Cn之化合物…………………………………………61
3-2-2-1實驗動機………………………………………………………61
3-2-2-2 NMR之鑑定……………………………………………………61
3-2-2-3質譜分析……………………………………………………62
3-2-2-4元素分析………………………………………………………62
3-2-2-5熱分析之數據…………………………………………………63
3-2-2-6偏光顯微鏡之觀察……………………………………………66
3-2-2-7系列Tpz-2Cn之粉末X-ray繞射………………………………67
3-2-3系列Tpz-2Cn-Ni之化合物………………………………………70
3-2-3-1實驗動機………………………………………………………70
3-2-3-2元素分析………………………………………………………71
3-2-3-3熱分析之數據…………………………………………………71
3-2-3-4偏光顯微鏡之觀察……………………………………………72
3-2-3-5系列Tpz-2Cn-Ni之粉末X-ray繞射…………………………73
3-2-3-6盤狀液晶之體積測量…………………………………………74
3-2-4系列Tiz-Cn之化合物……………………………………………77
3-2-4-1實驗動機………………………………………………………77
3-2-4-2元素分析………………………………………………………78
3-2-4-3熱分析之數據…………………………………………………81
3-2-4-4偏光顯微鏡之觀察……………………………………………82
3-3系列化合物之熱分析總整理………………………………………85
3-4結論…………………………………………………………………87
參考文獻………………………………………………………………88
附圖……………………………………………………………………90

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