臺灣博碩士論文加值系統

由於自然界中的各式香豆素衍生物具有強烈螢光發射的性質及生物活性而引起科學家的注意。近年來更有一些香豆素衍生物被應用在有機發光染料的領域裡。本實驗室曾製備一系列單取代及雙取代的3-苯並噻唑基香豆素衍生物，藉此探討香豆素及苯並噻唑上取代基對其紫外光/可見光吸收波長、螢光波長與強度的影響。本研究除了將先前研究之3-(6’-硝基苯並噻唑基)香豆素進行衍生化反應外，也將3-苯並雙噻唑基香豆素成功製備。於雙取代苯並噻唑基香豆素的製備上，我們利用的水楊醛衍生物與2-(6-取代基苯並噻唑基)乙腈於鹼性催化的條件下來進行縮合反應。而上述所有新的化合物也都藉由光譜分析加以確認。當苯並噻唑基上第六個位置的碳接上胺基及其衍生物時，此一系列的化合物的吸收光譜皆呈現紅位移的現象最高可達到71 nm之多而螢光之Stoke’s shift最高可達130 nm。另外，若以3-苯並雙噻唑基香豆素的螢光強度做比較可發現其螢光強度為3-苯並噻唑基香豆素之1.3倍。

The nature of coumarins, a class of the nature product, on emitting strong fluorescence with wide biological activities have drew the scientist’s attention. Nowadays, a series of coumarin derivatives has applied as orangic fluorescent dyes. A series of mono- and di-substituted 3-benzothiazolcoumarins have been prepared for investigating the influence of nature of substituents on the coumarin ring and benzothiazole ring on UV-Vis absorption and emission wavelength as well as fluorescence intensity.
Our study focus on derivatizatioon of 3-(6’-nitrobenzothiazoyl)- coumarin, and synthesis of 3-benzobisthiazoylcouamrin. Under a base- catalytic cyclization, di-substituted 3-benzothiazoylcoumarins were prepared from condensation of salicylic aldehyde derivatives and 2-(6-substitutedbenzothiazoyl)acetonitrile. All of new compounds were characterized by spectroscopic methods.
The compound with amino group at C-6 of benzothiazole ring demonstrates a larger bathochromic shift (71 nm) and Stoke’s shift(130 nm); moreover, 3-benzobisthiazoylcouamrin emits the fluorescence with intensity 1.3-fold of that form 3-benzothiazoylcoumarin.

中文摘要 I
英文摘要 II
第一章 緒論 1
一、 前言 1
二、 3-苯並噻唑基香豆素的相關合成方法 5
三、 3-苯並噻唑基香豆素命名 9
四、 核磁共振光譜法 9
五、 紫外光-可見光分子吸收光譜法 11
六、 螢光光譜法 12
七、 質譜法 14
八、 離子阱質譜儀 15
第二章 結果與討論 16
一、 3-(6’-胺基苯並噻唑基)香豆素7m的合成流程 16
二、 3-乙氧羰基香豆素20的製備 17
三、 2-胺基-6-硝基苯並噻唑22的製備 18
四、 6-硝基苯並噻唑23的製備 18
四-1、 6-硝基苯並噻唑23的結構確認 20
五、 2-巰基-4-硝基苯胺19a的製備 21
六、 3-(6’-硝基苯並噻唑基)香豆素7l的製備 22
七、 3-(6’-胺基苯並噻唑基)香豆素7m的製備 22
七-1、 3-(6’-胺基苯並噻唑基)香豆素7m的結構確認 23
八、 3-(6’-胺基苯並噻唑基)香豆素衍生物的製備 26
八-1、 3-(6’-胺基苯並噻唑基)香豆素衍生物的結構確認 27
九、 3-苯並雙噻唑基香豆素29的合成流程 30
十、 1,4-並苯基二硫脲25的製備 31
十-1、 1,4-並苯基二硫脲25的結構確認 32
十一、 2,6-雙胺基苯並雙噻唑26的製備 33
十一-1、 2,6-雙胺基苯並雙噻唑26的結構確認 34
十二、 苯並雙噻唑27的製備 35
十二-1、 苯並雙噻唑27的結構確認 35
十三、 5-巰基-6-胺基苯並噻唑28的製備 36
十三-1、 5-巰基-6-胺基苯並噻唑28的結構確認 36
十四、 3-苯並雙噻唑基香豆素29的製備 37
十四-1、 3-苯並雙噻唑基香豆素29的結構確認 38
十五、 雙取代苯並噻唑基香豆素衍生物的合成流程 41
十六、 2-(6-甲氧基苯並噻唑基)乙腈30的製備 42
十六-1、 2-(6-甲氧基苯並噻唑基)乙腈30的結構確認 43
十七、 3-(6’-甲氧基苯並噻唑基)-6-硝基香豆素7p的製備 45
十七-1、 3-(6’-甲氧基苯並噻唑基)-6-硝基香豆素7p的結構確認 46
十八、 染料電池材料的製備 49
十九、 3-(6’-胺基苯並噻唑基)香豆素7m的質譜探討 50
二十、 3-苯並雙噻唑基香豆素29的質譜探討 52
二十一、 3-(6’-甲氧基苯並噻唑基)-6-硝基香豆素7p的質譜探討 53
二十二、 3-(6’-胺基苯並噻唑基)香豆素衍生物紫外光-可見光分子吸收光譜探討 55
二十三、 3-(6’-胺基苯並噻唑基)香豆素衍生物的螢光光譜探討 56
第三章 結論 60
第四章 實驗步驟與數據 62
一、 3-乙氧羰基香豆素20的製備 62
二、 2-胺基-6-硝基苯並噻唑22的製備 63
三、 6-硝基苯並噻唑23的製備 63
四、 2-巰基-4-硝基苯胺19a的製備 64
五、 3-(6’-硝基苯並噻唑基)香豆素7l的製備 65
六、 3-(6’-胺基苯並噻唑基)香豆素7m的製備 66
七、 3-(6’-胺基苯並噻唑基)香豆素衍生物7n、7o的製備 67
八、 1,4-並苯基二硫脲25的製備 69
九、 2,6-雙胺基苯並雙噻唑26的製備 70
十、 苯並雙噻唑27的製備 71
十一、 5-巰基-6-胺基苯並噻唑28的製備 72
十二、 3-苯並雙噻唑基香豆素29的製備 72
十三、 2-(6-甲氧基苯並噻唑基)乙腈30的製備 74
十四、 3-(6’-甲氧基苯並噻唑基)-6-硝基香豆素7p的製備 75
第五章 實驗儀器與藥品 77
一、 儀器 77
二、 藥品 78
第六章 參考文獻 84
第七章 附圖 91

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