臺灣博碩士論文加值系統

本研究利用硫代胺脲(Thiosemicarbazide)、二硫化碳(Carbon disulfide)、對位取代苯甲酸三者在溶劑乙醇下加熱迴流反應製備1,3,4-噻二唑啉中間體3、5a~5d，再分別與N-取代砒硐中間體9a~9b、砒唑哢中間體11a~11b在冰浴下行偶合反應，合成一系列N-取代砒硐噻二唑啉與吡唑哢噻二唑啉偶氮染料12a~12j、13a~13j。
另外利用1,3,4-噻二唑啉中間體與氯化三聚氰(Cyanuric chloride)在低溫0~5℃下反應成為反應性染料20、再與聯胺(Hydrazine hydrate)、對-硝基苯甲醛(4-Nitrobenzaldehyde)行縮合反應得含次甲基(C=N)基團之染料26a~26b。
所合成之染料皆經FT-IR、UV、MS、1H-NMR及元素分析(EA)光譜儀測定分析其構造，進而利用紫外線光譜儀分析其在不同溶劑下的溶劑效應。

The investigation was prepared by the reaction with thiosemicarbazide, carbon disulfide, p-substiuented-benzoic acid in ethanol at refluxed to get 1,3,4-thiadiazole(3、5a~5d). Then 1,3,4-thiadiazole derivatives coupled with N-substiuented-pyridone derivatives(12a~12j) and pyroazolone derivatives(13a~13j). Furthermore, 1,3,4-thiadiazole intermediates were reacted with cyanuric chloride to give a reactive dyes (20), and these dyes condensed with hydrazine hydrate and 4-nitrobenzaldehyde in ethanol to obtain azo-methine dyes (26a~26b)。
Characterization of these dyes was carried out by spectral and elemental analysis. The solvent effect in the visible absorption spectra was also evaluated.

目錄
一、緒論 1
前言及研究目的 1
二、實驗部份 3
2-1實驗藥品 3
2-2實驗儀器 5
2-3紫外線-可見光吸收光譜測定(UV) 6
2-4熔點之測試 7
2-5紅外線吸收光譜測試 7
2-6實驗方法 8
2-6-1 5-amino-3H-1,3,4-thiadiazole-2-thione之合成(3) 8
2-6-2 5-amino-2-phenyl-1,3,4-thiadiazole之合成(5a) 8
2-6-3 5-amino-2-(4-methyl phenyl)-1,3,4-thiadiazole之合成(5b) 9
2-6-4 5-amino-2-(4-methoxy phenyl)-1,3,4-thiadiazole之合成(5c) 9
2-6-5 5-amino-2-(4-chloro phenyl)-1,3,4-thiadiazole之合成(5d) 10
2-6-6 6-Hydroxy-4-methyl-2-oxo-1,2-dihydro-pyridine-3- 10
carbonitrile之合成(9a) 10
2-6-7 6-Hydroxy-1,4-dimethyl-2-oxo-1,2-dihydro-pyridine-3- carbonitrile之合成(9b) 11
2-6-8 3-methyl-5-pyrazolone之合成(11a) 12
2-6-9 1-phenyl-3-methyl-5-pyrazolone之合成(11b) 12
2-6-10 2-(5-cyano-2-hydroxy-4-methyl-6-oxo-1,6- dihydro- 13
pyridin-3-ylazo)-1,3,4-thiadiazole-5-thione之合成(12a) 13
2-6-11 2-(5-cyano-2-hydroxy-1,4-dimethyl-6-oxo-6-hydro- 13
pyridin-3-ylazo)-1,3,4-thiadiazole-5-thione之合成(12b) 13
2-6-12 2-(5-cyano-2-hydroxy-4-methyl-6-oxo-1,6-dihydro- 14
pyridin-3-ylazo)-5-phenyl-1,3,4-thiadiazole之合成(12c) 14
2-6-13 2-(5-cyano-2-hydroxy-1,4-dimethyl-6-oxo-6-hydro- 15
pyridin-3-ylazo)-5-phenyl-1,3,4-thiadiazole之合成(12d) 15
2-6-14 2-(5-cyano-2-hydroxy-4-methyl-6-oxo-1,6-dihydro-pyridin- 15
3-ylazo)-5-(4-methyl phenyl)-1,3,4-thiadiazole之合成(12e) 15
2-6-15 2-(5-cyano-2-hydroxy-1,4-dimethyl-6-oxo-6-hydro-pyridin- 16
3-ylazo)-5-(4-methyl phenyl)-1,3,4-thiadiazole之合成(12f) 16
2-6-16 2-(5-cyano-2-hydroxy-4-methyl-6-oxo-1,6-dihydro- pyridin- 16
3-ylazo)-5-(4-methoxy phenyl)-1,3,4-thiadiazole之合成(12g) 16
2-6-17 2-(5-cyano-2-hydroxy-1,4-dimethyl-6-oxo-6-hydro-pyridin- 17
3-ylazo)-5-(4-methoxy phenyl)-1,3,4-thiadiazole之合成(12h) 17
2-6-18 2-(5-cyano-2-hydroxy-4-methyl-6-oxo-1,6-dihydro-pyridin- 17
3-ylazo)-5-(4-chloro phenyl)-1,3,4-thiadiazole之合成(12i) 17
2-6-19 2-(5-cyano-2-hydroxy-1,4-dimethyl-6-oxo-6-hydro-pyridin- 18
3-ylazo)-5-(4-chloro phenyl)-1,3,4-thiadiazole之合成(12j) 18
2-6-20 2-(4-methyl-2-pyrazolone-3-ylazo)-1,3,4-thiadiazole-5-thione 19
之合成(13a) 19
2-6-21 2-(1-phenyl-4-methyl-2-pyrazolone-3-ylazo)-1,3,4-thiadiazole- 19
5-thione之合成(13b) 19
2-6-22 2-(4-methyl-2-pyrazolone-3-ylazo)-5-phenyl-1,3,4-thiadiazole 20
之合成(13c) 20
2-6-23 2-(1-phenyl-4-methyl-2-pyrazolone-3-ylazo)-5-phenyl-1,3,4- 21
thiadiazole 之合成(13d) 21
2-6-24 2-(4-methyl-2-pyrazolone-3-ylazo)-5-(4-methyl phenyl)- 21
1,3,4-thiadiazole之合成(13e) 21
2-6-25 2-(1-phenyl-4-methyl-2-pyrazolone-3-ylazo)-5-(4-methyl 22
phenyl)-1,3,4-thiadiazole之合成(13f) 22
2-6-26 2-(4-methyl-2-pyrazolone-3-ylazo)-5-(4-methoxy phenyl)- 22
1,3,4-thiadiazole之合成(13g) 22
2-6-27 2-(1-phenyl-4-methyl-2-pyrazolone-3-ylazo)-5-(4-methoxy 23
phenyl)-1,3,4-thiadiazole之合成(13h) 23
2-6-28 2-(4-methyl-2-pyrazolone-3-ylazo)-5-(4-chloro phenyl)- 23
1,3,4-thiadiazole之合成(13i)
2-6-29 2-(1-phenyl-4-methyl-2-pyrazolone-3-ylazo)-5-(4-chloro 24
phenyl)-1,3,4-thiadiazole之合成(13j) 24
2-6-30 2-(4-dimethylamino-phenyl-ylazo)-1,3,4-thiadiazloe之合成(15) 24
2-6-31 2-chloroacetylamino-5-(4-methyl phenyl)-1,3,4-thiadiazole之 25
合成(17) 25
2-6-32 2-(4-methylamino-phenyl-ylazo)-2-(2-methylphenyl-5- 26
acetylamino-1,3,4-thiadiazole-2-mercaptoyl)-1,3,4-thiadiazole之合成(18) 26
2-6-33 2-(4-dimethylamino-phenyl-ylazo)-5-(4,6-chloro-s-triazine-2- 26
mercaptoyl)-1,3,4-thiadiazole之合成(20) 26
2-6-34 Ethyl-2-mercaptoyl-6-methylimidazo [2,1-b]-1,3,4- thiadiazole- 5-carboxylate之合成(22a) 27
2-6-35 Ethyl-2-(4-methyl phenyl)-6-methylimidazo [2,1-b]-1,3,4- thiadiazole-5-carboxylate之合成(22b) 28
2-6-36 2-mercaptoyl-6-methylimidazo[2,1-b]-1,3,4-thiadiazole-5- 28
carbohydrazide之合成(24a) 28
2-6-37 2-(4-methyl phenyl)-6-methylimidazo[2,1-b]-1,3,4- thiadiazole- 29
5-carbohydrazide之合成(24b) 29
2-6-38 2-mercaptoyl-6-methyl-4-nitro-phenylidene-imidazo[2,1-b]- 30
1,3,4-thiadiazole-5-carbohydrazides之合成(26a) 30
2-6-39 2-(4-methyl phenyl)-6-methyl-4-nitro- phenylidene-imidazo 30
[2,1-b]-1,3,4-thiadiazole-5-carbohydrazides之合成(26b) 30
三、結果與討論…………………………………………………………………….32
3-1中間體3之合成及分析鑑定……………………………………………..32
3-1-1中間體3的物理數據…………………………………………………..33
3-1-2中間體3之光譜數據分析 33
3-2中間體5a~5b之合成及分析鑑定………………………………………..35
3-2-1中間體5a~5b的物理數據……………………………………………..36
3-2-2中間體5a~5d之光譜數據分析 36
3-3中間體9a~9b之合成及分析鑑定………………………………………..39
3-3-1中間體9a~9b的物理數據……………………………………………..40
3-3-2中間體9a~9b之光譜數據分析 40
3-4中間體11a~11b之合成及分析鑑定……………………………………..42
3-4-1中間體11a~11b的物理數據…………………………………………..43
3-4-2中間體11a~11b之光譜數據分析 43
3-5化合物12a~12j之合成及分析鑑定……………………………………..45
3-5-1化合物12a~12j的物理數據………………………………………….. 45
3-5-2化合物12a~12j之光譜數據分析 46
3-6化合物13a~13j之合成及分析鑑定……………………………………..53
3-6-1化合物13a~13j的物理數據………………………………………….. 54
3-6-2化合物13a~13j之光譜數據分析 54
3-7化合物15之合成及分析鑑定……………… …………………………..62
3-7-1化合物15的物理數據……… ………………………………………..63
3-7-2化合物15之光譜數據分析 64
3-8化合物17~18之合成及分析鑑定………………………………………..65
3-8-1化合物17~18的物理數據……………………………………………..66
3-8-2化合物17~18之光譜數據分析 67
3-9化合物20之合成及分析鑑定…………… ……………………………..69
3-9-1化合物20的物理數據………………………………………………...70
3-9-2化合物20之光譜數據分析 71
3-10化合物26a~26b之合成及分析鑑定…… ……………………………..72
3-10-1化合物26a~26b的物理數據……… ………………………………..73
3-10-2化合物26a~26b之光譜數據分析 74
3-11化合物12a~12j、13a~13j、15、18、20及26~26b的UV光譜數據分析 77
四、結論 83

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