臺灣博碩士論文加值系統

本研究旨在以硫代尿素(thiourea)與單氯醋酸(chloroacetate)在水溶液中進行反應，合成2,4雙酮噻唑中間體(2,4-thiazolidinedione)( 3)，另並與乙醯苯(acetophenone)及4-氯基乙醯苯(4-chloroacetophenone)為起始原料，使用融溶法合成[4-(4-substituted-phenyl)-thiazol-
2-ylamine]衍生物6a~6b。首先以中間體3與含醛基化合物在乙醇溶劑中及鹼性觸媒存在下進行縮合反應，得到次甲基(methane)化合物8a~8f；另與重氮鹽化合物在低溫下進行偶合反應，得到偶氮型化合物11a~11b。進而利用化合物6與重氮化合物，在低溫下進行偶合反應，得到偶氮型化合物12a~12i；另將6b之第2位置的胺基進行重氮化，形成重氮鹽化合物時，續與二甲基胺(N,N-Dimethylaniline)進行偶合反應，得到偶氮型染料15；最後將所有合成之化合物經光譜分析(UV、IR及1H-NMR等)及元素分析(EA)來確定結構。

In this study, we herein to synthesize the intermediate of 2,4-thiazolidinedion 3 that was given by the thiourea condensed with mono chloroacetic acid in aqueous solution at reflux. Furthermore, the raw materials of acetophenone and 4-chloroaceto-phenone used was used by fused method to synthesize of compound 6a~6b.
First,the 2,4-thiazolidinedion 3 and was condensed with the aldehyde in ethanol under the base catalyst to obtain the compound 8a~8f of methine . Besides, the coupling reaction was proceed with the diazonium salt at temperature 0~5℃ to get the 11a~11b compound of azo type.Then, the intermediate 6 was coupled with the diazonium salt at the temperature 0~5℃to obtain the compound 12a~12i of azo type. The second situation of the amine of the intermediate 6b with N,N-Dimethylaniline to obtain the compound 15 of azo type. Finally, these compound was determined by the spectrometry of UV,FT-IR、1H-NMR and the elemental analysis of EA to ascertain the structure.

中文摘要-----------------------------------------------------I
英文摘要----------------------------------------------------II
目錄--------------------------------------------------------III
圖表索引 ---------------------------------------------------V
一、緒論----------------------------------------------------1
1.1前言及研究目的 --------------------------------------------1
二、實驗------------------------------------------------------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 ----------------------------6
2.4 熔點之測試. ------------------------------------------7
2.5 紅外線吸收光譜測 -------------------------------------7
2.6實驗方法---------------------------------------------------8
2.6.1中間體合成------------------------------------------8
2.6.1.1 2,4-thiazolidinedione ( 3 )--------------------8
2.6.1.2 4-phenyl-thiazol-2-ylamine (6a)-----------------8
2.6.1.3 4-(4-Chloro-phenyl)-thiazol-2-ylamine(6b)--------9
2.6.2 化合物之合成- --------------------------------------9
2.6.2.1 5-Benzylidine-thiazolidine-2,4-dione(8a)--------9
2.6.2.2 5-(2-Methyl-benzylidene)-thiazolidine-2,4-dione (8b)----------------------------------------------------- ----9
2.6.2.3 5-(4-Chloro-benzylidine)- thiazolidine-2,4-dione (8c)---------------------------------------------------------10
2.6.2.4 5-(4-Dimethylamino-benzylidine)-thiazolidine-2,4-
dione (8d)--------------------------------------------------11
2.6.2.5 5-(4-Nitro-benzylidine)- thiazolidine-2,4-dione (8e)---------------------------------------------------------11
2.6.2.6 5-(4-Cyano-benzylidine)-thiazolidine-2,4-dione(8f)---------------------------------------------------------12
2.6.2.7 5-Phenylazo-thiazolidine-2,4-dione (11a)------ 12
2.6.2.8 5-(4-Chloro-phenylazo)- thiazolidine-2,4-dione (11b)--------------------------------------------------------13
2.6.2.9 4-Phenyl-5-phenylazo-thiazol-2-ylamine (12a)---13
2.6.2.10 2-(2-Amino-4-phenyl-thiazol-5-ylazo)-benzo-
nitrile (12b)------------------------------------------------14
2.6.2.11 5-(2-Nitro-phenylazo)-4-phenyl-thiazol-2-
ylamine(12c)------------------------------------------------14
2.6.2.12 5-(4-Nitro-phenylazo)-4-phenyl-thiazol-2-
ylamine (12d)-----------------------------------------------15
2.6.2.13 5-(4-Chloro-2-methoxy-phenylazo)-4-phenyl-thiazol-
2-ylamine (12e) --------------------------------------------15
2.6.2.14 2-[2-Amino-4-(4-chloro-phenyl)-thiazol-5-ylazo]-
benzonitrile( 12f )------------------------------------------15
2.6.2.15 4-(4-Chloro-phenyl)-5-(4-chlorophenylazo)-thiazol-
2-ylamine (12g)----------------------------------------------16
2.6.2.16 4-(4-Chloro-phenyl)-5-(4-chlorophenylazo)-thiazol-
2-ylamine (12h)----------------------------------------------16
2.6.2.17 {4-[4-(4-Chloro-phenyl)thiazol-2-ylazo]phenyl}-
dimethyl-amine(12i)---------------------------------------17
2.6.2.18 {4-[4-(4-Chloro-phenyl)thiazol-2-ylazo]phenyl}-
dimethyl-amine (15)---------------------------------------18
三、結果與討論-----------------------------------------------19
3.1 中間體3之合成----------------------------------------19
3.1.1化合物3的物理數據----------------------------------20
3.1.2化合物3之光譜數據分析------------------------------20
3.2中間體6a~6b之合成-------------------------------------22
3.2.1化合物6a~6b之物理數據------------------------------23
3.2.2化合物6a~6b之光譜數據分析--------------------------23
3.3 化合物8a~8f之合成----------------------------------- 25
3.3.1 化合物8a~8f之物理數據-----------------------------26
3.3.2 化合物8a~8f的光譜數據分析-------------------------26
3.4化合物11a~11b之合成-----------------------------------30
3.4.1 化合物11a~11b之物理數據---------------------------31
3.4.2 化合物11a~11c之光譜數據分析-----------------------31
3.5 化合物12a~12i之合成----------------------------------33
3.5.1 化合物12a~12i之物理數據---------------------------34
3.5.2 化合物12a~12g之光譜數據分析-----------------------34
3.6化合物15之合成 ---------------------------------------41
3.6.1 化合物15之物理數據--------------------------------42
3.6.2 化合物15之光譜數據分析------------------------42
3.7化合物8a~8f、11a~11b、12a~12i及15的UV光譜數據分析---------44
四、結論-----------------------------------------------------47
參考文獻-----------------------------------------------------49

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