臺灣博碩士論文加值系統

本研究主要分成三部份，合成一系列偶氮(N=N)、氮次甲基(C=N)、次甲基(C=C)新穎雜環系色素，第一部份合成雜環中間體包含2,3,8-trisubstituted indeno[2,1-b]thiophene 5-7，利用中間體5-7分別與含醛基化合物合成出azo-methine (C=N) 化合物10-12，再分別以中間體5-7，各做成重氮鹽在冰浴下分別與偶合物9進行偶合反應得到azo(N=N) 化合物13-15。第二部份利用3-dicyanovinyl-indan-1-one 3 分別與苯胺化合物合成出enamine化合物17a-17c，再經由Gewald 反應，環化得到8-substituted-2-amino-indeno[2,1-b]thiophene 化合物18a-18c。中間體ethyl (1-indanylidene)-cyanoacetate 20作為起始物，經由Gewald 反應及Knoevenagel反應得到8-substituted-2-amino-indeno [2,1-b]thiophene化合物25a-25d。第三部份採用1,3-indandione 1為起始物與二氰基甲烷、氰基乙酸乙酯、苯胺化合物合成一系列中間體3、17a-17c 、26、27，再利用此中間體分別與含醛基化合物合成出methine化合物30a-30g。所合成之化合物經光譜分析(IR、1H-NMR、MS)及元素分析(EA)確定化學結構。所合成偶氮(N=N)、氮次甲基(C=N)、次甲基(C=C)新穎雜環系化合物，分別在丙酮溶劑中測定其紫外光/可見光吸收光譜，探討不同取代基對最大吸收波長之影響。所合成的化合物13-15含有偶氮(N=N) 發色體比化合物10-12含有氮次甲基(C=N)發色體更具深色效應。在thiophene 環第八位置導入C=C(CN)2基和C=C(CN)(COOEt)基，導致更大的深色效應。化合物25a-25d最大吸收波長的範圍是其421–492 nm。化合物25a結構中在苯環上有強拉電子NO2基，更往長波長移動，取代基深色效應的順序為NO2＞CN＞Cl＞N(CH3)2。化合物29d的enamine結構經由IR、1H-NMR光譜及X光繞射得到証實。化合物30e-30g含有C=N-phenyl基比化合物30b更往長波長移動，取代基深色效應的順序為C=C(CN)2 > C=N(p-NO2-ph) > C=N(p-OCH3-ph) > C=N(ph) > C=C(CN)(COOC2H5) > C=O，C=C(CN)2基對深色效應特別重要。

In this study, a series of novel heterocyclic colorants containing azo (N=N)、azo-methine (C=N)、methine(C=C) were elucidated. Firstly, the heterocyclic intermediates with 2,3,8-trisubstituted indeno[2,1-b] thiophene 5-7 were employed to synthesized the azo-methine (C=N) compounds 10-12 by condensation reaction of compounds 5-7 and aldehyde compound. The coupling reaction between diazo components 5-7 and the component 9 yields azo(N=N) compounds 13-15 in ice bath. Secondly, condensation of 3-dicyanovinylindan-1-one 3 with arylamines afforded enamine compounds 17a-17c, which were converted to 8-substituted-2-amino-indeno[2,1-b]thiophene compounds 18a-18c by Gewald reaction. Additionally, 2-amino-indeno[2,1-b]thiophene compounds 25a-25d were synthesized by using ethyl(1-indanylidene)- cyanoacetate 20 as a starting material via Gewald reaction and Knoevenagel reaction. Thirdly, a series of methine compounds 30a-30g were prepared by condensation of 1,3-indandione derivatives 3、17a-17c、26、27 with the aldehyde compound. All the products were characterized by elemental analysis, UV/Vis, IR, 1H-NMR and MS spectral data. The substituent effects of these compounds on the electronic absorption properties in acetone are also investigated. The compounds 13-15 containing azo chromophore (-N=N-) have the absorption maxima at longer wavelengths than the corresponding the compounds 10-12 with an imino chromophore (-N=CH-). The introduction of the substituents C(CN)2 and C(CN)(COOEt) group into the compound 10 at the 8-position of thiophene ring giving compounds 11 and 12 result in a large bathochromic shift. The λmax of compounds 25a-25d ranged from 421 to 492 nm. It was found that the compound 25a containing an stronger electron-withdrawing NO2 group at phenyl ring absorbed at longer wavelength. The effect of substituents were observed bathochromic shift in the order NO2 > CN > Cl > N(CH3)2. The structure of the compound 29d was actually identified by IR, 1H NMR spectra and X-ray diffraction as enamine structure. The absorption maxima of compounds 30e-30g containing C=N-phenyl group shifted to longer wavelengths than that of compound 30b, respectively. The effect of substituents were observed bathochromic shift in the order C=C(CN)2 > C=N(p-NO2-ph) > C=N(p-OCH3-ph) > C=N(ph) > C=C(CN)(COOC2H5) > C=O; the effect of bathochromic shift of C=C(CN)2 group is particularly significant.

摘要 …………………………………………………………………………………Ⅰ
Abstract ……………………………………………………………………………Ⅳ
誌 謝 ………………………………………………………………………………Ⅴ
目 錄 ………………………………………………………………………………Ⅵ
圖表索引 ……………………………………………………………………………Ⅹ
ㄧ 前言……………………………………………………………………………… 1
二 實驗……………………………………………………………………………… 7
2-1 實驗藥品 ……………………………………………………………………… 7
2-2 實驗儀器 ……………………………………………………………………… 9
2-3 合成方法……………………………………………………………………… 9
2-3-1 中間體(3)、(5)、(6)及(7)之合成 ……………………………………… 9
2-3-1-1 3-Dicycanovinylindan-1-one中間體(3)之合成 …………………… 9
2-3-1-2 2-Amino-8-oxo-8H-indeno[2,1-b]thiophene-3-carbonitrile 中間體(5)之合成 ……………………………………………………………………10
2-3-1-3 2-(2-Amino-3-cyano-indeno[2,1-b]thiophen-8-ylidene) -malononitrile 中間體(6)之合成 ………………………………………………………10
2-3-1-4 [2-Amino-3-cyano-indeno[2,1-b]thiophene-8-ylidene]-cyano-acetic acid ethyl ester 中間體(7)之合成 ………………………………………………11
2-3-2 氮次甲基(azomethine)化合物(10)、(11) and (12)之合成……………11
2-3-2-1 2-(4-N,N-dimethylamino-benzyldeneamino)-8-oxo-8H-indeno
[2,1-b]thiophene-3-carbonitrile化合物(10) ……………………11
2-3-2-2 2-(4-N,N-dimethylamino-benzyldeneamino)-8-oxo-8H-indeno
[2,1-b]thiophene-3-carbonitrile化合物(11) ……………………11
2-3-2-3 2-(4-N,N-dimethylamino-benzyldeneamino)-8-oxo-8H-indeno
[2,1-b]thiophene-3-carbonitrile (12) ……………………………12
2-3-3 偶氮(Azo)化合物(13), (14) and (15)之合成…………………………12
2-3-4 2-[3-(4-Substituted-phenylamino)-inden-1-ylidene]- malononitrile (17a-17c)之合成…………………………………………………………13
2-3-5 2-Amino-8-[phenylimino]-8H-indeno[2,1-b]thiophene-3- carbonitrile (18a-18c)之合成 ………………………………………13
2-3-6 中間體(20)、(21)及(23)之合成……………………………………………14
2-3-6-1 Ethyl(1-indanylidine)-cyanoanctate (20) ………………………………14
2-3-6-2 Ethyl 2-amino-indeno[2,1-b]thiophene-3-carboxylate (21) ……………14
2-3-6-3 Ethyl 2-acetyl-indeno[2,1-b]thiophene-3-carboxylate (23) ……………15
2-3-7 化合物(25a~25d)之合成 …………………………………………………15
2-3-7-1 2-Amino-8-[(4-nitro-phenyl)-ylidene]-indeno[2,1-b]thiophene-
carboxylic acid ethyl ester (25a) ………………………………………15
2-3-7-2 2-Amino-8-[(4-cyano-phenyl)-ylidene]-indeno[2,1-b]thiophene-
carboxylic acid ethyl ester (25b) ………………………………………15 2-3-7-3 2-Amino-8-[(4-chloro-phenyl)-ylidene]-indeno[2,1-b]thiophene-
carboxylic acid ethyl ester (25c) …………………………………16
2-3-7-4 2-Amino-8-[(4-dimethylamino-phenyl)-ylidene]-indeno[2,1-b] thiophene-carboxylic acid ethyl ester (25d) ………………16
2-3-8 中間體(26)及(27)之合成 ……………………………………………… 17
2-3-8-1 1,3-Bisdicycanovinylindan中間體(26) ……………………… 17
2-3-8-2 Cyano-[3-dicyanomethylene-indan-ylidene]-acetic acid ethyl ester 中間體之合成(27) …………………………………………… 17
2-3-9 中間體[1,2']biindenylidene-3,1',3'-trione (28)之合成…………18
2-3-10 化合物(29a-29d)的合成 ……………………………………………… 18
2-3-11 Methine化合物(30a-30g)之合成 …………………………………… 18
2-4紫外線-可見光吸收光譜測定(UV) ……………………………………………19
三、結果與討論………………………………………………………………………21
3-1中間體(3)、(5)、(6)及(7)之合成……………………………………………21
3-1-1 中間體(3)之合成……………………………………………………………21
3-1-2 中間體(5)之合成及光譜數據分析 ……………………………………… 23
3-1-3 中間體(6), (7)之合成及光譜數據分析 ………………………………25
3-2 化合物(10-14)之合成 ………………………………………………………27
3-2-1氮次甲基(azomethine)化合物(10), (11), (12)之合成及光譜數據分析 …………………………………………………………………………28
3-2-2 偶氮(azo)化合物(13), (14), (15)之合成及光譜數據分析 …………………………………………………………………………30
3.3 化合物(17a-17c) , (18a-18c)之合成………………………………………35
3-3-1 化合物(17a-17c)之合成及光譜數據分析…………………………………35
3-3-2 化合物(18a-18c)之合成及光譜數據分析…………………………………38
3-4 化合物(25a-25d)之合成………………………………………………………42
3-4-1 Ethyl(1-indanylidene)-cyanoacetate (20)合成 ……………………43
3-4-2 Ethyl 2-amino-indeno[2,1,b]thiophene-3-carboxylate(21)之合成及光譜數據分析………………………………………………………………………44
3-4-3 Ethyl 2-acetyl-indeno[2,1-b]thiophene-3-carboxylate (23)之合成 及光譜數據分析 …………………………………………………………46
3-4-4 化合物(25a~25d)之合成及光譜數據分析…………………………………49
3-5中間體(26), (27)之合成及光譜數據分析……………………………………53
3.6化合物(28), (29)之合成…………………………………………………………55
3-6-1 化合物(28)合成 ……………………………………………………………55
3-6-2 化合物(29a-29d)合成及光譜數據分析……………………………………57
3-6-3 化合物(29d)的X光單晶繞射晶體結構分析………………………………61
3-7 化合物(17a-17c), (26)合成…………………………………………………72
3-8 次甲基(methine)化合物(30a-30g)合成及光譜數據分析 …………………74
3-9 化合物10-15 UV/Vis光譜數據分析…………………………………………78
3-9-1取代基對化合物10-12,13-15 UV/Vis光譜之影響………………………78
3-9-2 不同發色體(chromophore) UV/Vis光譜之影響 …………………………81
3-10 取代基對化合物18a-18c UV/Vis光譜之影響 ……………………………82
3-11 取代基對化合物25a-25d UV/Vis光譜之影響 ……………………………84
3-12化合物29a-29dUV/Vis光譜 …………………………………………………86
3-13 取代基對化合物30a-30g UV/Vis光譜之影響………………………………88
四 結論………………………………………………………………………………91
參考文獻 ……………………………………………………………………………94
附錄 化合物 MS、IR、1H-NMR光譜圖……………………………………………97
作者簡介……………………………………………………………………………150

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