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研究生： 蔡弼丞
Pi-Chen Tsai
論文名稱： 吡唑[1,5-a]嘧啶衍生物為主體之新型對稱與非對稱性雜環雙偶氮染料之合成及溶劑變色性質之研究
Synthesis and Solvatochromic Properties of Some Novel Symmetrical and Asymmetrical Heterocyclic Disazo Dyes Based on Pyrazolo[1,5-a]Pyrimidine Derivatives
指導教授： 王英靖
Ing-Jing Wang
口試委員: 林河木
none
陳耿明
none
郭中豐
noen
顏明雄
none
郭坤土
noen
學位類別： 博士
Doctor
系所名稱： 工程學院 - 材料科學與工程系
Department of Materials Science and Engineering
論文出版年： 2007
畢業學年度： 95
語文別： 中文
論文頁數： 196
中文關鍵詞： 吡唑 、吡唑[1 、5-a]嘧啶 、雜環雙偶氮染料 、溶劑變色性質
外文關鍵詞： pyrazole, pyrazolo[1, 5-a]Pyrimidine, Heterocyclic Disazo Dyes, Solvatochromic
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    • 本研究主要以兩大主題所構成，分別論述如下：第一主題：(1)以聯胺分別與2-取代偶氮基丙二氰、3-取代偶氮基-2,4-戊二酮及3-亞胺基-2-取代偶氮基-丁腈在溶劑行環化反應，製備成3,5-(二胺基或二甲基)-4-(取代苯偶氮基)吡唑及3-胺基-5-甲基-4-取代偶氮基-吡唑之單偶氮化合物。(2)以苯胺衍生物為重氮鹽並在冰浴條件下，分別與偶合鹽3-胺基-5-吡唑哢及5-胺基-3-甲基吡唑行偶合反應，製備3-胺基-4-取代偶氮基-5-吡唑哢及5-胺基-3-甲基-4-取代偶氮基吡唑之單偶氮化合物。將上述所合成吡唑單偶氮染料，分別在丙酮溶劑下測定其紫外線光譜，探討染料結構中吡唑環第4位置取代苯偶氮基及吡唑環上各取代基種類及位置對最大吸收波長之影響，分析得知吡唑單偶氮染料其吡唑環上第5位置取代基對最大吸收波長的影響大於第3位置取代基。
    第二主題：(1)以2-(4-取代-苯偶氮基)丙二氰及3,5-二胺-4-(取代苯偶氮基)吡唑在乙醇溶劑中行環化反應，合成出第3位置及第6位置為苯偶氮基之吡唑[1,5-a]嘧啶雙偶氮染料。(2)以2-(4-取代-苯偶氮基)丙二氰、2-(5-取代-噻唑-2-偶氮基)-丙二氰、2-(6-取代-苯並噻唑-2-偶氮基)-丙二氰、3,5二胺-4-(4-取代-苯偶氮基)-吡唑及3,5二胺-4-(雜環取代偶氮基)-吡唑，合成出第3位置為(苯偶氮基或雜環偶氮基)第6位置為(苯偶氮基或雜環偶氮基)之吡唑[1,5-a]嘧啶雙偶氮染料。(3)以2-(5-取代-噻唑-2-偶氮基)-丙二氰、2-(6-取代-苯並噻唑-2-偶氮基)-丙二氰及3,5二胺-4-(雜環取代偶氮基)-吡唑合成出第3位置及第6位置為雜環偶氮基之吡唑[1,5-a]嘧啶雙偶氮染料。將上述所合成雜環雙偶氮染料，分別在不同溶劑下測定其紫外線光譜，探討染料結構中不同取代基與不同極性溶劑對最大吸收波長的影響，分析得知染料最大吸收波長會隨溶劑極性增加而具有紅位移傾向。以上所合成之雜環雙偶氮染料來比較出3,6位置之取代基為苯偶氮基或為雜環偶氮基，對於吡唑[1,5-a]嘧啶化合物對最大吸收波長的影響，分析得知染料最大吸收波長會因吡唑[1,5-a]嘧啶化合物3,6位置之取代基，改變為雜環偶氮基時而往長波長移動的趨勢。
    以上所合成之化合物均經(IR、UV及1H-NMR)等光譜鑑定及元素分析(EA)來確定其化學構造。

    The disertation consists of two main themes: Firstiy, (1) 3,5-Di-(amino or methyl)-4-substituted-azoly-pyrazole and 3-amino-5- methyl-4-substituted-azoly-pyrazole have been synthesized via the cyclization from hydrazine hydrate with 2-substituted-azoly-malono- nitrile, 3-sub-stituted-azoly-pentane-2,4-dione and 3-imino-2-substitu- ted-azoly-butyronitrile, respectively; and (2) 5-amino-3-methyl-4-substi -tuted-azoly-pyrazole and 3-amino-4-substituted-azoly-5-pyrazolone were prepared by coupling reaction of aniline derivatives with 3-amino-5-pyrazolone and 5-amino-3-methylpyrazole, respectively. The effect of maximum absorption spectra on synthesized pyrazole monoazo dyes with different substituents and their different locations was also evaluated by UV-ray in acetone. After a series of analyses, we can realize that the substituent effect of maximum absorption spectra on the 5th position of pyrazole ring is more dominant than the 3rd position of that.
    Secondly, (1) 3,6-Diphenylazo pyrazole[1,5-a]pyrimidine disazo dyes were synthesized both by the cyclization of 2-(4-substituted- phenylazo)- malononitrile with 3,5-diamino-4-(4-substituted-phenyl- azo)-pyrazole; (2) 4-(Aryl or hetaryl)azo-3,5-diaminopyrazole com- pounds with arylazo- and hetarylazo- malononitriles were prepared by the cyclization to obtain the 3,6-di-(aryl or hetaryl)- azo-2,5,7-triamino- pyrazolo[1,5-a]pyrimidine heterocyclic disazo dyes; (3) 3,6-dihetaryl- azo-2,5,7-triamino-pyrazolo[1,5-a]pyrimidine heterocyclic disazo dyes have been synthesized via the cyclization from some substituted hetarylazomalononitrile precursors with various substituted hetarylazo- pyrazole compounds. The effect of maximum absorption spectra on these prepared hetercyclic disazo dyes with and various solvents was investigated by the UV-ray test. In addition, the effect due to different substituents and polarities was also evaluated.The solvatochromic behavior of these dyes in various solvents with different dielectric constants reveals bathochromic shifts as the solvent polarity is increased. Although, the substituents can be arylazo or hetarylazo by comparing with the synthesized hetarcyclic disazo dye, we can know the different effect of maximum absorption spectrum for pyrazole- [1,5-a]pyrimidind compounds. By the related analyses, the maximum absorption spectrum of dyes may have a trend of moving to long wavelength when the substituted on the 3,6th position of pyrazole- [1,5-a]pyrimidind ring changing to hetarylazo group.
    All synthesized compounds in this disertation were analyzed to recognize their chemical structures through spectrum identification of FT-IR, UV, and 1H-NMR and EA.

    中文摘要 I ABSTRACT III 誌 謝 V 目錄 VI 表目錄 VIII 圖目錄 X 第1章 前言 1 第2章 實驗部份 5 2.1 實驗材料 5 2.2 實驗儀器 6 2.3 合成方法 7 2.3.1 2-Substituted-azoly-malononitrile derivatives 7 2.3.2 3-Substituted-azoly- pentane- 2,4-dione derivatives 9 2.3.3 3-Imino-2-substituted-azoly-butyronitrile derivatives 10 2.3.4 3-Amino-5-pyrazolone 10 2.3.5 5-Amino-3-methylpyrazole 11 2.3.6 4-Substituted-azoly-3,5-diaminopyrazole derivatives 11 2.3.7 4-Substituted-azoly-3,5-dimethyl pyrazole derivatives 13 2.3.8 3-Amino-5-methyl-4-substituted-azoly-pyrazole derivatives 14 2.3.9 3-Amino-4-substituted-azoly-5-pyrazolone derivatives 15 2.3.10 5-Amino-3-methyl-4-substituted-azoyl-pyrazole derivatives 15 2.3.11 3,6-Diphenylsubstituted-azoly-pyrazolo[1,5-a]pyrimidine-2,5,7-triamino derivatives 16 2.3.12 6-Arylazo-3-hetarylazo-pyrazolo[1,5-a]pyrimidine-2,5,7-tri-amino derivatives 19 2.3.13 3-Arylazo-6-hetarylazo-pyrazolo[1,5-a]pyrimidine-2,5,7-tri-amino derivatives 21 2.3.14 3,6-DiHetarylsubstituted-azoly-pyrazolo[1,5-a]pyrimidine-2,5,7-triamino derivatives 23 2.3.15 2,5,7-Trimethyl pyrazolo[1,5-a]pyrimidine 27 2.3.16 5,7-Dimethyl pyrazolo[1,5-a]pyrimidine 2-one 27 2.3.17 5,7-Dimethyl-3-phenylsubstituted-azoly-pyrazole[1,5-a]py-rimidine 2-one derivatives 28 第3章 結果與討論 29 3.1 中間體衍生物之合成及光譜分析 29 3.1.1 2-Substituted-azoly-malononitrile derivatives之合成 29 3.1.2 3-Substituted-azoly-pentane-2,4-dione derivatives之合成 32 3.1.3 3-Imino-2-substituted-azoly-butyronitrile derivatives之合成 34 3.1.4 3-Amino-5-pyrazolone之合成 36 3.1.5 5-Amino-3-methylpyrazole之合成 39 3.1.6 4-Substituted-azoly-3,5-diaminopyrazole derivatives之合成 41 3.1.7 4-Substituted-azoly-3,5-dimethylpyrazile derivatives之合成 48 3.1.8 3-Amino-4-substituted-azoly-5-methylpyrazole derivatives之合成 53 3.1.9 3-Amino-4-substituted-azoly-5-pyrazolone derivatives之合成 59 3.1.10 5-Amino-3-methyl-4-substituted-azoly-pyrazole derivatives之合成 64 3.2 雙偶氮化合物之合成及光譜分析 71 3.2.1 3,6-Diphenylsubstituted-azoly-pyrazolo[1,5-a]pyrimidine-2,5,7-triamino deri- vatives之合成 71 3.2.2 6-Arylazo-3-hetarylazo-pyrazolo[1,5-a]pyrimidine-2,5,7-triamino derivatives之合成 79 3.2.3 3-Arylazo-6-hetarylazo-pyrazolo[1,5-a]pyrimidine-2,5,7-tri-amino derivatives之合成 87 3.2.4 3,6-Dihetarylsubstituted-azoly-pyrazolo[1,5-a]pyrimidine-2,5,7-triamino dirivatives之合成 95 第4章 結論 107 參考文獻 110 附圖 116

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