聚噻吩是一種導電高分子，藉由在結構中的β位修飾不同的官能基可使其性質多變，摻雜後亦表現良好的光電化學性能等，因此獲得科學家廣泛的關注，並且已應用於有機太陽能電池（OPV）、有機電致發光（OLED）等有機光電材料中。文獻中常見合成聚噻吩的方法有：利用FeCl3進行化學氧化聚合反應；以過渡金屬催化耦聯反應；或是電化學聚合法。本論文嘗試以開環移位聚合反應（ring-opening metathesis polymerization，ROMP）合成聚噻吩，藉此合成具有不同性質的聚噻吩衍生物。本次研究主題以噻吩衍生物與炔烴做為起始物，進行狄耳士-阿爾德反應（Diels–Alder reaction）合成橋聯雜環衍生物（bridged heterocycles），再將此橋聯雜環單體應用於本論文嘗試使用的開環移位聚合反應，接著進行氧化反應製得聚噻吩。另外，也嘗試將此合成方法應用於聚吡咯的合成中。

Polythiophene is a conductive polymer. By modifying different functional groups in the β position of thiophene, the properties of the polymer can be altered. Since the photoelectric performance of the polythiophene is also excellent after doping, these have some applications like organic solar cells, organic electroluminescence display and other organic photoelectric materials. Common synthetic methods of polythiophene include: chemical oxidation by FeCl3, catalytic coupling reaction by transition metal or electrochemical polymerization. This thesis focus on the development of ROMP for the synthesis of polythiophene. Thiophene derivatives and alkynes were used to synthesize bridged heterocyclic derivatives by Diels-Alder reaction, the bridged heterocyclic monomers were then polymerized by ROMP followed by oxidation to produce polythiophene. In addition, the synthesis of polypyrrole by ROMP was also attempted.

研究生學位論文審定書 ............................................................................................................. i
論文公開授權書 ........................................................................................................................ ii
致謝 ........................................................................................................................................... iii
中文摘要 .................................................................................................................................... v
Abstract ..................................................................................................................................... vi
目次 .......................................................................................................................................... vii
圖目錄 ........................................................................................................................................ x
流程目錄 .................................................................................................................................. xii
表目錄 ..................................................................................................................................... xiii
光譜目錄 ................................................................................................................................. xiv
縮寫表 ...................................................................................................................................... xv
第一章 緒論 ............................................................................................................................. 1
1.1 研究背景 .................................................................................................................. 1
1.1.1 導電高分子（Conductive polymer）的簡介....................................................... 1
1.1.2 聚噻吩（Polythiophene）的簡介 ........................................................................ 2
1.1.3 聚吡咯（Polypyrrole）的簡介 ............................................................................ 2
1.2 聚噻吩與聚吡咯合成方法介紹 .............................................................................. 4
1.2.1 化學氧化聚合法 ................................................................................................... 4
1.2.2 電化學聚合法 ....................................................................................................... 4
1.2.3 金屬催化偶合法 ................................................................................................... 5
1.2.4 光致聚合法 ........................................................................................................... 9
1.2.5 光電化學聚合法 ................................................................................................. 11
1.2.6 固相聚合法 ......................................................................................................... 12
1.2.7 酸催化聚合法 ..................................................................................................... 13
viii
1.3 開環移位聚合法 .................................................................................................... 15
第二章 研究動機與實驗設計 ............................................................................................... 17
2.1 研究動機 ................................................................................................................ 17
2.2 實驗設計 ................................................................................................................ 18
第三章 結果與討論 ............................................................................................................... 19
3.1 Dimethyl 7-thiabicyclo[2.2.1]hepta-2,5-diene-2,3- dicarboxylate（4）之合成 ... 19
3.1.1 利用傳統加熱進行Diels-Alder反應 ................................................................ 19
3.1.2 利用微波加熱進行Diels-Alder反應 ................................................................ 20
3.1.3 以不同的路易斯酸輔助噻吩進行Diels-Alder反應 ........................................ 22
3.1.4 Thiophene 1-oxide（5）之合成 ....................................................................... 24
3.2 Benzo[c]thiophene（7）之合成 ............................................................................ 25
3.2.1 Benzo[c]thiophene（7）之合成 ....................................................................... 25
3.2.2 In situ生成Benzo[c]thiophene（7）進行Diels-Alder reaction ..................... 26
3.3 以苯炔與噻吩進行Diels-Alder反應 ................................................................... 28
3.4 7-(tert-butyl) 2,3-dimethyl 7-azabicyclo[2.2.1]hepta-2,5-diene-2,3,7-tricarboxylate（12）之合成 ..................................................................................................................... 30
3.5 Poly(1-(tert-butyl) 3,4-dimethyl 2,5-divinyl-2,5- dihydro-1H-pyrrole-1,3,4-tricarboxylate)（12）之合成.................................................... 33
3.6 結論 ........................................................................................................................ 34
第四章 引用文獻 ................................................................................................................... 35
第五章 實驗步驟與數據 ....................................................................................................... 39
5.1 儀器設備與藥品材料 ............................................................................................ 39
5.2 合成步驟與數據 .................................................................................................... 42
5.2.1 Dimethyl phthalate（4-1）之合成 ................................................................... 42
5.2.2 Dimethyl 7-oxabicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylate（F1）之合成 ......................................................................................................................................... 43
5.2.3 Tetramethyl 9-thiatricyclo[4.2.1.02,5]nona-3,7-diene-2,3,4,5- tetracarboxylate（4-2）之合成 ................................................................................................................ 44
5.2.4 1,3-dihydrobenzo[c]thiophene（6）之合成 ..................................................... 45
ix
5.2.5 1,3-dihydrobenzo[c]thiophene 2-oxide（8）之合成 ........................................ 45
5.2.6 Dimethyl naphthalene-2,3-dicarboxylate（9-1）之合成 ................................. 46
5.2.7 1,4-dihydro-1,4-epoxynaphthalene（F2）之合成 ............................................ 47
5.2.8 Dimethyl naphthalene-2,3-dicarboxylate（10-1）之合成 ............................... 47
5.2.9 tert-butyl 1H-pyrrole-1-carboxylate（11）之合成 .......................................... 48
5.2.10 7-(tert-butyl) 2,3-dimethyl 7-azabicyclo[2.2.1]hepta-2,5-diene-2,3,7 -tricarboxylate（12）之合成 .......................................................................................... 49
第六章 光譜資料 ................................................................................................................... 50

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