臺灣博碩士論文加值系統

在過去的幾年中，我們實驗室曾對烯雙炔類的化合物進行陰離子芳香性環化反應來得到異喹啉酮、啡啶酮和聯苯之產物，在本論文中我們將繼續對烯雙炔化合物的環化模式進行的研究與探討。
在此我們發現，利用(Z)-1-phenyltrideca-4-en-2,6-diyn-1-one (78b) 加入5當量的聯胺 (Hydrazine) 與4當量的氯化銅在無水乙腈下加熱迴流反應可得到吡唑 (Pyrazole) 衍生物產物 (81)，在充足的反應時間下，產率有85%。

Recently, we developed synthetic methods to a series of aromatic compounds such as isoquinolones, phenanthridinones, and biphenyls via anionic cycloaromatization of enediynes. We found that treatment of (Z)-1-phenyltrideca-4-en-2,6-diyn-1-one (78b) with 5 eq hydrazine and 4 eq copper(I) chloride in refluxing CH3CN afforded pyrazolo[1,5-a]pyridine (81) in 85 % yield.

目 錄
中文摘要....................................................................................................1
英文摘要....................................................................................................2
壹、前言…………………………………………………………………3
1.1 親電性試劑誘導烯炔或烯雙炔化合物的環化反應.................3
1.2 自由基誘導烯雙炔化合物的環化反應.....................................5
1.3 陰離子誘導烯雙炔類化合物的環化反應.................................7
1.4 過度金屬催化烯雙炔化合物進行環化反應...........................10
1.5 吡唑 (Pyrazole) 衍生物的探討..............................................14
貳、研究動機............................................................................................18
参、結果與討論........................................................................................19
3.1 烯雙炔主架構之合成...............................................................19
3.2 環化條件測試...........................................................................21
3.3 不同取代基之環化結果討論...................................................24
肆、結論....................................................................................................25
伍、實驗部份............................................................................................26
陸、化合物之製備方法............................................................................29
(Z)-1-Phenylundeca-4-en-2,6-diyn-1-ol (77a)………………………….30
(Z)-1-Phenyltrideca-4-en-2,6-diyn-1-ol (77b)..........................................31 (Z)-9-Methyl-1-phenyldeca-4-en-2,6-diyn-1-ol (77c)..............................32
(Z)-8,8-Dimethyl-1-phenylnona-4-en-2,6-diyn-1-ol (77d)......................32
(Z)-1,7-Diphenylhepta-4-en-2,6-diyn-1-ol (77e).....................................33
(Z)-1-Phenylundeca-4-en-2,6-diyn-1-one (78a) ………………………..33
(Z)-1-Phenyltrideca-4-en-2,6-diyn-1-one (78b)………………………...34
(Z)-9-Methyl-1-phenyldeca-4-en-2,6-diyn-1-one (78c)………………...35
(Z)-8,8-Dimethyl-1-phenylnona-4-en-2,6-diyn-1-one (78d)…………...35
(Z)-1,7-Diphenylhepta-4-en-2,6-diyn-1-one (78e)……………………...36
(Z)-5-(Dec-1-en-3-ynyl)-3-phenyl-1H-pyrazole (80)...............................36
7-Butyl-2-phenylpyrazolo[1,5-a]pyridine (81a)………………………...37
7-Hexyl-2-phenylpyrazolo[1,5-a]pyridine (81b)………………………..38
7-Isobutyl-2-phenylpyrazolo[1,5-a]pyridine (81c)……………………...38
7-Tert-butyl-2-phenylpyrazolo[1,5-a]pyridine (81d)…………………...39
2,7-Diphenylpyrazolo[1,5-a]pyridine (81e)…………………………….40
柒、參考文獻............................................................................................41
捌、光譜資料……………………………………………………………43

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