臺灣博碩士論文加值系統

利用高價碘試劑(Ⅲ)如:醋酸碘苯(PhI(OAc)2)和三氟乙醯基碘苯(PhI(OTFA)2)反應可以在溫和且環保的反應條件下將苯胺及吡啶進行合環生成苯并[4,5]咪唑并[1,2-a]吡啶衍生物，在本論文研究中，我們探討了溶劑以及取代基對反應性的影響。最好的條件以不外加溶劑的形式，將苯胺及吡啶利用高價碘試劑在室溫下反應15分鐘。同時我們也發現反應會產生偶氮化合物的副產物。從控制實驗反應機制的探討中，我們推測高價碘試劑為高價碘試劑為醋酸碘苯時，則是經由醯胺基離子產生產物，若是雙(三氟乙醯氧基)碘苯時，是經由陽離子自由基產生產物。

It was found that hypervalent iodine, such as (diacetoxyiodo)benzene and [bis(trifluoroacetoxy)iodo]benzene could mediate reaction of anilines with pyridines in mild reaction to give benzo[4,5]imidazo[1,2-a]pyridine derivatives. In this thesis, the effect of solvent and substituents group on reactivity are investigated. The optimized reaction conditions is the reaction of anilines with pyridines in the ratio of 1 to 77 without any additional solvent for 15 minutes at room temperature. The benzo[4,5]imidazo[1,2-a]pyridine was obtained in yield. It was also found that the azo compound were always obtained as the byproducts. The proposed mechanism for the reaction was presented base on all experimental evidence. It was assumed that the use of (diacetoxyiodo)benzene as the oxidant is by way of nitrenium ion as the intermediate, and the use of [bis(trifluoroacetoxy)iodo]benzene is through the cation radical intermediate.

第一章、 緒論 1
1-1 高價碘試劑的介紹 1
1-2 高價碘於有機合成中的應用 3
1-2-1 高價碘化合物於氧化反應中的應用 3
1-2-2 高價碘化合物於加成中的反應 5
1-2-3 高價碘化合物於取代中的反應 6
1-2-4 高價碘化合物於重排中的反應 7
1-2-5 高價碘鹽化合物的反應 8
1-2-6 手性高價碘化合物的對應選擇性反應 9
1-2-7 碘化合物作為有機催化試劑 10
1-2-8 可回收的高價碘化合物 12
1-3 苯并咪唑(benzimidazole) 16
第二章、主文 27
2-1 研究動機 27
2-3 結果與討論 29
2-3-1 最初反應條件 29
2-3-2 反應方法的改進 35
2-3-3 Neat的反應條件 37
2-3-4 最佳化反應條件篩選 37
2-3-5 反應物更換不同取代基 41
2-3-6 反應機制的探討 53
2-3-7結論 58
第三章、參考文獻 59
第四章、實驗部分 61
4-1儀器 61
4-2 試藥 62
4-3實驗流程 64
4-3-1苯并咪唑158a-159ab之合成步驟 64
4-3-2苯並咪唑162a-162j之合成步驟 67
4-3-3添加自由基清除劑反應 68
第五章、附錄 69
5-1光譜數據與物理性質 69
第六章、光譜附圖 87

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