臺灣博碩士論文加值系統

本研究最初使用具有不同取代基的苯醌二聚體如2及3為起始物與三級胺反應，期望能在二個苯醌分子間形成一個苯環，如同本實驗室之前研究所得之成果。雖然結果不如預期，但我們將這部份實驗所得到的結果重新整理並思考後，認為在二個苯醌分子間形成新的苯環應與起始物上的取代基有關。
接著我們以化合物5與三環己基磷(PCy3)作為反應物並加入Pd(OAc)2作為催化劑進行反應，得到兩個原先預期之外的產物6a與6b，同時我們也提出反應機構如Scheme 3-2-3所示。最後，我們將6a透過鈀金屬的催化與三級胺(NBu3)進行C-H鍵活化反應可得化合物8。我們有得到6a及疑似6b部份水解產物7的晶體結構，但是由於尚未得到6b之晶體數據，因此無法得知其分子的確切結構，只能從1H NMR、13C NMR及31P NMR光譜與由質譜所得之分子量數據進行結構的推測。而經由X-Ray的鑑定可得知化合物8的晶體結構，確實有形成吡咯環。
本研究提出了一項新穎的合成二苯併呋喃之方法，此法不需高溫加熱且產率相當良好，當二苯併呋喃接上PCy3後不僅可保留其中一個苯醌上的二個羰基以利合成吡咯環，也可嘗試作為磷的偶極體(ylide)應用於威悌反應(Wittig reaction)發展其他研究領域。此外我們也證實若要將苯醌上的醯胺取代基與三級胺進行環化反應形成吡咯環，位於苯醌上一號位與四號位之羰基是為不可或缺之條件。

Initially, benzoquinone dimers, 2 and 3, with methyl- and chloride- substituents, respectively, were used as the starting materials to react with tertiary amines. It was expected that a new benzene ring can be formed and bridging these two benzoquinone fragments, just like the results of our previous works. However, it turned out to be a failure. After carefully examing the experimental results, it is believed that the formation of new benzene ring has something to do with the property of substituent on it.
Later, compound 5, with amido-groups on each side of benzoquinone dimer, had been employed to react with tricyclohexylphosphine (PCy3) in the presence of Pd(OAc)2 as a catalyst. Two unexpected products, 6a and 6b, were obtained. Subsequently, it was followed by a palladium-catalyzed C-H bond activation reaction of 6a with tertiary amine (NBu3). As expected, a new pyrrole ring was formed in the product 8. The crystal structures of 6a, 7 and 8 were available. Since we were not able to get the crystal data of 6b, its conformation can only be supported by 1H NMR, 13C NMR, and 31P NMR spectra as well as mass spectrum.
This study provides a novel method for synthesizing dibenzofuran type compounds such as 6a. It does not require high reaction temperature and the final yield is acceptable. A new ylide bond (C=P) is formed between PCy3 and benzoquinone and could be reduced in Wittig reaction to form C=C bond. This field requires further efforts to explore.
We also believed that the retention of two carbonyl groups on one of the benzoquinone in 6a could facilitate the formation of pyrrole ring such as in the process of the conversion 6a to 8.

摘要 i
Abstract ii
目錄 iv
Scheme 目錄 vi
Figure 目錄 ix
Table 目錄 x
本研究化合物編號對照表 xi
第一章　序論 1
第一節 Dibenzofuran與dibenzofuran-1,4-dione簡介 2
第二節 C-H鍵的活化與官能基化簡介 7
第三節 苯醌上的C-H鍵活化反應 11
第四節 研究方向 15
第二章　實驗 17
第一節 儀器與設備 18
第二節 實驗與養晶溶劑處理 20
第三節 實驗藥品 21
第四節 合成與鑑定 24
第三章　結果與討論 35
第一節 Alkyl-substituted與halo-substituted diquinone與三級胺的催化反應 36
第二節 Amido-substituted diquinone與三環己基磷的催化反應 40
第三節 具有PCY3之amido-substituted diquinone與三級胺類的催化反應 52
第四章　結論 56
第五章　參考文獻 58
第六章　附錄 62
第一節 光譜數據 63
第二節 晶體數據 84

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