臺灣博碩士論文加值系統

本研究使用聯苯醯胺結構1為起始物，將其上的醯胺作為指向基團，在鈀金屬化合物的催化下，進行碳-磷鍵或碳-氮鍵的生成反應。嘗試改變醯胺上取代基的電子效應，包含推電子基如苯基與甲氧基或拉電子基如三氟甲基與五氟苯基，觀察對產物的影響。實驗中二級氧化磷基被緩慢滴加入反應中，此步驟對碳-磷鍵生成至關重大。總結此反應以金屬鈀化合物作為催化劑，進行磷酸化或胺化反應，可獲得碳-磷鍵產物3與咔唑產物4。
本研究發現指向基團醯胺上取代基的電子效應，對產物種類分布影響相當重要。當取代基為推電子基時，主要會形成咔唑產物4；而當取代基為拉電子基時，將使反應形成較多的碳-磷鍵產物3；當取代基為弱拉電子基如五氟苯時，將同時產生碳-磷鍵產物3與咔唑產物4。X-ray單晶繞射法證實4_eaa咔唑產物的晶體結構。利用同法，得到碳-磷鍵產物3_ecaa、3_ecfa、3_effa與4_eca、4_ecf咔唑產物的晶體結構。
本研究證實在磷苯醯胺化合物的醯胺上取代基，其電子效應會影響反應結果，形成兩種不同產物。本研究也根據實驗結果提出了生成產物3及4可能的反應機制。

A palladium-catalyzed phosphination or amination reaction had been controlled by the amido-substituent in a biphenyl compound 1 as directing group. The distribution of products 3 and 4 was greatly depending on the electron-withdrawing or -donating capacity of the substituent on the amido-fragment of 1.
The carbazole derivatives 4 were obtained when the substituent is electron-withdrawing group. While the substituent is electron-donating group, it trends to form secondary phosphine oxides substituted products 3. Both 3_eaaa and 4_eaa were obtained while the substituent in 1 was -C6H5. The structure of 4_eaa was determined by single crystal X-ray diffraction methods.
Several derivatives of 1 with different substitutions on biphenyl were also screened. Similar results followed the trend were obtained and produced 3_ecaa, 3_ecfa, 3_effa, 4_eca and 4_ecf. The structures of all were determined by single crystal X-ray diffraction methods.
It was found that the type of reaction products could be greatly affected by the substituents on the amidobiphenyl compounds. A mechanism to account for the formations of products was proposed based on the experimental results.

摘要 i
Abstract ii
目錄 iii
Scheme目錄 v
Figure目錄 vii
Table目錄 viii
本研究化合物分子結構與命名表 ix
第一章　序論 1
第一節　二級氧化磷基(Secondary Phosphine Oxide; SPO)簡介 2
第二節　碳-氫鍵活化反應(C-H activation reaction)簡介 8
第三節　咔唑衍生物(Carbazole derivatives)簡介 12
第四節　研究方向 16
第二章　結果與討論 18
第一節　2-Methylcarbamatebiphenyl與二級氧化磷基的反應 19
第二節　2-Benzamidebiphenyl與二級氧化磷基的反應 23
第三節　2-Trifluoroacetamidebiphenyl與二級氧化磷基的反應 26
第四節　2-Pentafluorobenzamidebiphenyl與二級氧化磷基的反應 29
第五節　不同取代基的2-Pentafluorobenzamidebiphenyl與二級氧化磷基的反應 39
第三章　結論 53
第四章　實驗 54
第一節　設備與儀器 55
第二節　藥品 58
第三節　合成與鑑定 60
第五章　參考文獻 84
第六章　附錄 90
第一節　光譜數據 91
第二節　晶體數據 138

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