Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/96270
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dc.contributor洪豐裕zh_TW
dc.contributor.authorChing-Yu Wangen_US
dc.contributor.author王靖諭zh_TW
dc.contributor.other化學系所zh_TW
dc.date2017zh_TW
dc.date.accessioned2018-12-17T03:58:04Z-
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dc.identifier.urihttp://hdl.handle.net/11455/96270-
dc.description.abstractThe synthesis of N-(2'-(diphenylphosphoryl)-[1,1'-biphenyl]-2-yl)-2,2,2-trifluoroacetamide (3a) has been achieved from the palladium catalytic and Ag(I)-assisted C-H functionalization of 2-trifluoroacetamidebipheny (1a) via phosphination. The source of diphenylphosphine oxide has to be added rather slowly by Syringe Pump (KDS100) to achieve the goal. The crystal structure of 3a was determined by X-ray crystal diffraction methods. Indeed, the phosphination took place at the ortho-position of interannular ring. A reaction mechanism is proposed based on the experimental results. While the substituent -CF3 in 1a is replaced by -C6H5, similar results were obtained and produced 3c. Nevertheless, a carbazole derivative 4b was obtained while the substituent is changed to an electron-withdrawing group, -CH3. It was found that the type of reaction product could be greatly affected by the substituent on the acetamidebiphenyl as well as by acidic or base reaction condition.en_US
dc.description.abstract本研究使用聯苯三氟乙酰胺1a做為起始物,與對甲苯基膦氧化物反應,後者利用自動注射幫浦緩慢加入。在金屬鈀化合物的催化下進行反應,最後形成碳-磷鍵產物3a,並且鑑定了3a的晶體結構。推測反應是透過金屬鈀化合物先將聯苯三氟乙酰胺活化,使對甲苯基膦氧化物脫去氫後接到金屬鈀化合物,再進行碳-磷鍵耦合反應,最終產生碳-磷鍵產物。根據優選條件推出可行的反應機制。 這研究也嘗試使用不同的推拉電子能力的取代基,在相同的條件下進行反應,發現當反應物是聯苯乙酰胺上的取代基是具有推電子能力的甲基時,其產物為carbazole型態的衍生物4b;當取代基是具有拉電子能力的五氟苯時,主產物是具有碳-磷鍵產物3c,和形成3a的情形類似。 這些反應結果發現聯苯乙酰胺上的取代基的不同推拉電子基效應會影響反應機制。另外,不同酸鹼性條件也會影響反應結果。zh_TW
dc.description.tableofcontents目錄 摘要 i Abstract ii 目錄 iii Scheme 目錄 v Figure 目錄 vii Table 目錄 viii 第一章 序論 1 第一節 交叉耦合反應(Cross-coupling Reaction) 2 第二節 二級氧化磷基(Secondary Phosphine Oxide;SPO)簡介 5 第三節 碳-氫鍵活化(C-H activation)簡介 12 第四節 研究方向 19 第二章 實驗 22 第一節 儀器與設備 23 第二節 藥品 26 第三節 合成與鑑定 29 第三章 結果與討論 37 第一節2-Trifluoroacetamidebipheny與Diphenylphosphine Oxide的反應 38 第二節 2-Acetamidebipheny與Diphenylphosphine Oxide的反應 48 第三節 2-Pentafluorobenzamidebiphenyl與Diphenylphosphine Oxide的反應 52 第四章 結論 59 第五章 參考文獻 60 第六章 附錄 62zh_TW
dc.language.isozh_TWzh_TW
dc.rights同意授權瀏覽/列印電子全文服務,2017-08-29起公開。zh_TW
dc.subject碳氫鍵活化zh_TW
dc.subject碳氫鍵官能化zh_TW
dc.subject指向基團zh_TW
dc.subject醯胺zh_TW
dc.subject二級氧化磷基zh_TW
dc.subjectzh_TW
dc.subject咔唑zh_TW
dc.subjectC-H activationen_US
dc.subjectC-Hfunctionalizationen_US
dc.subjectDirecting groupen_US
dc.subjectAcetamideen_US
dc.subjectSecondary phosphine oxideen_US
dc.subjectPalladiumen_US
dc.subjectCarbazole.en_US
dc.titleAmido-substituent in Biphenyl as Directing Group in Palladium-Catalyzed Phosphination Reaction through C-H Bond Functionalizationen_US
dc.title以醯胺作為指向基團利用鈀金屬催化進行聯苯碳-氫鍵活化的磷酸化反應zh_TW
dc.typethesis and dissertationen_US
dc.date.paperformatopenaccess2017-08-29zh_TW
dc.date.openaccess2017-08-29-
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