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The synthesis of the fully conjugated of extended bimetal-porphyrin and application
No full text本篇論文主要是利用微波技術合成出雙酮紫質化合物A5，比傳統上的方法來的更快速得到產物。但化合物A5在共溶劑下 (H2O, Et2O, CH2Cl2, MeOH)加入5,6-diamino-1,l0-phenanthroline卻會使得原本鄰位的雙酮官能基轉換成對位的雙酮化合物A9。A9在二甲基甲醯胺為溶劑下和氯化鈷進行螯合作用，雙酮紫質錯合物C1。此鈷金屬紫質錯合物應用在雙鍵的氧化上有不錯的效果，如反-二苯乙烯的氧化反應，可得到100%產率的跨苯乙烯氧化物。對於芳香醛類和硫醚的氧化反應則是以NHPI當自由基起始劑，利用氧氣當氧化劑來氧化反應物。不但符合綠色化學的觀念，而且反應的條件相當溫和，對於有機合成或是生化的應用上有很大幫助。To synthesize a conjugation system of porphyrins and to study their properties with metal ions are the major work of this thesis. With the assists of microwave technology, the target molecule was easily achieved. In the presence of the diketone porphyrin with 5,6-diamino-1,l0-phenanthroline in a co-solvent system (CH2Cl2:Et2O: MeOH:H2O) proceeded smoothly to yield the p-diketoone prophyrin (A9). Complexation of A9 with various metal ions were investigated. In a typical example, reaction of CoCl2 with A9 in the DMF, produced a metal-prophyrin species C1. This cobalt prophyrin complex can be used as a catalyst in oxidation olefin, benzaldehydes and sulfides under mild conditions.目錄 I
附圖目錄 III
附表目錄 IV
論文摘要 (中文) V
論文摘要 (英文) VI
第一章 緒論 1
第1-1節 紫質的簡介 1
第1-2節 紫質應用在醇類和醛類的氧化反應 1
第1-3節 飽和碳氫鍵或雙鍵的氧化反應 5
第1-4節 硫醚的氧化反應 6
第1-5節 雙金屬紫質探討 7
第1-6節 實驗動機 8
第二章 雙酮共軛紫質錯合物的合成與鑑定 10
第2-1節 雙酮紫質的合成 10
第2-2節 雙胺配位基的合成 12
第2-3節 延伸共軛紫的雛型研究 13
第2-4節 雙酮共軛紫質錯合物的合成與鑑定 17
第三章 氧化反應的結果與討論 25
第3-1節 醛類的氧化反應 25
第3-2節 烯類的環氧化反應 30
第3-3節 硫醚的氧化反應 34
第3-4節 不同紫質催化劑對於氧化反應上的研究 39
第四章 結論 42
第五章 實驗部分 43
第5-1節 一般實驗方法 43
第5-2節 反應試劑與溶劑的前處理 44
第5-3節 合成雙酮紫質 44
第5-4節 雙胺配位基的合成 48
第5-5節 共軛紫質化合物的合成 49
第5-6節 合成硫醚反應物 56
第5-7節 氧化反應 57
參考文獻 63
附錄 67
附圖目錄
圖1化合物A5和S1化合物氫核共振光譜圖比較 14
圖2 化合物S2在CDCl3下測得的氫核共振光譜圖 15
圖3化合物S2在d-acetone下測得的氫核共振光譜圖 16
圖4化合物A9氫核共振光譜圖 17
圖5化合物A9的QC光譜圖 18
圖6 化合物A10氫核共振光譜圖 21
圖7錯合物C1之單晶繞射圖 22
圖8化合物C2的氫核共振光譜圖 23
圖9化合物C2的QC光譜圖 24
附表目錄
Table 1-1 TON of Mn(TPP)OAc in the oxidation 3
of different alcohols using Bu4NHSO5
Table 1-2 Encapsulated MPs catalyzed oxidation of 4
1-phenylethanol by O2 in DCE
Table 2-1 化合物A5和不同雙胺化合物或鹼反應 19
Table 3-1 雙酮紫質化合物C1對4-甲基苯甲醛的氧化反應 27
Table 3-2 化合物C1氧化不同取代基的芳香環醛類 29
Table 3-3 輔助基影響催化反應的探討 30
Table 3-4 烯類的氧化反應 33
Table 3-5 化合物C1和不同氧化劑對於thioanisole的氧化反應 36
Table 3-6 NHPI系統中不同取代基的硫醚和光強弱的探討 38
Table 3-7 不同紫質化合物對trans-stilbene環氧化的反應 39
Table 3-8 不同紫質化合物對4-methoxybenzaldehyde的氧化反應探討 40
Table 3-9 不同紫質錯合物對於硫醚的氧化反應 4
Going Beyond Counting First Authors in Author Co-citation Analysis
Get PDFThe present study examines one of the fundamental aspects of author co-citation analysis (ACA) - the way co-citation
counts are defined. Co-citation counting provides the data on which all subsequent statistical analyses and mappings
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koamabayili/VECTRON-author-checklist: VECTRON author checklist
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Author-wise bibliometric analysis based on entropy.
No full textAuthor-wise bibliometric analysis based on entropy.</p
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