研究生: |
江建緯 Chiang Chien Wei |
---|---|
論文名稱: |
含氮氧多牙基之銅錯合物的合成、結構、催化反應與槲黃素氧化酶活性中心模擬之研究 Synthesis, Structure and Catalitic Study of Copper Complexes with a N/O Polydentate Ligand Relevant to the Active Site of Quercetin 2,3-dioxygenase |
指導教授: |
李位仁
Lee, Way-Zen |
學位類別: |
碩士 Master |
系所名稱: |
化學系 Department of Chemistry |
論文出版年: | 2008 |
畢業學年度: | 96 |
語文別: | 中文 |
論文頁數: | 77 |
中文關鍵詞: | 含氮氧多牙基 、槲黃素氧化酶 |
英文關鍵詞: | N/O Polydentate Ligand, Quercetin 2,3-dioxygenase |
論文種類: | 學術論文 |
相關次數: | 點閱:166 下載:0 |
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為了合成槲黃素氧化酶金屬活性中心的擬態化合物,本研究合成一含雙吡啶胺多牙基配子2,6-bis(3-bis(2-pyridinylmethyl)- aminopropanamide)toluene (BBPAT),由此配子成功地合成出兩個二價銅錯合物[Cu2(BBPAT)](ClO4)4•2H2O (1)和[Cu2(BBPAT)(CH3OH)2]- (CF3SO3)4 (2),並利用元素分析、紅外光和紫外光/可見光光譜儀及X-光結構解析法完成錯合物的鑑定。
由紅外光光譜可發現錯合物1在液態及固態時的光譜略有差異,在固態光譜中,於1657 cm-1有ㄧ個醯胺的C=O吸收峰,而在液態光譜中此吸收峰卻移動到了1676 cm-1,且配子的C=O吸收峰在1672 cm-1的位置,與錯合物醯胺的C=O吸收峰相當接近。故推測當錯合物在溶液狀態時,與銅離子鍵結的C=O,有可能被溶劑分子所取代,如此,將使受質(3-hydroxyflavone)有更多空間可與銅離子配位,以便於進行催化反應。
最後,將受質3-hydroxyflavone溶於二甲基甲醯胺中,加熱溶液至120 ºC並加入氧氣,接著將錯合物2 (5 mol %) 加入反應溶液中進行氧化反應,反應24小時後。經由管柱層析法及GC/MS將混合物分離鑑定得到產物為3-(dimethylamino)-3-phenyl-3H-chromene- 2,4-dione,2-(dimethylamino)-2-phenylbenzofuran-3(2H)-one,benzoic acid,N,N’-dimethylbenzamide以及2-hydroxybenzil。
A polydentate ligand with two symmetric side arms, 2,6-bis(3-bis- (2-pyridinylmethyl)aminopropanamide)toluene (BBPAT), was prepared to construct mimics for the active site of the quercetin 2,3-dioxygenase (2,3-QD). Two copper(II) complexes, [Cu2(BBPAT)](ClO4)4 (1) and [Cu2(BBPAT)(CH3OH)2](CF3SO3)4 (2), were synthesized and characterized by elemental analysis, IR and UV/Vis spectroscopies, and X-ray crystallography.
One absorption band at 1657 cm-1, corresponding to the carbonyl groups of amide of BBPAT, was observed in the solid IR spectrum (KBr) of complex 1. Interestingly, the absorption band was shifted to 1676 cm-1, close to that of free ligand at 1672 cm-1, as the IR spectrum of 1 was performed in CH3CN. We suspected that the carbonyl groups of BBPAT was dissociated from the copper centers, and the resulting open site of each copper was occupied by a solvent molecule. Once the substrate, 3-hydroxyflavone, was added to the solution of complexes 1 and 2, the coordinated solvent molecules were substituted by the substrate.
After the dry DMF solution of 3-hydroxyflavone was heated to 120 °C and bubbled with dioxygen, complex 2 (5 mol %) was added to the DMF solution. The reaction mixture were kept at 120 ºC and stirred for 24 hours, and the resulting solution was separated by column chromatography. Five products, 3-(dimethylamino)-3-phenyl-3H- chromene-2,4-dione, 2-(dimethylamino)-2-phenylbenzofuran-3(2H)-one, benzoic acid, N,N’-dimethylbenzamide and 2-hydroxybenzil were isolated and analyzed by GC/MS spectroscopy.
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