臺灣博碩士論文加值系統

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.

中文摘要………………………………………………………………Ι
英文摘要………………………………………………………………II
圖索引…………………………………………………………………III
表索引 VI
附錄索引………………………………………………………………VII



第一章 緒論
第一節 研究動機與目的…………………………………………1
第二節 槲黃素氧化酶的相關文獻探討…………………………3
第三節 二價銅錯合物的性質…...………………………………18

第二章 實驗部分
第一節 實驗儀器、藥品及條件……………..…………...………..23
第二節 配位基的合成與鑑定……………..……………………….30
第三節 金屬錯合物的合成……………………...…………………33
第四節 含氮氧八牙基二價銅錯合物與受質之反應…...…………37
第五節 含氮氧八牙基金屬錯合物對受質之氧化反應…………...37

第三章 槲黃素氧化酶模擬化合物的研究與討論
第一節 配子的合成探討……………………………………...……41
第二節 錯合物的結果與探討……………………………..……….45
第三節 紫外光/可見光光譜…………………………………….....50
第四節 紅外光光譜………………………………………………...52
第五節 電子順磁共振光譜………………………………………...56
第六節 含氮氧八牙基金屬錯合物與受質反應之討論……...……59
第七節 含氮氧八牙基金屬錯合物對受質催化反應之討論……...60

第四章 結論與展望………...…………………………………….….....75

參考文獻…………………………………………………………….…...78

附錄

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