臺灣博碩士論文加值系統

木質素（lignin）為植物細胞壁之成分，為含苯環之複雜聚合物。因為將木質素進行降解（degradation）可獲得化學原物料及石化燃料，因此木質素成為近年來最具有發展潛力之生質能材料。本研究藉由合成氧釩(oxovanadium)錯合物，探索其對於木質素模型化合物(lignin model compounds)降解之反應性。
　V001 [O=V(OCH3)C15H14N2O3]為六配位釩金屬錯合物其一配位為甲醇溶劑，其他配位為三牙基[O, N, O]、甲氧基（methoxide）及氧基的釩金屬錯合物，μV001[(O=V)2C28H20N4O5]為V001藉由氧原子形成橋接雙核結構之釩金屬錯合物。釩金屬錯合物皆由X-ray單晶繞射鑑定其化學結構。β-O-4木質素化合物有四個可反應的位置，分別為碳-氧鍵、碳-碳鍵、一級醇及二級醇等。在此研究中我將合成了一系列β-O-4木質素模型化合物來探討釩金屬錯合物與單體組成及不同反應位置之化學反應性及選擇性。實驗結果證實氧釩金屬錯合物可將β-O-4木質素模型化合物中二級醇以催化量選擇性氧化為酮結構。在含有吡啶條件下具有較高之氧化木質素模型化合物轉換率，不同反應位置和不同單體組成之木質素模型化合物會影響釩金屬催化劑之化學反應性。於反應機制探討中發現釩金屬錯合物以雙核結構進行反應，在含有吡啶的條件下將木質素模型化合物氧化須在有氧氣的條件下完成催化反應。氧化之木質素模型化合物經碳酸鹽類反應再透過甲酸鹽類反應可得斷碳-氧鍵之木質素單體化合物，如苯酚。

偶合反應(coupling reaction)在醫療及材料研究領域上有重大的貢獻。偶合反應中鹵化物(organohalide)扮演重要之角色，鹵化物選擇不同將影響反應之產率。
　V002 [(V=O)2C13H10N3O]為六配位釩金屬錯合物以三牙基[N, N, O] 及二氧釩(oxovanadium)配位之釩金屬錯合物，V002於過氧化氫水溶液條件下反應生成V002 peroxo [V=O(O-O)C13H10N3O]，V002 peroxo為六配位釩金屬錯合物其一配位為甲醇溶劑，其他配位為三牙基[N, N, O] 、過氧基(peroxo functional group)及氧基之釩金屬錯合物，釩金屬錯合物皆由X-ray單晶繞射鑑定其化學結構。V002 peroxo釩金屬中心結構類似於生物酵素釩溴過氧化物酶(Vanadium bromoperoxidase, V-BPO)此酵素可在溫和條件下進行有機物之溴化反應，因此我們將探討此氧釩錯合物與有機物進行溴化之化學反應性及選擇性並與溴化試劑比較其反應性之差異。選擇苯酚、苯乙烯及環己烯為本研究的有機物，經實驗結果發現以現有之溴化試劑反應皆有其特定之化學選擇性，加入釩金屬錯合物後能提升苯酚之溴化反應性，苯乙烯及環己烯則無顯著提升化學反應性。

Lignin is a major component of plant cell wall consisted of poly-phenol with diverse linkage modes. In order to obtain chemical feedstock from renewable biomass, development of highly efficient route to depolymerize lignin is essential. In this research, we have synthesized and characterized the oxovanadium complex by single-crystal X-ray diffraction to help to study the reactivity of degradation of the lignin model compound.
　　V001 [O=V(OCH3)C15H14N2O3] is described as six-coordinate vanadium complex chelated with [O,N,O] tridentate ligand methoxide, terminal oxo, and one coordinated methanol solvent. V001 forms a dimer structure, μV001 [(O=V)2C28H20N4O5]via oxo brigade. β-O-4 linkage of lignin compound has four reaction sites, the C-O bond, C-C bond, primary alcohol and second alcohol respectively. In a series of β-O-4 lignin model compounds, the reactivity and selectivity of vanadium complex on different reaction sites of lignin substrates have been investigated. We have found that V001 proceeds selective oxidation of secondary alcohol of β-O-4 lignin compound to ketone without cleaving the C-O bond or C-C bond. The plausible catalytic mechanism has been proposed and suggested with emphasis on the essential roles of pyridine and dioxygen. The oxidative cleavage of C-O bond of lignin dimeric substrates gave phenol which was resulted from the cleavage of the C-O bond of dimeric lignin substrates via addition of formate and formic acid.


Coupling reaction has made significant contributions in medical and material fields of research. The types of organohalide play a important role in coupling reaction regarding the selectivity and efficiency of chemical reactions.
　　V002 [(V=O)2C13H10N3O] is described as six-coordinate vanadium complex chelated with [N,N,O] tridentate ligand and two of coordination are provided by the oxo moiety of oxovanadium fragment. V002 reacted with hydrogen peroxide to yield the V002 peroxo [V=O(O-O)C13H10N3O] and its geometry is best described as six-coordinate vanadium complex chelated with [N,N,O] tridentate ligand and coordinated methanol solvent. The coordination environment of V002 peroxo is similar to vanadium bromoperoxidase which selectively brominates the organic compound under mild condition. We want to investigate the reactivity and selectivity of vanadium complex to the bromination of different organic compounds. We also want to compare the different commercial reagent of bromination to our V002 peroxo. We choose phenol, styrene and cyclohexene as organic substrates. We found that our metal complex can boost the brominated reactivity of phenol, yet not for styrene and cyclohexene.

(一)中文摘要 iii
1. Abstract iv
(二)中文摘要 v
2. Abstract vi
目錄 vii
(一)圖目錄 xi
(一)表目錄 xiv
(二)圖目錄 xv
(二)表目錄 xvii
合成與設計釩金屬催化劑應用於木質素降解反應以獲得化學原物料
第一章 緒論 2
1-1 石油之浩劫危機 2
1-2 生物質之發展與潛力 7
1-3 木質素之結構探討 8
1-4 文獻探討 14
1-5 研究方向及實驗設計 21
第二章 實驗部分 23
2-1 一般實驗 23
2-2 儀器 23
2-3藥品 24
2-4化合物合成與鑑定 26
2-5木質素降解反應 41
第三章 結果與討論 42
3-1配位基L001之合成及鑑定 42
3-2釩金屬錯合物V001[O=V(OCH3)C15H14N2O3]及μV001[(O=V)2C28H20N4O5]之合成及鑑定 44
　3-2-1 V001與μV001結構之比較 54
3-3 木質素模型化合物之設計 55
3-4 木質素模型化合物之降解反應 57
　3-4-1溶劑效應 59
　3-4-2吡啶效應 60
　3-4-3不同木質素模型化合物之反應性 62
　3-4-4反應機制探討 65
　　3-4-4-1木質素模型化合物反應機制探討(一) 66
　　3-4-4-2木質素模型化合物反應機制探討(二) 68
　　3-4-4-3木質素模型化合物反應機制探討(三) 71
　　3-4-4-4木質素模型化合物反應機制探討(四) 73
　　3-4-4-5木質素模型化合物反應機制探討(五) 74
　　3-4-4-6木質素模型化合物反應機制探討(六) 75
3-5 釩金屬催化劑之比較 78
3-6 木質素模型化合物KAH降解 80
第四章 結論 85
第五章 參考文獻 87
第六章 附錄 89
合成與設計釩金屬催化劑應用於生物擬態溴過氧化酶進行有機物溴化反應
第一章 緒論 198
1-1 偶合反應之發展 198
1-2 溴化物之製備 202
1-3 釩溴過氧化物酶(Vanadium bromoperoxidase, V-BPO) 204
1-4 研究方向及實驗設計 206
第二章 實驗部分 207
2-1 一般實驗 207
2-2 儀器 207
2-3藥品 208
2-4化合物合成與鑑定 209
2-5 有機物溴化反應 212
　2-5-1有機物與溴水(Br2)之溴化反應 212
　2-5-2有機物與N-溴代丁二醯亞胺(NBS)之溴化反應 212
　2-5-3有機物與釩金屬錯合物之溴化反應 213
第三章 結果與討論 214
3-1 配位基L002之合成與鑑定 214
3-2 釩金屬錯合物V002 [(V=O)2C13H10N3O]及V002 peroxo [V=O(O-O)C13H10N3O]之合成與鑑定 216
　3-2-1 V002與V002 peroxo之比較 226
3-3 有機物之選擇與溴化反應 227
　3-3-1苯酚(phenol) 227
　3-3-2苯乙烯(styrene) 232
　3-3-3環己烯(cyclohexene) 234
　3-3-4釩金屬錯合物溴化反應機制 236
第四章 結論 237
第五章 參考文獻 238
第六章 附錄 240

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