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研究生:朱宏彬
研究生(外文):Hon-Bein Chu
論文名稱:溶劑與陰離子(Y)之結構對一典型相轉移催化親核取代反應BzCl+Bu4NY→BzY+Bu4NCl之反應性之效應
論文名稱(外文):The solvent effects and the structural effects of anions(Y) on the reactivity of the nucleophilic substitution reaction BzCl + Bu4NY→BzBr + Bu4NCl.
指導教授:王天財
指導教授(外文):Ten-Tsai wang
學位類別:碩士
校院名稱:國立中央大學
系所名稱:化學工程與材料工程研究所
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2002
畢業學年度:90
語文別:中文
論文頁數:97
中文關鍵詞:四丁基銨鹽親核取代平衡親核取代動力學相轉移催化劑
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本研究探討溶劑效應(包含水分的影響)與陰離子結構效應對一典型液-液相轉移催化反應BzCl + Bu4NY→BzY + Bu4NCl(Y = OH, Br, I, AcO, HSO4, ClO4)之影響。
  溶劑效應方面 : 選擇脂肪族非質子(aprotic aliphatic)混合溶劑: propionitrile + heptane; 及芳香族非質子(aprotic aromatic)混合溶劑: benzene + nitrobenzene,以莫耳比BzCl : Bu4NBr : solvent = 1 : 0.03 : 30,反應溫度40 0C,以體積平均溶解度參數 (volume average solubility parameter)來探討溶劑效應。由實驗之結果發現,lnkf、lnkb與 呈一正比之線性關係,且溶劑效應對反應之相對速率影響不大,其大小差異僅10倍﹔而由不同的水量對芳香族非質子溶劑 : 苯、脂肪族非質子溶劑 : 丙烯月青,以莫耳比BzCl : Bu4NBr : solvent = 1 : 0.03 : 30,反應溫度40 0C,所得結果發現水分對芳香族非質子溶劑、脂肪族非質子溶劑之影響相差不大。
  陰離子結構方面 : 以不同陰離子(Y = OH, Br, I, AcO, HSO4, ClO4)結構之四丁基銨鹽,當Y≠OH時莫耳比BzCl : Bu4NY : CHCl3(solvent) = 1 : 0.03 : 30,當Y = OH時莫耳比BzY : Bu4NCl : CHCl3(solvent) = 1 : 0.03 : 30,反應溫度40C,探討陰離子結構對反應速率之影響。由實驗結果發現,由於離子半徑大小之差異及溶劑對陰離子之媒合作用影響,使得反應速率大小相差可達1000倍,對於平衡常數的影響甚至可達1000000倍,即對陰離子交換反應而言,陰離子結構效應之影響遠大於溶劑效應。


The reactivities (kf,kb) depend on the structures of the nucleophiles (Bu4NY), the solvent used. For the structural effects of Bu4NY, Y = Cl, Br, I, AcO, OH, ClO4, HSO4 were studied. And for the solvent effect, the relations between the reactivity and solvent properties (solubility parameter) has found for the various types of solvents (aprotic aliphatics, aprotic aromatics). And the effect of water on kf and kb were studies as well.


目 錄
摘要 …………………………………………………………………I
目錄 …………………………………………………………………II
圖表目錄 ……………………………………………………………III
符號說明 ……………………………………………………………IV
第一章 緒論
1-1-1相轉移催化之起源與定義…………………………………….1
1-1-2相轉移催化之機制…………..…………………………….1
1-2相轉移催化劑之種類………………………………..……………2
1-3一般之二分子親核取代反應…………………………..…………4
1-3-1親核取代反應之反應機構與類型………………………….4
1-3-2 一般SN2反應之影響因素…………………………………..6
1-4 Bu4N+X-之合成……………………………………….……………8
1-5 本文之動機與主旨………………………..………………………10
第二章 理論
2-1親核取代之反應機構及積分速率方程式………………………..14
2-1-1典型液-液相轉移系統油相反應機構………………………..14
2-1-2 SN2反應之積分速率方程式………………………………….14
2-2過渡狀態理論……………………………………………………...16
2-3溶劑效應…………………………………………………………...19
2-3-1溶質-溶劑間之作用能(interaction energy)與溶劑性質之關係………………………………..…………………20
2-3-2 ion-dipole interaction force…………………………….21
2-3-3dipole-dipole force……………………………………..22
2-3-4 kid與溶解度參數之關係……………………………...………23
2-3-5 k / kid與溶解度參數之關係…………………………………..23
2-4陰離子結構效應……………………………………………….…..25
第三章 實驗部分
3-1藥品………………………………………………………………...27
3-2實驗裝置與分析儀器……………………………………………...28
3-2-1實驗裝置………………………………………………………29
3-2-2 離子層析儀………………………………………..…………30
3-3實驗操作…………………………………………………………...30
3-4 樣品分析 …………………………………………………………30
3-5實驗步驟…………………………………………………………...32
3-5-1 Bu4NBr之製備與精製……………………………………….32
3-5-2溶劑效應之影響………………………………………………33
3-5-3水分之影響……………………………………………………34
3-5-4陰離子結構效應………………………………………………34
第四章 結果與討論
4-1 化學計量之關係…………………………………………………..40
4-2溶劑(芳香族非質子溶劑、脂肪族非質溶劑)效應………………40
4-2-1四丁基銨氯濃度與反應時間之關係…….…40
4-2-2體積平均溶解度參數 對平衡常數K、正向速率常數kf、逆向速率常數kb之影響……………………………………47
4-3水分之影響………………………………………………………...52
4-3-1四丁基銨氯濃度與反應時間之關係…………………………52
4-3-2水分對平衡常數K, 正向速率常數kf, 逆向速率常數kb之影響……………………………………….…………………52
4-4陰離子結構效應…………………………………………………...61
4-4-1四丁基銨氯濃度與反應時間之關係…………………………61
4-4-2陰離子結構對平衡常數K, 正向速率常數kf, 逆向速率常數kb之影響…………………………………………………61
第五章 結論 ………………………………………………………...66


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