本研究主旨在於探討溶劑、溫度效應與親核劑(QBr)陽離子結構效應對相
轉移催化反應BzCl + QBr<--> BzBr + QCl(Q = Et4N, Pr4N, Bu4N, Pent4N,
BzEt3N, BzPr3N, BzBu3N)之影響。
溶劑效應方面: 選擇芳香族非質子(aprotic aromatic)溶劑(δ= 9.2 ~
11.1)及脂肪族非質子(aprotic aliphatic)溶劑(δ= 7.3 ~ 13)，以莫耳比BzCl :
BzBu3NBr : solvent = 1 : 0.03 : 30，反應溫度40 0C，以溶解度參數δ
(solubility parameter)作為主要探討溶劑效應之依據。
由實驗之結果發現：ln kf、ln kb 與δ呈線性關係；由實驗結果得知當反應溶
劑為芳香族非質子溶劑時其反應速率常數比為kf,max / kf,min=13.6、kb.max /
kb,min=19.3，而當反應溶劑為脂肪族非質子溶劑時其反應速率常數比為kf,max
/ kf,min=21.2、kb.max / kb,min=163.1，由此可得知不同的溶劑對反應之影響不如
季化反應，這是由於反應物BzBu3NBr 為離子對(極強偶極)，而其活化複合
體為四極(quadrupole)，所以溶劑效應對反應之相對速率影響不如季化反應
明顯。
溫度效應方面：以芐基氯(3g)與芐基三丁基銨溴(0.253g)為反應物，溶
劑則使用三氯甲烷(84.87g)(莫耳比BzCl : BzBu3NBr : CHCl3 = 1 : 0.03 :
30)，反應溫度範圍30oC ~ 50 oC；以求取不同反應溫度下之反應速率常數，
則可求得此反應之反應動力學參數，如活化吉布氏自由能、活化焓、活化
熵和活化能( 0 , ≠
f G ∆ 、0 , ≠
b G ∆ 、0 G ∆ 、0 , ≠
f H ∆ 、0 , ≠
b H ∆ 、0 H ∆ 、0 , ≠
f S ∆ 、0 , ≠
b S ∆ 、0 S ∆ 、
af E 、ab E )。
kf
kb
由實驗結果發現： 而由實驗中所求得之Ea 和0 , ≠ ∆H 之值與理論
RT H Ea + = ≠ 0 , ∆ 相符合，故本研究所求得之動力學參數( 0 , ≠
f G ∆ 、0 , ≠
b G ∆ 、
0 G ∆ 、0 , ≠
f H ∆ 、0 , ≠
b H ∆ 、0 H ∆ 、0 , ≠
f S ∆ 、0 , ≠
b S ∆ 、0 S ∆ 、af E 、ab E )頗為正確。
陽離子結構效應方面: 以不同之QBr (Q = Et4N, Pr4N, Bu4N, Pent4N,
BzEt3N, BzPr3N, BzBu3N)為反應物，莫耳比BzCl : QBr : CHCl3(solvent) = 1 :
0.03 : 30，反應溫度40 0C，探討親核劑陽離子(Q)結構對反應速率之影響。
由實驗結果發現：發現隨著QBr 陽離子碳數的增加，及QBr(aq)之pH 值減
小，kf 與kb 隨著變大，且kb 皆大於kf，對稱型Q：Pent4N＞Bu4N＞Pr4N＞
Et4N 及非對稱型Q：BzBu3N＞BzPr3N＞BzEt3N；並分別從kf 及kb 大小可
判斷，接於Br-之Q+與接於Cl-之Q+之反應性亦隨Q+之碳數增加，而反應
性增加。

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