摘要
本研究探討溶劑、溫度效應與基質ROH、RCl 中之R 之結構對反應ROH
+ Bu4NCl RCl + Bu4NOH(R = Bz, Allyl, Et, Pent, Bu, Pr, sec-Bu, iso-Pr)
影響。
溶劑效應方面: 選擇脂肪族非質子(aprotic aliphatic)溶劑(δ= 7.3 ~ 13)
及芳香族非質子(aprotic aromatic)溶劑(δ= 8.9 ~ 11.1)，以莫耳比BzOH :
Bu4NCl : solvent = 1 : 0.03 : 30，反應溫度30 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，lnkf、lnkb、
lnK 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kb,max / kb,min=1.5；kf.max / kf,min=3.35，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kb,max / kb,min=1.8；kf.max / kf,min=7.98，由
此可得知不同的溶劑對反應之影響不大，其原因乃是由於反應物Bu4NCl 為
離子對(極強偶極)而活化複合體皆為四極(quadrupole)，因此溶劑對反應物和
活化複合體之媒合程度相當，故溶劑效應對反應之相對速率影響不大。
溫度效應方面：以芐醇(2.56g)與四丁基銨氯(0.1976g)為反應物，溶劑
則使用氯仿，莫耳比BzOH : Bu4NCl : CHCl3 = 1 : 0.03 : 30，反應溫度
範圍30oC ~ 50 oC，求得不同反應溫度下之反應速率常數，進而藉由反應溫
度和反應速率的相互關係而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。而由實驗中所求得之(Eab－ 0 , ≠ ∆ b H ) / RT = 1.05
~ 0.98 和(Eaf － 0 , ≠ ∆ f H ) / RT = 1.04 ~ 0.98 之值約等於理論值1，故本研究所
求得之動力學參數頗為正確。
基質中之R 之結構方面: 以不同之R(R = Bz, Allyl, Et, Pent, Bu, Pr,
sec-Bu, iso-Pr)結構，莫耳比ROH : Bu4NCl : CHCl3(solvent) = 1 : 0.03 : 30，
反應溫度30 0C，探討基質結構對反應速率之影響。由實驗結果發現以下結
果：(1)基質結構效應之逆向反應速率常數比為Bz ：Allyl：Et ：Pr ：Bu：
Pent ：sec-Bu：iso-Pr = 1.95：1.89：1.64：1.43：1.24：1.18：1.11：1，正
向反應速率常數比為Bz ：Allyl：Et ：Pr ：Bu：Pent ：sec-Bu：iso-Pr = 11.25：
9.37：5.98：4.29：3.37：2.25：1.93：1。其逆向反應之相對反應性差異不
大，此表親核劑OH－具有平準效應(leveling effect)，而正向反應之相對反應
性約為11 倍。(2)本研究之R(R = Et, Pent, Pr, sec-Bu, iso-Pr)之結構效應可由
Taft eq. 表之，
故此方程式可預測其它類似不含共振效應之基質於同系列反應條件下之反
應速率常數。
經由本研究所得之結果，可知某液-液相轉移催化親核取代反應之最大
轉化率及反應速率。

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