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中文摘要
本論文以不具毒性，熱穩定性高且易與金屬離子形成錯合物之聚乙二醇為相間轉移觸
媒，研究在由酚鈉鹽與烯丙基氯反應合成烯丙基苯基醚反應中，聚乙二醇所扮演的角
色及其應用潛力。
在乙醇溶液均勻相反應系統中結果顯示，在酚鈉鹽與烯丙基氯的反應中，真正的活性
反應物是（pho-）自由離子而非（phONa）離子對，而聚乙二醇的主要功能是促進酚
鈉鹽離子對的解離，提供更多的（phO-）自由離子，增加反應速率。根據實驗所得的
反應機構及離散結合座模式，可由一數學模式來描述在聚乙二醇存在下的均勻相反應
系統為：
（圖表省略）
聚乙二醇在水一油兩相中的反應，以電導度測量結果顯示其反應機構為離子萃取機構
。由於聚乙二醇具有與金屬陽離子錯合能力且是很好的有機溶劑，故聚乙二醇的加入
，不僅提高了油相的反應速率，水相亦然。根據本研究所倡導的反應機構及聚乙二醇
特性，其兩相反應動力學模式可表示為：
（圖表省略）
即油相的酚陰離子濃度與所加入的聚乙二醇量有正比關係，與水相的酚陰裡子濃度有
二次正比關係。而烯丙基氯在水相中的溶解度與加入之聚乙二醇量有正比關係。因此
，在兩相的反應系統中，聚乙二醇觸媒適合於高水相金屬鹽濃度的反應條件下進行。
在液─液兩相反應中的溶劑效應研究結果顯示，偽質子溶劑的種類對含與不含聚乙二
醇的反應速率比值，（-r）i, p/（-r）i,b，沒有影響，且其值不大（約2.2 左右）
，而偽質子溶劑的極性愈小，其總反應速率愈高，即n-decane > cyclohexane >
ethy1 ether > chlorobenzene > dichloromethane 。而質子溶劑的改變，其影響則
非常大，如以PEG-400 完全取代質子溶劑相中的水，其反應速率是不含PEG 的
n-decane/H2O系統的60倍。而在n-decane/（H2O:PEG-400）兩相系統中，當PEG-400
含量比例高於60% 時，其反應完全發生在（H2O:PEG-400 ）相中。雖然在n-decane/
（H2O:PEG-400 ）兩相反應中，100%所得的反應速率最高，但在不同H2O:PEG-400 比
例下求得的均勻相反應速率常數指出，在70% 的PEG-400 溶液中其反應速率常數最大
。
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ABSTRACT
In this dissertation, polyethylene glycols (PEGs), which are cheap,
non-toxic, high thermal stability, and easy recovey by conventional
separation technique are used as the phase transfer catalysts. The main
characteristic of PEGs is able to form complexes with metal cations. The
primary purpose of the present research is to study the role and its
application potential of PEGS in the allylation of phenoxide with allyl
chloride (or allyl bromide).
In the experiments of homogeneous EtoH solution, the reaction mechanism of
phenoxied allylation with allyl chloride, from which the sodiuum phenoxied
allylation with allyl chloride, from which the sodium phenoxide will
dissociate into free ions and complexes will form from sodium cation with
PEGs, is proposed. The free ions of the dissociated phenoxide is verified
as the active component in the allylation. Based on the prosposed reaction
mechanism and the discrete binding-site model, the homogeneous phase
reaction of phenoxide allylation under the existing of PEGs can be
described by the following mathematical model:
（圖表省略）
In the two-phase heterogeneous reactio system, PEGs are also used as the
phase transfer catalysts. The ion-extraction mechanism, which is verified
by the electroconductomeric method, is proposed. The reaction takes place,
either in ther organic phase or in the aqueous phase. This is due to the
easy formation of complexes from PEGs with metal cations and employment of
an excellent solvent. Based on the proposedeaction mechanism and the
characteristics of PEGs, the kinetic model of the two-phase reaction
system can be expressed as:
（圖表省略）
This model leads to a rigid conclusion that the phenoxide ions
concentration in the organic phase is linear proportional to the amount of
PEGs added and is also proportional to the phenoxide concentration in the
aqueous phase with a power of two. Therefore, it is more favorable to make
the reaction system in a high aquenous metal salts concentration by using
PEG as a phase transfer catalyst.
In studying the effects of solvents in a two-phase phase transfer
catalytic reaction by PEGs, the rectivity ration(-r)i,p/(-r)i,b, either
with PEGs or without PEGs is insensitive to the kinds of the organic
solvents used. The overall reactivity of the reaction is increased by
using an organic solvent with small polarigy., i.e.,n-decane >cyclohexane
> tyhyl ether > chlorobenzene > dichloromethane. However, the aqueous
phase solvent will dramatically influence the reactivity. The experimental
results indicates that the reactivity of the reaction in using PEG-400 for
replacing water as the aqueous phase is about 60 times of the reactivity
in a n-decane/H2O reaction system. The experimental results also indicates
that the reaction completely occurs in the H2O:PEG-400 phase when the
volume content of PEG is greater than 60%. In the n-decane/(H2O:PEG-400)
Two-phase reaction, the greatest reactivity of the reaction was carried
out in a 100% volume of PEG in (H2O:PEG-400) Phase. However, the greatest
reactivity of the reaction occurred at a 70% PEG homogeneous solution.
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