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Synthesis of 2-Phenoxyethyl Benzoate by Ultrasound-Assisted Phase-Transfer Catalysis with Dual-Site Phase-Transfer Catalyst in Tri-liquid System
|關鍵字:||Dual-site phase-transfer catalyst;雙活性基相間轉移觸媒;Third-liquid phase;Sonochemistry;Ether-esters;cavitation;第三液相;超音波化學;醚酯類;空穴效應;酯化反應||出版社:||化學工程學系所||引用:|| J. Jarrouse, “The Influence of quaternary chloride on the reaction of labike hydrogen compound and chlorine-substituted chlorine derivatives”, CR Heabd. Seances Acad. Scu., C332 (1951) 1424-1434.  C. M. Starks, “Phase Transfer Catalysis. I. Heterogeneous Reactions Involving Anion Transfer by Quaternary Ammonium and Phosphonium salts”, J. Am. Chem. Soc., 93(1) (1971) 195-199.  L. J. Mathias, R. A. Vaidya, “Inverse phase transfer catalysis. First report of a new class of interfacial reactions”, J. Am. Chem. Soc., 108 (1986) 1093-1094.  A. W. Herriott, D. Picker, “Phase transfer catalysis. An evaluation of catalysts”, J. Am. Chem. Soc., 97 (1975) 2345-2349  T. Ooi, Y. Uematsu, J. Fujimoto, K. Fukumoto, K. 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第三液相形成的變數探討包含觸媒添加量、水相反應物添加量、有機溶劑種類、水量與有機溶劑添加量和溫度。本系統中，第三液相的形成不需另外添加鹽類於水中，在操作條件為苯甲酸鈉0.003莫耳，BTHAMBB 0.0015莫耳，去離子水10毫升，甲苯10毫升，溫度60℃，攪拌速率250 rpm，攪拌20分鐘即可形成體積2 cm3的第三液相。由於觸媒中間體的結構使其對水相與甲苯溶劑的溶解度皆低，因此微量的觸媒即能與水相反應物形成觸媒中間體與第三液相，而水相反應物與觸媒添加量的比例在2：1時，第三液相中觸媒中間體的含量最高(為0.00135莫耳)，過多的觸媒添加會降低觸媒中間體於第三液相中的濃度。使用低極性的甲苯或非極性的正庚烷皆能形成第三液相，其體積分別為2.2 cm3與2 cm3，而使用高極性的氯苯當溶劑時，則會溶解觸媒與觸媒中間體，導致無法形成第三液相。溫度效應則會影響第三液相中觸媒中間體的量，在溫度80℃時，第三液相中觸媒中間體的含量為0.00141莫耳，而在溫度50℃時，則為0.00112莫耳。
在反應機制上，反應區域主要位在第三液相，有機相反應物與觸媒中間體在第三液相中進行本質反應，其反應速率表示式可用擬一階線性方程式描述。在攪拌速率300 rpm以及超音波28 kHz、300 W的輔助下在溫度60 ℃反應4小時可得到72.7 %的產率，而無觸媒添加時，產率僅有2 %。在攪拌速率為300 rpm時，其質傳阻力對反應速率的影響較小，而能忽略質傳阻力之作用。超音波輔助方面，當反應加入頻率28 kHz超音波輔助時，可增加反應速率，並且視反應速率常數可提升25 %，而45 ℃低溫時的輔助效應比高溫60 ℃時有較好的效率，視反應速率常數可提升91.7 %；而當超音波頻率越高時，會使超音波在傳遞時損失的能量越多，使系統獲得的能量越少，產率下降。
In this study, 2-phenoxyethyl benzoate was synthesized from the reaction of sodium benzoate and 2-phenoxyethyl bromide via a dual-site phase-transfer catalyst, 1,4-bis(trihexylammoniomethyl)benzene dibromide (BTHAMBB), under ultrasound irradiation in a tri-liquid batch system. The catalyst BTHAMBB was synthesized from the reaction of p-xylylene dibromide and excess trihexylamine in acetonitrile at 70 ℃. In this study, the investigations included the forming condition of the third-liquid phase by BTHAMBB and kinetics of synthesizing 2-phenoxyethyl benzoate.
The operating parameters of forming the third-liquid phase included the amounts of catalyst and sodium benzoate, types of organic solvent, amounts of water and organic solvent, and temperature. In the conditions of 0.003 mol of sodium benzoate and 0.0015 mol of BTHAMBB in 10 cm3 of de-ionized water, 10 cm3 of toluene, temperature at 60 ℃ and stirring speed at 250 rpm, a volume 2 cm3 of the third-liquid phase was formed after 20 min of reaction without adding any extra inorganic salt in the aqueous phase. This phenomenon is due to the structure of the catalytic intermediate that made the third-liquid phase having low solubility in both water and toluene. The catalytic intermediate had the highest amount (0.00135mol) in the third-liquid phase under the molar ratio of sodium benzoate to BTHAMBB being 2:1. An excess addition of BTHAMBB might transfer more catalyst into the third-liquid phase and reduced the effective concentration of the catalytic intermediate for reaction. In this study, the third-liquid phase could be formed by using toluene and heptane as the organic solvent with the volume of 2.2 cm3 and 2 cm3, respectively. But the high-polarity solvent chlorobenzene can not be used to form the third-liquid phase, because the catalyst and the catalytic intermediate can be dissolved by chlorobenzene. The effect of temperature influenced the amount of catalytic intermediate in the third-liquid phase . The amount of catalytic intermediate, 0.00141 mol, at 80 ℃ was higher than that, 0.00112mol, at 50 ℃.
In the kinetic part, the result indicated the reactions dominate to conduct in the third-liquid phase. The rate of apparent reaction could be described by pseudo-frist-order kinetic equation. The yield of the product of 2-phenoxyethyl benzoate in the organic phase was obtained 72.7 % by using BTHAMBB as the PTC in 4 h at the reaction condition of temperature at 60 ℃ , agitation speed at 300 rpm, ultrasonic frequency and power at 28 kHz and 300 W, while the yield of the product was obtained only 2 % at the same reaction condition without using BTHAMBB as the PTC. The reaction rate was not affected by stirring speed greater than 300 rpm and the kinetics was controlled by the chemical reaction. In the effect of ultrasonic irradiation, the rate of reaction increased and kapp increased 25 % as 28kHz ultrasound was applied in the reaction system. The efficiency of sonication at lower temperature, 45 ℃, was greater than that at higher temperature, 60 ℃, kapp increased 91.7 %. The fewer energy would be got in the reaction system and more energy was lost in the transport process at higher ultrasonic frequency, resulting in a lower reaction rate in this study.
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