Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3787
標題: 以超音波輔助雙活性基相間轉移觸媒在三液相系統下催化酯化合成苯甲酸2-苯氧乙基酯之研究
Synthesis of 2-Phenoxyethyl Benzoate by Ultrasound-Assisted Phase-Transfer Catalysis with Dual-Site Phase-Transfer Catalyst in Tri-liquid System
作者: 林岱汶
Lin, Dai-Wen
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: [1] 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. [2] 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. [3] 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. [4] A. W. Herriott, D. Picker, “Phase transfer catalysis. An evaluation of catalysts”, J. Am. Chem. Soc., 97 (1975) 2345-2349 [5] T. Ooi, Y. Uematsu, J. Fujimoto, K. Fukumoto, K. Maruoka., “Adavantage of in situ generation of N-artlsulfonyl imines from a-amide sulfones in the phase-transfer-catalyzed asymmetric Strecker reaction”, Tetrahedron Letters, 48 (2007) 1337-1340. [6] K. Manabe, “Synthesis of novel chiral quaternary phosphonium salts with a multiple hydrogen-bonding site, and their application to asymmetric phase-transfer alkylation”, Tetrahedron Letters, 54 (1998) 14465. [7] M. L. Wang, Z. F. Lee, F. S. Wang, “Synthesis of novel multi-site phase-transfer catalyst and its application in the reaction of 4,4''-bis(chloromethyl)-1,1''-biphenyl with 1-butanol”, Journal of Molecular Catalysis A: Chemical, 229 (2005) 259-269. [8] J. P. Jayachandran, M. L. Wang, “Selective dichlorocyclopropanation of dicyclopentadiene under controlled phase transfer catalysis conditions”, Applied Catalysis A: General, 206 (2001) 19-28. [9] E. Murugan, P. Gopinath, “Catalytic activity of novel soluble multi-site phase transfer catalyst in dichlorocarbene addition to α -pinene”, Journal of Molecular Catalysis A: Chemical, 294(2008) 68-73. [10] P.A. Vivekanand, T. Balakrishnan, “Synthesis and characterization of a novel multi-site phase transfer catalyst and akinetic study of the intramolecular cyclopentanation of indene”, Applied Catalysis A: General, 364 (2009) 27-34. [11] E. Murugan, P. Gopinath, “Synthesis and characterization of novel bead-shaped insoluble polymer-supported tri-site phase transfer catalyst and its efficiency in N-alkylation of pyrrole”, Applied Catalysis A: General, 319 (2007) 72-80. [12] T. Balakrishnan, E. Murugan, A. Siva, “Synthesis and characterization of novel soluble multi-site phase transfer catalyst; its efficiency compared with single-site phase transfer catalyst in the alkylation of phenylacetonitrile as a model reaction”, Applied Catalysis A: General, 273 (2004) 89-97. [13] R. Neumann, Y. Sasson, “Mechanism of Base Catalyzed Reactions in Phase-Transfer Systems with Poly(ethylene glycols) as catalysts. The Isomerization of Allylanisole”, Journal of Organic Chemistry, 49 (1984) 3448-3451. [14] D. H. Wang, H. S. Weng, “Preliminary Study on the Role Played by the Third Liquid Phase in Phase Transfer Catalysis”, Ind. Eng. Chem. Res, 43 (1988) 2019-2024. [15] D. Masson, S. Magdasi, Y. Sasson, “Role of a third liquid phase in phase transfer catalysis”, J. Org. Chem., 56 (1991) 7229-7232. [16] D. H. Wang, H. S. Weng, “Phase transfer catalytic reaction between n-butyl bromide and sodiu, phenolate-foemation of the third liquid phase and its effect.”, J. Chin. Inst. Chem. Eng., 26 (1995) 147-156. [17] T. Ido, T. Yamamoto, G. Jin, S. Goto, “Third-Phase Catalytic Activity of Halogen Exchange Reactions in Phase Transfer Catalytic System”, Chem. Eng. Sci., 52 (1997) 3511-3520. [18] H. S. Weng, S. M. Kao, H. C. Hsiao, “Synthesis of n-Butyl Phenyl Ether by Tri-Liquid-Phase Catalysis Using Poly ethylene glycols-600 as a catalyst. 1. Analysis of Factor Affecting the Formation of a Third Liquid Phase”, Ind. Eng. Chem. Res., 39 (2000) 2772-2778. [19] G. Jin, T. Ido, S. Goto, “Effect of third-phase properties on benzyl-n-butyl ether synthesis in phase transfer catalytic system”, Catalysis Today, 64 (2001) 279-287. [20] C. C. Huang, H. M. Yang, “Kinetics for benzoylation of sodium 4-acetylphenoxide via third-liquid phase in the phase-transfer catalysis”, Applied Catalysis A:General, 290 (2005) 65-72. [21] H. M. Yang, C. C. Li, “Kinetics for synthesizing benzyl salicylate by third-liquid phase-transfer catalysis”, Journal of Molecular Catalysis a-Chemical, 246 (2006) 255-262. [22] G.D. Yadav, B.G. Motirale, “Selective oxidation of methyl mandelate to methyl phenyl glyoxylate using liquid–liquid–liquid phase transfer catalysis”, Chemical Engineering Journal, 156 (2010) 328-336. [23] S.Baj, A.Siewniak, “Tri-liquid system in the synthesis of dialkyl peroxides using tetraalkylammonium salts as phase-transfer catalysts”, Applied Catalysis A:General, 385 (2010) 208-213. [24] G. Maerker, J. F. Carmichael, W. S. Port, “Glycidl Ester Method of preparation and study of Some reaction Variables”, J. Org. Chem., 26 (1961) 2681. [25] H. M. Yang, C. C. Huang, “Phase-transfer catalyzed benzoylation of 4-chloro-3-methylphenol sodium salt in liquid-liquid system”, Chemical Engineering Communications, 194 (2007) 1187-1200. [26] J. L. Louis, Synthetic Organic Sonochemistry, New York and London: Plenum Press.(1894) [27] K. S. Suslick, “The Chemical Effects Of Ultrasound”, Scientific American, 260 (1989) 80-86. [28] CAVITATION SICKNESS, http://www.deafwhale.com/stranded_whale/barotrauma.htm [29] Nano Cavitation, http://alfin2300.blogspot.com/2010/01/nano-cavitation-approach-to-algal-oil.html [30] M. L. Wang, V. Rajendran, “Ultrasound assisted phase-transfer catalytic epoxidation of 1,7-octadiene - A kinetic study”, Ultrasonics Sonochemistry, 14 (2007) 46-54. [31] M. L. Wang, V. Rajendran, “Kinetics for dichlorocyclopropanation of 1,7-octadiene under the influence of ultrasound assisted phase-transfer catalysis conditions”, Journal of Molecular Catalysis a-Chemical, 273 (2007) 5-13. [32] N. S. Nandurkar, M. J. Bhanushali, S. R. Jagtap, B. M. Bhanage, “Ultrasound promoted regioselective nitration of phenols using dilute nitric acid in the presence of phase transfer catalyst”, Ultrasonics Sonochemistry, 14 (2007) 41-45. [33] J. T. Li, and X. L. Li, “An efficient and practical synthesis of methylene dioximes by combination of ultrasound and phase transfer catalyst”, Ultrasonics Sonochemistry, 14 (2007) 677-679. [34] H. M. Yang, G. Y. Peng, “Ultrasound-assied third-liquid phase-transfer catalyzed rdterification of sodium salicylate in a continuous two-phase-flow reactor”, Ultrasonics Sonochemistry 17 (2010) 239-245 [35] 邱俊誠, 以超音波輔助之雙活性基相間轉移觸媒在三液相催化酯化合成苯甲酸4-乙醯基苯酯之研究, 台中市: 國立中興大學化學工程研究所碩士論文, 2009 [36] V. G. Devulapelli, and H. S. Weng, “Synthesis of cinnamyl acetate by solid-liquid phase transfer catalysis:Kinetic study with a batch reactor”, Catalysis Communication, 10 (2009) 1638-1642.
摘要: 本研究探討以超音波輔助雙活性基相間轉移觸媒在三液相系統下催化苯甲酸鈉與2-苯氧乙基溴合成苯甲酸2-苯氧乙基酯之酯化反應。雙活性基相間轉移觸媒是由二溴對二甲苯與三己胺以乙腈為溶劑在70℃下反應生成溴化1, 4-二(三己基銨甲基)苯(BTHAMBB)。研究內容包括探討以雙活性基相間轉移觸媒(BTHAMBB)形成之第三液相以及催化苯甲酸2-苯氧乙基酯的酯化反應動力學探討。 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.
URI: http://hdl.handle.net/11455/3787
其他識別: U0005-0201201123413700
文章連結: http://www.airitilibrary.com/Publication/alDetailedMesh1?DocID=U0005-0201201123413700
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