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Synthesis of Benzyl Salicylate by Dual-Site Phase Transfer Catalyst and Ionic Liquid in Tri-Liquid System
|關鍵字:||Dual-site phase-transfer catalyst|
|引用:|| J. Jarrouse, “The influence of Quaternary Chloride on the Reaction of Labike Hydrogen Compound and Chlorine-Substituted Chlorine Derivatives,’’ C.R Heabd. Seances Acad. Sci, C232 (1951) 1424  C.M. Starks, “Phase Transfer Catalysis. I. Heterogeneous Reactions Involving Anion Transfer by Quaternary Ammonium and Phosphonium Salts,” J. Am. Chem. Soc. 93 (1971) 195-199.  A.W. Herriott, D. Picker, “Phase transfer catalysis. An evaluation of catalysts”, J. Am. Chem. Soc. 97 (1975) 2345-2349.  A. Brandstrom, “Preparative Ion Pair Extraction, An Introduction to Theory and Pratice”, Apotekarsocieteten / Hassle, Lakemedel, Sweden (1974) 139-148.  M. Kitamura, Y. Arimura, S. Shirakawa, K. Maruoka, “Combinatorial approach for the design of new, simplified chiral phase-transfer catalysts with high catalytic performance for practical asymmetric synthesis of a-alkyl-a-amino acids”, Tetrahedron Letters 49 (2008) 2026-2030.  J. H. Lee, M. S. Yoo, J. H. Jung, S. S. Jew, H. G. Parka, B. S. Jeongb, “Polymeric chiral phase-transfer catalysts derived from cinchona alkaloids for enantioselective synthesis of α-amino acids”, Tetrahedron 63 (2007) 7906-7915.  E. Murugan, A. Sivab, “Preparation of a novel soluble multi-site phase transfer catalyst and the kinetic study for the C-alkylation of α-pinene”, Journal of Molecular Catalysis A: Chemical 235 (2005) 220-229.  P.A. Vivekanand, T. Balakrishnan, “Superior catalytic efficiency of a new multi-site phase transfer catalyst in the C-alkylation of dimedone -A kinetic study”, Catalysis Communications 10, (2009) 1371-1375.  M. L. Wang, Y. M. Hsieh, “Kinetic study of dichlorocyclopropanation of 4-vinyl-1-cyclohexene by a novel multisite phase transfer catalyst”, Journal of Molecular Catalysis A: Chemical 210 (2004) 59-68.  A. Siva, E. Murugan, “Synthesis and characterization of novel multi-site phase transfer catalyst and its catalytic efficiency for dichlorocarbene addition to citral”, Journal of Molecular Catalysis A: Chemical 241 (2005) 101-110.  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.  P. Tundo, P. Venturello, “Synthesis Catalytic Activity, and Behavior of Phase-Transfer Catalysts Supported on Silica Gel. Strong Influence of Substrate Adsorption on Polar Polymeric Matrix on the Efficiency of the Immobilized Phosphonium Salts” , J. Am. Chem. Soc. , Vol. 101 (1979) 6606-6613.  C.M. Starks, C.L. Loitta, M. Halpern, “Phase transfer catalysis: Fundamentals, Applications, and Industrial Perspectives; Chapman&Hall” , New York (1994).  S.L. Regen, J.J. Besse, J. Mcliick, “Solid Phase Cosolvent Triphase Catalytic Hydrolysis of 1-Bromoadamantane”, J. Am. Chem. Soc., 101 (1979) 166-120.  Sugden, S., Wilkins,H. J. Chemical Society ,(1929) 1291-1298.  Hurlcy, F.H., Wicr, T. P., J., Jr. Electrochemical Society, (1951) 07-212.  Edward M. Arne t t, James F. Wolf, “An Electrochemical Scrutiny of Organometallic Iron Complexes and Hexamethylbenzene in a Room Temperature Molten Salt”, Journal of the American Chemical Society, (1975) 3264-3265.  George W. Parshall, ” Catalysis in Molten Salt Media”, Journal of the American Chemical Society, 94 (1972) 8716-8719.  J. Adams Christopher, J. Earle Martyn, Glyn Roberts and R. Seddona Kenneth, “Friedel–Crafts reactions in room temperature ionic liquids”, Chemical Communications, (1998) 2097-2098.  J. Carmichael, Martyn J. Earle, John D. Holbrey, Paul B. McCormac, Kenneth R. Seddon, ” The Heck Reaction in Ionic Liquids:A Multiphasic Catalyst System”, Organic Letters , 1, (1999) 997-1000.  Peter Wasserscheid , H .Waffenschmidt,” Ionic liquids in regioselective platinum-catalysed hydroformylation”, Journal of Molecular Catalysis A: Chemical 164, (2000) 61-67  M. A. Judeh Zaher, Hao-Yu Shen, Ching Chi Bun, Li-Chun Feng , Selvaratnam Selvasothi, “A facile and efficient nucleophilic displacement reaction at room temperature in ionic liquids”, Tetrahedron Letters 43, (2002) 9381–9384  Hua Qian, Dabin Liu, Chunxu Lv, “Ultrasonically-promoted synthesis of mandelic acid by phase transfer catalysis in an ionic liquid”, Ultrasonics Sonochemistry 18, (2011) 1035–1037  吳榮宗, 離子液體在催化反應上的應用,化工期刊,第53卷,第5期(2006)  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.  R. Nouguier, M. Michich, ”Alkylation of Pentacrythritol by Phase Transfer Catalsis.2. Crucial Effect of the Aqueoes Sodium Hydroxide Solution”, Tetrahedron, 44, (1988) 2477.  D. Masson, S. Magdasi, Y. Sasson, “Role of a third liquid phase in phase transfer catalysis”, J. Org. Chem., 56, (1991) 7229-7232.  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.  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.  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.  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.  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.  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.  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.  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.  G. Maerker, J.F. Carmichael, W.S. Port, “Glycidl Ester Method of preparation and study of Some reaction Variables” , J. Org. Chem., 26 (1961) 2681-2688.  H. E. Hennis, J. P. Easterly, L. R. Collins, L. R. Thompson, “Esters from Reactions of Alkyl Halides and Salts of Carboxylic Acids. Reactions of Primary Alkyl Chlorides and Sodium Salts of Carboxylic Acids”, Ind. Eng. Chem. Prod. Res. Dev., 6 (1967) 193-195.  H. M. Yang, Y. S. Huang, “Green benzylation of sodium salicylate by phase-transfer catalysis with third-liquid phase in a continuous two-phase-flow reactor”, Journal of the Taiwan Institute of Chemical Engineers 42 (2011) 265-270.|
第三液相的形成變數探討包含觸媒添加量，水相反應物種類、水相反應物添加量、鹽類種類及添加量、有溶劑種類、水量和溫度。實驗結果顯示在水相反應物與觸媒莫耳數比值為4:1時所形成的第三液相中擁有較高的觸媒Q2+濃度；系統中若含有過量的溴離子則容易使第三液相為固體，用氯化鈉為添加鹽類則可避免第三液相為固體，在氯化鈉添加量為0.05莫耳時，第三液相觸媒Q2+濃度最高；選用極性高的甲基異丁酮及低極性的甲苯為溶劑皆能形成第三液相，其體積為0.8 cm3，但是使用甲基異丁酮有機相中會溶有部份的觸媒Q2+，而使用非極性的正庚烷第三液相體積為1 cm3，且其中的觸媒Q2+最多；溫度效應在本系統中對第三液相的組成有明顯的差異，當溫度為30°C時，第三液相體積為0.8 cm3，觸媒中間體濃度為0.426 mmol；當溫度升高至60°C時，第三液相體積為1 cm3，觸媒中間體濃度為0.648 mmol。
在反應機制上，反應區域主要位於第三液相，有機相反應物與觸媒中間體在第三液相中進行本質反應。所合成之雙活性基觸媒(BTPAMBC)較一般商用觸媒有較佳的催化效率，加入不同結構之離子液體對本系統的催化效果有顯著的增進。若都不添加離子液體及觸媒反應30分鐘產率僅有0.21%；僅添加觸媒而不加離子液體，反應30分鐘後產率僅有51.55%；加觸媒及離子液體在相同反應時間產率可達96.88%。攪拌速率250、350 rpm時，反應30分鐘產率已經十分接近，表示系統已克服質傳阻力造成產率的變化不大。以正庚烷為溶劑時，其實驗結果可用動力學方程式-ln(1-Y) =kappt表示，式中 為視反應速率常數。系統中以水相反應物為限量試劑，過量添加有機相反應物可使反應速率提升，實驗結果經Arrhenius方程式計算可得活化能為18.78 kcal/mol。|
The present study was to investgate esterification of sodium salicylate (Ph(OH)COONa) and benzyl bromide (RBr) to synthesize benzyl salicylate by dual-site phase transfer catalyst and ionic liquid in tri-liquid system. The novel dual-site phase transfer catalyst, 4,4'-bis tri(proplyammoniomethyl)- 1,1'-biphenyl dichloride (BTPAMBC, QCl2) was synthesized from the reaction of 4,4'-bis(chloromethyl)-1,1'-bisphenyl and tripropylamine. The operating parameters of forming the third-liquid phase included the amounts of catalyst,salt and water, types of reactant, organic solvent and salt,and temperature.The results indicated that the third-liquid phase had higher quantity Q2+ under the molar ratio of Ph(OH)COONa to BTPAMBC being 4:1.The solution containing the same bromide ion could result in the common-ion effect, which made third liquid phase become solid. Using NaCl could avoid the common-ion effect, and the tri-phase had highest Q2+ when adding 0.05 mole of NaCl. Both high polarity solvent,MIBK, and low polarity solvent, toluene, were used to form the third liquid phase, and the volumn were 0.8 cm3. However, Q2+ was distributed in MIBK phase but no Q2+ observed in the toluene phase. Using n-heptane as the solvent, the volumn of tri-phase was 1cm3 and had most Q2+ in tri-phase. In the system, the temperature effect influenced the amount of catalytic intermediate and composition of third liquid phase, the amount of catalytic intermediate,0.426 mmol, at 30°C, 0.648 mmol, at 60°C; the volume of third liquid phase,0.8 cm3, at 30°C, 1 cm3, at 60°C. In the kinetic part, the result indicated the reactions dominate to conduct in the tri-phase. When compared with commercial catalysts, BTPAMBC had better catalytic efficiency. At 30 min, the product yield was 0.21% without adding both ionic liquid and catalyst. The yield was 51.55% by adding BTPAMBC but without ionic liquid, and was 96.88% using both ionic liquid and BTPAMBC. With different structures of ionic liquids the catalytic efficiency was significantly enhanced. Stirring at 350 rpm, mass transfer resistance had not a significant effect on the reaction rate. Using n-heptane as the solvent, the kinetic results were correlated by using -ln(1-Y) =kappt equation successfully, where was the apparent reaction rate constant, and the apparent activation energy was 18.78 kcal/mol with high efficiency.
|Appears in Collections:||化學工程學系所|
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