Please use this identifier to cite or link to this item:
標題: 超音波及離子液體輔助相間轉移觸媒於三液相系統合成鄰-羥基苯甲酸正辛酯之研究
Synthesis of n-Octyl Salicylate by Ultrasound and Ionic Liquid Assisted Phase Transfer Catalyst in Tri-Liquid System
作者: 楊峻瑋
Yang, Chun-Wei
關鍵字: 相間轉移觸媒;Phase-transfer catalyst;超音波;三液相;動力學;離子液體;鄰-羥基苯甲酸正辛酯;Ultrasound;Tri-liquid phase;Kinetics;Ionic liquid;N-Octyl salicylate
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,’’ C.R Heabd. Seances Acad. Sci, C232 (1951) 1424 [2] 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. [3] A.W. Herriott, D. Picker, “Phase transfer catalysis. An evaluation of catalysts”, J. Am. Chem. Soc. 97 (1975) 2345-2349. [4] A. Brandstrom, “Preparative Ion Pair Extraction, An Introduction to Theory and Pratice”, Apotekarsocieteten / Hassle, Lakemedel, Sweden (1974) 139-148. [5] C.J. Pederson, “Cyclic Polyeyhers and Their Complexes with Metal Salts”, J. Am. Chem. Soc. 89,(1967a) 7071-7036. [6] 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. [7] 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. [8] 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. [9] 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 [10] 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. [11] M. L. Wang, Y.M.Hsieh, “Kinetic study of dichlorocyclopanation of 4-vinyl-1-cyclohexene by a novel multisite phase transfer catalyst ”, Jounal of Molecular Catalyst A: A Chemical, 210 (2004) 59-68. [12] H. M. Yang, D. W. Lin, “ Third-liquid phase-transfer catalyzed esterification of sodium benzoate with novel dual-site phase-transfer catalyst under ultrasonic irradiation”, Catalysis Communications 14(2011)101–106 [13] 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. [14] 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. [15] 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. [16] 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. [17] 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. [18] 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. [19] C.M. Starks, C.L. Loitta, M. Halpern, “Phase transfer catalysis: Fundamentals, Applications, and Industrial Perspectives; Chapman&Hall” , New York (1994). [20] 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. [21] 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. [22] R. Nouguier, M. Michich, ”Alkylation of Pentacrythritol by Phase Transfer Catalsis.2. Crucial Effect of the Aqueoes Sodium Hydroxide Solution”, Tetrahedron, 44, (1988) 2477. [23] 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. [24] Y. Sasson, S. Magdasi, D. Masson, “Role of a third liquid phase in phase transfer catalysis”, J. Org. Chem., 56, (1991) 7229-7232. [25] 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. [26] 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. [27] 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. [28] 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. [29] 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. [30] 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. [31] 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. [32] 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. [33] G. D. Yadav, P.R. Sowbna, “Modeling of microwave irradiated liquid–liquid–liquid (MILLL) phase transfer catalyzed green synthesis of benzyl thiocyanate”, Chemical Engineering Journal, 179(2012) 221– 230 [34] P. Walden , “Molecular weights and electrical conductivity of several fused salts” ,Bull. Russian Acad. Sci. ,(1914) 405-422. [35] Hurlcy, F.H., Wicr, T. P., J., Jr. Electrochemical Society, (1951) 07-212. [36] 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. [37] George W. Parshall, ” Catalysis in Molten Salt Media”, Journal of the American Chemical Society, 94 (1972) 8716-8719. [38] 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. [39] 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. [40] 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 [41] 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 [42] Ao Fan, Gaik-Khuan Chuah, Stephan Jaenicke , “Phosphonium ionic liquids as highly thermal stable and efficient phase transfercatalysts for solid–liquid Halex reactions”, Catalysis Today 198(2012). 300–304 [43] 劉鷹,離子液體在催化過程中的應用,化學工業出版社,(2008), ISBN:978-7-122-02071-0 [44] 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) [45] 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. [46] 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. [47] H. M. Yang, C. C. Huang, “Phase-transfer catalyzed benzoylation of 4-chloro-3-methylphenol sodium salt in liquid-liquid system”, Chemical Engineering Communication, 194 (2007)1187-1200. [48] 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. [49] K. S. Suslick, “The Chemstry of Ultrasound”, The Yearbook of Science & the Future 1994;Encyclopaedia Britannica: Chicago (1994) 138-155. [50] K. S. Suslick, “Sonochemistry”, Comprehensive Coordination Chemistry II(2003)731-739 [51] WIKIPEDIA, [52] K. S. Suslick, “The Chemical Effects Of Ultrasound”, Scientific American, 260 (1989) 80-86. [53] M. L. Wang, V. Rajendran, “Ultrasound assisted phase-transfer catalytic epoxidation of 1,7-octadiene - A kinetic study”, Ultrasonics Sonochemistry, 14 (2007) 46-54. [54] 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. [55] 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. [56] 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. [57] Yang, H. M, Chen C.H., ” Catalytic esterification of sodium salicylate in third-liquid phase under ultrasound-assisted tri-liquid phase-transfer catalysis” ,Journal of Molecular Catalysis A, pp. 107-113(2009) [58] 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 [59] Gregory Chatel, Catherine Goux-Henry, Nathalie Kardos, Joel Suptil , Bruno Andrioletti ,Micheline Draye , “Ultrasound and ionic liquid: An efficient combination to tune the mechanism of alkenes epoxidation”, Ultrasonics Sonochemistry 19 (2012) 390-394 [60] 王志刚,张露明,一锅法合成水杨酸辛酯,广东化工,第39卷第225 期(2012)。 [61] 李玲玟,以雙活性基相間轉移觸媒及離子液體在三液相系統合成 鄰-羥基苯甲酸苯甲酯之研究,中興大學化工研究所碩士論文,台 中市(2012) [62] 洪瑜鴻,超音波輔助相間轉移觸媒在含離子液體的三液相下合成鄰-羥基苯甲酸丁酯之研究,中興大學化工研究所碩士論文,台 中市(2012)
本研究探討超音波與離子液體輔助相間轉移觸媒於三液相系統中催化鄰-羥基苯甲酸鈉與溴辛烷合成鄰-羥基苯甲酸正辛酯之酯化反應。研究內容包含探討超音波、溫度、觸媒種類、觸媒添加量、離子液體、鹽類的添加及攪拌速率對三液相之催化酯化反應的影響,其中比較單活性基及雙活性基相間轉移觸媒對本系統的催化效果,雙活性基觸媒是以二溴對二甲苯及三己胺反應合成雙活性基相間轉移觸媒溴化1,4-二(三己基銨基甲基)苯(BTHAMBB, QBr2)。


從反應機制來觀察,反應主要位於第三液相,有機相反應物與觸媒中間體在第三液相中進行本質反應,當加入離子液體時,則會同時於第三液相及有機相中產生反應。而加入超音波輔助催化,在同樣反應時間的情況下,可以提升反應產率4%~20%,所合成之雙活性基觸媒溴化1,4-二(三己基銨基甲基)苯於本系統在相同反應時間可得到與使用商用單活性基觸媒相近的催化效果,而雙活性基觸媒使用量僅為商用單活性基觸媒的1/10,且不需加入鹽類即可形成第三液相。加入鏻類離子液體(phosphonium-based ionic liquid)對本系統的催化有非常大的助益。在不添加離子液體及觸媒時產率為0%;而添加觸媒不加離子液體,反應5小時後產率僅有43.5%;添加觸媒及離子液體在相同反應時間產率可達99.5%;反應結果可用虛擬一階反應動力式來描述,以對環境溫和的正庚烷為溶劑,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。經Arrhenius方程式計算可得活化能為20.14 kcal/mol。

In this study, the esterification of sodium salicylate and octyl bromide to synthesize n-octyl salicylate by ultrasound and ionic liquid promoted phase-transfer catalyst in tri-liquid system was investigated. The explored operating parameters included ultrasound, temperature, types of catalyst, addition catalyst and ionic liquid, addition of salt, agitation speed, etc..The novel dual-site phase transfer catalyst, 1,4’-bis(trihexyl ammoniomethyl) benzene dibromide (BTHAMBB, QBr2), was synthesized from P-xylene dibromide and trihexylamine in acetonitrile at 70˚C. Comparison of commercial catalysts with dual-site phase transfer catalyst in catalytic activity was performed.
  The operating parameters of forming the third-liquid phase included the amounts of catalyst, addition of salt , organic solvent, the amount of aqueous reactant and water, ionic liquid and temperature effect. The results indicated that the volume of third-liquid phase and amount of Ph(OH)COOQ would be raised by the increasement of the amount of catalyst, aqueous reactant and salt. Under the optimum condition, the system would separate out 2.1ml of third-liquid phase. While using MIBK as an organic solvent, the third-liquid phase disappeared because with its highly chemical polarity, it will dissolve third-liquid phase and take Ph(OH)COOQ away form the third-liquid phase, thus, there are nearly 99% be concentrated in the organic phase. With the addition of ionic liquid, because of its highly solubility it can bring Ph(OH)COOQ to the organic phase, it’s beneficial to accelerate the rate of reaction. The molecular kinect energy will be raised when the temperature increase, the conversion of Ph(OH)COOQ can reach 99% and above. The amount of Ph(OH)COOQ in third-liquid phase comes to 93% of overall amount of catalyst while the temperature gets to 70℃.

  In the kinetic part, the reactions dominate to conduct in the tri-phase; while adding ionic liquid in the reaction, the reactions occured in the tri – phase and organic phase simultaneously. The esterification was promoted to an increase of 4% to 20% in product yield under ultrasound irradiation. In the same reaction time, the dual-site phase transfer catalyst BTHAMBB resulted in an equivalent product yield when compared with commercial catalysts, merely with one tenth usage of BTHAMBB to the commercial catalyst Furthermore, the third-liquid phase was formed from BTHAMBB without adding any extra salt. Using ionic liquid would be beneficial to the present esterification, especially phosphonium-based ionic liquid. The product yield is 0% without adding both ionic liquid and catalyst. The yield goes to 43.5% while adding catalyst but without ionic liquid; marvelously, the yield is as high as 99.5% when using both ionic liquid and catalyst. Pesudo-first-order kinetic equation was applied to correlate experimental results. Using n-heptane as environmently friendly 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 20.14 kcal/mol with high efficiency.
其他識別: U0005-3006201316363600
Appears in Collections:化學工程學系所

Show full item record

Google ScholarTM


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.