Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3176
標題: 以超音波及離子液體促進第三液相相間轉移催化合成對-羥基苯甲酸正辛酯之研究
Synthesis of n-Octyl 4-Hydroxybenzoate by Ultrasound and Ionic Liquid Promoted Third-Liquid Phase-Transfer Catalysis
作者: 蘇瑞恩
Su, Juei-En
關鍵字: 相間轉移觸媒;phase transfer catalyst;三液相;離子液體;Logistic Growth Model;對-羥基苯甲酸正辛酯;Third-liquid phase;Ionic liquid;Logistic Growth Model;Octyl 4-Hydroxybenzoate
出版社: 化學工程學系所
引用: 參考文獻 [1] P.Anastas,J.C. Warner, “Pursuing practical elegance in chemical synthesis Ryoji Noyori ’’Chemical Communications, 2005, (14), 1807 - 1811 Abstract [2] 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 [3] 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. [4] C.M. Starks, and R.M.,Owens,“Phase Transfer Catalysis. Ⅱ. Kinetic Details of Cyanide Displacement on1-Halooctanes” J. Am. Chem. Soc. 95 (1973) 3613. [5] A.W. Herriott, D. Picker, “Phase transfer catalysis. An evaluation of catalysts”, J. Am. Chem. Soc. 97 (1975) 2345-2349. [6] 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. [7] 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. [8] E. Murugan, A. Sivab, “Preparation of a novel soluble multi-site phase transfer catalyst and the kinetic study for the C-alkylation ofα-pinene”, Journal of Molecular Catalysis A: Chemical 235 (2005) 220-229. [9] 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. [10] 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. [11] 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. [12] C.M.,Starks,“Phase Transfer Catalysis.I. Heterogeneous Reactions Involving Anion Transfer by Quaternary Ammonium and Phosphonium Salts”,J Am Chem Soc,93(1),195-199(1971) [13] M.Makosza, Pure Appl Chem, 43, (1975)439-462 [14] M.Makosza,and Bialecka,E., Tetrahedron Lett, 2, (1977) 183-186 [15] 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. [16] 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. , 101 , (1979) 6606-6613. [17] C.M. Starks, C.L. Loitta, M. Halpern, “Phase transfer catalysis: Fundamentals, Applications, and Industrial Perspectives; Chapman&Hall” , New York (1994). [18] 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. [19] W. T., &quot;Room-Temperature Ionic Liquids. Solvents for Synthesis and Catalysis&quot;. Chem.Rev., 99,(1999), 2071-2084. [20] F.H. Hurlcy., Wicr, T. P., J., Jr. Electrochemical Society, (1951) 07-212. [21] F. H. Hurley, T. P. Wier, J. Electrochem. Soc. 98,( 1951) 203. [22] H. L. Chum, V. R. Koch, L. L. Miller, R. A. Osteryong, J. Am. Chem. Soc., 97, (1975)3264. [23] G.W. Parshall, ” Catalysis in Molten Salt Media”, Journal of the American Chemical Society, 94 (1972) 8716-8719. [24] J. Adams Christopher, J. Earle Martyn, G. Roberts and R. Seddona Kenneth, “Friedel–Crafts reactions in room temperature ionic liquids”, Chemical Communications, (1998) 2097-2098. [25] M. Badri, J. Brunet” Ionic liquids as solvents for the regioselective O-alkylation of C/O ambident nucleophiles.”, Tetrahedron Letters, Volume 33, (1992) 4435–4438. [26] A.Z. Paulo Suarez, Jeane E.L. Dullius, Sandra Einloft, Roberto F. De Souza, Jairton Dupont” The use of new ionic liquids in two-phase catalytic hydrogenation reaction by rhodium complexes”, Polyhedron Volume 15, (1996)1217–1219. [27] 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. [28] P. Wasserscheid , H .Waffenschmidt,” Ionic liquids in regioselective platinum-catalysed hydroformylation”, Journal of Molecular Catalysis A: Chemical 164, (2000) 61-67 [29] H. Qian, D. Liu, C. Lv, “Ultrasonically-promoted synthesis of mandelic acid by phase transfer catalysis in an ionic liquid”, Ultrasonics Sonochemistry 18, (2011) 1035–1037 [30] M. Ghiaci, B. Aghabarari , S. Habibollahi , A. Gil “Highly efficient Bronsted acidic ionic liquid-based catalysts for biodiesel synthesis from vegetable oils”, Bioresource Technology 102 (2011) 1200–1204 [31] M. Ghiaci, B. Aghabarari, S. Habibollahi, A. Gil, “Highly efficient Bronsted acidic ionic liquid-based catalysts for biodiesel synthesis from vegetable oils”, Bioresource Technology 102 (2011) 1200–1204 [32] Y. Yang, W. He, C. Jia , Y. Ma, X. Zhang, B. Feng, “Efficient synthesis of phytosteryl esters using the Lewis acidic ionic liquid”, Catalysis Today, (2012) xxx– xxx [33] A. H. Jadhav , H. Kim, I. T, Hwang, “Efficient selective dehydration of fructose and sucrose into 5-hydroxymethylfurfural (HMF) using dicationic room temperature ionic liquids as a catalyst”, Catalysis Communications 21 (2012) 96–103 [34] T. Uragami, J. Kishimoto, T. Miyataa, “Membrane reactor for acceleration of esterification using a special ionic liquid with reaction and separation and microwave heating”, Catalysis Today, (2012) xxx– xxx [35] 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. [36] I. T.;Saiki,M.;Goto,S., “Effect of Addition of Methanolon Catalytic Activity of Polyethylene Glycols as Phase Transfer Catalyst”,Kagaku Kogaku Robunshu.,15(2),403(1989) [37] D. Masson, S. Magdasi, Y. Sasson, “Role of a third liquid phase in phase transfer catalysis”, J. Org. Chem., 56, (1991) 7229-7232. [38] 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. [39] 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. [40] 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. [41] 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. [42] 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. [43] 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. [44] 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. [45] 王昌鈞,<有機化學>,第二版,藝軒圖書出版社 [46] 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. [47] 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. [48] J.L. Louis, Synthetic organic sonochemistry, Plenum Press, New York and London [49] CAVITATION SICKNESS, http://www.deafwhale.com/stranded_whale/barotrauma.htm [50] K. S. Suslick, “The Chemical Effects Of Ultrasound”, Scientific American, 260 (1989) 80-86. [51] M.H.Entezari,A.Keshavarzi,A.A.Shameli,Phase-transfer catalysis and ultrasonic wave I.Cannizzaro reaction.Ultrasonics Sonochemistry 7, (2000)169-172 [52] M.H.Entezari,Venugopal Rajendran,Ultrasound assisted Phase-transfer catalysis epoxidation of 1,7-octadiene-A kinetic study.Ultrasonics Sonochemistry 14, (2007)46-54 [53] 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. [54] X. Z Zheng , Y. Shan, “Studies on the sunthetis methods for octyl and isopropyl Nipagin Ester” Chem. World , 19, (1997) 12–17. [55] H. Yan-bing, Y. Ri-an, H. Cai-huan, D. Han-ying, “Synthesis of long-chian esters of p-hydroxybenzoic acid”Food Science and Science And Technology”, 36 (2011) [56] G. Wang,1 Lu Li,2 C. Xie,1 S. Yu,2. F. Liu,2 and X. Ye1“Synthesis Of Nipagin Esters Using Acid functional Ionic Liquids As Catalysts”, Synthetic Communications1, 41:(2011)945–952
摘要: 
  本論文探討以超音波及離子液體促進第三液相相間轉移催化合成對-羥基苯甲酸正辛酯之動力學研究。
第三液相的形成變數包括溴化四丁基鏻添加量、有機溶劑種類、鹽種類、鹽添加量和不同溫度。實驗結果顯示當觸媒溴化四丁基鏻莫耳數與水相反應物為1:1時,第三液相內所含的觸媒Q+濃度最高;以高極性的甲基異丁基酮和非極性的正庚烷4:1的體積比例混合,正庚烷能將觸媒Q+集中在第三液相中,甲基異丁基酮能提高反應速率;系統無法自行生成第三液相,添加氯化鈉,容易將觸媒中間體析出集中在第三液相,當氯化鈉添加量逐漸上升,會使得水中之觸媒溶解度下降,第三液相體積增加,當添加到0.04莫耳時,有最大的第三液相體積2.2 cm3,所含之觸媒Q+也最多。溫度對本系統之第三液相的組成有很明顯的影響,但溫度為30度時,部分氯化鈉尚未完全溶解,使得第三相成為固體,當溫度上升到60度時,第三液相中觸媒Q+為3.63 mmol。
 以對-羥基苯甲酸鈉與溴辛烷進行酯化反應合成對-羥基苯甲酸正辛酯,其有機相反應物與觸媒會在第三液相中進行催化反應,以四級鹽類溴化四丁基鏻(TBPB)有最佳的產率,當溶劑使用正庚烷與甲基異丁基酮4:1之混合比例時,能夠將產率提升到80%以上,此時之動力學機制符合Logistic Growth Model
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Ea= 6.12 kcal/mol。添加微量離子液體0.5毫莫耳可以將反應時間縮短,並溶解第三液相,其作用與高極性溶劑類似。最佳三液相反應條件為: 對-羥基苯甲酸鈉0.005莫耳、去離子水10毫升、溴化四丁基鏻0.005莫耳、氯化鈉0.04莫耳,甲基異丁基酮2毫升、正庚烷8毫升,溴辛烷0.05莫耳,反應四小時後產率為86.3%。

The present study was to investgate ultrasound-assisted For Synthesizing Octyl 4-Hydroxybenzoate by Phase Transfer Catalyst and Ionic Liquid in Tri-Liquid System.

The operating parameters of forming the third-liquid phase included the amounts of catalyst,salt organic solvent ,temperature and reaction time.The results indicated that the third-liquid phase had higher quantity Q+ under the molar ratio of TBPB to Ph(OH)COONa being 1:1. Heptane can gather Q+ in the third-phase,and few MIBK can improve the reaction rate with the volume ratio of MIBK to heptanes to be 4:1.

The system cannot form the third liquid phase byitself,the addition of NaCl , gives the third-liquid were 2.2 cm3.

With molar ratio of the low-polarity heptane to high-polarity MIBK being 4:1,Q+ can be accumulated in the third-liquid phase ,and few MIBK can improve the Reaction rate.When the addition of sodium chloride was increased, the solubilitu of catalyst in water will decrease,leading to the increase of third-liquid volume,which is 2.2 cm3 for 0.04ml of NaCl add, when added to 0.04 mole.

In the system,the temperature effect influenced the amount of catalytic intermediate and composition of third liquid phase. Parts of NaCl were not dissolved completely with the third phase observed as solid at 30℃;and Q+ in the thied-liquid phase is determined to be 3.63 mmol at 60℃.

Esterification of 4- hydroxybenzoate(Ph(OH)COONa) with octyl bromide(RBr) to produce Octyl 4-Hydroxybenzoate was performed, the reaction of organic reactant and catalytic intermediate was conducted in third-liquid, the use of tetrabutyl phosphonium bromide (TBPB) has the best yield with the molar ratio of the solvent heptane to solvent MIBK being 4:1,the product yield was over 80%,and the kinetic results were well correlated by Logistic Growth Model.The apparent activation energy was 6.12 kcal/mol.Adding few ionic liquid can improve the reaction time,and parts of third-liquid phase would be dissolved by using even 0.5 mmole of ionic liquid ,the function of ionic liquid is similar to a hight polarity solvent.
The best third- phase reaction conditions : 0.005 mole of 4- hydroxybenzoate,0.005 mole of TBPB,0.04 mole of NaCl,10 cm3 of water,2 cm3 of MIBK, 8 cm3 of heptane,0.05 mole of bromooctane,the product yield was 86.3% after 4 hours.
URI: http://hdl.handle.net/11455/3176
其他識別: U0005-3006201317000800
Appears in Collections:化學工程學系所

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