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Synthesis of n-Octyl 4-Hydroxybenzoate by Ultrasound and Ionic Liquid Promoted Third-Liquid Phase-Transfer Catalysis
|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  P.Anastas,J.C. Warner, “Pursuing practical elegance in chemical synthesis Ryoji Noyori ’’Chemical Communications, 2005, (14), 1807 - 1811 Abstract  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.  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.  A.W. Herriott, D. Picker, “Phase transfer catalysis. An evaluation of catalysts”, J. Am. Chem. Soc. 97 (1975) 2345-2349.  M. Kitamura, Y. 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Ye1“Synthesis Of Nipagin Esters Using Acid functional Ionic Liquids As Catalysts”, Synthetic Communications1, 41:(2011)945–952||摘要:||
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.
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