臺灣博碩士論文加值系統

摘 要
本研究主要探討固-液相之溴化苯甲基與酚鈉鹽在相間轉移觸媒催化下，合成苯甲基苯基醚之取代反應。在反應系統中，除了兩相反應物因素外，各項探討的變因包括：攪拌效應、觸媒添加量效應、水量添加效應、有機溶劑種類效應、觸媒種類效應、溫度效應等，並進一步研究反應機構及求得反應動力學速率常數。
在聚乙二醇系統中，聚乙二醇在化學製程及工業上，已十分普遍的被應用。在固-液相系統中，利用聚乙二醇的結合基會和金屬離子形成鍵結的特性，可將固相反應物由固相質傳至油相。聚乙二醇利用此一特性便可催化酚鈉鹽與溴化苯甲基進行醚化反應。反應中錯合物PEG-Na+的形成及反應的操作變數皆有探討。實驗結果顯示反應速率隨著觸媒量的增加而增加。聚乙二醇的分子量效應方面，以PEG-1000與PEG-1500的反應活性較相近而 PEG-600較差。在有機溶劑效應方面，PEG系列的反應過程中，低極性的正庚烷反應2小時後苯甲基苯基醚的產率在85%以上。實驗結果顯示利用聚乙二醇在適當的條件下，能夠有效的進行固-液相之間的醚化反應。
在TBAB系統中，酚鈉鹽與溴化苯甲基在固-液相系統中反應生成苯甲基苯基醚，反應過程中相間轉移觸媒(TBAB)和酚鈉鹽形成的觸媒中間體也會被探討。實驗結果：觸媒中間體在有機相中的濃度愈高則反應速率愈快。當攪拌速率超過300 rpm 時，固-液相界面之間的質傳阻力可以忽略不計。不同觸媒反應活性大小為TBPB>TBAB>PEG1000>TBAHS。水量愈多則反應速率愈慢。實驗結果可以以虛擬一階方程式完整而清楚的解釋此一系統。以溴化四丁基銨為觸媒，溶劑氯苯得到的視反應活化能為53.66 kJ/mol而產物產率為90%以上。

Abstract
The objectives of the present study are to apply phase-transfer catalytic technique in synthesizing benzyl phenyl ether by conducting nucleophilic substitutions in the organic solution in solid-liquid system. The operating conditions for investigation include agitation speeds、reaction temperatures、catalyst amounts、types of solvents、molar ratio of reactants、type of phase-transfer catalysts、volume ratio of aqueous and solvent and so on. The reaction mechanism and apparent reaction rate constants were obtained from the experimental results.
In PEG system, polyethylene glycols are widely used as the phase-transfer catalyst and commonly applied in the chemical processes and industries. The characteristics of binding for an alkali metal ion with polyethylene glycol, enabling to transport the reactive anion from the solid into the organic phase, is applied in solid-liquid phase-transfer catalysis, and PEG is used as the phase-transfer catalyst to catalyze the etherification of sodium phenoxide with benzyl bromide in this system. The formation of the binding site by solid reactant with PEG in the organic phase to produce the intermediate complex PEG-Na+ and the effects of operating parameters on the overall reaction were investigated.
The experimental results show that the dependence of amounts of catalyst on the reaction rate for different molecular weight of PEG shows that the catalytic activites of PEG-1000 and -1500 are similar but higher than that of PEG-600. Effects of different organic solvents for PEG series are carried out, and above 85% yield of benzyl Phenyl ether is easily achieved within 2h even using heptane as the solvent. The kinetics of pseudo-first-order reaction can be applied to describe the overall reaction rate successfully. The results show that PEGs are effective catalysts for
the solid-liquid phase-transfer catalysis.
In TBAB system, the product selectivity and kinetics of sodium phenoxide with benzyl bromide to produce benzyl phenyl ether via solid-liquid phase-transfer catalysis were investigated. The behavior of phase-transfer catalytic intermediate in the solid-liquid system was explored. The concentraction of catalytic intermediate increased as increasing molar quantity catalyst used after induction period. When the agitation speed exceeds 300 rpm，the mass transfer resistance at the solid-liquid interface can be ignored. Different phase-transfer catalysts were employed to compare their catalytic efficiency： TBPB>TBAB>PEG1000>TBAHS. Moreover，the addition of water would inhibit the overall reaction rates. A kinetic model was also proposed to describe the phase-transfer catalytic alkylation. The experimental data were well described by the pseudo-first-order kinetics. The apparent activation energy was obtained 53.66 kJ/mol and the product yield wsa achieved as above 90% for using tetra-n-butyl-ammonium bromide as the catalyst.

目 錄
中文摘要----------------------------------------------------Ⅰ
英文摘要----------------------------------------------------Ⅲ
誌謝目錄----------------------------------------------------Ⅵ
圖目錄------------------------------------------------------Ⅷ
表目錄----------------------------------------------------ⅩⅢ
符號說明--------------------------------------------------ⅩⅣ
第一章 緒論-------------------------------------------------1
1-1.相間轉移觸媒反應簡介------------------------------1
1-2.聚乙二醇簡介--------------------------------------7
1-3.固-液相反應---------------------------------------9
1-4.醚化反應------------------------------------------12
1-5.研究目的與方法------------------------------------15
第二章 實驗藥品及設備--------------------------------------19
2-1.實驗藥品-------------------------------------------19
2-2.實驗裝置與儀器-------------------------------------22
2-3.校正曲線-------------------------------------------23
第三章 以聚乙二醇為觸媒合成苯甲基苯基醚之反應動力學----27
3-1.前言--------------------------------------------- 27
3-2.實驗步驟------------------------------------------28
3-3.理論模式------------------------------------------29
3-4.實驗結果與討論------------------------------------33
3-5.結論----------------------------------------------69
第四章 四級銨鹽為觸媒催化酚鈉鹽之醚化反應動力學---------70
4-1.前言----------------------------------------------70
4-2.實驗步驟------------------------------------------74
4-3.反應動力學模式------------------------------------75
4-4.實驗結果與討論------------------------------------79
4-5.結論----------------------------------------------115
第五章 在氰甲烷中之聚乙二醇催化酚鈉鹽醚化反應之動力學-117
5-1.前言----------------------------------------------117
5-2.實驗步驟------------------------------------------118
5-3.反應動力學模式------------------------------------119
5-4.實驗結果與討論------------------------------------124
5-5.結論----------------------------------------------152
第六章 總結------------------------------------------------153
參考文獻----------------------------------------------156
附 錄----------------------------------------------162
1.苯甲基苯基醚之HNMR圖譜-----------------------------162

參考文獻
1. Freedman,H.H.,Pure Appl. Chem.,58,857(1986)
2.Jarrouse,J.,”The influence of Quaternary Chloride on the Reaction ofLabike Hydrogen Compound and Chlorine-Substituted ChlorineDerivatives.” C.R. Heabd.Seances Acad. Sci., C232,1424(1951)
3.Starks,C. M.,”Phase Transfer Catalysis. I. Heterogeneous ReactionsInvolving Anion Transfer by Quaternary Ammonium and
Phosphonium Salts”,J. Am. Chem. Soc.93(1),195(1971)
4.Starks, C.M.and Owens,R.M.,”Phase Transfer Catalysis.Ⅱ. Kinetic Details of Cyanide Displacement on 1-Halooctanes”,J. Am.Chem.Soc.,95,3613(1973)
5.Wang D.H.and H.S.Weng,Chen.Eng.Sci.,43.2019(1988)
6.Herriott,A.W. and Picker,D.,”Phase Transfer Catalysis.An Evaluation of Catalysts”,J.Am.Chem.Soc.,97,2345(1975)
7.Landini,D.,Maia,A.and Rampoldi, A.,”Stability of Quaternary Onium Salts under Phase-transfer Conditions,in the Presence of Aqueous Alkaline Solution”,J.Org.Chem.,51,3187(1986)
8.Sanjeev D. Naik and L. K. Doraiswamy .,“Mathematical modeling of solid-liquid phase-transfer catalysis” ,Chemical Engineering Science,Vol. 52,No. 24, 4533(1997)
9.Dehmlow,E.V;Dehmlow,S.S.Phase transfer Catalysis.2nded;Verlag
Chemie:Weinheim(1983)
10.B.Czapkiewicz-Tutaj and J.Czapkiewica,Rocz.Chem.,49,1353(1975)
11.Brandstrom,A.,Principles of Phase-Transfer Catalysis by Quaternary Ammonium Salts,adv.Phys.Org.chem.,15,267(1977)
12.Dehmlow,E.V.;Dehmlow,S.S.,”Phase Transfer Catalysis
“,Weinheim;Deerfield Bemch,Florida;Basel Verlag Chemie(1983)
13.Starks,C.M.Loitta,C.L.andHalPern,M.,”Phase transfer catalysis:Fundamentals, Applications, and Industrial Perspectives;Chapman&Hall”, New York(1994)
14. Sasson,Y.and R.Neumann,edtied,Handbook of Phase Transfer
Catalysis, Blackie Academic & Professional,(1997)
15.Starks,C.M. and C.L.Loitta,Phase Transfer Catalyst:Principles and Techniques; Academic Press,New York(1978)
16.Santaniello, E.; Ferraboschi, P.,”Efficient and Selective Oxidation of Alcohols by Potassium Dichromate Solution “,Synthesis ,6461980)
17.Santaniello, E.;Manzocchi, A.;Sozzani. P.,”Polyethylene Glycols as Host Solvents:Applications to Organic Synthesis”,Tetrahedron Letts.,4581(1979)
18.Suzuki,N.; Shimazu, K.;Ito, T.;Izawa, Y.,”Photocyanation of Anisole in the Presence of Polyethylene
Glycol”,J.Chem.Soc.,Chem.Commun.,1253(1980)
19.Yanagida, S.;Noji, Y.;Okahara,M.,”Phase Transfer Catalysis of Poly(oxyethylene) Dimethyl Ethers(Glymes)”,Tetrahedron
Letts.,2893(1977)
20.Balasubramanian, D.;Sukumar ,P.;Chandani,B.,”Linear Unsubstituted Polyethylene Glycols as Phase Transfer Catalysis”,Tetrahedron Letts.,3543(1979)
21.Angeletti, E.;Tundo, P.;Venturello ,P.,”Gas-Liquid Phase-Transfer Synthesis of Phenyl Ethers and Sulphides with Carbonate as Base and Carbowax as Catalyst”,J. Am.Chem.Soc.,Perkin Trans . I.,1137(1982)
22.Hogan, J.C.;Gandour,R.D.,”The Remarkable Catalytic Power of Glymes in Estes Aminolysis Carried out in Nonpolar Media “,J.
Am.Chem.Soc.,102,2865(1980)
23.Zupancic, B.;Kokalj, M.,:Aromatic α,β-Unsaturated Nitriles via Polyethylene Glycol-Catalyzed Two-Phase Aldol-Type
Condensation“,Synthesis,913(1981)
24.Kimura, Y.; Regan,S. L.,”Poly(ethylene glycols) are Extraordinary Catalysts in Liquid-Liquid Two Phase Dehydrohalogenation”,J. Org. Chem.,47,2493(1982).
25.張光榮,”以聚乙二醇為相間轉移觸媒反應合成烯丙基苯基醚之研
究”,七十九年清華大學化工研究所博士論文
26.吳俊民,”應用固-液及液-液相相間轉移觸媒合成丙烯基苯基醚之醚
化反應動力學研究”,八十八年中興大學化工研究所碩士論文
27.Neumann,R.;Sasson,Y.J.Org.Chem.,49,3448(1984)
28.孫成方,”聚乙二醇系相轉移觸媒固定化及其應用之研究”, 七十七
年成功大學化工研究所碩士論文
29.Loitta,C.L.and H.P.Harris,J.Am.Chem.Soc.,96,2250(1974)
30.Montanari,F.,Landini and F.Rolla,Top.Curr.Chem.,101,147(1982)
31.Mason,D.,S.Magdassi,and Y.Sasson,J.Org.Chem.,56,7229(1991)
32.Delmas , M.;Bigot,Y.L.;Gaset,A.Tetrahedron Letters, 21,4831(1980)
33.Gerbi,D.J.;Dimotsis,G.;Morgan,J.L.;Williams,R.F.J.Poly.Sci.,
23,551(1985)
34.Zahalka,H.A.;Sasson,Y.J.Chem.Soc.Chem.Commun,1652(1984)
35.吳秉誼,”固-液及固-液-液之相間轉移催化反應動力學研究:I.鹵酯
類之醚化反應II.直鏈二酸之酯化反應”,八十八年中興大學化工
研究所碩士論文
36.Fedorynski,M.,k.Wojciechowski,Z. Matacz and M.Makosa,”Sodium and Potassium Carbonates:Efficient Strong Bases in Solid-Liquid Two Phase System”,J.Org.Chem.,43(24),4682(1978)
37. Freedman, H. H. and Dubois,R.A.,”An improved Williamson Ether Synthesis using Phase Transfer Catalysis”,Tetrahedron Letters,38,3251(1975)
38.Shan, Y.,Kang,R.,and Li,W.,”Investigation of Phase-transfer Reactions Catalyzed By Poly(ethylene Glycol) Bound of Macroporous Polystyrene Supports”,Ind.Eng.Chem. Res.,28,1289(1989)
39.Cincin Siswanto, Turgut Battal,Oron E.Schuss,and Rathman,J.F., ”Synthesis of Alkylphenyl ethers in Aqueous Surfactant Solutions by Micellar Phase-Transfer Catalysis.1.Single phase systems”,Langmuir,13,6047(1997)
40.Turgut Battal,Cincin SiswantoOron,and Rathman,J.F.,”Synthesis of Alkylphenyl ethers in Aqueous Surfactant Solutions by Micellar Phase-Transfer Catalysis. 2. Two-phase system”,Langmuir,13,6053(1997)
41.Andreas Schulze ; “Combating pests with benzyl phenyl ethers”United States patent,4220663(1980)
42. Charles M. Starks ;Allan J. Lundeen;“Preparation of o-benzylphenol”United States patent,4117243(1978)
43. Minoru Hosoda ;“Aqueous epoxy resin paint composition” United States patent,4104223(1978)
44. Minoru Hosoda ;“Aqueous epoxy resin paint composition” United States patent,4117243(1978)
45. Pederson, C. J.,”Cyclic Polyethers and Their Complexes with Metal Salts”,J. Am.Chem.Soc.,89,7017(1967)
46.Liu, K. J.,”Nuclear Magnetic Resonance Studies of Polymer Solution.V. Cooperative Effects in the Ion-Dipole Interaction between Iodide and Poly(Ethylene Oxide)”,Macromolecules, 1,308(1968)
47.Yanagida, S.;Takahashi, K.;Okahara, M.,”Metal-Ion Complexation of Noncyclic Poly(oxyethylene) Derivatives. I. Solvent Extraction of Alkali and Alkaline Earth Metal Thiocyanates and Iodides”,Bull.Chem.Soc.,Jpn.,50(6),1386(1977)
48.Yanagida, S.;Takahashi,K.;Okahara, M.,”Metal-Ion Complexation of Noncyclic Poly(oxyethylene) Derivatives. II. NMR Studies of the Complexation with Alkali and Alkaline Earth Metal Cations”, Bull.Chem.Soc.,Jpn.,51,1294(1978)
49.Yanagida, S.;Takahashi, K.;Okahara M.,”Metal-Ion Complexation of Noncyclic Poly(oxyethylene) Derivatives.III. Complexation in Aprotic Solvent and Isolation of Their Solid Complexes”,Bull.Chem.Soc.,Jpn.,51,3111(1978)
50.Poonia, N. S.;Sarad, S. K.;Tayakumar, A.;Kumar,G.C.,”Coordination Chemistry of Alkali and Alkaline Earth Cation —I. Lower Glycols as Ligands”,Inorg.Nucl.Chem.,41,1759(1979)
51.Ono, K.; Konamir, H.;Murakaml, K.,”Conductometric Studies of Ion Binding to Poly(oxyethylene) in Methanol”,J.Phys.Chem.,83, 2665(1979)
52. J.G.Heffernan, D. C. Sherrington , J .C. S. Perkin Ⅱ, 514(1981)
53. W. M. MacKenzie , D. C. Sherrington , Polymer , 21, 791(1980)
54.Alkabori, S;Miyamoto, S.;Tanabe, H.,”Allylation of Phenoxide by Crown ethers and Their Polymers”,J.Polym.Sci.,Polym.Ed.,17, 3933(1979)
55.Zahalka H.A.and Sasson Y.,J.Chem.Soc.,Chem.Commun.,1347(1983)
56.Yang,H.M.and Wu,H.E.,”Kinetic Study for Synthesizing Dibenzyl Phalate via Solid-Liquid Phase-transfer Catalysis”,Ind.Eng.Chem.Res.,37,4536(1998)
57.Wang.M.L.and H.M.Yang,”Kinetic study of Synthesizing 2,4,6-
Tribromophenyl Allyl Ether by phase transfer Catalytic Reaction”,Ind. Eng. Chem. Res,29,522(1990)
58.Gokel, G. W.; Goli, D. M., Schultz, R. A.,”Binding Profiles for oligoethylene Glycols and oligoethylene Glycol Monomethyl Ethers and an Assessment of Their Abilities to Catalyze Phase-Transfer Reaction”, J. Org. Chem.,48,2837,(1983)
59.Neumann, R.; Sasson, Y.,”Mechanism of Base-Catalyzed Reaction in Phase-Transfer Systems with Poly(ethylene glycols) as Catalysts. The Isomerization of Allylanisole”, J. Org.Chem.,49,3448(1984)