臺灣博碩士論文加值系統

本研究探討溶劑效應(包含水分的影響)與陰離子結構效應對一典型液－液相轉移催化反應BzCl + Bu4NY→BzY + Bu4NCl(Y = OH, Br, I, AcO, HSO4, ClO4)之影響。
　　溶劑效應方面 : 選擇脂肪族非質子(aprotic aliphatic)混合溶劑: propionitrile + heptane; 及芳香族非質子(aprotic aromatic)混合溶劑: benzene + nitrobenzene，以莫耳比BzCl : Bu4NBr : solvent = 1 : 0.03 : 30，反應溫度40 0C，以體積平均溶解度參數 (volume average solubility parameter)來探討溶劑效應。由實驗之結果發現，lnkf、lnkb與 呈一正比之線性關係，且溶劑效應對反應之相對速率影響不大，其大小差異僅10倍﹔而由不同的水量對芳香族非質子溶劑 : 苯、脂肪族非質子溶劑 : 丙烯月青，以莫耳比BzCl : Bu4NBr : solvent = 1 : 0.03 : 30，反應溫度40 0C，所得結果發現水分對芳香族非質子溶劑、脂肪族非質子溶劑之影響相差不大。
　　陰離子結構方面 : 以不同陰離子(Y = OH, Br, I, AcO, HSO4, ClO4)結構之四丁基銨鹽，當Y≠OH時莫耳比BzCl : Bu4NY : CHCl3(solvent) = 1 : 0.03 : 30，當Y = OH時莫耳比BzY : Bu4NCl : CHCl3(solvent) = 1 : 0.03 : 30，反應溫度40C，探討陰離子結構對反應速率之影響。由實驗結果發現，由於離子半徑大小之差異及溶劑對陰離子之媒合作用影響，使得反應速率大小相差可達1000倍，對於平衡常數的影響甚至可達1000000倍，即對陰離子交換反應而言，陰離子結構效應之影響遠大於溶劑效應。

The reactivities (kf,kb) depend on the structures of the nucleophiles (Bu4NY), the solvent used. For the structural effects of Bu4NY, Y = Cl, Br, I, AcO, OH, ClO4, HSO4 were studied. And for the solvent effect, the relations between the reactivity and solvent properties (solubility parameter) has found for the various types of solvents (aprotic aliphatics, aprotic aromatics). And the effect of water on kf and kb were studies as well.

目 錄
摘要 …………………………………………………………………I
目錄 …………………………………………………………………II
圖表目錄 ……………………………………………………………III
符號說明 ……………………………………………………………IV
第一章 緒論
1-1-1相轉移催化之起源與定義…………………………………….1
1-1-2相轉移催化之機制…………..…………………………….1
1-2相轉移催化劑之種類………………………………..……………2
1-3一般之二分子親核取代反應…………………………..…………4
1-3-1親核取代反應之反應機構與類型………………………….4
1-3-2 一般SN2反應之影響因素…………………………………..6
1-4 Bu4N+X-之合成……………………………………….……………8
1-5 本文之動機與主旨………………………..………………………10
第二章 理論
2-1親核取代之反應機構及積分速率方程式………………………..14
2-1-1典型液-液相轉移系統油相反應機構………………………..14
2-1-2 SN2反應之積分速率方程式………………………………….14
2-2過渡狀態理論……………………………………………………...16
2-3溶劑效應…………………………………………………………...19
2-3-1溶質-溶劑間之作用能(interaction energy)與溶劑性質之關係………………………………..…………………20
2-3-2 ion-dipole interaction force…………………………….21
2-3-3dipole-dipole force……………………………………..22
2-3-4 kid與溶解度參數之關係……………………………...………23
2-3-5 k / kid與溶解度參數之關係…………………………………..23
2-4陰離子結構效應……………………………………………….…..25
第三章 實驗部分
3-1藥品………………………………………………………………...27
3-2實驗裝置與分析儀器……………………………………………...28
3-2-1實驗裝置………………………………………………………29
3-2-2 離子層析儀………………………………………..…………30
3-3實驗操作…………………………………………………………...30
3-4 樣品分析 …………………………………………………………30
3-5實驗步驟…………………………………………………………...32
3-5-1 Bu4NBr之製備與精製……………………………………….32
3-5-2溶劑效應之影響………………………………………………33
3-5-3水分之影響……………………………………………………34
3-5-4陰離子結構效應………………………………………………34
第四章 結果與討論
4-1 化學計量之關係…………………………………………………..40
4-2溶劑(芳香族非質子溶劑、脂肪族非質溶劑)效應………………40
4-2-1四丁基銨氯濃度與反應時間之關係…….…40
4-2-2體積平均溶解度參數 對平衡常數K、正向速率常數kf、逆向速率常數kb之影響……………………………………47
4-3水分之影響………………………………………………………...52
4-3-1四丁基銨氯濃度與反應時間之關係…………………………52
4-3-2水分對平衡常數K, 正向速率常數kf, 逆向速率常數kb之影響……………………………………….…………………52
4-4陰離子結構效應…………………………………………………...61
4-4-1四丁基銨氯濃度與反應時間之關係…………………………61
4-4-2陰離子結構對平衡常數K, 正向速率常數kf, 逆向速率常數kb之影響…………………………………………………61
第五章 結論 ………………………………………………………...66

參考文獻[1]J. Jarrouse and C. R. Hebd. Seances Acad. Sci. Ser., C232, 1424 (1951).[2]C. M. Starks, “Phase-transfer Catalysis. I. Heterogeneous Reaction Involving Anion Transfer by Quaternary Ammonium and Phosphonium Salts”, J.Am. Chem. Soc., 93(1), 195(1971).[3]C. M. Starks, “Selecting a Phase Transfer Catalysis”, Chemtech, 110 (1980). [4]P. Hodge, and D. C. Sherrington, “Polymer-supported Reaction in Organic Synthesis”, John Wiley and Sons(1980).[5]徐金榮, “葡萄糖之有機金屬相轉移催化氫化研究”, 碩士論文, 國立中央大學化工系 (1994).[6]T. W. G. Solomons, “Organic Chemistry”, 4rd, Wie Wiley, Ch5., pp193-245 (1988).[7]張其晃,”有機氯化物與溴芐基三丁基銨之親核取代反應研究”, 碩士論文, 中央大學化 工系(1991).[8]W. Y. Su (Texaco Chemical Co.), ”Continuous Process for Preparing Quaternary Ammonium Salts”, U. S. US 5,041,664 (Cl.564-269; C07C209/12) (CA.115:207507j).[9]蘇國銘, “叔胺與碘丁烷之親核取代反應之溶劑效應與結構效應”, 碩士論文, 國立中 央大學化工系(1996).[10]沈雨生,“離子對的聚集作用及幾種對稱溴化烷基銨鹽的合成(IV)”, 吉林大學自然科 學學報, l.3, P113-116(1987).[11]Sumitomo Chemical Co., Ltd.; “Tetra-n-butylammonium Bromide”, Jpn. Kokai Tokkyo Koho JP 59 27,854 [84,27,854] (Cl. C07C87/30) (C.A., Vol.101, 54549h).[12]Hesse , Carsten ; Jansen , Ursula ; Rechner , Johann ; ”Method for The Preparation of Tetrabutylammonium Phenolate-Diphenol Adduct Phenolic Resin Catalyst Precursor” , Ger. Offen. DE 19,730,022 (Cl. C07C211/62) (C.A., Vol.130, 95972h).[13]Yamashita , Yukya ; ”Preparation of Organic Quaternary Ammonium Fluorides” , Jpn. Kokai Tokkyo Koho JP 06,219,998 [94,219,998] (Cl. C07C211/63) (C.A., Vol.122, 80712j).[14]Dermeik , Salman ; Sasson , Yoel ; ”Effect of Water on The Extraction and Reactions of Fluoride Anion by Quaternary Ammonium Phase-Transfer Catalysts” , J. Org. Chem., No.50, P879-882(1985).[15]Danilova , O. I. ; Esikova , I. A. ; Yufit , S. S. ; ”Exchange Reactions in Two-Phase Catalytic Systems. II. Ionic Halide Exchange Between an Onium Salt and Solid Alkali Metal Salts”, Izv. Akad. Nauk USSR, Ser. Khim., Vol.2, P314-316(1988).[16]Brandstrom, A.; ”Preparative Ion Pair Extraction”, Apotekarsocieteten╱ Hassle, Lakemedel, Sweden, P139-148(1974).[17]Ochoa Gomez, Jose Ramon ; Tarancon Estrada, Maria; “Electrolytic Preparation of Quaternary Ammonium Hydroxides and Alkoxides”, Span. ES 2,019,550 (Cl. C25B3/00) (C.A., Vol.116, 58931j).[18]Ochoa Gomez, J. R. ; Tarancon Estrada , M. ; ”Electrosynthesis of Quaternary Ammonium Hydroxides” , J. Appl. Electrochem., l.21, 4, P365-367 (1991).[19]T. T. Wang and T. C. Huang, “Kinetics of Quaternization s of Tertiray Amines with Benzyl Chloride”, Chem. Eng. J., 53, 107-113(1992).[20]S. S. Yufit and I. A. Esikova, “New Ideals on Phase Transfer Catalysis : SN2 Reaction with a Solid Ionophoric Salt”, J. Phys. Org. Chem., 4, 336-340 (1991).[21]T. T. Wang, C. H. Chang, “Kinetics of the Nucleophilic Substitution of Benzyltributylammonium Bromide with Allyl, Butyl, and Benzyl Chloride and with Benzyl Acetate and Benzyl Ether”, International J. of Chem. Kinetics., 28, 615-626(1996).[22]T. T. Wang, G. M. Su, “Solvent Effect and Structural Effect of Tertiary Amines on the Reactivity of the Quaternization of These Amines with Butyl Iodide”, J. CIChE., 33, 2, 1-10(2002).[23]T. T. Wang and Q. L. Iou, “The Solvent Effect and the Structural Effect of Halides on the Quaternization Et3N + RX →Et3RNX” ,J. Chem. Eng., 3909, 1- 10(2001). [24]鹵化四丁基銨之合成動力學、溶解、萃取及精製研究”, 高志宏, 碩士論文,國立中央 大學化工系(2000).[25]A.J. Parker, “Protic-Dipolar Aprotic Solvent Effects on the Rates of Bimolecular Reactions”, Chem. Reviews. 69, 1-32(1969).[26]P. Haberfield, “Trapping the Single Electron Transfer Intermediate in an SN2 Reaction”, J. Am. Chem. Soc., 117, 3314-3315(1995). [27]C. M. Starks and C. Liotta, “Phase Transfer Catalysis Principles and Techniques”, Academic Press, N.Y.(1978).[28]R.C. Hahn, “Conversion of an Alkyl Chloride to Bromide (or Vice Versa) by Homogeneous Nucleophile Exchange” , J. Chem. Educ., 74, 836-838(1997).[29]O. Levenspiel, “Chemical Reaction Engineering”, 2nd , John Wiley &Sons. Inc., New York Ch5 pp171-209(1972).[30]C. H. Bamford; C.F. Tipper, ”The Theory of Kinetics : Comprehensive Chemical Kinetics”, vol.2, Amsterdam, Elserier Pub. Co., New York, Ch4 (1969-1986).[31]J. M. Moore and R.G. Pearson, ”Kinetics and Mechanism”, 3rd, Wiely, New York, Ch7(1981).[32]N. S. Isaacs, “Physical Organic Chemistry”, 2nd, Wiely, New York, Ch5, pp171-209(1992).[33]M. H. Abraham and P. L. Grellier, “Substitution at Saturated Carbon. Part. ΧⅠⅩ. The Effect of Alcohols And Water on The Free Energy of Solutes and on The Free Energy of Transition State in S and S Reaction “, J. Chem. Soc. Perkin Ⅱ, 1856-63(1975).[34]J. O’M Bockrics and A.K.N. Reddy, “Modern Electrochemistry” Plenum Press, New York(1977).[35]J. M. Prausnitz; R. N. Lichtenthaler; Azevodo Edmundo Gomes de, “Molecular Thermodynamics of Fluid-Phase Equilibria”, 2nd, Prentic Hall, Englewood Cliffs, New Jersey, Ch4., pp48-90(1986). [36]C. Reichardt, “Solvents and Solvents Effect in Organic Chemistry”, Verlagsgesell schaft mbH, Ch2, Ch3, Ch5, pp4-70, pp121-281(1988).[37]J. M. Moore and R. G. Pearson, “Kinetics and Mechanism”, 3rd, Wiely, New York, Ch7(1981). [38]J. Mcmurry, “Organic Chemistry”, Cole Publishing Company, Montery, California,(1988).[39]L. Pauling, “The Nature of The Chemical Bond”, Cornell university press. Ithaca, New York(1969).