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研究生:陳宏亦
研究生(外文):Chen Hung I
論文名稱:阻礙性苯甲化合物及取代醯氯溶離反應的研究
論文名稱(外文):Studies on the Solvolysis of Hindered Benzylic Substrates and Substituted Acyl Chlorides
指導教授:劉廣定劉廣定引用關係
指導教授(外文):Liu Kwang Ting
學位類別:博士
校院名稱:國立臺灣大學
系所名稱:化學研究所
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:1999
畢業學年度:87
語文別:中文
論文頁數:282
中文關鍵詞:溶離反應溶劑離子化指標取代基常數理論計算過渡狀態
外文關鍵詞:solvolysissolvent ionizing powersubstituent constanttheoretical calculationtransition state
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在1-芳基-2,2-二甲基丙基反應物(I-T-X,I-B-X,I-C-X)中,鄰位甲基對反應中心的影響可分為兩方面:一為供電子效應,另一為增加立體阻礙。當帶有兩個鄰位甲基時,此立體阻礙會影響芳環與反應中心的共平面性,及改變溶劑對離去基溶合效應(親電性拉)。對-甲苯磺酸酯的過渡狀態最早,芳環偏離共平面程度最大,相對下溶劑親電性拉影響最大;含三氟乙醇的溶劑溶合能力較好,所受到鄰位效應較小,而甲醇、乙醇、丙酮水溶液相對下所受的影響較大。溴化物的過渡狀態較晚,效應次之。氯化物過渡狀態最晚,效應最小。
將強拉電子基三氟甲基置於反應中心的a位置時,可使反應中心的缺電子性加大,芳環的供電子效應在過渡狀態的影響特別明顯。由1-溴-1-芳基-1-苯基-2,2,2-三氟乙烷的溶離反應,發現芳環上有強供電子基的化合物(如II-B-1、II-B-2、II-B-3)的溶離活性logk與溶劑離子化能力YBnBr有良好的線性關係。而化合物II-B-4∼II-B-10中,卻只有II-B-9對另種溶劑離子化能力YxBnBr有良好線性關係。其他化合物線性雖然變佳,但仍未達到良好(R≧0.990)。若改對化合物II-Q-19的溶離活性logk做迴歸分析,則線性改善,而化合物II-B-5、II-B-6、II-B-10的線性可達良好的標準。可推測化合物II-B-X的過渡狀態的電荷分散程度很大。由於1-溴-1-(4''-苯氧苯基)-1-苯基-2,2,2-三氟乙烷(II-B-4)的溶離反應及理論計算電荷分佈,推測過渡狀態有非正則共振貢獻的可能性。
對芳甲醯氯的溶離反應,可使用取代基常數s+及溶劑離子化能力YBnCl進行分析反應機構。芳甲醯氯的溶離反應機構,會隨著取代基及溶劑的離子化能力而變。化合物III-C-2乃極限SN1反應。化合物III-C-3、III-C-4、III-C-5之溶離反應有溶劑親核性參與。隨著取代基供電子能力減弱,溶劑參與反應愈強烈。而帶強拉電子基的III-C-10則可能進行加成脫去反應。但在溶劑離子化能力較強的50E、50A、60M及100T中,化合物III-C-4、III-C-5、III-C-8及III-C-9的溶離活性logk對取代基常數s+可成r值約為-2∼-3的線性關係,顯示反應機構應是接近極限SN1反應。理論計算結果顯示化合物III-C-4、III-C-5及III-C-8在相同的溶劑的溶離活性對dDE,約可成斜率為負值的一直線,推測應是進行解離反應機構。
N,N-二苯胺甲醯氯的溶離活性logk可適用雙變數Grunwald-Winstein關係式mYxBnCl+lNOTs,顯示電荷分佈到兩個苯環,理論計算電荷分佈的結果亦相同,故推測過渡狀態有非正則共振的可能性。
In the solvolysis of the 1-aryl-2,2-dimethylpropyl substrates (I-T-X,I-B-X,I-C-X), the effect of ortho-methyl group on the reaction center could be reflected in two aspects. One was electron-donating effect and the other was steric hindrance. Introduction of two ortho-methyl groups in the phenyl ring, the steric hindrance will cause the deviation from the coplanarity of the aryl ring and the reaction center, and will change the extent of solvation between solvents and leaving groups (electrophilic pull). From the rate data, the deviation from the coplanarity was the largest for tosylates, which had the earliest transition state of solvolysis among three substrates in this study. The ortho effect in solvents containing trifluoroethanol was smaller because of the better solvation effect, whereas in aqueous methanol, ethanol, and acetone it was larger. On the other hand, the ortho effect was smaller for bromides and was the smallest for chlorides, which was consistent to the later transition state for bromides and the latest transition state for chlorides.
The reaction center would be more electron-deficient by introducing the strongly electron-withdrawing trifluoromethyl group at the a position and thus the electron-donating effect of the aryl ring in the transition state of solvolysis would be more important. In the solvolysis of 1-bromo-1-aryl-1-phenyl-2,2,2-trifluoroethane with strong electron-donating substituents in the aryl ring (e.g. II-B-1, II-B-2, and II-B-3), the log ks of the substrates gave excellent linear correlation with YBnBr. Although II-B-4∼II-B-10 showed better linear correlation with YxBnBr, only II-B-9 gave excellent R value. However, the other substrates, such as II-B-5, II-B-6, and II-B-10, excellent linear correlation with II-Q-19 was found. These results suggested the charge distributions in the solvolytic transition state for II-B-X were highly extended. The theoretical calculation of charge distributions in 1-(4''-phenoxyphenyl)-1-phenyl-2,2,2-trifluoroethyl cation indicated a possibility of the existence of non-canonical resonance in the transition state.
The substituent constant s+ and the solvent ionizing power YBnCl could also be used to study the mechanism of the solvolysis of aroyl chlorides. The mechanism of the solvolysis of aroyl chlorides would be substituent- and solvent-dependent. We found that III-C-2 solvolysed with limiting SN1 mechanism. The solvolysis for III-C-3, III-C-4, and III-C-5 involved nucleophilic solvent participation. The extent of solvent participation was increasing while the electron-donating ability of the substituent reduced. The solvolysis of III-C-10, the substrate containing strong deactivating substituent, was likely to proceed with with the addition-elimination mechanism. In highly ionizing-power solvents, e.g. 50E, 50A, 60M, and 100T, linear correlations between log ks of III-C-4, III-C-5, III-C-8, and III-C-9 against s+ constants were observed with r values about -2∼-3, which suggested the limiting SN1 mechanism. Moreover, the log ks for III-C-4, III-C-5, and III-C-8 in those solvents showed linear relationship against dDE. A dissociation mechanism could also be deduced.
The log ks of N,N-diphenylcarbamoyl chloride were found to give linear correlation with the dual-parameter Grunwald-Winstein equation, mYxBnCl+lNOTs. Obviously, the partial positive charge in the solvolytic transition state delocalized throughout both phenyl rings. The calculation of theoretical charge distributions indicated the same result. Therefore, the possibility of the non-canonical resonance at the transition state could be proposed.
摘要(中文)-----------------------------------------------------------------I
摘要(英文)-----------------------------------------------------------------III
謝誌-------------------------------------------------------------------------V
第一章 有鄰位甲基二級苯甲反應物溶離反應研究-----------------1
零、本章編號與結構對照------------------------------------------------2
一、緒論-------------------------------------------------------------------4
二、結果-------------------------------------------------------------------15
三、討論-------------------------------------------------------------------32
四、結論-------------------------------------------------------------------68
五、實驗部份--------------------------------------------------------------69
六、參考資料--------------------------------------------------------------78
第二章 高阻礙性三級苯甲溴化物溶離反應的研究-----------------82
零、本章編號與結構對照------------------------------------------------83
一、緒論-------------------------------------------------------------------86
二、結果-------------------------------------------------------------------96
三、討論-------------------------------------------------------------------115
四、結論-------------------------------------------------------------------156
五、實驗部份--------------------------------------------------------------157
六、參考資料--------------------------------------------------------------163
第三章 芳甲醯氯反應物溶離反應的研究-----------------------------166
零、本章編號與結構對照------------------------------------------------167
一、緒論-------------------------------------------------------------------168
二、結果-------------------------------------------------------------------171
三、討論-------------------------------------------------------------------188
四、結論-------------------------------------------------------------------241
五、實驗部份--------------------------------------------------------------242
六、參考資料--------------------------------------------------------------243
第四章 N,N-二苯胺甲醯氯溶離反應的研究-----------------------246
零、本章編號與結構對照------------------------------------------------247
一、緒論-------------------------------------------------------------------249
二、結果-------------------------------------------------------------------252
三、討論-------------------------------------------------------------------261
四、結論-------------------------------------------------------------------279
五、實驗部份--------------------------------------------------------------280
六、參考資料--------------------------------------------------------------281
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第二章
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27.林岩錫,博士論文, 國立臺灣大學化學研究所, 1997。
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33.陳宏亦,碩士論文, 國立臺灣大學化學研究所, 1990。
34.Vogel,A.I."Vogel''s Textbook of Practical Organic Chemistry",5rd ed.;Wiley: New York,1989.
35.Yukawa,Y.;Tsuno,Y.;Sawada,M.Bull.Chem.Soc.Jpn.1972,45,1198.
36.段葉芳, 博士論文, 國立臺灣大學化學研究所, 1998。。
37.Hehre,W.J.;Radom,L.;Schleyer,P.v.R.;Pople,J.A.,
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38.Peters,E.N.J.Am.Chem.Soc.1976,98,5627.
39.Peters,E.N.J.Org.Chem.1977,42,1419.
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41.Hoffmann,H.M.R.J.Chem.Soc.1965,6753.
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44.Liu,K.-T.;Lin,Y.-S.;Tsao,M.-L.J.Phys.Org.Chem.1998,11,223.
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47.Fujio,M.;Hiroshi,M.;Kim,H.-J.;Tsuno,Y.Bull.Chem.Soc.Jpn.1997, 70,3081.
48.Nakata,K.;Fujio,M.;Saeki,Y.;Mishima,M.;Tsuno,T.Nishimoto,K. J.Phys.Org.Chem.1996,9,561.
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50.例如Glendening,E.D.;Badenhoop,J.K.;Weinhold,F.J.Comput.Chem. 1998,19,593,610,628.
51.Brown,H.C.;Ravindranathan,M.;Peters,E.N.;Rao,C.G.;Rho,M.M.
J.Am.Chem.Soc.1977,99,5373
52.Murata,M.;Sakaguchi,S.;Fujiyama,R.;Mishima,M.;Fujio,M.;Tsuno,Y.Bull.Chem.Soc.Jpn.1990,63,1138
53.Liu,K.-T.;Chang,S.-M.;Chen,H.-I.;Chiu,P.-F.;Wu,T.-R. J.Org.Chem.1991,56,1315.
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55.Evans,D.P.;Gordon,J.J.;Watson,H.B.J.Chem.Soc.1937,1430.
56.Schuda,P.F.;Price,W.A.J.Org.Chem.1987,52,1972.
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(b)Norris,J.F.;Young,H.H.,Jr.J.Am.Chem.Soc.1935,57,1420.
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6.Hudson,R.F.;Archer,B.L.J.Chem.Soc.1950,3259.
7.Hudson,R.F.;Brown,D.A.J.Chem.Soc.1953,883.
8.Hudson,R.F.;Brown,D.A.J.Chem.Soc.1953,3352.
9.Gold,V.;Hilton,J.;Jefferson,E.G.J.Chem.Soc.1954,2756.
10.Bender,M.L.J.Am.Chem.Soc.1951,73,1626.
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16.Bentley,T.W.;Koo,I.S.;Norman,S.J.J.Org.Chem.1991,56,1604.
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22.Bentley,T.W.;Carter,G.E.;Harris,H.C.J.Chem.Soc.Perkin Trans.II,1985,983.
23.Hehre,W.J.;Radom,L.;Schleyer,P.v.R.;Pople,J.A.,
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28.Grunwald,E.;Winstein,S.J.Am.Chem.Soc.1948,70,846.
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54.林岩錫,博士論文, 國立臺灣大學化學研究所, 1997。
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