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| 研究生： |
侯惠芳 Hou Hui-Fang |
|---|---|
| 論文名稱： |
掩飾鄰苯醌與相關2,4-環己二烯酮的Diels-Alder反應之研究 The Diels-Alder Reactions of Masked o-Benzoquinones and Related 2,4-Cyclohexadienones |
| 指導教授： |
廖俊臣
Liao Chun-Chen |
| 口試委員: | |
| 學位類別： |
博士 Doctor |
| 系所名稱： |
理學院 - 化學系 Department of Chemistry |
| 論文出版年： | 2004 |
| 畢業學年度： | 92 |
| 語文別： | 中文 |
| 論文頁數： | 253 |
| 中文關鍵詞： | 掩飾鄰苯醌 、反應的活化能 、指數前因子 、活化焓 、活化熵 、活化自由能 |
| 相關次數： | 點閱：3 下載：0 |
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中文摘要
本論文研究掩飾鄰苯醌與相關2,4-環己二烯酮的Diels-Alder反應。主要探討掩飾鄰苯醌24a的Diels-Alder反應之位向、立體選擇性、不對稱2,4-環己二烯酮24b-e的Diels-Alder反應之位向、立體及面向選擇性及2,4-環己二烯酮43的Diels-Alder反應之動力學。
5-甲氧基的掩飾鄰苯醌(24a)及不對稱2,4-環己二烯酮(24b-e)與甲基乙烯基酮、苯乙烯及苄基乙烯基醚的Diels-Alder反應，具有很好的位置及立體選擇性，而面向選擇性方面，親雙烯劑加成的方向與六號位置上的甲氧基同向(syn)。根據HOMO-LUMO的理論計算，可以幫助了解不對稱2,4-環己二烯酮的Diels-Alder反應之位置選擇性。
6,6-二甲氧基-、6-甲氧基-6-甲基及6,6-二甲基-2,4-環己二烯酮(43)的Diels-Alder反應的動力學實驗首先是在甲苯中進行。在6-甲氧基-6-甲基-2,4-環己二烯酮(43b)的反應中，親雙烯劑加成的方向與六號位置上的甲氧基同向(syn)。從實驗數據了解2,4-環己二烯酮的Diels-Alder反應速率與雙烯劑及親雙烯劑濃度的ㄧ次方成正比，總反應是一個二級的反應級數。當與反應性較好的甲基乙烯基酮及丙烯酸酯時，在溫度為63 ℃ 時，6,6-二甲氧基-2,4-環己二烯酮(43a)的反應速率比6-甲氧基-6-甲基-及6,6-二甲基-2,4-環己二烯酮(43b-c)快約7至9倍；當與反應性較差的二甲氧基呋喃時，越能比較出三者的速率差。從溶劑效應的結果了解，2,4-環己二烯酮的Diels-Alder反應的速率與溶劑的性質關係不大，推測可能是經由協同式的反應機制。
由反應的活化能(ΔE‡)、指數前因子ln A、活化焓(ΔH‡)、活化熵(ΔS‡)及活化自由能(ΔG‡)等活化參數可知，這類的Diels-Alder反應是一個吸熱且為非自發性的反應。根據理論計算結果了解，甲氧基的電子效應對面向選擇性影響很大(由於親雙烯劑從甲氧基加成的過渡態能量遠比從甲基面向加成低)，而且過渡狀態的結構是以非同步進行反應。
The thesis is concerned with the regio-, stereo- and facial diastereoselective Diels-Alder reactions of dissymmetric 2,4-cyclohexadienones 24b-e and deals with the kinetic studies of Diels-Alder reactions of 2,4-cyclohexadienones 24a-c.
We have observed that 5-methoxy masked o-benzoquinone (24a) and simple dissymmetric 2,4-cyclohexadienones (24b-e) undergo Diels-Alder reactions with methyl vinyl ketone, styrene and benzyl vinyl ether in highly chemo-, regio-, and stereoselective manner and the dissymmetric 2,4-cyclohexadienones (24b-e) reacted with dienophiles form syn adducts (dienophile approach is syn to allylic methoxy group) exclusively. HOMO-LUMO theoretical calculations further helped us to understand the regioselectivity of these reactions.
The kinetic studies of 6,6-dimethoxy, 6-methoxy-6-methyl and 6,6-dimethyl-2,4-cyclohexadienones (45) were performed in toluene. In the reactions where diene is 45b the dienophile approaches syn to 6-methoxy. From the experimental data, the Diels-Alder reaction is first order in diene and first order in dienophile, and thus the overall cycloaddition is second order. The rate of Diels-Alder reaction of 6,6-dimethoxyl-2,4-cyclohexadienone (45a) is faster than 6-methoxy-6-methyl- and 6,6-dimethyl-2,4-cyclo-
hexadienones (45b-c) with methyl vinyl ketone and ethyl acrylate (about 7-9 times at 63 ℃) as dienophiles. When the less reactive dienophile 2-methoxyfuran was employed, the relative rates of 2,4-cyclohexadienones differed by a large magnitude. From the solvent effect studies, the Diels-Alder reaction is found to be independent of solvent so it may proceed through concerted mechanism. From the kinetic parameters viz. activation energy (Ea) and pre-exponential factor (ln A), enthalpy (ΔH‡), entropy (ΔS‡) of activation and Gibbs free energy (□G‡), we know that these Diels-Alder reactions are exothermic and non-spontaneous reactions. Theoretical calculations have supported the experimentally observed facial selectivity i.e., syn-approach of the dienophile to methoxy group in the diene (whose activation energy is less compared to the dienophile approaching from other face), which is apparently due to the electronic effect of the methoxy group. The transition state calculations showed that these reactions go through asynchronous concerted pathway.
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