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研究生： 莊敬
Gary Jing Chuang
論文名稱： 芳香雜環駢苯駢於Di-π-methane反應中之取代基效應
Substituent Effect on Di-π-Methane Reaction of Benzopyrazinobarrelene and Benzoquinoxalinobarrelene
指導教授： 廖俊臣
Chun-Chen Liao
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： 2007
畢業學年度： 96
語文別： 英文
論文頁數： 156
中文關鍵詞： 蓓菉苓 、取代基效應 、光重排反應 、雙自由基中間體
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    • 本研究主題為利用苯基雜芳香環蓓菉苓(桶狀烯)作為研究模型，用以探討取代基效應對於此類化合物在di-π-methane(DPM)重排反應時的影響。本實驗在設計上借鑑以往之相類似研究所得之成果，利用雜芳香環之取代基的影響，使目標反應之化學選擇性(chemoselectivity)限制於雜環-烯基(pyrazino-vinyl)橋聯之單一反應途徑，故可使反應單純化，以便於探討其取代基效應在此光重排反應中位向選擇性(regioselectivity)的引導作用。文中除了以DPM反應中特有的雙自由基中間體(biradical intermediate)的相對穩定性作為反應途徑探論之基礎，同時亦佐理論計算以求對實驗結果作完善合理的解釋。

    The target research is regard of utilizing benzopyrazinobarrelene (BPB) and benzoquinoxalinobarrelene (BQB) as experimental platforms to examine the substituent effect on the di-π-methane (DPM) rearrangement of barrelene-like skeleton. By selecting the appropriate functionality on the pyrazine ring (in this case, the di-cyano groups or an extra benzene ring), the photoreaction could be limited into chemoselectivity of aza-di-π-methane reaction only, thus facilitate the examination of regioselectivity induced by installations of substituents on the bicyclo[2.2.2] skeleton of substrates. The result of the photoreaction was then given rationale by the relative stability of intermediate (biradical) along with theoretical calculation.

    TABLE OF CONTENTS Page ACKNOWLEDGEMENTS i ABSTRACT OF THE DISSERTATION v ABSTRACT OF THE DISSERTATION (in Chinese) vi ABBREVIATIONS vii LIST OF CHARTS viii LIST OF TABLES ix Chapter I. Introduction and Research Motive I-1. Di-π-Methane Rearrangement -1- I-2. Chemistry of Masked-o-Benzoquinones -5- I-3. Research on Photochemistry of Benzopyrazinobarrelenes -7- I-4. Purpose and Research Proposal of the Current Study -10- Chapter II. Synthesis of Benzopyrazinobarrelenes and Benzoquinoxalinobarrelenes II-1. The Synthesis of Benzobicyclo[2.2.2]octenones -15- II-2. The Synthesis of Benzobicyclo[2.2.2]octendiones -25- II-3. Condensation of Benzobicyclo[2.2.2]octendiones to 1,2-Diamines -30- Chapter III. Photolysis of Benzopyrazinobarrelenes and Benzoquinoxalinobarrelenes III-1. General Reaction Condition and Procedure -40- III-2. Result and Analysis III-2-1. Starting Model Compound -43- III-2-2. Group I: Steric Effect Target Compounds III-2-2-1. Group I-1: Alkyl Substitutions on the Olefin. -48- III-2-2-2. Group I-2: Alkyl Substitutions on Bridgehead Position -50- III-2-2-3. Group I-3: Alkyl Substitutions on Both Bridgehead Position and Olefin -54- III-2-3. Group II: Electronic Effect Target Compounds III-2-3-1. Group II-1: Functional Groups on the Olefin -57- III-2-3-2. Group II-2: Functional Groups on the Bridgehead -61- III-3. Result Summary -65- Chapter IV. Discussion and Theoretical Calculation IV-1. Results Concluded in Reported Literatures of Past Research -66- IV-2. Regioselectivity Ratio Obtained From This Study -70- IV-3. Prediction of Biradical Intermediate’s (BR-1) Stability by Theoretical Calculation -73- Chapter V. Conclusions -79- General Experimental Details -84- Spectral Data Section -102- References and Notes -153- Appendix A-0

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