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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