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研究生:黃敏惠
研究生(外文):Miin-Huey Huang
論文名稱:雜環奎若林鄰昆二前驅物的合成及其在Diels-Alder反應上的應用
論文名稱(外文):The Synthesis of Precursors for Quinoxalino-o-quinodimethane and their Application in Diels Alder Reaction
指導教授:鍾文聖
指導教授(外文):Wen-Sheng Chung
學位類別:碩士
校院名稱:國立交通大學
系所名稱:應用化學系
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:262
中文關鍵詞:碳六十雷射瞬態光解鄰崑二烯雜環鄰崑二烯前驅物
外文關鍵詞:Diels-Alder ReactionquinoxalineO-quinodimethanesultineC60laser flash photolysis
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雜環鄰二烯前驅物的合成
及其在 Diels-Alder 反應上的研究
研究生:黃敏惠 指導教授:鍾文聖 博士
國立交通大學應用化學研究所
摘 要
近年來,本實驗室致力於雜環鄰二烯前驅物的研究,我們已製備出多種quinoxalino-sultine作為鄰二烯的前驅物,利用sultine分子易於脫去SO2的性質,所製備的前驅物在高溫(150 ~ 200 oC)及照光(254 nm)下,可生成其鄰二烯,並與一些常見的親雙烯體進行Diels-Alder反應。在本論文中,我們合成出2,3-diphenylquinoxalino-6,7-sultine (55c) 鄰二烯的前驅物,並對它們的熱化學與光化學反應進行研究。
這一系列的雜環 sultine 分子在 200 oC 封管反應時,均會脫去SO2分子生成其o-QDM中間體,與親雙烯體反應時均可以高產率地得到其Diels-Alder環化加成產物。而在光化學反應中 (以 254nm 波長照光),我們除了獲得與熱化學相同的環合產物外,亦會得到其異構化產物sulfolene和一些不溶的高分子聚合物。
將 quinoxalino-fused sultine (47d)、(55b-c)、2,3-bis(bromomethyl)- 5,10-benzo[g]quinoxalinedione (94) 和 naphtho-sultine (113) 與 C60反應時,均可以很成功地到和 C60 的單一加成產物。經由變溫 1H-NMR 實驗研究發現,這些 C60 單一加成產物中氮原子存在與否以及和 C60間的距離對於其上六員環的構形交換速率有很大的影響。
在雷射瞬態光譜的研究中,我們以 248 nm 的雷射光光解 sultine,可以偵測到中間物的生成,極有可能是我們所欲偵測的 o-QDM 或 biradical 中間體,但仍須進一步的理論計算與實驗來驗證。

Abstract
The goal of our research is to synthesize the precursors for quinoxalino-o-quinodimethanes, and to explore their potential application in Diels-Alder reaction. The advantage of using sultines is their ease of SO2 extrusion at lower temperature than the corresponding sulfolenes. After successfully synthesizing 2,3-diphenylquinoxalino-6,7-sultine (55c), we have studied their thermochemistry and photochemistry.
These heterocyclic sultines extrude SO2 and form the corresponding o-quinodimethanes at high temperature (200 oC), which in turn react with dienophiles to give excellent yield of cycloadducts. The products from photochemical reactions (irradiated with 254 nm UV-light) are similar to those from thermochemical reactions besides that corresponding sulfolene and some quantity of insoluble ploymers are formed photochemically.
When quinoxalino-fused sultine (47d)、(55b-c), 2,3-bis (bromomethyl) -5,10-benzo[g]quinoxalinedione (94) and naphtho-sultine (113) are heated with C60, the mono-Diels-Alder-adducts of the C60 are obtained successfully. Variable temperature 1H-NMR experiments show that the sxistence of nitrogen atoms and the distance between the nitrogen atoms and C60 core may have a great influence on the rate of boat-to-boat conformations exchange of C60 mono-adducts.
Laser flash photolysis (248 nm) on these quinoxalino-sultine leads to the detection of a new transient spices, which is very likely to be the corresponding o-quinodimethane or biradical intermediates. Further work and theoretical calculation is needed to confirm these observations.

目錄
中文摘要…………………………………………………………….i
英文摘要…………………………………………………………….iii
誌謝………………………………………………………………….v
目錄………………………………………………………………….vi
式圖目錄…………………………………………………………….viii
圖目錄………………………………………………………………xi
表目錄……………………………………………………………….xiii
第一章、緒論……………………………………………………….1
1-1 研究背景與文獻回顧………………………………………1
1-2 雜環分子 Quinoxaline 的 o-QDM 系列…………………5
1-3 Sultine的合成及其性質……………………………………10
1-4 C60 的簡介及其衍生化…………………………………….19
1-5 C60 多重加成產物之位向化學……………………………..26
第二章 結果與討論…………………………………………………32
2-1 Quinoxalino-o-QDM 前驅物的熱化學研究………………32
2-1-1 2,3-Diphenylquinoxalino-6,7-sultine (55c) 的合成…..32
2-0-0 2,3-Diphenylquinoxalino-6,7-sultine (55c) 的熱化學反
應………………………………………………………33
2-2 雜環quinoxalinedione-o-QDM 前驅物之熱化學研究……40
2-0-0 2,3-Bis(bromomethyl)-5,10-benzo[g]quinoxalinedione
的合成………………………………………………….41
2-0-0 2,3-Bis(bromomethyl)-5,10-benzo[g]quinoxalinedione
的熱化學反應………………………………………….44
2-3 雜環quinoxalino-o-QDM 應用在 C60 衍生化的研究……48
2-3-1 Quinoxalino-2,3-sultine 系列和 C60 的衍生化反應….48
2-0-0 2,3-Substituted-quinoxalino-6,7-sultine 系列和C60 的
衍生化反應…………………………………………….53
2-3-2 Naphtho-sultine 和 C60 衍生化反應………………….61
2-3-2 Nitrile Oxide 和 C60 衍生化反應……………………65
2-3-2 2,3-Bis(bromomethyl)-5,10-benzo[g]quinoxalinedione
和 C60 衍生化反應……………………………………66
2-4 雙官能基在 C60 上進行衍生化之研究……………………76
2-4-1 C60 衍生物 110c,115 和 nitrile oxide 的衍生化反
應……………………………………………………….76
2-4-1 環糊精對 C60 加成多當量衍生化反應之位向選擇性
探討……………………………………………………79
2-5 Quinoxalino-sultine 之光化學研究……………………….84
2-5-1 2,3-Diphenylquinoxalino-6,7-sultine 光化學反應……88
2-6 雷射瞬態光譜研究…………………………………………91
2-6-1 Benzosultine 雷射瞬態光解之研究………………….91
2-6-2 Quinoxalino-2,3-sultine (47a) 雷射瞬態光解之研究..95
2-6-3 6,7-dimethylquinoxalino-2,3-sultine (47b) 雷射瞬態光
解之研究………………………………………………99
2-6-3 2,3-diphenylquinoxalino-6,7-sultine (55c) 雷射瞬態光
解之研究……………………………………………….103
2-6-5 Naphtho-sultine (113) 雷射瞬態光解之研究…………106
第三章 結論…………………………………………………………112
第四章 實驗…………………………………………………………114
4-1 一般敘述…………………………………………………….114
4-2 實驗步驟及光譜資料………………………………………116
第五章 參考文獻……………………………………………………146
附圖………………………………………………………………….152
自傳………………………………………………………………….262

第五章 參考文獻
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