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研究生:陳亮勳
研究生(外文):Liang-Hsun Chen
論文名稱:第一部份芳香醛在水溶液中進行金屬銦促進的不對稱丙烯基化反應第二部份含環丙烷之環己烯酮化合物之光化學反應
論文名稱(外文):Part I. An Indium Promoted Asymmetric Allylation in Aqueous Cyclodextrin Solution Part II. Photochemistry of Cyclohexenones Containing Cyclopropyl Coumpounds
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:2004
畢業學年度:92
語文別:中文
論文頁數:110
中文關鍵詞:環糊精金屬銦1-萘香豆素光化學
外文關鍵詞:cyclodextrinindium1-naphthaldehydecoumarinphotochemistry
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第一部份 芳香醛在水溶液中進行金屬銦促進的不對稱丙烯基化反應
本論文取芳香醛利用金屬銦在水溶液中進行丙烯基化反應,配合環糊精作為掌性輔助基,分別探討不同當量的環糊精、反應試劑及不同溫度對反應的影響,實驗結果得到芳基丙烯醇產率在60∼90%,而最高鏡像超越值 (e.e.值) 約在24%。由實驗結果推論以環糊精作為掌性輔助基並不能有效的達到高鏡像超越值,推測其原因是客體分子與環糊精只是淺淺的錯合,而且在溶液中是以一種動態平衡存在,所以環糊精對客體分子立體方位保護之差異性並不大所致。另外由1H-NMR滴定實驗證實化合物40與-環糊精形成錯合,推算出兩者40℃下的結合常數為K11 = 140  15 M-1及最大位移差11 = 16.4  5.0 Hz。
第二部份 含環丙烷之環己烯酮化合物之光化學反應
此部分對含有三員環取代之環己烯酮化合物74、75進行光化學反應探討,分析此二化合物能否會因為開環而進行其他的光化學反應,結果兩者均無開環反應,其中化合物74是進行[2+2]光化學加成形成化合物 76。產物76之結構經由NMR化學位移及文獻值的參考推斷化合物構形為anti-hh,此外,利用X-ray繞射結果證實為anti-hh之構形。化合物75則進行類似Photo-Fries重排反應形成化合物77,由核磁共振光譜及X-ray繞射光譜鑑定其結構,但是目前無法確定其實際之反應機制。

Part I. An Indium Promoted Asymmetric Allylation in Aqueous Cyclodextrin Solution
In this thesis we discussed about the allylation reaction promoted by indium using cyclodextrins as an auxiliary in aqueous solution. The effects of indium equivalent, cyclodextrin concentrations and solution temperature were studied, and the allyl aryl alcohols were obtained in 60~90% yield and a maximum of 24% e.e. was achieved. The failure to achieve a high e.e. value when using cyclodextrins as an auxiliary is due to the shallow binding of cyclodextrin complexes and a dynamic equilibrium exists in the guest and host (CD), therefore only a small difference in the stereo-selectivity was achieved.
Part II. Photochemistry of Cyclohexenones Containing Cyclopropyl Coumpounds
In the second part of this work, we have studied the photochemistry of cyclohexenone compounds containing cyclopropyl group, i.e. 74 and 75. The expected ring-opening reactions of these cyclopropyl containing compounds were not observed, instead, compound 74 underwent a photo-[2+2]cycloaddition to yield 76. The configuration of compound 76 was assigned to be an anti-hh dimmer based on its 1H- and 13C NMR spectra and its similarity in chemical shifts with known structures. The anti-hh 76 was latter confirmed by an X-ray crystallographic analysis. Compound 75 underwent a Photo-Fries rearrangement and also gave compound 77 as the sole product. The structure of compound 77 was also confirmed by NMR and X-ray studies. Presently the reaction mechanism is not known.

頁次
中文摘要 ………………………………………………………… i
英文摘要 ………………………………………………………… ii
目錄 ………………………………………………………… iii
圖目錄 ……………………………………………………………. vi
式圖目錄 ………………………………………………………………. ix
表目錄 ……………………………………………………………. xi
附圖目錄 ……………………………………………………………. xii
附錄目錄 ……………………………………………………………. xv
第一部份 芳香醛在水溶液中進行金屬銦促進的不對稱丙烯基化反應
第一章 緒論……………………………………………….………... 1
1.1 前言………………………………………………….……... 1
1.2 環糊精…………………………………………….………... 2
1.2.1 發展…………………….…………………………………... 3
1.2.2 命名………………................................................................ 4
1.2.3 結構性質………………………………………………….... 5
1.2.4 物理或化學之性質與特性.................................................... 9
1.2.5 以環糊精為反應媒介………………………………….…... 10
1.2.5.1 環糊精包含現象……………………………………….…... 10
1.2.5.2 環糊精對反應的效應………………………………….…... 14
1.2.6 環糊精的合成方式………………………………….…....... 16
1.2.7 應用…………………………………………………….…... 18
1.3 金屬銦反應……………………………………………........ 19
1.3.1 簡介……………………………………………………........ 19
1.3.2 金屬銦丙烯基化水溶液反應………………………….…... 25
1.3.2.1 反應機制……………………………………………….…... 27
第二章 研究動機…………………………………………….…....... 34
第三章 結果與討論…………………………………………….…... 35
3.1 1-(1-Naphthyl)-3-buten-1-ol 42之製備……………………. 35
3.2 利用環糊精對1-Naphthbenzaldehyde 40進行丙烯基化反應之立體選擇性研究………………………………………
41
第四章 結論………………………………………………………… 63
第五章 實驗步驟及光譜資料............................................................ 64
5.1 試藥及測試方法…………………………………………… 64
5.2.1 化合物1-(1-Naphthyl)-3-buten-1-ol 42之合成………........ 65
5.2.2 化合物1-(3-Methylphenyl)-3-buten-1-ol 47之合成…….... 67
5.2.3 化合物1-(4-Methylphenyl)-3-buten-1-ol 48之合成…….... 68
5.2.4 化合物1-(2-Pyridyl)-3-buten-1-ol 49之合成…………....... 69
5.3 化合物1-(1-Naphthyl)-3-buten-1-ol 42在-環糊精中的不對稱合成……………………………………………………
71
第二部份 含環丙烷之環己烯酮化合物之光化學反應
第六章 緒論……………………………………………………….... 72
6.1 小環結構的光化學裂解………………………………….... 72
6.2 自由基捕捉試劑…………………………………………… 74
6.3 香豆素 (Coumarin) 類化合物的照光反應……………….. 76
第七章 研究動機………………………………………………….... 79
第八章 結果與討論………………………………………………… 81
8.1 4-Cyclopropanecarbonyloxy-coumarin 75之光化學反應.... 81
8.1.1 UV光譜…………………………………………………..… 81
8.1.2 4-Cyclopropanecarbonyloxy-coumarin 75之光化學反應追蹤……………………………………………………………
82
8.1.3 4-Cyclopropanecarbonyloxy-coumarin 75之照光結果…… 84
8.1.4 產物結構判定……………………………………………… 85
8.2 N-(3-Oxo-cyclohex-1-enyl)-cyclopropanecarboxamide 74之光化學反應……………………………………………....
91
8.2.1 UV光譜…………………………………………………….. 91
8.2.2 N-(3-Oxo-cyclohex-1-enyl)-cyclopropanecarboxamide 74之光化學反應追蹤………………………………………....
92
8.2.3 N-(3-Oxo-cyclohex-1-enyl)-cyclopropanecarboxamide 74之照光結果………………………………………………....
94
8.2.4 產物結構判定…………………………………………........ 97
第九章 結論………………………………………………………… 100
第十章 實驗步驟及光譜資料…………………………………….... 101
10.1 試藥及測試方法…………………………………………… 101
10.2 化合物75及74之光譜資料…………………………........ 101
10.3 4-Cyclopropanecarbonyloxy-coumarin 75之照光反應獲得化合物76……………………………………………….…..
102
10.4 N-(3-Oxo-cyclohex-1-enyl)-cyclopropanecarboxamide 74之照光反應獲得化合物77……………………………........
104
第十一章 參考文獻………………………………………………........ 106
附圖 …………………………………………………………….. 111
附錄 ……………………………………………………………. 136

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