臺灣博碩士論文加值系統

在有機不對稱合成的領域中，掌性輔助劑一直被廣泛研究與矚目。掌
性輔助劑除了本身的應用之外，亦可以由此而製得更具有效力、且更經濟的掌性催化劑。(R)及(S)-BINOL因為互相消旋化的能障相當大，是目前化學界最著名的掌性輔助劑之一，在合成上的運用範圍很廣。
希望將兩個在1、3-位置上有拉電子基、2-位置上有羥基及在4、8-位置上有立體能障夠大的官能基之薁類化合物(200)，進行偶合反應後所形成的雙薁類化合物(201)能夠像BINOL那樣具有掌性輔助劑之效果。
為了要合成出目標分子(201)之前趨化合物(200)，因此本實驗將觀察以2-氯薁-1,3-二羧酸乙酯(12a)為起始物，分別與各種鋰試劑進行烷化反應(又稱親核性反應)後所產生的結果:(1)探討起始物進行烷化反應後，所產生的主產物與各種副產物、(2)烷化反應之條件將如何控制才能得到較高產率的主產物、(3)各產物之間的光譜差異。
未來並將探討薁類化合物(200)，在4-位置上之立體能障夠大的官能基改變時，對於目標分子(201)之(R)型與(S)型互相消旋化的能障有何影響?

In the region of incoherent synthesis of the organic chemistry, chiral
auxiliaries have been extensively researched. The chiral auxiliaries, aside from
their own application, can also be used to manufacture more effective, and more
economic chiral catalyst. (R) and (S)-BINOL, being gigantic energy obstacle in their co-racemization, has been one of the most famous chiral auxiliaries in the field of chemistry nowadays, and also widely used in synthesis.
We hope that the formation of biazulene compound(201), under the coupling reaction of 1、3-position being along with electron-withdrawing group, 2-position being along with hydroxy group, and four 4、8-position being along with static energy obstacle large enough functional group of azulene compound(200), may have the chiral auxiliary effect like that of the BINOL.
In order to synthesize precursor compound(200) of the objective molecule(201), this experiment will try to observe the results of start-materials, diethyle 2-choroazulene-1, 3-dicarboxylate(12a), under variouly respective alkyle lithium reagent alkylation reaction to explore:
1. the products and various by-products.
2. the condition to control the crops of high proficiency in the main product.
3. the variation of spectroscopic among the products.

中文摘要………………………………………………………………………Ⅰ
英文摘要………………………………………………………………………Ⅱ
謝誌……………………………………………………………………………Ⅲ
總目錄…………………………………………………………………………Ⅳ
圖目錄…………………………………………………………………………Ⅵ
第一章 緒論……………………………………………………………………1
1-1 前言………………………………………………………………………..1
1-2 薁類化學…………………………………………………………………..6
1-2-1 薁類的簡介………………………………………………….. …...6
1-2-2 薁類的合成………………………………………………….. …..11
1-2-3 薁類的反應………………………………………………….. …..18
1-2-4 薁類的應用………………………………………………….. …..37
1-2-5 雙薁類……………………………………………………… ……46
1-3 掌性化學………………………………………………………………….50
1-3-1 掌性純物質………………………………………………….. …..50
1-3-2 不對稱合成………………………………………………….. …..58
1-3-3 BINOL的合成…………………………………………………..…64
1-3-4 BINOL的光學離析………………………………………………..67


1-3-5 BINOL的應用……………………………………………………..70
第二章 合成構想……………………………………………………………...75
第三章 實驗方法……………………………………………………………...77
3-1 儀器與藥品……………………………………………………………….77
3-2 實驗步驟………………………………………………………………….80
第四章 結果與討論…………………………………………………………...90
4-1 製備2M烷基鋰試劑……………………………………………………..91
4-2 製備2-氯基-4-乙基薁-1-羧酸乙酯………………………………………92
4-3 製備2-氯基-4-丙基薁-1-羧酸乙酯……………………………………..100
4-4 製備2-氯基-4-丁基薁-1-羧酸乙酯……………………………………..104
第五章 結論………………………………………………………………….109
第六章 參考文獻…………………………………………………………….112
第七章 附錄……………………………………………………………….....118
7-1質量光譜…………………………………………………………………118
7-2 核磁共振光譜…………………………………………………………...122
7-3 紫外線吸收光譜………………………………………………………...129
7-4 紅外線吸收光譜………………………………………………………...132

圖目錄
7-1 質量光譜
附圖1：2-氯-4-乙基薁-1-羧酸乙酯(140)之質譜圖…………………………118
附圖2：2-氯-4-乙基薁(140a)之質譜圖…………………………………….118
附圖3:6-乙基薁-1,3-二羧酸乙酯(140b)之質譜圖…………………………119
附圖4:2-氯-5-乙基薁-1,3-二羧酸乙酯(140c)之質譜圖……………………119
附圖5:2-氯-4-丙基薁-1-羧酸乙酯(141)之質譜圖………………………….120
附圖6:2-氯-4-丙基薁(140a)之質譜圖………………………….………….120
附圖7:2-氯-4-丁基薁(142a)之質譜圖………………………….………….121
7-2 核磁共振光譜
附圖8：2-氯-4-乙基薁-1-羧酸乙酯(140)之1H-NMR光譜圖…………….122
附圖9：2-氯-4-乙基薁-1-羧酸乙酯(140)之13C-NMR光譜圖…………….122
附圖10: 2-氯-4-乙基薁(140a)之1H-NMR光譜圖…………….……………123
附圖11: 2-氯-4-乙基薁(140a)之13C-NMR光譜圖……………. ………….123
附圖12: 6-乙基薁-1,3-二羧酸乙酯(140b)之1H-NMR光譜圖…………….124
附圖13: 6-乙基薁-1,3-二羧酸乙酯(140b)之13C-NMR光譜圖…………….124
附圖14: 2-氯-5-乙基薁-1,3-二羧酸乙酯(140c)之 1H-NMR光譜圖……….125
附圖15: 2-氯-5-乙基薁-1,3-二羧酸乙酯(140c)之13C-NMR光譜圖……….125
附圖16: 2-氯-4-丙基薁-1-羧酸乙酯(141)之1H-NMR光譜圖……….……126

附圖17: 2-氯-4-丙基薁-1-羧酸乙酯(141)之13C-NMR光譜圖……….……126
附圖18: 2-氯-4-丙基薁(140a)之1H-NMR光譜圖……….…………………127
附圖19: 2-氯-4-丙基薁(140a)之13C-NMR光譜圖……….………………..127
附圖20: 2-氯-4-丁基薁(142a)之1H-NMR光譜圖……….…………………128
附圖21:2-氯-4-丁基薁(142a)之13C-NMR光譜圖……….…………………128
7-3 紫外線吸收光譜
附圖22：2-氯-4-乙基薁-1-羧酸乙酯(140)之紫外線吸收光譜……………..129
附圖23：2-氯-4-乙基薁(140a)之紫外線吸收光譜…………….. …………..129
附圖24:6-乙基薁-1,3-二羧酸乙酯(140b)之紫外線吸收光譜……………...130
附圖25:2-氯-5-乙基薁-1,3-二羧酸乙酯(140c)之紫外線吸收光譜………..130
附圖26:2-氯-4-丙基薁-1-羧酸乙酯(141)之紫外線吸收光譜…….. ………131
7-4 紅外線吸收光譜
附圖27:2-氯-4-乙基薁-1-羧酸乙酯(140)之紅外線吸收光譜…….. ………132
附圖28:2-氯-4-乙基薁(140a)之紅外線吸收光譜…….. …………………...132
附圖29:6-乙基薁-1,3-二羧酸乙酯(140b)之紅外線吸收光譜…….. ………133
附圖30: 2-氯-5-乙基薁-1,3-二羧酸乙酯(140c)之紅外線吸收光譜……….133
附圖31: 2-氯-4-丙基薁-1-羧酸乙酯(141)之紅外線吸收光譜…….. ……...134

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