臺灣博碩士論文加值系統

本研究利用2-取代基-4-甲氧酚，成功合成出各種不同官能基的掩飾對苯醌化合物(MPBs) 49、54、58及63。分別和Corey-Chaykovsky試劑反應，進行環丙烷化反應，得到雙環[4.1.0]庚烯酮50、55、59和64，在此我們發現，拉電子基與推電子基的電子效應對Corey-Chaykovsky試劑與掩飾對苯醌上的雙鍵，進行環丙烷化反應的位置會有不同， 接著經由水解得到雙酮化合物51、56、60和65；我們亦將雙環[4.1.0]庚烯酮化合物50及59與不同的格林納試劑進行反應，得到酮類化合物的前驅物68及69。

The present studies were 2-substituted-4-meethoxyphenol as starting materials to prepare different kinds of masked p-benzoquinones (MPBs) 49, 54, 58 and 63. These compounds subsequently underwent cyclopropanation with Corey-Chaykovsky reagent to obtain bicycle[4.1.0]heptenones 50, 55, 59 and 64. We have found that the effects of electron-withdrawing group and electron donating group will cause the rigioselectivity of the cyclopropanation of MPB’s double bonds. After hydrolysis, the diketones 51, 56, 60 and 65 were obtained. Wealso treated bicycle [4.1.0] heptenone 50 and 59 with Grignard reagents to generate the precursors 68 and 69 of troponoids.

目錄
摘 要 ........................................................................................................................ Ⅰ
Abstract ......................................................................................................................II
謝誌 ...........................................................................................................................III
目 錄 ........................................................................................................................ IV
圖 目 ....................................................................................................................... VI
表 目 .......................................................................................................................VII
縮寫對照表..............................................................................................................VIII
壹、 緒論 .................................................................................................................... 1
一、酮類之文獻回顧.................................................................................................1
1. 酮類之結構與生 物活性....................................................................................1
2. 酮類化合物的合 成方法....................................................................................3
二、掩飾對苯醌之製備及應用....................................................................................7
三、 Corey-Chaykovsky之製備及應用 .....................................................................9
四、研究動機…………………………………………………………………………11
貳、結果與討論 ....................................................................................................... 12
一、 掩飾對苯醌之 合成.......................................................................................... 12
二、 掩飾對苯醌 之環丙烷化反應……………………………………………………16
三、雙環[4.1.0]庚烯酮之水解反應………………………………………………………22
四、雙環[4.1.0]庚烯酮與格林納試劑之反應…………………………………………26
叁、結論..................................................................................................................... 29
肆、實驗步驟 ........................................................................................................... 30
一、實驗方法 ........................................................................................................... 30
二、 實驗步驟 .......................................................................................................... 32
1. 起始物之合成 ................................................................................................... 32
2. 掩飾對苯醌之合成 ............................................................................................. 33
3. 掩飾對苯醌環丙烷化反應之合成 ..................................................................... 36
4. 水解雙環[4.1.0]庚烯酮化合物…………………………………………………39
5. 雙環[4.1.0]庚烯酮與格林納試劑之合成……………………………………………42
三、參考資料 ............................................................................................................ 44
附錄一 化合物的碳、氫核磁共振光譜圖 ............................................................. 46
附錄二 化合物的紅外線吸收光譜圖 .................................................................... 78

圖目
圖1- 1：酮及酚酮的構造...........................................1
圖1- 2：酚酮陰離子之共振與芳香結構................................ 2
圖1- 3：具有活性之酚酮化合物...................................... 3
圖1- 4：環己-2,5二烯酮類化合物.......................................7
圖2- 1：化合物 54 之氣相層析質譜圖..................................12
圖2- 2：三環上氫的偶合常數..........................................18
圖2- 3：化合物 59 之氣相層析質譜圖..................................20

表目
表1- 1：七員環化合物之偶極矩比較.....................................1
表2- 1：化合物54上氫的化學位移 (δ)及偶合常數 (Hz).................. 13
表2- 2：化合物58上氫的化學位移 (δ)及偶合常數 (Hz).................. 14
表2- 3：化合物63上氫的化學位移 (δ)及偶合常數 (Hz).................. 15
表2- 4：掩飾對苯醌之碳原子的化學位移................................ 16
表2- 5：化合物55上氫的化學位移 (δ)及偶合常數 (Hz).................. 18
表2- 6：化合物59上氫的化學位移 (δ)及偶合常數 (Hz).................. 20
表2- 7：雙環[4.1.0]庚烯酮化合物的化學位移............................ 21
表2- 8：化合物64上氫的化學位移 (δ)及偶合常數 (Hz).................. 21
表2- 9：化合物56上氫的化學位移 (δ)及偶合常數 (Hz).................. 23
表2-10：化合物60上氫的化學位移 (δ)及偶合常數 (Hz).................. 24
表2-11：水解雙環[4.1.0]庚烯酮之碳原子的化學位移..................... 25
表2-12：化合物68上氫的化學位移 (δ)及偶合常數 (Hz).................. 27

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