□酚酮類化合物之合成｜國立清華大學博碩士論文庫

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研究生：	黃冠勳 Huang, Kuan-Hsun
論文名稱：	□酚酮類化合物之合成 Synthesis of Troponoids from 2-Methoxyphenols via Masked o-Benzoquinones
指導教授：	廖俊臣 Liao, Chun-Chen
口試委員:
學位類別：	碩士 Master
系所名稱：	理學院 - 化學系 Department of Chemistry
論文出版年：	2009
畢業學年度：	97
語文別：	中文
論文頁數：	144
中文關鍵詞：	□酚酮、與掩飾鄰苯醌、□酮類化合物
外文關鍵詞：	Corey-Chaykovsky
相關次數：	點閱：2 下載：0
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本研究成功的利用 Corey-Chaykovsky 試劑與掩飾鄰苯醌反應合
成雙環[4.1.0]庚烯酮化合物，並將其水解、擴環得到□酚酮類化合物。
若使用兩當量 Corey-Chaykovsky 試劑與掩飾鄰苯醌反應，得此
類產物可在矽膠作用下重排成為環庚三烯化合物，且此產物預期可作
為□酮類化合物之前驅物。

Abstract
The derivatives of tropolone and tropone with various substituted
groups are seven-membered-ring nonbenzenoid aromatic compounds
some natural products contain such moieties. Furthermore, troponoids
have fascinating biological activities such as antiviral, antitumor, and
antioxidant.
According to our research, the cyclopropanation reactions of MOBs
to give bicyclo[4.1.0]heptenone skeletons were successful with 1 eq. of
Corey-Chaykovsky reagent (CCR). The acid hydrolysis of
dimethoxyketal follow by ring enlargement with lewis acid provided
desired tropolones.
Moreover, epoxide derivatives of bicycle[4.1.0]heptenones which
were obtained when 2 eq. of CCR reacted with MOBs gave
cycloheptatriene derivatives, a potential precursor to tropone upon
treatment with silica gel.

摘 要 ........................................................................................................... I
ABSTRACT ............................................................................................. II
謝誌 .......................................................................................................... III
縮寫對照表 .............................................................................................. IV
圖 目 ..................................................................................................... VIII
表 目 ........................................................................................................ IX
第一章 緒論 ............................................................................................... 1
第一節 天然物□酮及□酚酮之文獻回顧 ........................................... 1
1.1.1 天然物□酮及□酚酮結構與生物活性 ................................... 1
1.1.2 □酮與□酚酮及其衍生物之合成方法 ................................... 7
第二節 掩飾鄰苯醌之反應回顧 .........................................................15
1.2.1 掩飾鄰苯醌之製備方法 .........................................................15
1.2.2 掩飾鄰苯醌反應之文獻回顧 .................................................17
第三節 Corey-Chavkovsk文獻回顧 ...................................................21
1.3.1 Corey-Chavkovsky試劑之發展與應用性 .............................21
1.3.2 Sulfur ylide之化學性質 .........................................................23
第四節 研究構思 .................................................................................28
第二章 結果與討論 .................................................................................29
第一節 MY3-469□酚酮化合物之合成 ..............................................29
第二節 由二甲氧基酚合成□酚酮類化合物 .....................................31
2.2.1 掩飾鄰苯醌之合成 ..................................................................31
2.2.2 雙環[4.1.0]庚烯酮化合物之合成 ..........................................32
2.2.3 水解雙環[4.1.0]庚烯酮化合物 ..............................................36
2.2.4 利用路易士酸將雙環[4.1.0]庚烯雙酮擴環之反應 ..............38
2.2.5 □酚酮類化合物之合成 .........................................................42
2.2.6 掩飾鄰苯醌與兩當量Corey-Chaykovsky試劑反應之研究 43
第三節 結論 .........................................................................................46
第三章 實驗步驟 .....................................................................................48
第一節 一般實驗方法 .........................................................................48
第二節 化合物之實驗步驟 .................................................................50
3.2.1 實驗起始物之合成 ..................................................................50
3.2.2 利用二乙醯氧基碘(III)苯 (diacetoxtiodobenzene, DAIB) 氧
化2-甲氧基酚化合物合成掩飾鄰苯琨(MOBs) ..............................55
3.2.3 利用Corey-Chaykovsky 試劑與掩飾鄰苯醌反應合成雙環
[4.1.0]庚烯酮化合物84a-j ...............................................................56
3.2.4 水解雙環[4.1.0]庚烯酮化合物84a-j .....................................57
3.2.5 利用路易士酸將雙環[4.1.0]庚烯酮化合物雙酮擴環 ..........58
3.2.6 □酚酮類化合物之合成 .........................................................59
3.2.7 化合物 89 與化合物 90 之合成 .........................................60
3.2.8 化合物 91之合成 ..................................................................60
3.2.9 化合物 92 之合成 .................................................................61
第三節 化合物之光譜分析資料 .........................................................62
第四章 參考資料 .....................................................................................78
附錄一 化合物的碳、氫核磁共振光譜圖 ............................................82

                                

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