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研究生:郭玲惠
研究生(外文):Lin-Hui Kuo
論文名稱:利用克萊森轉位及新穎的閉環置換反應將對苯二酚合成2,5,8,11-四氫-1,7-雙氧苯[1,2,4,5]雙環庚烯
論文名稱(外文):A Novel Synthesis of 2,5,8,11-Tetrahydro-1,7-dioxabenzo[1,2,4,5]dicycloheptene from Hydroquinone via Claisen Rearrangement and Ring-closing Metathesis Reaction
指導教授:王英基
指導教授(外文):Eng-Chi Wang
學位類別:碩士
校院名稱:國立高雄醫學大學
系所名稱:藥學研究所碩士在職專班
學門:醫藥衛生學門
學類:藥學學類
論文種類:學術論文
論文出版年:2002
畢業學年度:90
語文別:中文
論文頁數:52
中文關鍵詞:14-對位雙烯丙氧基苯25-雙烯丙基對苯二酚25-雙烯丙基-14-雙烯丙氧基苯25811-四氫-17-雙氧苯[1245]雙環庚烯烯丙基反應克萊森轉位Grubbs催化劑閉環置換反應
外文關鍵詞:14-diallyloxybenzene25-diallylhydroquinone25-diallyl-14- diallyloxybenzene25811-tetrahydro-17-dioxabenzo[1245]dicyclohepteneallylationClaisen rearrangementGrubbs catalystsring-closing metathesis reaction
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在本研究中,我們先以對苯二酚(hydroquinone) (1)和烯丙基溴 (allyl bromide)合成雙烯丙基苯基醚(diallyl phenyl ethers)類化合物的1,4-對位雙烯丙氧基苯(1,4-diallyloxybenzene) (2),再經克萊森轉位後得到主要產物:雙鄰位烯丙基酚(di-O-allyl phenol)類化合物的2,5-雙烯丙基對苯二酚(2,5-diallylhydroquinone) (3)。
然後,我們將2,5-diallylhydroquinone (3)和烯丙基溴再度進行烯丙基反應來合成2,5-雙烯丙基-1,4-雙烯丙氧基苯(2,5-diallyl-1,4- diallyloxybenzene) (4)。
將化合物2,5-diallyl-1,4-diallyloxybenzene (4)利用Grubbs催化劑,經過RCM的閉環置換反應來進行合成,得到一個新奇的7-6-7三環的化合物,2,5,8,11-四氫-1,7-雙氧苯[1,2,4,5]雙環庚烯(2,5,8,11-tetrahydro-1,7-dioxabenzo[1,2,4,5]dicycloheptene) (5)。
In this study, the diallyl phenyl ether, 1,4-diallyloxybenzene (2), was synthesized from hydroquinone (1) with allyl bromide. 1,4-di- allyloxybenzene (2) was performed the Claisen rearrangement to obtain di-O-allyl phenols, 2,5-diallylhydroquinone (3).
Furthermore, compound 3 was performed the allylation again with allyl bromide to give 2,5-diallyl-1,4-diallyloxybenzene (4).
Then, 2,5-diallyl-1,4-diallyloxybenzene (4) used the Grubbs catalysts to undergo the ring-closing metathesis reaction, and furnished a novel 7-6-7 tricyclic compound, 2,5,8,11-tetrahydro-1,7-dioxabenzo[1,2,4,5]dicyclo- heptene (5).
目錄
目錄------------------------------------------------------I
圖之目錄---------------------------------------------------II
表之目錄---------------------------------------------------IV
中文摘要---------------------------------------------------1
英文摘要---------------------------------------------------2
第一章緒論-------------------------------------------------3
第二章閉環置換反應的過去研究概要---------------------------9
第三章研究目的---------------------------------------------12
第四章研究策略的合成設計途徑-------------------------------13
第五章結果與討論-------------------------------------------14
第一節Hydroquinone (1)的烯丙基化反應-----------------------14
第二節1,4-Diallyloxybenzene (2)的Claisen轉位反應-----------16
第三節2,5-Diallylhydroquinone (3)的烯丙基化反應------------18
第四節2,5-Diallyl-1,4-diallyloxybenzene (4)的閉環置換反應--20
第六章結論-------------------------------------------------22
誌謝-------------------------------------------------------24
第七章實驗部分---------------------------------------------26
第一節儀器與材料-------------------------------------------26
第二節製備1,4-Diallyloxybenzene (2)的合成方法--------------27
第三章製備2,5-Diallylhydroquinone (3)的合成方法-------------28
第四節製備2,5-Diallyl-1,4-diallyloxybenzene (4)的合成方法---29
第五節製備2,5,8,11-tetrahydro-1,7-dioxabenzo[1,2,4,5]dicyclo- heptene (5)的合成方法--------------------------------------30
第八章參考文獻---------------------------------------------31
圖之目錄
圖一:A variety of olefin metathesis reaction----------------3
圖二:Mechanism of olefin metathesis -----------------------4
圖三:釕催化劑的製備方法----------------------------------6
圖四:Mechanism of Claisen Rearrangement--------------------7
圖五. Naphthalene類化合物的閉環置換反應 (I)-----------------10
圖六. Naphthalene類化合物的閉環置換反應 (II)----------------11
圖七. N-Aryl ,-unsaturated -lactam類化合物的閉環置換反應11
圖八. 合成設計途徑-----------------------------------------13
圖九:1,4-Diallyloxybenzene (2)的IR光譜---------------------34
圖十:1,4-Diallyloxybenzene (2)的質譜----------------------35
圖十一:1,4-Diallyloxybenzene (2)的1H NMR圖譜--------------36
圖十二:1,4-Diallyloxybenzene (2)的13C NMR圖譜-------------37
圖十三:1,4-Diallyloxybenzene (2)的DEPT圖譜----------------38
圖十四:2,5-Diallylhydroquinone (3)的IR光譜----------------39
圖十五:2,5-Diallylhydroquinone (3)的質譜------------------40
圖十六:2,5-Diallylhydroquinone (3)的1H NMR圖譜------------41
圖十七:2,5-Diallylhydroquinone (3)的13C NMR圖譜------------42
圖十八:2,5-Diallylhydroquinone (3)的DEPT圖譜---------------43
圖十九:2,5-Diallyl-1,4-diallyloxybenzene (4)的質譜---------44
圖二十:2,5-Diallyl-1,4-diallyloxybenzene (4)的1H NMR圖譜----45
圖二十一:2,5-Diallyl-1,4-diallyloxybenzene (4)的13C NMR圖譜--46
圖二十二:2,5-Diallyl-1,4-diallyloxybenzene (4)的DEPT圖譜--47
圖二十三:2,5,8,11-Tetrahydro-1,7-dioxabenzo[1,2,4,5]dicyclo- heptene (5)的IR光-----------------------------------------48
圖二十四:2,5,8,11-Tetrahydro-1,7-dioxabenzo[1,2,4,5]dicyclo- heptene (5)的質譜----------------------------------------49
圖二十五:2,5,8,11-Tetrahydro-1,7-dioxabenzo[1,2,4,5]dicyclo- heptene (5)的1H NMR圖譜---------------------------------50
圖二十六:2,5,8,11-Tetrahydro-1,7-dioxabenzo[1,2,4,5]dicyclo- heptene (5)的13C NMR圖譜--------------------------------51
圖二十七:2,5,8,11-Tetrahydro-1,7-dioxabenzo[1,2,4,5]dicyclo- heptene (5)的DEPT圖譜------------------------------------52
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