(1)利用Ring-Closing Metathesis合成十環化合物：多取代之 5,14-dihydro-8H-13-oxadibenzo[a,f]cyclodecene (2)利用Mitsunobu反應將醇類轉變成氯化烷類的新法合成

(1)Synthesis of Substituted 5,14-dihydro-8H-13-oxadibenzo[a,f]cyclodecene via Ring-Closing Metathesis (2)Conversion of alcohols into alkyl halides via Mitsunobu reaction

林于莉(Yu-Li Lin)

指導教授 ： 王英基

高雄醫學大學/生命科學院/醫藥暨應用化學研究所/碩士(2004年)

摘要

Part Ⅰ
本篇論文描述一連串的10環醚類化合物之合成方式。論文中由起使原料異香草醛 (isovanillin) 經由克萊森轉位(Claisen rearrangement)及拜耳-比利格氧化反應(Baeyer-Villiger oxidation)等反應而得到O-allylbenzylalcohols和O-allylphenols，經由Mitsunobu反應進行分子間脫水合成出閉環置換反應 (RCM) 之前身物--雙烯化合物。最後，加入Grubbs催化試劑進行閉環置換反應得到多取代的10 環醚類化合物5,14-dihydro-8H-13-oxadibenzo[a,f]cyclodecene。

Part Ⅱ
建立醇類化合物轉變為氯化烷基的二個新的方法。方法 1，將醇類化合物與偶氮二甲酸二異丙酯(diisopropyl azodicarboxylate, DIAD)、三苯基膦 (TPP) 和2-巰基噻唑啉 (2-thiothiazoline) 經由 Mitsunobu反應得2-alkylthiothiazolines後，再與氯甲酸乙酯(ethyl chloroformate)反應可獲得高產率之氯化烷類化合物。方法2，醇類化合物於四氫呋喃 (THF) 中加入TPP、DIAD及氯甲酸乙酯 (ethyl chloroformate)，在一壺反應中可獲得極高產率之氯化烷類化合物。

關鍵字

Mitsunobu反應 ； 閉環置換反應

並列摘要

Part Ⅰ
As part of an ongoing study of the chemistry of benzoheterocyclic compounds, a series of 10-membered macrocyclic ethers annulated with substituted benzene is described. O-allylbenzylalcohols and O-allyl- phenols, derived from isovanillin, were coupled by the Mitsunobu reaction to construct the intramolecular dienes as precursor for ring- closing metathesis (RCM). Finally, by the treatment of Grubbs’ catalyst the intramolecular dienes were cyclized to give the desired compounds, 10-membered macrocyclic ethers, respectively.

Part Ⅱ
Two new methods for the conversion of alcohols into alkyl chloride are established. Method 1, alcohols were reacted with DIAD, TPP and 2-thiothiazoline to undergo Mitsunobu reaction to produce 2-alkylthio- thiazolines which were subsequently treated with ethyl chloroformate to produce alkyl chlorides in good yields. Mothod 2, alcohols were reacted with triphenylphosphine (TPP), diisopropyl azodicarboxylate (DIAD) in THF, followed by treating with ethyl chloroformate to afford alkyl chlorides in one pot in moderate yields.

並列關鍵字

Mitsunobu reaction ； RCM

參考文獻

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