薁併[4,5-b]吡咯類與氮環戊併[8,1-cd]薁類之合成研究

Study on the Synthesis of Azuleno[4,5-b]pyrroles and azacyclopent[8,1-cd]azulenes

吳漢強(Han-Chiang Wu)

指導教授 ： 吳吉輝

中原大學/理學院/化學系/碩士(2008年)

https://doi.org/10.6840/cycu200900129

摘要

研究方向以4-乙氧基-1-乙氧羰基薁與聯胺反應取代乙氧羰基，形成1-乙氧羰基-4-腙基薁衍生物，以4-腙基薁衍生物與酮基反應，形成1-乙氧羰基-4-肼基薁衍生物，再以磷醯氯(POCl3)試劑反應進行費希爾吲哚合成法(Fischer indole)，得以使第四位置上胺基改以聯胺進行反應，形成7-乙氧羰基薁併[4,5-b]吡咯 。
4-腙基薁衍生物利用磷醯氯(POCl3)試劑，在N,N-二甲基甲醯胺(DMF) 溶劑下，進行費希爾吲哚合成法，取1-乙氧羰基-3-烷基-4-肼基薁進行反應，反應方向往由薁核第四位置向第五位置併環，反應所形成之產物具有兩種型態之結構，薁核第三位置如有取代基存在，則醛基取代薁核第二位置，如第三位置無取代，醛基則取代薁核第三位置反應，判斷反應進行的同時，薁核內的電子轉移使得第二位置上易進行甲醯化反應。
以4-乙氧基-1-乙氧羰基薁，與胺基衍生物反應，使得第四位置取代為4-胺基衍生物-1-乙氧羰基薁，再進行醯化反應形成4-胺基衍生物-3-醯基-1-乙氧羰基薁，加入酮類進行縮合反應，再進行麥可加成(Michael Addition)反應，形成4-乙氧羰基-1-氮環戊併[8,1-cd]薁 ; 4-胺基衍生物-3-醯基-1-乙氧羰基薁與活性亞甲基(ECA、DEM)反應，進行縮合反應，再進行麥可加成(Michael Addition)反應，形成6-乙氧羰基-薁併[8,1-bc]氮呯 ，反應速率快，約10分鐘即反應完全，且處理方便，使得其產率可高達96%。

關鍵字

薁 ； ?咯

並列摘要

The reaction of 4-ethoxyl-1-ethoxycarbonylazulene and hydrazine to give 1-ethoxycarbonyl-4-hydrazoazulene derivatives, and then reacted with ketones to affored 1-ethoxycarbonyl-4-hydrazoazulene derivatives, while proceed with Fischer indole reaction to afford 7-ethoxycarbonyl- azuleno [4,5-b] pyrrole which is used phosphorus chloride oxide reagent.
　　1-ethoxycarbonyl-3-alkyl-4-hydrazoazulene was synthesized by 4-hydrazoazulene derivatives with phosphorus chloride oxide, which was further proceed with Fischer indole reaction. The ring-closed was 4-position and 5-position of azulene. The 3-substituted azulene was exist while the aldehydes substituted to 2-position of azulene, and the 3-position was no substituted while the aldehydes substituted to 3-position of azulene.
　　4-amino-1-ethoxycarbonylazulene was synthesized by substitution of 4-ethoxyl-1-ethoxycarbonylazulene with amino groups and reacted with acetylate reaction to give 4-amino-3-formyl-1-ethoxylcarbonylazulene. The condensation reaction shows that 4-amino-3-formyl-1-ethoxyl carbo- nylazulene reacted with ketones , which was further proceeded with the Michael addition to affored 4-ethoxycarbonyl-1-azacyclopent[8,1-cd]azulene.
　　4-amino-3-formyl-1-ethoxylcarbonylazulene reacted with ECA or DEM which proceed the condensation reaction, and the Michael addition to affored 1H-azuleno[8,1-bc]azepine.

並列關鍵字

Azulene ； Pyrrole

參考文獻

(5). D. A. Becker J. Am. Chem. Soc. 1996, 118, 905.

(12). A. G. Anderson ; J.A.Nelson ; J.J.Tazuma Am.Soc. 1953,75,4980.

Cell. Mol. Neurobiol. 2006, 26, 1493.

(28). 洪伯誠，Bioorganic & Medicinal Chemistry Letters. 2001, 11, 1981.

(31). B Robinson. Chemical Reviews. 1963, 4 , 373.