2-取代基-5-乙氧羰基-2H-薁併[8,1-cd]噠嗪類的合成研究

Study on the Synthesis of 2-Substituted-5-ethoxycarbonyl-2H-azuleno[8,1-cd]pyridazine

陳宏昌(Hong-Chang Chen)

指導教授 ： 吳吉輝

中原大學/理學院/化學研究所/碩士(2008年)

https://doi.org/10.6840/cycu200900205

摘要

摘要
2取代基-5-乙氧羰基薁併[8,1-cd]噠嗪類化合物可經由以下三種方法製得：(1)利用1-乙氧羰基-4-腙基薁衍生物與POCl3/DMF進行Vilsmeier-Haack反應。(2)利用1-乙氧羰基-3-烷醯基-4-乙氧基薁與苯基聯胺反應。(3) 利用5-乙氧羰基-1H-薁併[8,1-cd]噠嗪類化合物與烷基碘進行烷化反應。
由1H NMR圖譜觀察發現，5-乙氧羰基-2取代基-薁併[8,1-cd]噠嗪類化合物的4-、6-、7-、8-、9-位置氫的化學位移與起始物的相對位置氫化學位移比較，有著向高磁場移動的現象，顯然5-乙氧羰基-2取代基-薁併[8,1-cd]噠嗪類化合物的性質與以往薁衍生物有所不同，推論此特性有利於在4-位置進行親電性反應。
將5-乙氧羰基-2取代基-薁併[8,1-cd]噠嗪類化合物與POCl3/DMF進行Vilsmeier-Haack反應，可得到5-乙氧羰基-2取代基-4 or 7-甲醯基薁併[8,1-cd]噠嗪類化合物。
在高溫條件下，5-乙氧羰基-1H-薁併[8,1-cd]噠嗪與POCl3/DMF反應，可在第4位置接上甲醯基，得到5-乙氧羰基-1H-4-甲醯基薁併[8,1-cd]噠嗪；5-乙氧羰基-1H-3-三氟甲基薁併[8,1-cd]噠嗪與POCl3/DMF反應，可在第7位置接上甲醯基，得到5-乙氧羰基-1H-3-三氟甲基-7-甲醯基薁併[8,1-cd]噠嗪。
5-乙氧羰基-1H-薁併[8,1-cd]噠嗪可與甲基乙烯基酮進行Michael addition反應，在酸性條件下，進行α,β不飽和共軛加成，得到3個化合物，分別為5-乙氧羰基-1H-4-(3-氧基丁基)薁併[8,1-cd]噠嗪24；5-乙氧羰基-2,4-二(3-氧基丁基)薁併[8,1-cd]噠嗪25；5-乙氧羰基-1H-4,7-二(3-氧基丁基)薁併[8,1-cd]噠嗪26。

關鍵字

薁

並列摘要

Abstract
In thesis,the 5-ethylcarbonyl-2H-azuleno[8,1-cd]pyridazine have been synthesized,while the property was also discussed.
The synthesis of 2-substituted-5-ethylcarbonyl-2H-azuleno[8,1-cd]pyridazine which have three methods. (a) Using the POCl3/DMF to proceed Vilsmeier-Haack reaction. (b) The reaction of 1-ethylcarbonyl-3-acetyl(or trifluroacetyl)-4-ethoxylazulene with phenyl hydrazine. (c) The reaction of 5-ethylcarbonyl-1H-azuleno[8,1-cd]pyridazine derivatives with methyl iodide to proceed alkylation.
A comparison of 1HNMR observed for 2-substituted-5-ethylcarbonyl -2H- azuleno[8,1-cd]pyridazine with starting material, which is found that the 4,6,7,8,9-position of 2-substituted-5-ethylcarbonyl-2H-azuleno[8,1-cd] pyrida- zine chemical shift toward high fields. It was apparent that the property of 2-substituted-5-ethylcarbonyl-2H-azuleno[8,1-cd]pyridazine differs from the azulene derivatives in the past.
2-substituted-5-ethylcarbonyl-2H-azuleno[8,1-cd]pyridazine by POCl3/DMF as the Vilsmeier-Haack reaction reagent to synthesize 2-substituted- 5- ethyl- carbonyl- 4 or 7- formylazuleno[8,1-cd]pyridazine derivatives.
The reaction of 5-ethylcarbonyl-1H-azuleno[8,1-cd]pyridazine derivatives with POCl3/DMF in high temperature to afford 5-ethylcarbonyl-1H-azuleno- 4-formyl[8,1-cd]pyridazine derivatives, while the reaction of 5-ethylcarbonyl- 1H-azuleno[8,1-cd]pyridazine and methyl vinyl ketone in acid condition give three products: 5-ethylcarbonyl-4-(3-oxo-propyl)-1H-azuleno[8,1-cd]pyridazine 24;5-ethylcarbonyl-2,4-(3-oxo-propyl)-2H-azuleno[8,1-cd]pyridazine25; 5-ethylcarbonyl-4,7-(3-oxo-propyl)-1H-azuleno[8,1-cd]pyridazine 26.

並列關鍵字

azulene

參考文獻

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