1-氮雜薁-2-酮類及1-氮雜薁類之選位性甲基化反應

Regloselective Methylation of I-Azaazulan-2-ones and I-Azaazulenes

吳吉輝(Chi-Rhi Wu) ； 楊寶旺(Paw-Wang Yang)

《化學》 66年2期 (1977/06) Pp. 45-50

https://doi.org/10.6623/chem.1977009

摘要

3-取代基-1-氮雜薁-2-酮類於鹼性溶液中可與碘甲烷進行選擇性的N-甲基化反應，3位取代基為拉電子基時收率較高，推電子基時收率較低。2-氯及2-甲氧基-1-氮雜薁與碘甲烷不反應，但分別和硫酸二甲酯能進行N-甲基化反應，而以過氯酸塩析出新的具有第四級胺結構的喹啉異構物；N-甲基-2-氯-1-氮雜薁過氯酸塩與N-甲基-2-甲氧基-1-氮雜薁過氯酸塩，且有相當產量。同時報告3-乙醯-1-氮雜薁-2-酮的甲基化反應合成新化合物2-甲氧基-3-乙醯-1-氮雜薁之方法。此等生成物的結構均依據元素分折，光譜分析等確定之。

並列摘要

The reaction s of 3-substituted-l-azaazulan-2-ones with methyl iodide in the presence of base were found to be N-selective methylations, the yield was found to be higher when the substituent is electron-withdrowing, and lower when it is electrondonating. On the other hand, 2-chloro, and 2-methoxy-l-azaazulene did not reaet with methyl iodid e, but did react with dimethyl sulfat e and per chl oric acid giving N-methyl-2-Chloro-l-azaazulenium perchlorate (V) and N- methyl-2-methoxy-l-azaazulenium per chlo rate (VI) , respect ively, in fair yields. Compounds (V) and (VI) are derivatives of isomers of quinoline both possessing with the structure of a quaternary amine. The synthesis of 2-methoxy-3-acetyl-l-azaazulene from 3-acetyl-l-azaazulan-2-one is also reported. The structure assignment was based on elemental analysis and spectroscopic methods.