哈米克反應

哈米克反應(英語:Hammick reaction),得名於英國化學家達爾齊爾·哈米克,指在羰基化合物存在下,α-吡啶甲酸及其類似物受熱轉變為2-吡啶原醇[1][2][3]

哈米克反應
哈米克反應

對異丙基甲苯作溶劑可提高反應產率。[4]

反應機理

加熱時,α-吡啶甲酸發生脫羧,生成兩性離子(2)。該離子與強親電試劑(如)作用,發生對羰基的親核加成。加成產物發生質子轉移,便得到原醇(4)。

 
哈米克反應的機理

參見

參考資料

  1. ^ Dyson, P.; Hammick, D. L. 362. Experiments on the mechanism of decarboxylation. Part I. Decomposition of quinaldinic and isoquinaldinic acids in the presence of compounds containing carbonyl groups. J. Chem. Soc. 1937: 1724. doi:10.1039/jr9370001724. 
  2. ^ Hammick, D. L.; Dyson, P. 172. The mechanism of decarboxylation. Part II. The production of cyanide-like ions from α-picolinic, quinaldinic, and isoquinaldinic acids. J. Chem. Soc. 1939: 809. doi:10.1039/jr9390000809. 
  3. ^ Brown, E. V.; Shambhu, M. B. Hammick reaction of methoxypyridine-2-carboxylic acids with benzaldehyde. Preparation of methoxy-2-pyridyl phenyl ketones. J. Org. Chem. 1971, 36: 2002. doi:10.1021/jo00813a034. 
  4. ^ Sperber, N.; Papa, D.; Schwenk, E.; Sherlock, M. Pyridyl-Substituted Alkamine Ethers as Antihistaminic Agents. J. Am. Chem. Soc. 1949, 71: 887. doi:10.1021/ja01171a034.