烷基卤代物和六亚甲基四胺反应得到铵盐,接着用HCl乙醇溶液酸解得到伯胺的反应。反应机理和Gabriel反应(产物为胺),Sommelet反应(产物为醛)类似。对于Delépine反应, 活性卤代物(如苄基卤代物,烯丙基卤代物和α-卤代酮)的反应效果都很好。
优点为底物易得,副反应少,反应步骤简单,条件温和。六亚甲四胺已为叔胺,第一步只能在氮上引入一个烷基,因此水解后生成比较纯净的伯胺。
反应机理
经过 SN2 反应得到六亚甲基四铵盐,在氯仿中,原料是可溶的反应后产物可以结晶出来,通常不需要继续纯化。
反应实例
参考文献
1. (a) Delépine, M. Bull. Soc. Chim. Paris 1895, 13, 352-355; (b) Delépine, M. Bull.Soc. Chim. Paris 1897, 17, 292-295. Stephe Marcel Delépine (1871-1965) was born in St. Martin le Gaillard, France. He was a professor at the Collège de France after working for M. Bertholet at that institute. Delépine’s long and fruitful career in science encompassed organic chemistry, inorganic chemistry, and pharmacy.
2. Galat, A.; Elion, G. J. Am. Chem. Soc. 1939, 61, 3585-3586.
3. Wendler, N. L. J. Am. Chem. Soc. 1949, 71, 375-384.
4. Quessy, S. N.; Williams, L. R.; Baddeley, V. G. J. Chem. Soc., Perkin Trans. 1 1979, 512-516.
5. Blažzević, N.; Kolnah, D.; Belin, B.; Šunjić, V.; Kafjež, F. Synthesis 1979, 161-176.(Review).
6. Henry, R. A.; Hollins, R. A.; Lowe-Ma, C.; Moore, D. W.; Nissan, R. A. J. Org.
Chem. 1990, 55, 1796-1801.
7. Charbonnière, L. J.; Weibel, N.; Ziessel, R. Synthesis 2002, 1101-1109.
8. Xie, L.; Yu, D.; Wild, C.; Allaway, G.; Turpin, J.; Smith, P. C.; Lee, K.-H. J. Med.
Chem. 2004, 47, 756-760.
9. Loughlin, W. A.; Henderson, L. C.; Elson, K. E.; Murphy, M. E. Synthesis 2006,
1975-1980.
编译自:Name Reactions (A Collection of Detailed Reaction Mechanisms), Jie Jack Li, Delépine amine synthesis,page 198-199.