Sommelet反应
卤化苄在六甲基四胺(HMTA)的作用下转化为相应的芳基甲醛的反应。反应机理与Delépine胺化反应类似。HMTA有刺鼻的臭鱼味,使用时要注意。
反应机理
氢的转移和六甲基四胺的开环也有可能是同时进行的。
反应实例
参考文献
1. Sommelet, M. Compt. Rend. 1913, 157, 852-854. Marcel Sommelet (1877-1952) was born in Langes, France. He received his Ph.D. In 1906 at Paris where he joined the Faculté de Pharmacie after WWI and became the chair of organic chemistry in 1934.【Marcel Sommelet (1877-1952)生于法国兰格。1906年在巴黎大学获得Ph.D.学位。一战后任职于巴黎大学药学院,并在1934年成为有机化学教授。】
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编译自:Name Reactions (A Collection of Detailed Reaction Mechanisms), Jie Jack Li, Sommelet reaction,page 568-569.
相关反应
Delépine胺合成反应
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.
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编译自:Name Reactions (A Collection of Detailed Reaction Mechanisms), Jie Jack Li, Delépine amine synthesis,page 198-199.