Arndt–Eistert同系化反应

羧酸经过重氮甲烷处理得到多一个碳的同系物的反应。此反应是非常好的制备多一个碳的羧酸的方法。此反应中羧酸首先转化为酰氯或活性酯，接着和重氮甲烷反应得到α-重氮甲基酮，最后进行Wolff重排得到产物。Wolff重排过程可以在氧化银/水条件下进行，也可以在苯甲酸银/三乙胺条件下进行。产率一般在50-80%之间。反应如果在醇类或胺类存在下进行，则生成相应的酯或酰胺。其他金属（Pt, Cu）也可催化重氮酮的分解。另外在加热或光照条件下在亲核溶剂(H2O, ROH, or RNH2)中也可以进行反应，不需要另外加入催化剂。

反应机理

反应实例

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相关文献

1. Arndt, F.; Eistert, B. Ber. 1935, 68, 200-208. Fritz Arndt (1885-1969) was born in Hamburg, Germany. He discovered the Arndt-Eistert homologation at the University of Breslau where he extensively investigated the synthesis of diazomethane and its reactions with aldehydes, ketones, and acid chlorides. Fritz Arndt’s chain-smoking of cigars ensured that his presence in the laboratories was always well advertised. Bernd Eistert (1902-1978), born in Ohlau, Silesia, was Arndt’s Ph.D. student. Eistert later joined I. G. Farbenindustrie, which became BASF after the Allies broke up the conglomerate following WWII. 【 Fritz Arndt (1885-1969) 出生于德国汉堡。他在布雷斯劳大学任教期间发现了Arndt-Eister同系化反应，在这期间他主要研究重氮甲烷的合成以及重氮甲烷和醛酮及酰氯的反应。 另外有趣的是Fritz Arndt广为人知的形象是一个做实验的老烟鬼。Bernd Eistert (1902-1978), 出生于Ohlau, Silesia，是Arndt的 Ph.D.学生。他后来进入了法本化学工业股份公司（二战同盟国胜利后被重组为巴斯夫）工作。】

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编译自：J.J. Li, Name Reactions: A Collection of Detailed Mechanisms and Synthetic Applications,  Arndt–Eistert homologation，page10-11.