A Remarkably Efficient Markovnikov Hydrochlorination of Olefins and Transformation of Nitriles into Imidates by Use of AcCl and an Alcohol

Abstract HCl generated by mixing AcCl with EtOH brings about Markovnikov hydrochlorination of olefins in excellent yields. The products are isolated in states of high purity simply by removal of the volatile components under reduced pressure. Further, nitriles are transformed into imidate hydrochlorides on similar treatment with AcCl and an alcohol. This procedure for nitrile‐imidate transformation is much more efficient than that used previously, which involved continuous passing of HCl gas into the solution of a nitrile in a solvent such as Et 2 O or benzene and an alcohol until one equivalent had been absorbed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)