FIELD: chemistry.
SUBSTANCE: invention relates to processes of preparing aromatic or fatty-aromatic ketones by reaction of aromatic chlorides or bromides or iodides with an aliphatic or aromatic nitriles, including intramolecular reactions containing nitrile group of aromatic chlorides, bromides or iodides, initially resulting compound with bond C=N undergoes subsequent hydrolysis to form the desired product. In particular, a process of preparing aromatic or aliphatic-aromatic ketones of the general formula R1C(O)R2, where R1 - aryl or hetaryl, and R2 - aryl or hetaryl or alkyl comprises reacting aromatic halide R1X, wherein R1 - aryl or hetaryl, and X=Cl, Br, I with nitriles R2CN, where R2 - aryl or hetaryl, or alkyl, which is carried out in the presence of a catalyst comprising nickel atom coordinated with a chelate ligand containing 1,4-diazabutadiene fragment (N=C-C=N), and a reducing agent in an ether solvent at molar ratios: R1X:R2CN, located within the range of from 2:1 to 1:20, Ni:(chelating ligand) is located within the range of from 1:1 to 1:2, Ni:R1X, is located in the range of from 1:200 to 1:2, the reducing agent: R1X, is located in the range of from 1:2 to 10:1, and the volume of the solvent with respect to the amount of the halide R1X is in the range of 0.5 to 20 ml/mmol, at a reaction temperature of 0-120°C, and the subsequent hydrolysis of the initially formed compound with the connection of C=N.
EFFECT: expansion of the arsenal of tools, the use of compounds as starting aryl bromides and aryl chlorides, cheaper and more readily available; use of at least twice lower catalyst loads; possibility of carrying out the reaction at a lower temperature; the possibility of carrying out the reaction in a shorter time.
18 cl, 40 ex
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Authors
Dates
2017-08-21—Published
2016-05-23—Filed