A New Sustainable Multistep Catalytic Process from Benzene to Caprolactam: Amination, Hydroximation and Beckmann Rearrangement Promoted and Catalyzed by Trifluoroacetic Acid.

Unlabelled: Here we report some results on a 3 steps benzene caprolactam process via amination, aniline Hydroxymation and Beckmann rearrangement. The amination proceeds with hydroxylamine trifluoroacetate, with 97% of conversion and selectivity of 90%, catalyzed by V compounds. We achieve 98% of conversion and 95% of selectivity in the hydroxymation of aniline in the presence of hydroxylamine trifluoroacetate, sulfonic resin and Pd/C. While in the absence of the resin, hydrogenation of hydroxylamine trifluoroacetate occurs readily to the ammonium salt. The reaction occurs likely by the exchanged hydroxylamine and the aniline reduction intermediate. The use of hydroxylamine trifluoroacetate, instead of the chloride, favors the sustainability of the process by avoiding the ammonium chloride formation. The absence of salt except those derived from the trifluoroacetic acid allows a complete reuse of the trifluoroacetic acid and the only byproduct is ammonium nitrate obtained by resin regeneration. Beckmann rearrangement of the so produced cyclohexanone oxime occurs easily after diethyl ether evaporation and additions of a solution trifluoroacetic acid acetonitrile in high yield and selectivity.

Graphical Abstract: New three steps caprolactam process via benzene amination and aniline hydrogenation.

Supplementary Information: The online version contains supplementary material available at 10.1007/s10562-022-04207-9.