Selective Reduction of Halogenated Nitroarenes with Hydrazine Hydrate in the Presence of Pd/C

Abstract

A large variety of halogenated nitroarenes have been selectively reduced with hydrazine hydrate in the presence of Pd/C to give the corresponding (halogenated) anilines in good yield.

Key words

reduction - nitroarenes - hydrazine hydrate - palladium on carbon - aromatic amines - transfer hydrogenation

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• 12 General Procedures; Method A: To a mixture of halogenated nitroarene (1 mmol), Pd/C(5%), and MeOH (5 mL) was added NH₂NH₂·H₂O (10 mmol), and the resulting solution was heated at 80 °C reflux condition for 5 min. Then the mixture was filtered and concentrated in vacuo. The crude material was purified by flash column chromatography using hexanes and EtOAc. Method B: To a mixture of halogenated nitroarene (1 mmol), Pd/C(10%), and MeOH (5 mL) was added NH₂NH₂·H₂O (10 mmol), and the resulting solution was heated at 120 °C by Biotage Initiator Classic microwave synthesizer for 15 min. The mixture was filtered and condensed in vacuo. The crude material was purified by flash column chromatography using hexanes and EtOAc. 2-Bromo-5-(tert-butyl)aniline (3a): compound 3a was prepared in 95% yield according to the general procedure (Method A). ¹H NMR (400 MHz, CDCl₃): δ = 7.31 (d, J = 8.4 Hz, 1 H), 6.79 (d, J = 2.3 Hz, 1 H), 6.66 (dd, J = 8.3, 2.4 Hz, 1 H), 4.02 (br s, 2 H), 1.27 (s, 9 H). ¹³C NMR (100 MHz, CDCl₃): δ = 151.8, 143.5, 132.0, 117.0, 113.1, 106.3, 34.5, 31.2 (3 × C).