tert-Butyl Peroxybenzoate Mediated Selective and Mild N-Benzoylation of Ammonia/Amines under Catalyst- and Solvent-Free Conditions

Abstract

A new protocol for the synthesis of amides from tert-butyl peroxybenzoate (TBPB) and ammonia/amines has been developed under catalyst- and solvent-free conditions. The ammonia, primary and secondary amines reacted smoothly with TBPB to furnish the corresponding primary, secondary, and tertiary amides in excellent yields. TBPB proved to be an efficient and highly chemoselective benzoylating reagent for aliphatic amines in the presence of aromatic amines/ ­hydroxyl groups.

Key words

tert-butyl peroxybenzoate - N-benzoylation - catalyst-free - solvent-free - amides

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• 18 General Experimental Procedure for the Synthesis of Amide from Ammonia/Amine and TBPBA mixture of TBPB (1 mmol) and requisite aq NH₃ or amine (1.1 mmol) were charged in a round-bottom flask. The reaction mixture was stirred at r.t. for the indicated time, and progress of the reaction was monitored by TLC/GC. The crude product was directly purified by column chromatography (silica gel, 100–200 mesh, PE–EtOAc) to provide the desired pure product. The identity of the compound was confirmed by ¹H NMR and ¹³C NMR spectroscopic methods. N-(4-Methoxybenzyl)benzamide (3c) ^{17a 1}H NMR (400 MHz, CDCl₃): δ = 7.77 (d, J = 7.1 Hz, 2 H), 7.48 (t, J = 7.2 Hz, 1 H), 7.41 (t, J = 7.7 Hz, 2 H), 7.27 (d, J = 8.5 Hz, 2 H), 6.87 (d, J = 8.6 Hz, 2 H), 6.45 (br s, 1 H), 4.56 (d, J = 5.56 Hz, 2 H), 3.79 (s, 3 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 167.29, 159.11, 134.43, 131.50, 130.25, 129.31, 128.57, 126.95, 114.15, 55.31, 43.63 ppm. N-(4-Fluorobenzyl)benzamide (3e) ^{17a 1}H NMR (400 MHz, CDCl₃): δ = 7.78 (d, J = 8.0 Hz, 2 H), 7.49 (t, J = 7.3 Hz, 1 H), 7.40 (t, J = 7.7 Hz, 2 H), 7.31–7.25 (m, 2 H), 7.0 (t, J = 8.6 Hz, 2 H), 6.67 (br s, 1 H), 4.58 (d, J = 5.58 Hz, 2 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 167.45, 162.2 (d, J _C–F = 244 Hz), 134.21, 134.07, 131.64, 129.53 (d, J _C–F = 8 Hz), 128.60, 126.98, 115.56 (d, J _C–F = 21 Hz), 43.33 ppm. N-(3-Chlorobenzyl)benzamide (3f) ^{17b 1}H NMR (400 MHz, CDCl₃): δ = 7.78 (d, J = 7.16 Hz, 2 H), 7.49 (t, J = 8.4 Hz, 1 H), 7.41 (t, J = 7.7 Hz, 2 H), 7.30 (s, 1 H), 7.25–7.18 (m, 3 H), 6.77 (br s, 1 H), 4.58 (d, J = 5.72 Hz, 2 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 167.54, 140.34, 134.52, 134.04, 131.71, 129.99, 128.62, 127.80, 127.68, 127.01, 125.89, 43.42 ppm. N-(4-Cyanobenzyl)benzamide (3g) ^{17c 1}H NMR (400 MHz, CDCl₃): δ = 7.80 (d, J = 7.9 Hz, 2 H), 7.59 (d, J = 6.6 Hz, 2 H), 7.52 (t, J = 7.3 Hz, 1 H), 7.45–7.41 (m, 4 H), 6.89 (br s, 1 H), 4.67 (d, J = 6.0 Hz, 2 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 167.67, 143.96, 133.76, 132.47, 131.93, 128.70, 128.19, 127.02, 118.73, 111.21, 43.48 ppm.