A Microwave-Assisted Three-Component Synthesis of Arylaminomethyl ­Acetylenes: A Facile Access to Terminal Alkynes

Abstract

A simple, rapid, one-pot synthesis of arylaminomethyl acetylenes is achieved under microwave-assisted conditions (power = 5 W) using aromatic boronic acids, aqueous ammonia, propargyl halides, copper(I) oxide and water as the solvent. The reactions are complete within ten minutes affording good to excellent yields of the products.

Key words

microwave-assisted - three-component - ammonia - propargyl halide - terminal alkynes

• References and Notes

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• 11 Compounds 4; General Procedure To a microwave reaction tube were added aromatic boronic acid 1 (0.5 mmol), ammonia (2) (0.6 mmol, 25% aq solution), propargyl halide 3 (0.5 mmol), K₂CO₃ (138 mg, 1 mmol), and H₂O (2 mL). The reaction was conducted under microwave irradiation (5 W, CEM Discover-SP) for 10 min (with monitoring by TLC). After completion, the mixture was diluted with H₂O (30 mL) and then extracted with EtOAc (3 × 20 mL). The combined organic layer was washed with H₂O (3 × 10 mL) and brine (3 × 10 mL), and then dried over anhydrous Na₂SO₄. Evaporation of the solvent provided a crude residue, which was subjected to column chromatography over silica gel (EtOAc–PE, 1:8→1:3) to afford arylaminomethyl acetylene 4. 4-Methyl-N-(prop-2-ynyl)aniline (4a) Yield: 64 mg (88%); yellow oil. IR (KBr): 3397, 3289, 1616, 1519, 1482, 809 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 7.03 (d, J = 8.18 Hz, 2 H), 6.62 (d, J = 8.27 Hz, 2 H), 3.91 (d, J = 2.22 Hz, 2 H), 3.73 (s, 1 H), 2.25 (s, 3 H), 2.20 (s, 1 H). ^2a N-(Prop-2-ynyl)aniline (4b) Yield: 56 mg (86%); yellow oil. IR (KBr): 3405, 3288, 1505, 1440, 752 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 7.22 (t, J = 7.89 Hz, 2 H), 6.79 (t, J = 7.33 Hz, 1 H), 6.69 (d, J = 7.85 Hz, 2 H), 3.94 (d, J = 2.25 Hz, 2 H), 3.87 (s, 1 H), 2.21 (s, 1 H).^1c