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

Yubo Jiang; Shaojun Huang

doi:10.1055/s-0033-1340331

Synlett, Table of Contents

Synlett 2014; 25(3): 407-410
DOI: 10.1055/s-0033-1340331

letter

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

Yubo Jiang*

^aFaculty of Science, Kunming University of Science and Technology, Kunming 650500, P. R. of China Fax: +86(871)65312526 Email: ybjiang@kmust.edu.cn

,

Shaojun Huang

^bResearch Center for Analysis and Measurement, Kunming University of Science and Technology, Kunming 650093, P. R. of China

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Abstract

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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

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References

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

Supplementary Material

Supporting Information

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

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