Direct Synthesis of 1-Arylprop-1-ynes with Calcium Carbide as an Acetylene Source

Abstract

A simple method is described for the synthesis of 1-arylprop-1-ynes directly from aromatic aldehyde p-tosylhydrazones by using calcium carbide as an acetylene source. The salient features of this protocol are its use of a readily available and easily handled source of acetylene, its operational simplicity, its high yield, and its broad substrate scope.

Key words

arylpropynes - calcium carbide - tosylhydrazones - aralkynes

• References and Notes

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• 23 1-Arylprop-1-ynes (2a–x); General Procedure A mixture of the appropriate aromatic aldehyde p-tosylhydrazone (1 mmol), calcium carbide (3 mmol, 0.20 g for 98% purity), ^t BuOK (2 mmol, 0.22 g), CuI (1.2 mmol, 0.23 g), and H₂O (4 mmol, 0.07 mL) in DMF (4 mL) was stirred at 90 °C for 6 h. When the reaction was complete, the mixture was filtered to remove solids and the liquor was extracted with EtOAc (3 × 10 mL) then washed with sat. brine (3 × 10 mL). The resulting organic phase was dried (Na₂SO₄) and concentrated under reduced pressure. The residue was purified by column chromatography (silica gel, PE). 1-Phenylprop-1-yne (2a) Colorless liquid; yield: 83.6 mg (72%). ¹H NMR (600 MHz, CDCl₃): δ = 7.39 (dd, J = 7.7, 2.0 Hz, 2 H), 7.30–7.24 (m, 3 H), 2.05 (s, 3 H). ¹³C NMR (151 MHz, CDCl₃): δ = 131.46, 128.17, 127.48, 124.01, 85.76, 79.71, 4.29. HRMS: m/z [M + H]⁺ calcd for C₉H₉: 117.0699; found: 117.0698. (2-Prop-1-yn-1-ylphenyl)amine (2h) Brown liquid; yield: 87.1 mg (66%). ¹H NMR (600 MHz, CDCl₃): δ = 7.24 (d, J = 7.8 Hz, 1 H), 7.10–7.06 (m, 1 H), 6.75 (d, J = 8.1 Hz, 1 H), 6.70 (t, J = 7.5 Hz, 1 H), 2.11 (s, 3 H). ¹³C NMR (151 MHz, CDCl₃): δ = 146.97, 132.01, 128.77, 118.29, 114.52, 109.40, 91.18, 76.06, 4.53. HRMS: m/z [M + H]⁺ calcd for C₉H₁₀N: 132.0808; found: 132.0808.
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