Synthesis of Diarylethynes from Aryldiazonium Salts by Using Calcium Carbide as an Alkyne Source in a Deep Eutectic Solvent

Abstract

An efficient method for the synthesis of diarylethynes from aryldiazonium salts by using calcium carbide as an alkyne source at room temperature in a deep eutectic solvent is described. The salient features of this protocol are an inexpensive and easy-to-handle alkyne source, a nonvolatile and recyclable solvent, mild conditions, and a simple workup procedure.

Key words

calcium carbide - aryldiazonium salts - deep eutectic solvents - diarylethynes - alkynes

Publication History

Received: 10 October 2020

Accepted after revision: 16 November 2020

Article published online:
14 December 2020

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• 21 Diarylethynes 2a–r: General Procedure The appropriate aryldiazonium tetrafluoroborate 1 (0.4 mmol), CaC₂ (77 mg, 1.2 mmol), Pd(PPh₃)₄ (23 mg, 0.02 mmol), CuI (8 mg, 0.04 mmol), NaI (180 mg, 1.2 mmol), and H₂O (173 mg, 9.6 mmol) in DES (1:2 choline chloride–urea) (4 mL) were stirred at r.t. for 5 h. When the reaction was complete (TLC), H₂O (2 mL) and EtOAc (2 mL) were added. The resulting mixture was subjected to ultrasonication for 5 min, then filtered to remove solids. The liquor was extracted with EtOAc (3 × 10 mL), and the extracts were washed with saturated 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–EtOAc). Diphenylethyne (2a) White solid; yield: 29.5 mg (83%); mp 59–61 °C. ¹H NMR (600 MHz, CDCl₃): δ = 7.53 (dd, J = 8.0, 2.0 Hz, 4H), 7.35–7.33 (m, 6 H). ¹³C NMR (100 MHz, CDCl₃): δ = 131.6, 128.3, 128.2, 123.3, 89.3. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₄H₁₁: 179.0855; found: 179.0852. Bis(4-ethoxyphenyl)ethyne (2j) Yellow solid; yield: 35.6 mg (67%); mp 163–166 °C. ¹H NMR (600 MHz, CDCl₃): δ = 7.42 (d, J = 8.8 Hz, 4 H), 6.84 (d, J = 8.7 Hz, 4 H), 4.04 (q, J = 7.0 Hz, 4 H), 1.41 (t, J = 7.0 Hz, 6 H). ¹³C NMR (150 MHz, CDCl₃): δ = 158.7, 132.8, 115.6, 114.5, 87.9, 63.5, 14.7. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₈H₁₉O₂: 267.1380; found: 267.1382.