Transition-Metal-Free Synthesis of Quinoxalines from o-Phenylenediamines and Arylacetaldehydes under Basic Conditions

Abstract

A novel method for the synthesis of quinoxalines via transition-metal-free cyclization of o-phenylenediamine and aryl­acetaldehyde in a one-pot procedure has been developed. In this process, an inorganic base (K₂CO₃) is the only reagent required, and it proceeds smoothly in the absence of adding transition metal catalysts. The reaction appears to be very general and suitable for the construction of a variety of quinoxalines.

Key words

quinoxalines - o-phenylenediamine - arylacetaldehyde - oxidation - condensation - transition-metal-free

• References and Notes

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• 22 General Procedure of the Reaction between o-Phenylenediamines and Arylacetaldehydes – Synthesis of 2-Phenylquinoxaline (3aa) o-Phenylenediamine (1a, 27 mg, 0.25 mmol), phenylacetaldehyde (2a, 58 μL, 0.5 mmol), K₂CO₃ (69 mg, 0.5 mmol), and toluene (2 mL) were added to a flask with a magnetic stirred bar. The reaction mixture was stirred for 8 h at 90 °C. The solution was then cooled to r.t., diluted with EtOAc and filtered. The filtrate was removed under the reduced pressure to get the crude product. The crude product was purified by column chromatography on silica gel (PE–EtOAc = 20:1) to afford 3aa (83% yield) as light yellow solid; mp 62–64 °C. ¹H NMR (300 MHz, CDCl₃): δ = 9.32 (s, 1 H), 8.20–7.80 (m, 4 H), 7.79–7.71 (m, 2 H), 7.59–7.51 (m, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 151.8, 143.3, 142.2, 141.5, 136.7, 130.2, 130.1, 129.6, 129.5, 129.1, 127.5 ppm. ESI-HRMS: m/z calcd for C₁₄H₁₀N₂ [M + H]⁺: 207.0917; found: 207.0913.