Suzuki–Miyaura Reactions of 2,7-Dichloro-1,8-naphthyridine

Abstract

2,7-Diaryl- and 2,7-dialkenyl-1,8-naphthyridines were prepared in high yields by Suzuki–Miyaura reactions of 2,7-dichloro-1,8-naphthyridines. While most of the products proved to be not or only weakly fluorescent, we observed a strong fluorescence in case of 2,7-bis(4-methoxyphenyl)-1,8-naphthyridine containing two electron-donating aryl groups.

Key words

catalysis - heterocycles - palladium - cross-coupling ­reactions - nitrogen

• References and Notes

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• 21 General Experimental Procedure: To an argon-flushed glass pressure tube were added Pd₂(dba)₃ (0.01 mmol, 2.5 mol%), S-Phos (0.04 mmol, 10 mol%), 3 (80 mg, 0.4 mmol), the arylboronic acid (1.2 mmol, 3.0 equiv), K₃PO₄ (1.2 mmol, 3.0 equiv), followed by anhyd 1,4-dioxane (3 mL). The tube was closed by a teflon screw cap and the reaction mixture was stirred at 100 °C for 20 h. Subsequently the mixture was cooled to r.t. and diluted with H₂O and CH₂Cl₂. The layers were separated and the aqueous layer was extracted twice with CH₂Cl₂. The combined organic layers were dried with Na₂SO₄, filtered and the solvent was evaporated. The residue was purified by column chromatography (silica gel, hexane–CH₂Cl₂).
• 22 Synthesis of 2,7-Diphenyl-1,8-naphthyridine (4a): Following the general procedure, 4a was isolated as a colorless solid (101 mg, 90%); mp 195–197 °C. ¹H NMR (300 MHz, CDCl₃): δ = 7.37–7.47 (m, 6 H, CH_Ar), 7.86 (d, ³ J = 8.7 Hz, 2 H, CH_Hetar), 8.15 (d, ³ J = 8.5 Hz, 2 H, CH_Hetar), 8.21 (dd, ³ J = 8.0 Hz, ⁴ J = 1.6 Hz, 4 H, CH_Ar). ¹³C NMR (75 MHz, CDCl₃): δ = 119.6 (CH_Ar/Hetar), 120.6 (C_Ar/Hetar), 128.1, 128.7 (CH_Ar), 130.0, 137.4 (CH_Ar/Hetar), 138.7, 156.1, 160.9 (C_Ar/Hetar). IR (ATR): 3045 (w), 1583 (m), 1537 (m), 1463 (m), 1305 (m), 1141 (m), 1117 (m), 922 (m), 849 (s), 781 (s), 611 (m) cm^–1. MS (EI, 70 eV): m/z (%) = 282 (100) [M⁺], 253 (2), 205 (4), 203 (4), 177 (4), 151 (4), 140 (8), 127 (4). HRMS (EI, 70 eV): m/z calcd for C₂₀H₁₄N₂: 282.11515; found: 282.11479.