One-Pot Synthesis of Unsymmetrical Bis(4-Hydroxycoumarin-3-yl)methanes

Abstract

Unsymmetrical bis(4-hydroxycoumarin-3-yl)methane derivatives have been synthesized from 4-hydroxycoumarins, aldehydes, and secondary amines via 3-(aminoalkyl)-4-hydroxycoumarin intermediates, followed by substitution.

Key words

Mannich base - Michael addition - bishydroxycoumarinylmethane - methylenebischromenone

• References and Notes

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• 25 -Hydroxy-3-[(4-hydroxy-2-oxo-2H-chromen-3-yl)(phenyl)methyl]-6-methyl-2H-chromen-2-one (6a); Typical Procedure Equimolar amounts of 4-hydroxycoumarin (1a; 0.162 g, 1 mmol), benzaldehyde (2a, 0.106 g, 1 mmol), and pyrrolidine (3; 0.071 g, 1mmol) in MeCN (5 mL) were stirred at r.t. for 2 h until the reaction was complete (TLC). During this period a precipitate appeared. 4-Hydroxy-6-methylcoumarin (5a; 0.176 g, 1 mmol) was added, and the mixture was reflux for 4.5 h until the reaction was complete (TLC). The mixture was cooled and the solid product was collected by filtration and crystallized (MeCN). The filtrate was diluted with hexane (20 mL) and passed through a short column of silica gel. The pyrrolidine that remained in the column was eluted with MeOH. Colorless crystalline solid; yield: 0.366 g (86%); mp 201 °C. IR (KBr) = 3158.6, 3023.0, 1609.2, 1649.1, 1560.3 cm^–1. ¹H NMR (500 MHz, DMSO-d ₆): δ = 2.30 (s, 3 H), 6.16 (s, 1 H), 7.30–8.19 (m, 12 H), 11.58 (s, 2 H). ¹³C NMR (125 MHz, DMSO-d ₆): δ = 20.8, 36.4, 103.8 (2C), 119.8, 119.9, 120.2, 120.3, 123.1, 125.1, 126.9 (2 C), 128.0 (2 C), 131.2, 131.9, 132.0, 132.1, 132.2, 142.8, 150.9, 152.8, 164.9 (2 C), 165.0 (2 C). HRMS (–ESI); m/z [M – H]^– Calcd for C₂₆H₁₈O₆: 425.1025; found: 425.1026.
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