A Mild and Efficient Method for the Deformylation of 5-Formyl Uracils and Synthesis of 4,4′-Methylidenebis(1-phenyl-3-methyl-5-pyrazolone)

Abstract

6-Substituted 5-formyl uracils undergo an interesting reaction with 1-phenyl-3-methyl-5-pyrazolone in the presence of base catalyst to afford deformylated uracils and 4,4′-methylidenebis(1-phenyl-3-methyl-5-pyrazolone) in excellent yields.

Key words

uracil - deformylation - pyrazolone - 4,4′-methylidene­bis(1-phenyl-3-methyl-5-pyrazolone)

References and Notes

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18

In a simple experimental procedure, N,N-dimethyl-5-formyl-6-hydroxyuracil (1a; 184 mg, 1 mmol) and 1-phenyl-3-methyl-5-pyrazolone (2; 348 mg, 2 mmol) were stirred in ethanol (8 mL) at r.t. in the presence of two drops of piperidine for 30 min. The dark-orange solid compound 4 that appeared was filtered, washed with cold ethanol and dried in air. Yield: 286 mg (80%); mp 182-184 ˚C (Lit.^¹³ 183-184 ˚C); ^¹H NMR (300 MHz, CDCl₃): δ = 2.36 (s, 6 H), 7.18-7.31 (m, 3 H), 7.45 (t, J = 7.52 Hz, 4 H), 7.91 (d, J = 7.72 Hz, 4 H); ^¹³C NMR (75 MHz, CDCl₃): δ = 13.46, 110.03, 121.60, 127.08, 129.44, 138.18, 138.82, 153.27, 161.78; MS: m/z = 357.5 [M - H]⁺. The solvent was evaporated and the residue was purified by column chromatography using CH₂Cl₂ as eluent. The yield of product 3a = 80% (125 mg); mp 120-122 ˚C (Lit.^¹9 121-122 ˚C); ^¹H NMR (300 MHz, CDCl₃): δ = 3.31 (s, 6 H), 3.69 (s, 2 H); IR: 3364, 1706, 1651 cm^-¹; MS (EI): m/z = 157
[M + H]⁺, 155 [M - H]⁺.