Hexamethylenetetramine → 3,5-Difluoro-2,4-dihydroxybenzaldehyde

HRID 355405Notes

Reaction equation

HRID 355405 reaction equation
[F:1][C:2]1[C:8]([OH:9])=[C:7]([F:10])[CH:6]=[CH:5][C:3]=1[OH:4].C1N2CN3CN(C2)CN1C3.FC(F)(F)[C:23](O)=[O:24]>>[F:1][C:2]1[C:3]([OH:4])=[C:5]([CH:6]=[C:7]([F:10])[C:8]=1[OH:9])[CH:23]=[O:24]

Participants

4

Reactant 3

HCID 4101HexamethylenetetramineHCID 6422Trifluoroacetic acidHCID 108445152,4-Difluororesorcinol

Product 1

HCID 189423273,5-Difluoro-2,4-dihydroxybenzaldehydeYield 59%

Procedure

A solution of 2,4-difluororesorcinol (0.50 g, 3.4 mmol) and hexamethylenetetraamine (0.96 g, 6.8 mmol) in 4 mL trifluoroacetic acid is heated to reflux for 24 hours. After cooling, the reaction is quenched by the addition of 2 mL 20% H2SO4, and then stirred for an additional hour. The reaction mixture is then poured into 50 mL water and extracted with EtOAc (50 mL×2), washed with brine (30 mL), dried over anhydrous MgSO4, and concentrated in vacuo. The residue is purified by sublimation to yield 0.35 g (59%) of Compound 13 as a colorless powder. Mp. 141°-143° C. 1H-NMR (DMSO-d6) δ 9.7 (s, 1H), 7.21 (dd, J=9.8; 6.5 Hz, 1H). 19 F-NMR(DMSO-d6) Φ 143.78 (t, J=9.8 Hz, 1F), 158.31 (d, J=6.5 Hz, 1F). Anal. calcd for C7H4F3O3 : C, 48.29; H, 2.32. Found: C, 47.87, H, 2.62.

Workup

  1. temperatureto reflux for 24 hours
  2. temperatureAfter cooling
  3. customthe reaction is quenched by the addition of 2 mL 20% H2SO4
  4. additionThe reaction mixture is then poured into 50 mL water
  5. extractionextracted with EtOAc (50 mL×2)
  6. washwashed with brine (30 mL)
  7. dry with materialdried over anhydrous MgSO4
  8. concentrationconcentrated in vacuo
  9. customThe residue is purified by sublimation

Sources & evidence

ORD record
ord-68f75e9935eb40d284fac4d0c4413604
Source dataset
uspto-grants-1998_11
Patent number
US05830912

Reaction notes

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