Formaldehyde → HCID 54283426, compound

HRID 2398702Notes

Reaction equation

HRID 2398702 reaction equation
[OH:1][C:2]1[CH:3]=[C:4]([CH2:10][C:11]([OH:13])=[O:12])[CH:5]=[CH:6][C:7]=1[O:8][CH3:9].C1(C[C:21](O)=[O:22])C=CC=CC=1.C=O>C1C=CC=CC=1>[OH:1][C:2]1[C:3]([CH2:21][OH:22])=[C:4]([CH2:10][C:11]([OH:13])=[O:12])[CH:5]=[CH:6][C:7]=1[O:8][CH3:9]

Participants

5

Reactant 3

HCID 712FormaldehydeHCID 999Phenylacetic AcidHCID 1605623-Hydroxy-4-methoxybenzeneacetic acid

Product 1

HCID 54283426HCID 54283426, compoundYield 83%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

11.0 g of 3-hydroxy-4-methoxyphenylacetic acid is dissolved in 550 ml of benzene and refluxed to remove water as azeotrope. Then, 14.0 g of benzeneboronic acid is added thereto, and refluxed for approximately 1 hour while removing the water produced. (In this reaction, the starting phenylacetic acid works as the carboxylic acid catalyst). At 2-3 hour intervals, each 2-3 g of paraformaldehyde is added while continuing the removal of water, and after the lapse of 9 hours an additional 1.0 g of benzeneboronic acid is added thereto. The reaction is completed within a period of 20 hours, and the solvent is completely distilled off under reduced pressure. The crystalline residue after addition of 150 ml of water is kept on an oil bath at 90°-100° C. for 1.5 hours under stirring. The reaction mixture is cooled to room temperature, and the precipitated crystals are collected and recrystallized from acetone-ether to give 9.70 g (83% yield) of 3-hydroxy-2-hydroxymethyl-4-methoxyphenylacetic acid as the δ-lactone having mp. 183°-185° C. IR νmaxCHCl 3 3540, 1740, 1600, 1277, 1030, 983cm-1. NMR (d6 -DMSO) δ 3.80 (3H. singlet), 3.65 (2H, singlet), 5.32 (2H, singlet), 6.70, 6.90 (AB quartet, J = 8.0 Hz), 8.07 (1H, singlet) ppm. Anal. Aclcd. for C10H10O4 : C, 61.85; H, 5.19 (%). Found: C, 61.70; H, 5.17 (%).

Workup

  1. temperaturerefluxed
  2. customto remove water as azeotrope
  3. additionThen, 14.0 g of benzeneboronic acid is added
  4. temperaturerefluxed for approximately 1 hour
  5. customwhile removing the water
  6. customproduced
  7. custom(In this reaction
  8. customthe removal of water
  9. additionafter the lapse of 9 hours an additional 1.0 g of benzeneboronic acid is added
  10. waitThe reaction is completed within a period of 20 hours
  11. distillationthe solvent is completely distilled off under reduced pressure
  12. additionThe crystalline residue after addition of 150 ml of water
  13. waitis kept on an oil bath at 90°-100° C. for 1.5 hours
  14. customthe precipitated crystals are collected
  15. customrecrystallized from acetone-ether

Sources & evidence

ORD record
ord-482b83c2486640aab9204ded4cabd08c
Source dataset
uspto-grants-1977_05
Patent number
US04025553

Reaction notes

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