Water → 3-Formyl-4-hydroxy-5-methylbenzoic acid

HRID 855109Notes

Reaction equation

HRID 855109 reaction equation
[OH:1][C:2]1[CH:10]=[CH:9][C:5]([C:6]([OH:8])=[O:7])=[CH:4][C:3]=1[CH3:11].[CH2:12]1N2CN3CN(C2)CN1C3.[OH2:22]>CS(O)(=O)=O>[CH:11]([C:3]1[CH:4]=[C:5]([CH:9]=[C:10]([CH3:12])[C:2]=1[OH:1])[C:6]([OH:8])=[O:7])=[O:22]

Participants

5

Reactant 3

HCID 962WaterHCID 4101HexamethylenetetramineHCID 681384-Hydroxy-3-methylbenzoic acid

Product 1

HCID 865994903-Formyl-4-hydroxy-5-methylbenzoic acidYield 75%

Reagents, catalysts & solvents 1

HCID 6395Methanesulfonic AcidSolvent

Conditions

Temperature
0 °C

Procedure

The 4-hydroxy-3-methylbenzoic acid (10.1 g, 66.38 mmole) was suspended in methanesulfonic acid (50 mL) and cooled to 0° C. (ice bath). Hexamethylenetetramine (18.6 g, 132.75 mmole) was added portionwise over 1 hour. The reaction was warmed to room temperature followed by heating to 90° C. (oil bath) for 5 hours. The reaction was allowed to cool to room temperature and stired for 18 hours. The contents were poured into water (100 mL) and extracted with EtOAc (2×100 mL). The combined extracts were washed with brine (50 mL), dried over MgSO4, filtered and concentrated in vacuo to give an off-white solid (9.0 g, 75%). 1H NMR (DMSO/400 MHz) 12.84 (brs, 1H), 11.40 (s, 1H), 10.09 (s, 1H), 8.20 (s, 1H), 7.98 (s, 1H), 2.21 (s, 3H).

Workup

  1. temperatureThe reaction was warmed to room temperature
  2. temperatureby heating to 90° C. (oil bath) for 5 hours
  3. temperatureto cool to room temperature
  4. extractionextracted with EtOAc (2×100 mL)
  5. washThe combined extracts were washed with brine (50 mL)
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-c590acba076f44329984d03a91994eeb
Source dataset
uspto-grants-2007_08
Patent number
US07259266B2

Reaction notes

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