Hydrochloric Acid → Benzoic acid, 3-formyl-4-hydroxy-, methyl ester

HRID 2219456Notes

Reaction equation

HRID 2219456 reaction equation
[OH:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][CH:3]=1.[CH3:12]S(O)(=O)=O.C1N2CN3CN(C2)CN1C3.Cl.[OH2:28]>>[CH:12]([C:11]1[CH:10]=[C:5]([CH:4]=[CH:3][C:2]=1[OH:1])[C:6]([O:8][CH3:9])=[O:7])=[O:28]

Participants

6

Reactant 5

HCID 313Hydrochloric AcidHCID 962WaterHCID 4101HexamethylenetetramineHCID 6395Methanesulfonic AcidHCID 7456Methylparaben

Product 1

HCID 212595Benzoic acid, 3-formyl-4-hydroxy-, methyl esterYield 31%

Conditions

Temperature
100 °C

Procedure

To a mixture of methyl 4-hydroxybenzoate (20 g, 131 mmol) and methanesulfonic acid (80 mL), hexamethylenetetramine (20 g, 144 mmol) was added in small portions at room temperature. After stirring at 100° C. for 3.5 hours, concentrated hydrochloric acid (10 mL) and water (300 mL) were added. The reaction mixture was extracted twice with ethyl acetate and the organic phase was dried over anhydrous magnesium sulfate. After the solvent was distilled off under reduced pressure, the resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate=80:20-65:35) to give methyl 3-formyl-4-hydroxy-benzoate (7.24 g, 31%, mp 87.5-89.0° C.) as a colorless powder.

Workup

  1. additionwas added in small portions at room temperature
  2. extractionThe reaction mixture was extracted twice with ethyl acetate
  3. dry with materialthe organic phase was dried over anhydrous magnesium sulfate
  4. distillationAfter the solvent was distilled off under reduced pressure
  5. customthe resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate=80:20-65:35)

Sources & evidence

ORD record
ord-a7cc1990e9f941dfb49fcdb5105def2d
Source dataset
uspto-grants-2008_08
Patent number
US07414072B2

Reaction notes

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