Methanol → Methyl 2,6-dichloro-4-(hydroxymethyl)benzoate

HRID 875412Notes

Reaction equation

HRID 875412 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([C:8](OC)=[O:9])[CH:5]=[C:4]([Cl:12])[C:3]=1[C:13]([O:15][CH3:16])=[O:14].[BH4-].[Na+].CO>O1CCCC1>[Cl:1][C:2]1[CH:7]=[C:6]([CH2:8][OH:9])[CH:5]=[C:4]([Cl:12])[C:3]=1[C:13]([O:15][CH3:16])=[O:14]

Participants

5

Reactant 3

HCID 887MethanolHCID 4311764Sodium borohydrideHCID 7730227Dimethyl 2,6-dichloroterephthalate

Product 1

HCID 66712920Methyl 2,6-dichloro-4-(hydroxymethyl)benzoateYield 80%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of dimethyl 2,6-dichlorobenzene-1,4-dicarboxylate (2.3 g, 8.7 mmol) in tetrahydrofuran (10 mL) was treated with sodium borohydride (0.496 g, 13 mmol) and heated to refluxing temperature. The reaction mixture was then treated drop wise with methanol (1 mL) and continued refluxing for about 2 hours. The reaction mixture was warmed to room temperature and quenched with saturated aqueous ammonium chloride solution followed by partitioning with ethyl acetate. The combined organic layer was washed with brine, dried over sodium sulfate, filtered and concentrated. The crude product was purified by silica gel column chromatography using ethyl acetate in hexane (10%) as an eluant to yield methyl 2,6-dichloro-4-(hydroxymethyl)benzoate as a colorless liquid (1.6 g, 80%).

Workup

  1. temperatureheated
  2. temperatureto refluxing temperature
  3. temperaturecontinued refluxing for about 2 hours
  4. customquenched with saturated aqueous ammonium chloride solution
  5. customby partitioning with ethyl acetate
  6. washThe combined organic layer was washed with brine
  7. dry with materialdried over sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe crude product was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-6dc1f2d7982d47929c08e708e487565d
Source dataset
uspto-grants-2015_03
Patent number
US08980911B2

Reaction notes

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