Hydrochloric Acid → 5-Chloro-2-(hydroxymethyl)phenol

HRID 1433042Notes

Reaction equation

HRID 1433042 reaction equation
[H-].[H-].[H-].[H-].[Li+].[Al+3].[Cl:7][C:8]1[CH:9]=[C:10]([OH:17])[C:11](=[CH:15][CH:16]=1)[C:12](O)=[O:13].O.Cl>C1COCC1.C(OCC)(=O)C>[Cl:7][C:8]1[CH:16]=[CH:15][C:11]([CH2:12][OH:13])=[C:10]([OH:17])[CH:9]=1

Participants

7

Reactant 4

HCID 313Hydrochloric Acid2×HCID 962WaterHCID 787824-Chlorosalicylic acidHCID 21226445Aluminium lithium hydride

Product 1

HCID 3271485-Chloro-2-(hydroxymethyl)phenolYield 70.4%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

To 7 g of LiAlH4 in 200 ml of THF is added portionwise 15 g of 4-chlorosalicylic acid. The resulting mixture is heated under reflux for one hour, cooled and stirred at room temperature for 21 hours. Water (7 ml) in THF (50 ml) is added dropwise, followed by 1N hydrochloric acid (250 ml), concentrated hydrochloric acid (50 ml) and ethyl acetate (200 ml). After filtration on a pad of celite the two layers are separated, the organic layer washed with brine, dried over magnesium sulfate, concentrated. The brown oil is dissolved in iso-propyl ether and filtered on a short column of silica gel. After concentration the solid is crystallized in cyclohexane, filtered, washed and dried to give 4-chloro-2-hydroxy-benzylalcohol as a white solid (9.7 g, 70% yield) C7H7ClO2 MS (M+) m/z: 158, 160, Cl pattern.

Workup

  1. temperatureThe resulting mixture is heated
  2. temperatureunder reflux for one hour
  3. temperaturecooled
  4. filtrationAfter filtration on a pad of celite the two layers
  5. customare separated
  6. washthe organic layer washed with brine
  7. dry with materialdried over magnesium sulfate
  8. concentrationconcentrated
  9. dissolutionThe brown oil is dissolved in iso-propyl ether
  10. filtrationfiltered on a short column of silica gel
  11. concentrationAfter concentration the solid
  12. customis crystallized in cyclohexane
  13. filtrationfiltered
  14. washwashed
  15. customdried

Sources & evidence

ORD record
ord-07613e44d00a45078b24cc3fcdd58026
Source dataset
uspto-grants-2009_11
Patent number
US07612075B2

Reaction notes

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