Lithium hydroxide, monohydrate → HCID 12068888, compound

HRID 1267829Notes

Reaction equation

HRID 1267829 reaction equation
[C:1]([O:4][C:5]1[CH:14]=[CH:13][CH:12]=[C:11]([O:15]C(=O)C)[C:6]=1[C:7]([O:9][CH3:10])=[O:8])(=[O:3])[CH3:2].O[Li].O.CO.C1COCC1.O.OC1C=CC=C(O)C=1C(OC)=O>CCCCCC.CCOC(C)=O>[C:1]([O:4][C:5]1[CH:14]=[CH:13][CH:12]=[C:11]([OH:15])[C:6]=1[C:7]([O:9][CH3:10])=[O:8])(=[O:3])[CH3:2]

Participants

6

Reactant 4

HCID 168937Lithium hydroxide, monohydrateHCID 519869Methyl 2,6-dihydroxybenzoateHCID 14343346Methyl 2,6-diacetoxybenzoateHCID 21892291Methanol tetrahydrofuran water

Product 1

HCID 12068888HCID 12068888, compoundYield 27.2%

Reagents, catalysts & solvents 1

HCID 21226206Ethyl acetate hexaneSolvent

Procedure

A solution of Part C methyl 2,6-diacetoxybenzoate (3.4 g, 14 mmol) and LiOH.H2O (60 mg, 1.5 mmol) in 2:2:1 MeOH/THF/H2O (30 mL) was stirred for 2 hr at 20° until tlc analysis (4:1 hexane/EtOAc) revealed comparable amounts of starting bis-acetate and methyl 2,6-dihydroxybenzoate. The solution was quenched with pH 7 Na2HPO4 buffer, diluted with H2O prior to 4 EtOAc extractions. The combined organic phase was washed with H2O 2×, brine 1× prior to drying over Na2SO4. After removal of the volatiles, chromatography on silica gel using 3:2 hexane/CH2Cl2 eluted 1.1 g of a 1:2 mixture of methyl 2,6-dihydroxybenzoate/methyl 2-acetoxy-6-hydroxybenzoate followed by 0.7 g of pure methyl 2-acetoxy-6-hydroxybenzoate. Re-chromatography of the mixed fraction yielded another 0.8 g of methyl 2-acetoxy-6-hydroxybenzoate.

Workup

  1. customThe solution was quenched with pH 7 Na2HPO4 buffer
  2. additiondiluted with H2O
  3. extractionto 4 EtOAc extractions
  4. washThe combined organic phase was washed with H2O 2×, brine 1×
  5. dry with materialto drying over Na2SO4
  6. customAfter removal of the volatiles, chromatography on silica gel using 3:2 hexane/CH2Cl2
  7. washeluted
  8. addition1.1 g of a 1:2 mixture of methyl 2,6-dihydroxybenzoate/methyl 2-acetoxy-6-hydroxybenzoate

Sources & evidence

ORD record
ord-a349e73a81b34668b41b3ea9620549d6
Source dataset
uspto-grants-2003_04
Patent number
US06555519B2

Reaction notes

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