Acetic Acid → 5-Acetoxy-3-ethynyl-4-methoxybenzenemethanol

HRID 24280Notes

Reaction equation

HRID 24280 reaction equation
[C:1]([O:4][C:5]1[C:10]([C:11]#[C:12][Si](C)(C)C)=[CH:9][C:8]([CH2:17][OH:18])=[CH:7][C:6]=1OC)(=O)C.[C:21]([OH:24])(=[O:23])[CH3:22].[F-].C([NH+](CCCC)CCCC)CCC.[NH4+].[Cl-]>C1COCC1>[C:21]([O:24][C:6]1[C:5]([O:4][CH3:1])=[C:10]([C:11]#[CH:12])[CH:9]=[C:8]([CH2:17][OH:18])[CH:7]=1)(=[O:23])[CH3:22]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 25517Ammonium ChlorideHCID 11217984Tributylammonium fluorideHCID 225713874-Acetoxy-3-methoxy-5-[(trimethylsilyl)ethynyl] benzenemethanol

Product 1

HCID 225713855-Acetoxy-3-ethynyl-4-methoxybenzenemethanolYield 90.8%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Compound 4 (10 g, 34 mmol) was dissolved in THF (100 mL), then acetic acid (4.0 mL, 70 mmol) and tributylammoniumfloride (1.0 M in THF) (51 mL, 51 mmol) were added at room temperature. After stirring for 40 min at the same temperature, a saturated aqueous solution of NH4Cl (50 mL) was added, followed by extraction with ethyl acetate (3×60 mL), and the combined extracts was dried (Na2SO4). The solvent was removed under a vacuum, and the residue was purified by flash chromatography (dichloromethane) to give 5 (Rf=0.5, ethyl acetate/hexane 1:1) as a yellowish liquid (6.8 g, 90%). 1H NMR (500 MHz, CDCl3): δ 7.11 (s, 1H), 7.05 (s, 1H), 4.68 (s, 2H), 3.87 (s, 3H), 3.23 (s, 1 H), 2.38(s, 3H). 13C NMR (500 MHz, CDCl3): δ 168.85, 151.75, 140.85, 139.92, 122.99, 117.37, 111.86, 82.08, 78.54, 64.66, 56.31, 20.75.

Workup

  1. extractionfollowed by extraction with ethyl acetate (3×60 mL)
  2. dry with materialthe combined extracts was dried (Na2SO4)
  3. customThe solvent was removed under a vacuum
  4. customthe residue was purified by flash chromatography (dichloromethane)

Sources & evidence

ORD record
ord-deff352fbdf3419ba51a0a9449483c3d
Source dataset
uspto-grants-2005_02
Patent number
US06855822B2

Reaction notes

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