Acetonitrile → Methyl 2-{[2-(methyloxy)ethyl]oxy}-3-[(phenylcarbonyl)oxy]benzoate

HRID 253308Notes

Reaction equation

HRID 253308 reaction equation
[OH:1][C:2]1[C:11]([O:12][C:13]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)=[O:14])=[CH:10][CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].C(=O)([O-])[O-].[K+].[K+].C(#N)C.Br[CH2:31][CH2:32][O:33][CH3:34]>C(OCC)(=O)C>[CH3:34][O:33][CH2:32][CH2:31][O:1][C:2]1[C:11]([O:12][C:13]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)=[O:14])=[CH:10][CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5]

Participants

6

Reactant 4

HCID 6342AcetonitrileHCID 11430Potassium CarbonateHCID 809722-Bromoethyl methyl etherHCID 66891613Methyl 3-(benzoyloxy)-2-hydroxybenzoate

Product 1

HCID 66889877Methyl 2-{[2-(methyloxy)ethyl]oxy}-3-[(phenylcarbonyl)oxy]benzoateYield 87.2%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

To a mixture of methyl 2-hydroxy-3-[(phenylcarbonyl)oxy]benzoate (21.2 g, 78 mmol), potassium carbonate (21.5 g, 156 mmol) and acetonitrile (370 mL) was added 1-bromo-2-(methyloxy)ethane (12.1 mL, 116 mmol). The resulting mixture was heated at reflux 18 hour. After cooling to room temperature, the reaction mixture was diluted with ethyl acetate (400 mL), filtered and concentrated. The residue was then diluted with ethyl acetate (200 mL) and washed with 5% sodium hydroxide solution, water and brine (100 mL each), dried over sodium sulfate, filtered, concentrated, and the residue was chromatographed (silica gel, 30-50% ethyl acetate-hexane) to provide methyl 2-{[2-(methyloxy)ethyl]oxy}-3-[(phenylcarbonyl)oxy]benzoate, (22.5 g, 68 mmol, 87% yield). 1H NMR (400 MHz, CDCl3): 8.25-8.23 (d, d, 2H), 7.76-7.74 (d, d, 1H), 7.68-7.64 (d, d, 1H), 7.55-7.51 (d, d, 2H), 7.40-7.38 (d, d, 1H), 7.23-7.19 (d, d, 1H), 4.17-4.15 (m, 2H), 3.92 (s, 3H), 3.58-3.55 (m, 2H), 3.14 (s, 3H).

Workup

  1. temperatureThe resulting mixture was heated
  2. temperatureat reflux 18 hour
  3. filtrationfiltered
  4. concentrationconcentrated
  5. additionThe residue was then diluted with ethyl acetate (200 mL)
  6. washwashed with 5% sodium hydroxide solution, water and brine (100 mL each)
  7. dry with materialdried over sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customthe residue was chromatographed (silica gel, 30-50% ethyl acetate-hexane)

Sources & evidence

ORD record
ord-d45b2993edc84304a7bdbc96dc63b529
Source dataset
uspto-grants-2011_01
Patent number
US07872014B2

Reaction notes

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