Citric Acid → Benzyl 2-(benzyloxy)-3-chlorobenzoate

HRID 454476Notes

Reaction equation

HRID 454476 reaction equation
[C:1](=O)([O-])[O-].[K+].[K+].[CH2:7](Br)[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1.[Cl:15][C:16]1[CH:24]=[CH:23][CH:22]=[C:18]([C:19]([OH:21])=[O:20])[C:17]=1[OH:25].[C:26](O)(=O)[CH2:27][C:28]([CH2:33][C:34](O)=O)([C:30](O)=O)O>C(OCC)(=O)C.CN(C)C(=O)C>[CH2:7]([O:25][C:17]1[C:16]([Cl:15])=[CH:24][CH:23]=[CH:22][C:18]=1[C:19]([O:21][CH2:30][C:28]1[CH:33]=[CH:34][CH:1]=[CH:26][CH:27]=1)=[O:20])[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1

Participants

7

Reactant 4

HCID 311Citric AcidHCID 7498Benzyl Bromide2×HCID 11430Potassium Carbonate2×HCID 745853-Chlorosalicylic acid

Product 1

HCID 66990653Benzyl 2-(benzyloxy)-3-chlorobenzoate

Reagents, catalysts & solvents 2

HCID 8857Ethyl AcetateSolventHCID 31374DimethylacetamideSolvent

Conditions

Temperature
80 °C

Procedure

N,N-Dimethylacetamide (9.2 mL), potassium carbonate (2.2 g), and benzyl bromide (1.4 mL) were sequentially added to 3-chlorosalicylic acid (0.92 g), followed by stirring at 80° C. for 1 hour. The reaction mixture was cooled to room temperature, and then potassium carbonate (0.37 g) and benzyl bromide (0.19 mL) were sequentially added thereto, followed by stirring at 80° C. for 1 hour. The reaction mixture was cooled to room temperature, and then a 10% aqueous solution of citric acid and ethyl acetate were added thereto. The organic layer was separated, washed with a 10% aqueous solution of citric acid and a saturated aqueous solution of sodium chloride sequentially, and dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography [Fuji Silysia Chemical Ltd., PSQ100B (spherical), eluent: 100-95% hexane/ethyl acetate] to obtain 1.8 g of benzyl 2-(benzyloxy)-3-chlorobenzoate as a colorless oily substance.

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. stirringby stirring at 80° C. for 1 hour
  3. temperatureThe reaction mixture was cooled to room temperature
  4. customThe organic layer was separated
  5. washwashed with a 10% aqueous solution of citric acid
  6. dry with materiala saturated aqueous solution of sodium chloride sequentially, and dried over anhydrous magnesium sulfate
  7. customthe solvent was evaporated under reduced pressure
  8. customThe obtained residue was purified by silica gel column chromatography [Fuji Silysia Chemical Ltd., PSQ100B (spherical), eluent: 100-95% hexane/ethyl acetate]

Sources & evidence

ORD record
ord-49520a78410e486ba6b3c34b7d2b5226
Source dataset
uspto-grants-2013_07
Patent number
US08492582B2

Reaction notes

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