Reaction #1726717

ord-05281bd2597847fd9a7a65b38c57c19f

Reaction equation

O=C(OCc1ccccc1)c1cc(Br)ccc1OCc1ccccc1
benzyl 2-benzyloxy-5-bromobenzoate
O=C([O-])[O-].[Na+].[Na+]
sodium carbonate
CC(=O)N(C)C
dimethylacetamide
→
N#Cc1ccc(OCc2ccccc2)c(C(=O)OCc2ccccc2)c1
benzyl 2-benzyloxy-5-cyanobenzoate
Yield 72.0%

Reactants

O=C(OCc1ccccc1)c1cc(Br)ccc1OCc1ccccc1
benzyl 2-benzyloxy-5-bromobenzoate
O=C([O-])[O-].[Na+].[Na+]
sodium carbonate
CC(=O)N(C)C
dimethylacetamide

Reagents

O.O.O.[C-]#N.[C-]#N.[C-]#N.[C-]#N.[C-]#N.[C-]#N.[Fe+2].[K+].[K+].[K+].[K+]
potassium hexacyanoferrate(II) trihydrate
CC(=O)[O-].CC(=O)[O-].[Pd+2]
palladium(II) acetate

Solvents

O
water

Conditions

Temperature
120°CELSIUS
Detailed conditions
See reaction.notes.procedure_details.

Workup

  1. 1
    Extractionextracted several times with ethyl acetate
  2. 2
    WashCombined extracts are washed with brine
  3. 3
    Dryingdried over Na2SO4
  4. 4
    OtherAfter solvent removal by rotoevaporation
  5. 5
    Otherthe crude product is purified by preparative TLC

Procedure

A mixture of 695 mg (1.76 mmol) of benzyl 2-benzyloxy-5-bromobenzoate, 175 mg (0.41 mmol) of potassium hexacyanoferrate(II) trihydrate, 41 mg (0.8 mmol) of palladium(II) acetate, and 189 mg (1.75 mmol) of sodium carbonate in 3 mL of dimethylacetamide is heated at 120° C. for 24 hrs. The reaction mixture is diluted with water and extracted several times with ethyl acetate. Combined extracts are washed with brine and dried over Na2SO4. After solvent removal by rotoevaporation, the crude product is purified by preparative TLC to give 436 mg (1.27 mmol, 72% yield) of benzyl 2-benzyloxy-5-cyanobenzoate.

Source

DOI: 10.6084/m9.figshare.5104873.v1Patent: US08110570B2uspto-grants-2012_02