Dimethylformamide → Benzyl (2,4-difluoro-3-formylphenyl)carbamate

HRID 250629Notes

Reaction equation

HRID 250629 reaction equation
[CH2:1]([O:8][C:9](=[O:19])[NH:10][C:11]1[CH:16]=[CH:15][C:14]([F:17])=[CH:13][C:12]=1[F:18])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[O:20]1CCC[CH2:21]1.C([Li])CCC.CN(C)C=O>O>[CH2:1]([O:8][C:9](=[O:19])[NH:10][C:11]1[CH:16]=[CH:15][C:14]([F:17])=[C:13]([CH:21]=[O:20])[C:12]=1[F:18])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 8028TetrahydrofuranHCID 11954520Benzyl (2,4-difluorophenyl)carbamateHCID 178418339Butyllithium

Product 1

HCID 58086235Benzyl (2,4-difluoro-3-formylphenyl)carbamateYield 71%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
-78 °C

Procedure

Into a round bottom flask was added (2,4-difluoro-phenyl)-carbamic acid benzyl ester (613, 3.83 g, 14.5 mmol) in tetrahydrofuran (148 mL, 1.82 mol). The solution was chilled to −78° C. and n-butyllithium (1.60 M in hexane, 19.1 mL, 30.0 mmol) was added over 30 minutes followed by the addition of, N,N-dimethylformamide (1.12 mL, 14.5 mol). The reaction mixture was allowed to warm to ambient temperature and was stirred overnight. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with brine, dried over sodium sulfate, concentrated and crystallized from ether to give compound 614 (3.0 g, 71%).

Workup

  1. temperatureto warm to ambient temperature
  2. extractionextracted with ethyl acetate
  3. washThe organic layer was washed with brine
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated
  6. customcrystallized from ether

Sources & evidence

ORD record
ord-a49ae1dc9361467cadcea4ce6165a31b
Source dataset
uspto-grants-2011_01
Patent number
US07863288B2

Reaction notes

Loading…