Triethylamine → HCID 58234722, compound

HRID 68250Notes

Reaction equation

HRID 68250 reaction equation
[CH3:1][C:2]1([CH3:8])[O:6][C:5](=[O:7])[NH:4][CH2:3]1.ClC(Cl)(O[C:13](=[O:19])[O:14][C:15](Cl)(Cl)Cl)Cl.C(N(CC)CC)C.[F:28][C:29]1[CH:36]=C(O)[CH:34]=[C:33]([F:38])[C:30]=1[CH:31]=[O:32]>O.C(Cl)Cl.C1COCC1>[CH3:1][C:2]1([CH3:8])[O:6][C:5](=[O:7])[N:4]([C:13]([O:14][C:15]2[CH:36]=[C:29]([F:28])[C:30]([CH:31]=[O:32])=[C:33]([F:38])[CH:34]=2)=[O:19])[CH2:3]1

Participants

8

Reactant 4

HCID 8471Triethylamine2×HCID 94429TriphosgeneHCID 1368922-Oxazolidinone, 5,5-dimethyl-HCID 249035482,6-Difluoro-4-hydroxybenzaldehyde

Product 1

HCID 58234722HCID 58234722, compoundYield 130.3%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a 250 mL dry round bottom flask were added 5,5-dimethyl-oxazolidin-2-one (5.10 g, 44.3 mmol), triphosgene (5.26 g, 17.7 mmol) and anhydrous THF (80 mL). The mixture was stirred in an ice-water bath, then triethylamine (8.6 mL, 62.0 mmol) was added slowly. The resulting mixture was stirred at room temperature overnight. The reaction mixture was filtered and the filtrate was concentrated. To the residue was added 2,6-difluoro-4-hydroxybenzaldehyde (5.03 g, 31.9 mmol) and 80 mL of CH2Cl2. The resulting solution was cooled in an ice-water bath, then triethylamine (6.0 mL, 42.5 mmol) was added. After stirring at room temperature for 7 hours, water (100 mL) was added to the reaction mixture. The CH2Cl2 layer was separated, and the aqueous layer was extracted continually with CH2Cl2 (50 mL×3). The combined CH2Cl2 solution was dried over Na2SO4. After removal of the solvent, the residue was purified with a silica gel chromatography (heptane/ethyl acetate, gradient eluting) to give 3,5-difluoro-4-formylphenyl 5,5-dimethyl-2-oxooxazolidine-3-carboxylate (6.9 g) as a pale yellow crystal. Yield: 52%. 1H NMR (CDCl3, 300 MHz): δ=10.39 (s, 1H), 7.09 (d, J=9.0 Hz, 2H), 3.97 (s, 2H), 1.67 (s, 6H).

Workup

  1. customTo a 250 mL dry round bottom flask
  2. stirringThe resulting mixture was stirred at room temperature overnight
  3. filtrationThe reaction mixture was filtered
  4. concentrationthe filtrate was concentrated
  5. temperatureThe resulting solution was cooled in an ice-water bath
  6. stirringAfter stirring at room temperature for 7 hours
  7. customThe CH2Cl2 layer was separated
  8. extractionthe aqueous layer was extracted continually with CH2Cl2 (50 mL×3)
  9. dry with materialThe combined CH2Cl2 solution was dried over Na2SO4
  10. customAfter removal of the solvent
  11. customthe residue was purified with a silica gel chromatography (heptane/ethyl acetate, gradient eluting)

Sources & evidence

ORD record
ord-90b80955cadc4724b7431f2c55b7b4e8
Source dataset
uspto-grants-2014_09
Patent number
US08822435B2

Reaction notes

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