4-Fluorobenzoyl chloride → HCID 54070194, compound

HRID 2288988Notes

Reaction equation

HRID 2288988 reaction equation
CC(C)([O-])C.[K+].[CH3:7][O:8][C:9](=[O:17])[CH2:10][N:11]=[C:12](SC)[S:13][CH3:14].[F:18][C:19]1[CH:27]=[CH:26][C:22]([C:23](Cl)=[O:24])=[CH:21][CH:20]=1>O1CCCC1.O>[CH3:7][O:8][C:9]([C:10]1[N:11]=[C:12]([S:13][CH3:14])[O:24][C:23]=1[C:22]1[CH:26]=[CH:27][C:19]([F:18])=[CH:20][CH:21]=1)=[O:17]

Participants

6

Reactant 3

HCID 678794-Fluorobenzoyl chlorideHCID 5007923N-[Bis(methylthio)methylene]glycine methyl esterHCID 23665647Potassium tert-butoxide

Product 1

HCID 54070194HCID 54070194, compoundYield 16.4%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent3×

Procedure

A suspension of potassium tert-butoxide (1.18 g; 10.52 mmol) in dry tetrahydrofuran (20 ml), cooled at -78 C., under argon, is treated with a solution of N-[bis(methylthio)methylene] glycine methyl ester (1.02 g; 5.26 mmol) in dry tetrahydrofuran (7 ml). After stirring for 45 minutes, it is added a solution of 4-fluorobenzoyl chloride (0.75 g; 6.31 mmol) in tetrahydrofuran (7 ml). After stirring at -78 C. for 20 minutes, it is brought to room temperature and stirred an additional 16 hours. The reaction mixture is diluted with water (30 ml) and extracted with ethyl acetate (70 ml). The aqueous phase is washed with ethyl acetate (20 ml). The combined organic phases are washed with saturated brine (20 ml), dried over sodium sulfate and concentrated to dryness. Purification by radial chromatography on silica gel using an ethyl acetate/hexane gradient (10%-70%) affords the product as a white solid (0.23 g; 16%). HNMR (CDCl3): 8.07 (m, 2H), 7.16 (t, 2H, J=8.9 Hz), 3.93 (s, 3H), 2.73 (s, 3H). Mass spectrum: m/e calculated (MH+)=268.3; observed (MH+)=268.1.

Workup

  1. temperaturecooled at -78 C
  2. stirringAfter stirring at -78 C
  3. waitfor 20 minutes
  4. customis brought to room temperature
  5. stirringstirred an additional 16 hours
  6. extractionextracted with ethyl acetate (70 ml)
  7. washThe aqueous phase is washed with ethyl acetate (20 ml)
  8. washThe combined organic phases are washed with saturated brine (20 ml)
  9. dry with materialdried over sodium sulfate
  10. concentrationconcentrated to dryness
  11. customPurification by radial chromatography on silica gel using an ethyl acetate/hexane gradient (10%-70%)

Sources & evidence

ORD record
ord-021d719dfeda417f823bce854850e1ba
Source dataset
uspto-grants-2000_07
Patent number
US06090825

Reaction notes

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