Water → HCID 117737171, compound

HRID 1504467Notes

Reaction equation

HRID 1504467 reaction equation
C([S:8][C:9]1[CH:10]=[C:11]2[C:16](=[CH:17][CH:18]=1)[N:15]([C:19]1[CH:24]=[C:23]([CH3:25])[C:22]([Br:26])=[CH:21][C:20]=1[O:27][CH3:28])[C:14](=[O:29])[CH:13]=[CH:12]2)C1C=CC=CC=1.ClN1C(C)(C)C(=[O:38])N(Cl)C1=O.[F:41][C:42]1[C:47]([F:48])=[C:46]([F:49])[C:45]([F:50])=[C:44]([F:51])[C:43]=1[OH:52].C(N(CC)CC)C.[OH2:60]>C(O)(=O)C.C(Cl)Cl>[Br:26][C:22]1[C:23]([CH3:25])=[CH:24][C:19]([N:15]2[C:16]3[C:11](=[CH:10][C:9]([S:8]([O:52][C:43]4[C:42]([F:41])=[C:47]([F:48])[C:46]([F:49])=[C:45]([F:50])[C:44]=4[F:51])(=[O:38])=[O:60])=[CH:18][CH:17]=3)[CH:12]=[CH:13][C:14]2=[O:29])=[C:20]([O:27][CH3:28])[CH:21]=1

Participants

8

Reactant 5

HCID 962Water2×HCID 83601,3-Dichloro-5,5-dimethylhydantoinHCID 8471TriethylamineHCID 13041PentafluorophenolHCID 117737520HCID 117737520, compound

Product 1

HCID 117737171HCID 117737171, compoundYield 62.9%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 6344DichloromethaneSolvent

Procedure

A RBF was charged with 6-(benzylthio)-1-(4-bromo-2-methoxy-5-methylphenyl)quinolin-2(1H)-one (4.23 g, 9.07 mmol), DCM (71.1 ml), acetic acid (2.67 ml), and water (1.778 ml) to give clear, light-brown. The flask was cooled in an ice-water bath for 10 min, then 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione (3.66 g, 18.59 mmol) was added in one portion. After 40 min, an additional portion of oxidant (850 mg) was added. The mixture was stirred for another 20 min, then 2,3,4,5,6-pentafluorophenol (2.504 g, 13.60 mmol) and triethylamine (5.06 ml, 36.3 mmol) (added dropwise) were added in sequence. After 20 min, the mixture was diluted with water. The layers were separated, and the aq. layer was extracted with DCM (1×). The combined organic extracts were dried over sodium sulfate, filtered, and concentrated. The residue was purified by chromatography on silica gel (80-g Redi-Sep Gold column, 25-g silica gel loading column, 10-60% EtOAc/Heptane with 10% DCM). Fractions containing the main spot were combined and concentrated to give an off-white foam. LCMS and NMR showed that it was contaminated with 30 mol % of the peak with a mass of 425. This was equal to 82 wt % purity. This meant a yield of product: perfluorophenyl 1-(4-bromo-2-methoxy-5-methylphenyl)-2-oxo-1,2-dihydroquinoline-6-sulfonate (3.37 g, 5.71 mmol, 62.9% yield). m/z (ESI) 590.0 (M+H)+.

Workup

  1. customto give clear
  2. temperatureThe flask was cooled in an ice-water bath for 10 min
  3. additionan additional portion of oxidant (850 mg) was added
  4. additionwere added in sequence
  5. waitAfter 20 min
  6. customThe layers were separated
  7. extractionthe aq. layer was extracted with DCM (1×)
  8. dry with materialThe combined organic extracts were dried over sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customThe residue was purified by chromatography on silica gel (80-g Redi-Sep Gold column, 25-g silica gel loading column, 10-60% EtOAc/Heptane with 10% DCM)
  12. additionFractions containing the main spot
  13. concentrationconcentrated
  14. customto give an off-white foam

Sources & evidence

ORD record
ord-0954673e929a49838cd7312ab2c96cc9
Source dataset
uspto-grants-2015_12
Patent number
US09212182B2

Reaction notes

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