Water → Perfluorophenyl 1-(4-bromo-5-fluoro-2-methylphenyl)-2-oxo-1,2-dihydroquinoline-6-sulfonate

HRID 1504448Notes

Reaction equation

HRID 1504448 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]([F:25])[C:22]([Br:26])=[CH:21][C:20]=1[CH3:27])[C:14](=[O:28])[CH:13]=[CH:12]2)C1C=CC=CC=1.ClN1C(C)(C)C(=[O:37])N(Cl)C1=O.[F:40][C:41]1[C:46]([F:47])=[C:45]([F:48])[C:44]([F:49])=[C:43]([F:50])[C:42]=1[OH:51].C(N(CC)CC)C.[OH2:59]>C(O)(=O)C.C(#N)C>[Br:26][C:22]1[C:23]([F:25])=[CH:24][C:19]([N:15]2[C:16]3[C:11](=[CH:10][C:9]([S:8]([O:51][C:42]4[C:41]([F:40])=[C:46]([F:47])[C:45]([F:48])=[C:44]([F:49])[C:43]=4[F:50])(=[O:37])=[O:59])=[CH:18][CH:17]=3)[CH:12]=[CH:13][C:14]2=[O:28])=[C:20]([CH3:27])[CH:21]=1

Participants

8

Reactant 5

HCID 962WaterHCID 83601,3-Dichloro-5,5-dimethylhydantoinHCID 8471TriethylamineHCID 13041PentafluorophenolHCID 1177368916-(benzylthio)-1-(4-bromo-5-fluoro-2-methylphenyl)quinolin-2(1H)-one

Product 1

HCID 117736966Perfluorophenyl 1-(4-bromo-5-fluoro-2-methylphenyl)-2-oxo-1,2-dihydroquinoline-6-sulfonateYield 85%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 6342AcetonitrileSolvent

Conditions

Temperature
0 °C

Procedure

A RBF was charged with 6-(benzylthio)-1-(4-bromo-5-fluoro-2-methylphenyl)quinolin-2(1H)-one (2.45 g, 5.39 mmol), acetonitrile (16.91 ml), acetic acid (0.643 ml), and water (0.423 ml). After cooling to 0° C., 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione (1.594 g, 8.09 mmol) was added as a solid in a single portion. The reaction was maintained at 0° C. for 40 min. At 0° C., 2,3,4,5,6-pentafluorophenol (1.191 g, 6.47 mmol) was added followed by triethylamine (3.01 ml, 21.57 mmol) dropwise. After maintaining at 0° C. for 30 min, the whole was warmed to rt and stir for 20 min. The reaction was quenched with water (15 mL). The whole was extracted with EtOAc (2×25-mL), then with DCM (2×20 mL). The organic layer was dried over MgSO4, filtered, and concentrated to afford yellow residue. The crude material was absorbed onto a plug of silica gel and purified by chromatography through a Redi-Sep pre-packed silica gel column (40 g), eluting with a gradient of 0% to 30% EtOAc in heptane, to provide perfluorophenyl 1-(4-bromo-5-fluoro-2-methylphenyl)-2-oxo-1,2-dihydroquinoline-6-sulfonate (2.65 g, 85% yield) as off-white solid. m/z (ESI) [M+H]+=578.1. NMR (400 MHz, CHLOROFORM-d) δ ppm 1.99 (s, 3 H) 6.80 (d, J=9.02 Hz, 1 H) 6.94 (d, J=9.64 Hz, 1H) 7.04 (d, J=7.98 Hz, 1 H) 7.71 (dd, J=7.15, 0.52 Hz, 1 H) 7.86-7.95 (m, 2 H) 8.29 (d, J=2.18 Hz, 1 H).

Workup

  1. temperatureThe reaction was maintained at 0° C. for 40 min
  2. temperatureAfter maintaining at 0° C. for 30 min
  3. temperaturethe whole was warmed to rt
  4. customThe reaction was quenched with water (15 mL)
  5. extractionThe whole was extracted with EtOAc (2×25-mL)
  6. dry with materialThe organic layer was dried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customto afford yellow residue
  10. customThe crude material was absorbed onto a plug of silica gel
  11. custompurified by chromatography through a Redi-Sep pre-packed silica gel column (40 g)
  12. washeluting with a gradient of 0% to 30% EtOAc in heptane

Sources & evidence

ORD record
ord-632e68252a5d427b8055bd53d291f730
Source dataset
uspto-grants-2015_12
Patent number
US09212182B2

Reaction notes

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