Water → (S)-Perfluorophenyl 1-(4-bromo-2-methoxyphenyl)-2-oxo-1,2-dihydroquinoline-6-sulfonate

HRID 1504474Notes

Reaction equation

HRID 1504474 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]=[CH:23][C:22]([Br:25])=[CH:21][C:20]=1[O:26][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:25][C:22]1[CH:23]=[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]([O:26][CH3:27])[CH:21]=1

Participants

8

Reactant 5

HCID 962Water2×HCID 83601,3-Dichloro-5,5-dimethylhydantoin2×HCID 8471TriethylamineHCID 13041PentafluorophenolHCID 1177371856-(benzylthio)-1-(4-bromo-2-methoxyphenyl)quinolin-2(1H)-one

Product 1

HCID 117737057(S)-Perfluorophenyl 1-(4-bromo-2-methoxyphenyl)-2-oxo-1,2-dihydroquinoline-6-sulfonateYield 72.6%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 6342AcetonitrileSolvent

Procedure

A RBF was charged with 6-(benzylthio)-1-(4-bromo-2-methoxyphenyl)quinolin-2(1H)-one (1.777 g, 3.93 mmol), acetonitrile (18.49 ml), acetic acid (0.693 ml), and water (0.462 ml) to give a solution. The flask was cooled in an ice-water bath for 10 min, then 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione (0.813 g, 4.12 mmol) was added in one portion. After 20 min, an additional portion of 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione (0.813 g, 4.12 mmol) was added in one portion. After another 20 min, 2,3,4,5,6-pentafluorophenol (1.085 g, 5.89 mmol) was added, and the mixture was stirred for 5 min. Triethylamine (2.190 ml, 15.71 mmol) was added dropwise over 30 s then the mixture was stirred for 20 min. The reaction mixture was diluted with water and extracted with DCM (3×). The combined organic extracts were dried over sodium sulfate, filtered, and concentrated. The residue was purified by chromatography on silica gel (50-g SNAP Ultra column, 25-g silica gel loading column, 10-60% EtOAc/Heptane). Perfluorophenyl 1-(4-bromo-2-methoxyphenyl)-2-oxo-1,2-dihydroquinoline-6-sulfonate (1.644 g, 2.85 mmol, 72.6% yield) was isolated as a white foam. 1H NMR (400 MHz, DMSO-d6) □=8.59 (d, J=2.2 Hz, 1H), 8.24 (d, J=9.6 Hz, 1 H), 7.95 (dd, J=2.3, 9.1 Hz, 1 H), 7.56 (d, J=1.9 Hz, 1 H), 7.44-7.26 (m, 2 H), 6.86 (dd, J=9.4, 13.7 Hz, 2 H), 3.72 (s, 3 H). m/z (ESI) 575.9 (M+H)+.

Workup

  1. customto give a solution
  2. temperatureThe flask was cooled in an ice-water bath for 10 min
  3. waitAfter another 20 min
  4. stirringthe mixture was stirred for 20 min
  5. extractionextracted with DCM (3×)
  6. dry with materialThe combined organic extracts were dried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue was purified by chromatography on silica gel (50-g SNAP Ultra column, 25-g silica gel loading column, 10-60% EtOAc/Heptane)

Sources & evidence

ORD record
ord-79b235affb6d48dead76ec4cadfac29f
Source dataset
uspto-grants-2015_12
Patent number
US09212182B2

Reaction notes

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