Water → HCID 117737274, compound

HRID 1504479Notes

Reaction equation

HRID 1504479 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[C:20]([O:28][CH3:29])=[CH:21][C:22]([Br:27])=[C:23]([CH:26]=1)[C:24]#[N:25])[C:14](=[O:30])[CH:13]=[CH:12]2)C1C=CC=CC=1.ClN1C(C)(C)C(=[O:39])N(Cl)C1=O.[F:42][C:43]1[C:48]([F:49])=[C:47]([F:50])[C:46]([F:51])=[C:45]([F:52])[C:44]=1[OH:53].C(N(CC)CC)C.[OH2:61]>CCOC(C)=O.C(O)(=O)C.C(#N)C>[Br:27][C:22]1[C:23]([C:24]#[N:25])=[CH:26][C:19]([N:15]2[C:16]3[C:11](=[CH:10][C:9]([S:8]([O:53][C:44]4[C:43]([F:42])=[C:48]([F:49])[C:47]([F:50])=[C:46]([F:51])[C:45]=4[F:52])(=[O:39])=[O:61])=[CH:18][CH:17]=3)[CH:12]=[CH:13][C:14]2=[O:30])=[C:20]([O:28][CH3:29])[CH:21]=1

Participants

9

Reactant 5

HCID 962Water2×HCID 83601,3-Dichloro-5,5-dimethylhydantoin3×HCID 8471TriethylamineHCID 13041PentafluorophenolHCID 117737033HCID 117737033, compound

Product 1

HCID 117737274HCID 117737274, compoundYield 56.3%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent

Procedure

A RBF was charged with 5-(6-(benzylthio)-2-oxoquinolin-1(2H)-yl)-2-bromo-4-methoxybenzonitrile (798 mg, 1.672 mmol), acetonitrile (7867 μl), acetic acid (295 μl), and water (197 μl) 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 (165 mg, 0.836 mmol) was added (0.5 equiv). After 10 min, an additional portion of 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione (165 mg, 0.836 mmol) was added. After another 10 min, a final portion of 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione (165 mg, 0.836 mmol) was added to the mixture. 2,3,4,5,6-pentafluorophenol (385 mg, 2.090 mmol) was added. After another minute, triethylamine (932 μl, 6.69 mmol) was added dropwise over 15 s. The mixture was stirred for 10 min then was diluted with water and EtOAc, and the layers were separated. The aq. layer was extracted with DCM (2×). The combined organic extracts were dried over sodium sulfate, filtered, and concentrated. The residue was concentrated from EtOAc, then taken up in EtOAc and filtered. The collected solid was washed with EtOAc (3×), then dried under a stream of N2 (g) for 14 h to give perfluorophenyl 1-(4-bromo-5-cyano-2-methoxyphenyl)-2-oxo-1,2-dihydroquinoline-6-sulfonate (566 mg, 0.941 mmol, 56.3% yield) as an off-white solid. 1H NMR (400 MHz, DMSO-d6) □=8.61 (d, J=2.3 Hz, 1 H), 8.27 (d, J=9.6 Hz, 1 H), 8.18 (s, 1H), 7.93 (dd, J=2.3, 9.0 Hz, 1 H), 7.88 (s, 1 H), 6.98 (d, J=9.0 Hz, 1 H), 6.90 (d, J=9.7 Hz, 1 H), 3.83 (s, 3 H). m/z (ESI) 601.0 (M+H)+.

Workup

  1. customto give a solution
  2. temperatureThe flask was cooled in an ice-water bath for 10 min
  3. waitAfter another 10 min
  4. customthe layers were separated
  5. extractionThe aq. layer was extracted with DCM (2×)
  6. dry with materialThe combined organic extracts were dried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. concentrationThe residue was concentrated from EtOAc
  10. filtrationfiltered
  11. washThe collected solid was washed with EtOAc (3×)
  12. dry with materialdried under a stream of N2 (g) for 14 h

Sources & evidence

ORD record
ord-d2f6853033484837901a08478e034896
Source dataset
uspto-grants-2015_12
Patent number
US09212182B2

Reaction notes

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