Water → HCID 86687446, compound

HRID 1473400Notes

Reaction equation

HRID 1473400 reaction equation
C([S:8][C:9]1[CH:10]=[C:11]2[C:16](=[CH:17][CH:18]=1)[C:15]([Cl:19])=[N:14][N:13]=[CH:12]2)C1C=CC=CC=1.ClN1C(C)(C)C(=[O:28])N(Cl)C1=O.[F:31][C:32]1[C:37]([F:38])=[C:36]([F:39])[C:35]([F:40])=[C:34]([F:41])[C:33]=1[OH:42].C(N(CC)CC)C.[OH2:50]>CCOC(C)=O.C(O)(=O)C.C(#N)C>[Cl:19][C:15]1[C:16]2[C:11](=[CH:10][C:9]([S:8]([O:42][C:33]3[C:32]([F:31])=[C:37]([F:38])[C:36]([F:39])=[C:35]([F:40])[C:34]=3[F:41])(=[O:28])=[O:50])=[CH:18][CH:17]=2)[CH:12]=[N:13][N:14]=1

Participants

9

Reactant 5

HCID 962WaterHCID 83601,3-Dichloro-5,5-dimethylhydantoinHCID 8471TriethylamineHCID 13041PentafluorophenolHCID 86687445HCID 86687445, compound

Product 1

HCID 86687446HCID 86687446, compoundYield 67.7%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent

Procedure

A round-bottom flask was charged with 6-(benzylthio)-1-chlorophthalazine (2.20 g, 7.67 mmol), acetonitrile (72.2 ml), acetic acid (2.71 ml), and water (1.805 ml) to give a clear, orange solution. The flask was cooling in an ice-bath for 10 min, then 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione (3.02 g, 15.34 mmol) was added in one portion. After 30 min, 2,3,4,5,6-pentafluorophenol (2.82 g, 15.34 mmol) and triethylamine (4.28 ml, 30.7 mmol) were added in sequence. After 30 min, the mixture was diluted with EtOAc (100 mL), washed with water (50 ml), washed with 0.5 N aq. HCl (100 mL), washed with brine, and dried over sodium sulfate. The residue was dissolved in DCM and loaded onto a chilled 25-g silica gel loading column. The column was dried with a vacuum hose, then eluted onto a pre-equilibrated 80-g column with 0 to 50% EtOAc/Heptane to give perfluorophenyl 1-chlorophthalazine-6-sulfonate (2.134 g, 5.20 mmol, 67.7% yield) as a yellow solid: 1H NMR (400 MHz, CHLOROFORM-d) δ ppm=9.64 (d, J=0.7 Hz, 1H), 8.72 (d, J=1.8 Hz, 1H), 8.65-8.59 (m, 1H), 8.56-8.50 (m, 1H); m/z (ESI) 411.2 (M+H)+.

Workup

  1. customto give a clear, orange solution
  2. temperatureThe flask was cooling in an ice-bath for 10 min
  3. waitAfter 30 min
  4. washwashed with water (50 ml)
  5. washwashed with 0.5 N aq. HCl (100 mL)
  6. washwashed with brine
  7. dry with materialdried over sodium sulfate
  8. dissolutionThe residue was dissolved in DCM
  9. customThe column was dried with a vacuum hose
  10. washeluted onto a pre-equilibrated 80-g column with 0 to 50% EtOAc/Heptane

Sources & evidence

ORD record
ord-7011ebfa47c94cf787844b469da6fe1e
Source dataset
uspto-grants-2015_04
Patent number
US09012443B2

Reaction notes

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