Water → Perfluorophenyl 1-(4-chloro-2-methoxyphenyl)phthalazine-6-sulfonate

HRID 1473536Notes

Reaction equation

HRID 1473536 reaction equation
C([S:8][C:9]1[CH:10]=[C:11]2[C:16](=[CH:17][CH:18]=1)[C:15]([C:19]1[CH:24]=[CH:23][C:22]([Cl:25])=[CH:21][C:20]=1[O:26][CH3:27])=[N:14][N:13]=[CH:12]2)C1C=CC=CC=1.ClN1C(C)(C)C(=[O:36])N(Cl)C1=O.[F:39][C:40]1[C:45]([F:46])=[C:44]([F:47])[C:43]([F:48])=[C:42]([F:49])[C:41]=1[OH:50].C(N(CC)CC)C.[OH2:58]>C(=O)(O)[O-].[Na+].C(O)(=O)C.C(Cl)Cl>[Cl:25][C:22]1[CH:23]=[CH:24][C:19]([C:15]2[C:16]3[C:11](=[CH:10][C:9]([S:8]([O:50][C:41]4[C:40]([F:39])=[C:45]([F:46])[C:44]([F:47])=[C:43]([F:48])[C:42]=4[F:49])(=[O:36])=[O:58])=[CH:18][CH:17]=3)[CH:12]=[N:13][N:14]=2)=[C:20]([O:26][CH3:27])[CH:21]=1

Participants

9

Reactant 5

HCID 962WaterHCID 83601,3-Dichloro-5,5-dimethylhydantoin2×HCID 8471TriethylamineHCID 13041PentafluorophenolHCID 866875956-(Benzylthio)-1-(4-chloro-2-methoxyphenyl)phthalazine

Product 1

HCID 86687594Perfluorophenyl 1-(4-chloro-2-methoxyphenyl)phthalazine-6-sulfonateYield 48.2%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 6344DichloromethaneSolventHCID 516892Sodium BicarbonateSolvent

Procedure

A round-bottom flask was charged with 6-(benzylthio)-1-(4-chloro-2-methoxyphenyl)phthalazine (369 mg, 0.939 mmol), DCM (8839 μl), acetic acid (331 μl), and water (221 μl) to give a clear, orange solution. The flask was submerged in an ice-water bath. After 5 min, 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione (379 mg, 1.925 mmol) was added in one portion. After 40 min, an additional portion of 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione (ca. 180 mg) was added. After 5 min, 2,3,4,5,6-pentafluorophenol (259 mg, 1.409 mmol) was added, then triethylamine (524 μl, 3.76 mmol) was added drop wise. The mixture was stirred for 10 min, then diluted with saturated aq. sodium bicarbonate solution, and the mixture was stirred vigorously for 5 min. The mixture was then extracted with DCM (2×). The combined organic extracts were dried over sodium sulfate, filtered, and concentrated. The residue was purified by chromatography on silica gel (40-g Redi-Sep Gold column, 0-40% EtOAc/Heptane) to give perfluorophenyl 1-(4-chloro-2-methoxyphenyl)phthalazine-6-sulfonate (234 mg, 0.453 mmol, 48.2% yield) as a cream-colored foam. m/z (ESI) 517.0 (M+H)+.

Workup

  1. customto give a clear, orange solution
  2. customThe flask was submerged in an ice-water bath
  3. waitAfter 40 min
  4. waitAfter 5 min
  5. stirringthe mixture was stirred vigorously for 5 min
  6. extractionThe mixture was then extracted with DCM (2×)
  7. dry with materialThe combined organic extracts were dried over sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe residue was purified by chromatography on silica gel (40-g Redi-Sep Gold column, 0-40% EtOAc/Heptane)

Sources & evidence

ORD record
ord-ee6122281022430caad50f83afd06c49
Source dataset
uspto-grants-2015_04
Patent number
US09012443B2

Reaction notes

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