Hydroquinone → HCID 9801288, compound

HRID 1939304Notes

Reaction equation

HRID 1939304 reaction equation
[F:1][CH:2]([F:28])[C:3]1[C:11]2[CH2:10][CH2:9][C:8]3[CH:12]=[C:13]([O:16][CH3:17])[CH:14]=[CH:15][C:7]=3[C:6]=2[N:5]([C:18]2[CH:23]=[CH:22][C:21]([S:24]([NH2:27])(=[O:26])=[O:25])=[CH:20][CH:19]=2)[N:4]=1.ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl.C1(C=CC(O)=CC=1)O>O1CCOCC1>[F:28][CH:2]([F:1])[C:3]1[C:11]2[C:6](=[C:7]3[CH:15]=[CH:14][C:13]([O:16][CH3:17])=[CH:12][C:8]3=[CH:9][CH:10]=2)[N:5]([C:18]2[CH:19]=[CH:20][C:21]([S:24]([NH2:27])(=[O:26])=[O:25])=[CH:22][CH:23]=2)[N:4]=1

Participants

5

Reactant 3

HCID 785HydroquinoneHCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinone3×HCID 22315385HCID 22315385, compound

Product 1

HCID 9801288HCID 9801288, compoundYield 85%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

4-[3-(Difluoromethyl)-4,5-dihydro-7-methoxy-1H-benz[g]indazol-1-yl]benzenesulfonamide (Example 1, Step 2) (600 mg, 1.5 mmol) was dissolved in 1,4-dioxane (200 ml), and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (341 mg, 1.5 mmol) was added. The reaction was heated to reflux for 16 hours, at which time a second equivalent of DDQ (340 mg, 1.5 mmol) was added and the reaction was heated to reflux for an additional 24 hours. At three successive 24 hour intervals, 1.5 mmol additional DDQ was added and heating continued until no starting material was left (as determined by thin layer chromatography). The reaction was cooled to room temperature, at which time most of the hydroquinone by-product precipitated. The reaction was filtered and concentrated. The residue was chromatographed on silica gel eluting with 50% ethyl acetate in hexane to yield 4-[3-(difluoromethyl)-7-methoxy-1H-benz[g]indazol-1-yl]benzenesulfonamide (514 mg, 85%): 1H NMR (acetone d6) δ=3.9 (s, 3H), 7.05 (m, 1H), 7.2 (t, 1H j=54.0 Hz), 7.5 (m, 2H), 7.7 (m, 1H), 7.9 (m, 3H), 8.2 (d, 2H, j=8.7 Hz); 19F NMR (acetone d6) δ-113.3 ppm (d, 2F).

Workup

  1. temperatureThe reaction was heated
  2. additionwas added
  3. temperaturethe reaction was heated
  4. temperatureto reflux for an additional 24 hours
  5. temperatureheating
  6. waitwas left (as determined by thin layer chromatography)
  7. customprecipitated
  8. filtrationThe reaction was filtered
  9. concentrationconcentrated
  10. customThe residue was chromatographed on silica gel eluting with 50% ethyl acetate in hexane

Sources & evidence

ORD record
ord-d79df01966124762b1cd49cc72614c20
Source dataset
uspto-grants-1997_12
Patent number
US05696143

Reaction notes

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