Acetic Acid → 3-Acetoxymethyl-7-(4-fluorobenzyloxy)-2-methyl-1-[(1S,2S)-2-methylcyclopropylmethyl]pyrrolo[2,3-d]-pyridazine

HRID 1582317Notes

Reaction equation

HRID 1582317 reaction equation
[F:1][C:2]1[CH:25]=[CH:24][C:5]([CH2:6][O:7][C:8]2[N:9]=[N:10][CH:11]=[C:12]3[C:16]([CH3:17])=[C:15]([CH3:18])[N:14]([CH2:19][C@H:20]4[CH2:22][C@@H:21]4[CH3:23])[C:13]=23)=[CH:4][CH:3]=1.[N+]([O-])([O-])=O.[Ce+4].[NH4+].[N+]([O-])([O-])=O.[N+]([O-])([O-])=O.[N+]([O-])([O-])=O.[N+]([O-])([O-])=O.O.[C:49]([OH:52])(=[O:51])[CH3:50]>>[C:49]([O:52][CH2:17][C:16]1[C:12]2[C:13](=[C:8]([O:7][CH2:6][C:5]3[CH:24]=[CH:25][C:2]([F:1])=[CH:3][CH:4]=3)[N:9]=[N:10][CH:11]=2)[N:14]([CH2:19][C@H:20]2[CH2:22][C@@H:21]2[CH3:23])[C:15]=1[CH3:18])(=[O:51])[CH3:50]

Participants

5

Reactant 4

HCID 176Acetic AcidHCID 962WaterHCID 9833312CS-526HCID 9869224Ammonium cerium (IV) nitrate

Product 1

HCID 120947683-Acetoxymethyl-7-(4-fluorobenzyloxy)-2-methyl-1-[(1S,2S)-2-methylcyclopropylmethyl]pyrrolo[2,3-d]-pyridazineYield 28%

Conditions

Temperature
60 °C

Procedure

To a solution of 7-(4-fluorobenzyloxy)-2,3-dimethyl-1-[(1S,2S)-2-methylcyclopropylmethyl]pyrrolo[2,3-d]pyridazine (0.679 g, 2.00 mmol) in acetic acid (40 ml) was added ammonium cerium (IV) nitrate (6.58 g, 12.0 mmol) at room temperature. The mixture was stirred at 60° C. for 3 hours, poured into water and extracted with ethyl acetate. The extract was washed with a saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated in vacuo. The residue was chromatographed on a silica gel column using hexane/ethyl acetate=1/1 as the eluant to afford an oil which was crystallized in hexane to give the title compound (0.255 g, 28%) as pale yellow crystals.

Workup

  1. extractionextracted with ethyl acetate
  2. washThe extract was washed with a saturated aqueous sodium chloride solution
  3. dry with materialdried over anhydrous magnesium sulfate
  4. concentrationconcentrated in vacuo
  5. customThe residue was chromatographed on a silica gel column
  6. customto afford an oil which
  7. customwas crystallized in hexane

Sources & evidence

ORD record
ord-a8e2c1d68a0047278b60071b8f3eaee6
Source dataset
uspto-grants-2004_05
Patent number
US06734181B2

Reaction notes

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