2-Methyl-2-butene → 4-methoxy-6-(1-methyl-1H-pyrazol-4-yl)pyrazolo[1,5-a]pyridine-3-carboxylic acid

HRID 1253537Notes

Reaction equation

HRID 1253537 reaction equation
[CH3:1][O:2][C:3]1[C:4]2[N:5]([N:15]=[CH:16][C:17]=2[CH:18]=[O:19])[CH:6]=[C:7]([C:9]2[CH:10]=[N:11][N:12]([CH3:14])[CH:13]=2)[CH:8]=1.P([O-])(O)(O)=[O:21].[Na+].CC(=CC)C.Cl([O-])=O.[Na+]>O.C(OCC)(=O)C.C(O)CCC>[CH3:1][O:2][C:3]1[C:4]2[N:5]([N:15]=[CH:16][C:17]=2[C:18]([OH:21])=[O:19])[CH:6]=[C:7]([C:9]2[CH:10]=[N:11][N:12]([CH3:14])[CH:13]=2)[CH:8]=1

Participants

8

Reactant 4

HCID 105532-Methyl-2-butene2×HCID 23668197Sodium Chlorite2×HCID 23672064Monosodium phosphateHCID 866570544-methoxy-6-(1-methyl-1H-pyrazol-4-yl)pyrazolo[1,5-a]pyridine-3-carbaldehyde

Product 1

HCID 584048684-methoxy-6-(1-methyl-1H-pyrazol-4-yl)pyrazolo[1,5-a]pyridine-3-carboxylic acid

Reagents, catalysts & solvents 3

HCID 2631-ButanolSolventHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a suspension of 4-methoxy-6-(1-methyl-1H-pyrazol-4-yl)pyrazolo[1,5-a]pyridine-3-carbaldehyde (25.0 mg, 0.098 mmol) in water (1 ml) was added sodium dihydrogen phosphate (82 mg, 0.68 mmol). After 5 minutes, n-butanol (5 ml), 2-methyl-2-butene (0.145 ml, 1.37 mmol), and sodium chlorite (79 mg, 0.88 mmol) were added. After 3 hours, LCMS indicated incomplete conversion to product. Sodium chlorite (44 mg, 0.49 mmol) and 2-methyl-2-butene (0.104 ml, 0.98 mmol) were added. After 16 hours, reaction mixture was diluted with ethyl acetate, washed with water and brine, then dried over magnesium sulfate, filtered, and concentrated to give 4-methoxy-6-(1-methyl-1H-pyrazol-4-yl)pyrazolo[1,5-a]pyridine-3-carboxylic acid as white solids which were used without further purification. LRMS (ESI) calculated for C13H13N4O3 [M+H]+, 273.1 found 273.0.

Workup

  1. waitAfter 3 hours
  2. waitAfter 16 hours
  3. customreaction mixture
  4. washwashed with water and brine
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-9be1c5d56140433c8da9301335e81bf7
Source dataset
uspto-grants-2013_06
Patent number
US08455477B2

Reaction notes

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