Sodium Carbonate → 5-(3,4-dihydro-2H-1-benzopyran-6-yl)-1,3-dimethyl-1H-pyrazole-4-carbaldehyde
Reaction equation
Cl[C:2]1[N:6]([CH3:7])[N:5]=[C:4]([CH3:8])[C:3]=1[CH:9]=[O:10].C(=O)([O-])[O-].[Na+].[Na+].CC1(C)C(C)(C)OB([C:25]2[CH:26]=[C:27]3[C:32](=[CH:33][CH:34]=2)[O:31][CH2:30][CH2:29][CH2:28]3)O1>C(COC)OC.O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd]>[O:31]1[C:32]2[CH:33]=[CH:34][C:25]([C:2]3[N:6]([CH3:7])[N:5]=[C:4]([CH3:8])[C:3]=3[CH:9]=[O:10])=[CH:26][C:27]=2[CH2:28][CH2:29][CH2:30]1Participants
Reactant 3
Product 1
Reagents, catalysts & solvents 3
Conditions
- Temperature
- 85 °C
Procedure
A solution of 5-chloro-1,3-dimethyl-1H-pyrazole-4-carboxaldehyde (200 mg, 1.26 mmol), sodium carbonate (282 mg, 2.66 mmol), 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)chroman (426 mg, 1.64 mmol) and palladium tetrakis(triphenylphosphine) (73 mg, 0.063 mmol) in a mixture of dimethoxyethane (4 mL) and water (1.35 mL) was heated at 85° C. for 24 hours. After cooling to room temperature, the mixture was poured into water (10 mL). The aqueous layer was extracted with ethyl acetate (2×10 mL). The organic layer was washed with brine (10 mL), dried over sodium sulfate and concentrated in vacuo. The residue was purified by flash chromatography on silica gel (cyclohexane/ethyl acetate 80/20 then 50/50) to provide the desired product (27a) (110 mg, 0.43 mmol, 34%) as a beige solid.
Workup
- temperatureAfter cooling to room temperature
- extractionThe aqueous layer was extracted with ethyl acetate (2×10 mL)
- washThe organic layer was washed with brine (10 mL)
- dry with materialdried over sodium sulfate
- concentrationconcentrated in vacuo
- customThe residue was purified by flash chromatography on silica gel (cyclohexane/ethyl acetate 80/20
Sources & evidence
- ORD record
- ord-9812fcb2319c47f0a3c7d309fdb338a6
- Source dataset
- uspto-grants-2016_01
- Patent number
- US09238026B2
Reaction notes
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