4-Methylpyrazole → HCID 44190586, compound

HRID 468747Notes

Reaction equation

HRID 468747 reaction equation
[CH3:1][C:2]1[CH:3]=[N:4][NH:5][CH:6]=1.[O:7]1[CH:12]=[CH:11][CH2:10][CH2:9][CH2:8]1.[H-].[Na+]>FC(F)(F)C(O)=O>[CH3:1][C:2]1[CH:3]=[N:4][N:5]([CH:8]2[CH2:9][CH2:10][CH2:11][CH2:12][O:7]2)[CH:6]=1

Participants

5

Reactant 3

HCID 34064-MethylpyrazoleHCID 80803,4-dihydro-2H-pyranHCID 24758Sodium hydride

Product 1

HCID 44190586HCID 44190586, compoundYield 83.2%

Reagents, catalysts & solvents 1

HCID 6422Trifluoroacetic acidCatalyst

Conditions

Temperature
90 °C

Procedure

Trifluoroacetic acid (40.0 uL, 0.519 mmol) was added to a solution of 4-methylpyrazole (0.901 g, 11.0 mmol) in dihydropyran (2.0 mL, 22 mmol). The reaction mixture was stirred at 90° C. for 20 hours. The mixture was cooled to room temperature, and then quenched with Sodium hydride (92 mg, 2.3 mmol). After stirring at room temperature for 10 minutes more, the solvent was removed under vacuum. The residue was suspended in dichloromethane, and passed through a short plug of silica, rinsed with dichloromethane. The filtrate was evaporated in vacuo to yield 1.5213 g (83%) of 4-methyl-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole. LCMS (ESI): M+H=167.4; 1H NMR (400 MHz, DMSO-d6) δ 7.60 (s, 1H), 7.27 (s, 1H), 5.29 (d, J=9.9 Hz, 1H), 3.89 (d, J=11.2 Hz, 1H), 3.64-3.51 (m, 1H), 2.00 (overlapping s and m, 4H), 1.88 (dd, J=27.1, 13.0 Hz, 1H), 1.64 (m, 1H), 1.51 (m, 2H).

Workup

  1. temperatureThe mixture was cooled to room temperature
  2. stirringAfter stirring at room temperature for 10 minutes more
  3. customthe solvent was removed under vacuum
  4. washrinsed with dichloromethane
  5. customThe filtrate was evaporated in vacuo

Sources & evidence

ORD record
ord-a89f70462d7e4afcad49918f8600feda
Source dataset
uspto-grants-2014_01
Patent number
US08623889B2

Reaction notes

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