Sodium hydride → HCID 67388455, compound

HRID 908475Notes

Reaction equation

HRID 908475 reaction equation
[H-].[Na+].[Br:3][C:4]1[C:5]([N:9]([CH3:11])[CH3:10])=[N:6][NH:7][CH:8]=1.CS(O[CH:17]1[CH2:22][CH2:21][N:20]([C:23]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])[CH2:19][CH2:18]1)(=O)=O>CN(C=O)C>[Br:3][C:4]1[C:5]([N:9]([CH3:11])[CH3:10])=[N:6][N:7]([CH:17]2[CH2:22][CH2:21][N:20]([C:23]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])[CH2:19][CH2:18]2)[CH:8]=1

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 41848691-(tert-Butoxycarbonyl)-4-(methanesulfonyloxy)piperidineHCID 178483114HCID 178483114, compound

Product 1

HCID 67388455HCID 67388455, compoundYield 43.9%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Conditions

Temperature
23 °C

Procedure

Sodium hydride (0.498 g, 60% in mineral oil) was added to a stirred solution of 4-bromo-N,N-dimethyl-1H-pyrazol-3-amine (1.97 g) dissolved in DMF (20 ml) under argon. The resulting mixture was stirred at 23° C. for 30 minutes. A solution of Tert-butyl 4-methylsulfonyloxypiperidine-1-carboxylate (3.19 g) in DMF (10 ml) was added and the reaction mixture was stirred at 95° C. for 5 hours and left at 23° C. overnight. DMF was evaporated and the residue was taken up in dichloromethane, washed with H2O and sat NaCl. The organic was dried (magnesium sulphate), filtered and concentrated. The residue was purified by flash chromatography on silica gel eluting with 0 to 30% ethyl acetate in petroleum ether. The solvent was evaporated to afford tert-butyl 4-(4-bromo-3-dimethylamino-pyrazol-1-yl)piperidine-1-carboxylate (1.700 g) as a clear colorless oil which crystallised on standing. NMR Spectrum: (DMSOd6) 1.40 (s, 9H), 1.65 (d, 1H), 1.71 (d, 1H), 1.89-1.87 (m, 2H), 2.74 (s, 6H), 2.85 (bs, 2H), 3.93-4.06 (m, 2H), 4.09-4.17 (m, 1H), 7.82 (s, 1H); Mass spectrum: M+H+ 373-375

Workup

  1. stirringthe reaction mixture was stirred at 95° C. for 5 hours
  2. waitleft at 23° C. overnight
  3. customDMF was evaporated
  4. washwashed with H2O
  5. dry with materialThe organic was dried (magnesium sulphate)
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue was purified by flash chromatography on silica gel eluting with 0 to 30% ethyl acetate in petroleum ether
  9. customThe solvent was evaporated

Sources & evidence

ORD record
ord-c52a598822ee4bea9b5b85451bf4f049
Source dataset
uspto-grants-2011_09
Patent number
US08017611B2

Reaction notes

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