Cesium carbonate → tert-Butyl 3-[3,5-dichlorophenyl)-1-[4-(methoxycarbonyl)benzyl]-1H-pyrazole-5-carboxylate

HRID 1865414Notes

Reaction equation

HRID 1865414 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([C:9]2[CH:13]=[C:12]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[NH:11][N:10]=2)[CH:5]=[C:6]([Cl:8])[CH:7]=1.C(=O)([O-])[O-].[Cs+].[Cs+].Br[CH2:28][C:29]1[CH:38]=[CH:37][C:32]([C:33]([O:35][CH3:36])=[O:34])=[CH:31][CH:30]=1>CN(C)C=O.C(OCC)(=O)C>[Cl:1][C:2]1[CH:3]=[C:4]([C:9]2[CH:13]=[C:12]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[N:11]([CH2:28][C:29]3[CH:30]=[CH:31][C:32]([C:33]([O:35][CH3:36])=[O:34])=[CH:37][CH:38]=3)[N:10]=2)[CH:5]=[C:6]([Cl:8])[CH:7]=1

Participants

6

Reactant 3

HCID 10796Cesium carbonateHCID 256687Methyl 4-(bromomethyl)benzoateHCID 86620042tert-Butyl 3-(3,5-dichlorophenyl)-1H-pyrazole-5-carboxylate

Product 1

HCID 86620043tert-Butyl 3-[3,5-dichlorophenyl)-1-[4-(methoxycarbonyl)benzyl]-1H-pyrazole-5-carboxylate

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of the product from step D (6.8 g, 21.7 mmol) in 50 mL of N,N-dimethylformamide was added cesium carbonate (10.6 g, 32.6 mmol) and the resultant mixture stirred at ambient temperature for 15 min. Methyl 4-(bromo-methyl)benzoate (5.46 g, 23.9 mmol) was added and stirring continued for 3 h. The reaction mixture was diluted with ethyl acetate and the organic layer washed successively with six portions of water and one portion of brine then dried over magnesium sulfate and concentrated in vacuo. The residue was purified by flash column chromatography (SiO2, 5% ethyl acetate/hexanes) to give the title compound as a light tan solid. 1H NMR (500 MHz, CDCl3) δ; 8.03 (d, J=8.4 Hz, 2H); 7.75 (d, J=1.8 Hz, 2H); 7.35 (m, 3H); 7.12 (s, 1H); 5.88 (s, 2H); 3.94 (s, 3H); 1.57 (s, 9H).

Workup

  1. washthe organic layer washed successively with six portions of water and one portion of brine
  2. dry with materialthen dried over magnesium sulfate
  3. concentrationconcentrated in vacuo
  4. customThe residue was purified by flash column chromatography (SiO2, 5% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-560e428016964bfeb5432877c3595a7e
Source dataset
uspto-grants-2009_12
Patent number
US07625938B2

Reaction notes

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