Ethyl Acetate → HCID 67260634, compound

HRID 2359050Notes

Reaction equation

HRID 2359050 reaction equation
[Br:1][C:2]1[NH:6][N:5]=[C:4]([C:7]2[S:8][C:9]([Cl:12])=[CH:10][CH:11]=2)[C:3]=1[C:13]1[CH:18]=[CH:17][N:16]=[CH:15][CH:14]=1.[H-].[Na+].[CH3:21][O:22][C:23]1[CH:30]=[CH:29][C:26]([CH2:27]Cl)=[CH:25][CH:24]=1.C(OCC)(=O)C>CN(C)C=O>[Br:1][C:2]1[N:6]([CH2:27][C:26]2[CH:29]=[CH:30][C:23]([O:22][CH3:21])=[CH:24][CH:25]=2)[N:5]=[C:4]([C:7]2[S:8][C:9]([Cl:12])=[CH:10][CH:11]=2)[C:3]=1[C:13]1[CH:18]=[CH:17][N:16]=[CH:15][CH:14]=1.[Br:1][C:2]1[C:3]([C:13]2[CH:18]=[CH:17][N:16]=[CH:15][CH:14]=2)=[C:4]([C:7]2[S:8][C:9]([Cl:12])=[CH:10][CH:11]=2)[N:5]([CH2:27][C:26]2[CH:29]=[CH:30][C:23]([O:22][CH3:21])=[CH:24][CH:25]=2)[N:6]=1

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 24758Sodium hydrideHCID 699934-Methyloxybenzyl chlorideHCID 67260874HCID 67260874, compound

Product 2

HCID 67260634HCID 67260634, compoundYield 168.3%HCID 67261945HCID 67261945, compoundYield 80%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of 4-[5-bromo-3-(5-chloro-2-thienyl)-1H-pyrazol-4-yl]pyridine (14.7 mmol) in 80 mL of N,N-dimethylformamide was added slowly at 0° C. sodium hydride (16.1 mmol). The mixture was stirred 30 min at room temperature prior to dropwise addition of 4-methoxybenzyl chloride (16.1 mmol). The mixture was then stirred for further 5 hours. The mixture was then poured on water and ethyl acetate was added. The aqueous layer was extracted with ethyl acetate and the combined organic extracts were washed with brine, dried over MgSO4, filtered and concentrated. The residue was purified by chromatography on silica gel (heptane/ethyl acetate 4:1 to 1:1) to afford 5.7 g of 4-[5-bromo-3-(5-chloro-2-thienyl)-1-(4-methoxybenzyl)-1H-pyrazol-4-yl]pyridine and 4-[3-bromo-5-(5-chloro-2-thienyl)-1-(4-methoxybenzyl)-1H-pyrazol-4-yl]pyridine (80% yield) as a mixture 2:1 which was used as such in the following step.

Workup

  1. stirringThe mixture was then stirred for further 5 hours
  2. additionwas added
  3. extractionThe aqueous layer was extracted with ethyl acetate
  4. washthe combined organic extracts were washed with brine
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue was purified by chromatography on silica gel (heptane/ethyl acetate 4:1 to 1:1)

Sources & evidence

ORD record
ord-36f3f46a52074ab1b29cba55602ed53e
Source dataset
uspto-grants-2014_04
Patent number
US08685974B2

Reaction notes

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