Sodium hydride → Ethyl 3-amino-1-[(4-methoxyphenyl)methyl]-1H-pyrazole-4-carboxylate

HRID 478594Notes

Reaction equation

HRID 478594 reaction equation
[NH2:1][C:2]1[C:6]([C:7]([O:9][CH2:10][CH3:11])=[O:8])=[CH:5][NH:4][N:3]=1.[H-].[Na+].[CH3:14][O:15][C:16]1[CH:23]=[CH:22][C:19]([CH2:20]Cl)=[CH:18][CH:17]=1>C(#N)C.CCOC(C)=O>[NH2:1][C:2]1[C:6]([C:7]([O:9][CH2:10][CH3:11])=[O:8])=[CH:5][N:4]([CH2:20][C:19]2[CH:22]=[CH:23][C:16]([O:15][CH3:14])=[CH:17][CH:18]=2)[N:3]=1

Participants

6

Reactant 3

HCID 24758Sodium hydrideHCID 699934-Methyloxybenzyl chlorideHCID 178469928HCID 178469928, compound

Product 1

HCID 18002488Ethyl 3-amino-1-[(4-methoxyphenyl)methyl]-1H-pyrazole-4-carboxylate

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 3-amino4-carbethoxypyrazole (15 g, 96.7 mmol) in acetonitrile (750 mL) was add NaH (60% oil dispersion, 4 g, 100 mmol) at rt. After 15 min., 4-methoxybenzyl chloride (15.7 g, 100 mmol) was added with stirring. The reaction was allowed to run for 24 h. The reaction mixture was then diluted with EtOAc and washed with H2O, brine and dried (Na2SO4). Removal of the solvent gave the crude product which was further purified by flash column (silica gel, EtOAc/hexane, 1:1) to give ethyl 5-amino-2-p-methoxybenzyl-4-pyrazolecarboxylate (4.2 g, LC: 3.10′ MH+: 276) along with Ethyl 5-amino-1-p-methoxybenzyl-4-pyrazolecarboxylate (4.5 g) (LC: 3.07′ [Gradient 1] MH+: 276) and mixture of the two (10.2 g).

Workup

  1. waitto run for 24 h
  2. washwashed with H2O, brine
  3. dry with materialdried (Na2SO4)
  4. customRemoval of the solvent
  5. customgave the crude product which
  6. customwas further purified by flash column (silica gel, EtOAc/hexane, 1:1)

Sources & evidence

ORD record
ord-0e03825d72704e228d255b0965693007
Source dataset
uspto-grants-2003_11
Patent number
US06642244B2

Reaction notes

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