Oxalyl chloride → HCID 86665169, compound

HRID 1893709Notes

Reaction equation

HRID 1893709 reaction equation
[CH3:1][O:2][C:3]1[CH:18]=[CH:17][C:6]([CH2:7][N:8]2[CH:12]=[C:11]([C:13](O)=[O:14])[C:10]([CH3:16])=[N:9]2)=[CH:5][CH:4]=1.C(Cl)(=O)C([Cl:22])=O>CN(C=O)C.C(Cl)Cl>[CH3:1][O:2][C:3]1[CH:18]=[CH:17][C:6]([CH2:7][N:8]2[CH:12]=[C:11]([C:13]([Cl:22])=[O:14])[C:10]([CH3:16])=[N:9]2)=[CH:5][CH:4]=1

Participants

5

Reactant 2

HCID 65578Oxalyl chlorideHCID 64450941HCID 64450941, compound

Product 1

HCID 86665169HCID 86665169, compound

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideCatalystHCID 6344DichloromethaneSolvent

Procedure

According to Scheme 2, Step 2: To a solution of 1-(4-methoxybenzyl)-3-methyl-1H-pyrazole-4-carboxylic acid (37.8 mmol, 9.30 g) and five drops of DMF in DCM (94 mL) was added oxalyl chloride (76 mmol, 6.66 mL) dropwise, at 0° C. The reaction mixture was allowed to warm up to room temperature and was stirred for 3 hours. After concentration, the residue was treated with toluene and was co-evaporated to dryness to yield 1-(4-methoxybenzyl)-3-methyl-1H-pyrazole-4-carbonyl chloride. To a solution of 1-(4-methoxybenzyl)-3-methyl-1H-pyrazole-4-carbonyl chloride (37.8 mmol) in acetonitrile (94 mL) was added a solution of TMSCHN2 (41.5 mmol, 83.0 mL) dropwise, at 0° C., and then the reaction mixture was allowed to warm up to room temperature and was stirred overnight. After cooling the reaction mixture to −10° C., HBr 48% (14.8 mL) was added dropwise and the reaction mixture was stirred for 2 hours at −10° C. At 0° C., 10% NaOH solution was added to the reaction mixture to reach pH=7. The reaction mixture was diluted with water and EtOAc and the aqueous phase was extracted with EtOAc. The organic phase was dried over MgSO4, was filtered and was concentrated under reduced pressure to yield 2-bromo-1-(1-(4-methoxybenzyl)-3-methyl-1H-pyrazol-4-yl)ethanone (30.6 mmol, 9.90 g, 81%) which was used without any purification.

Workup

  1. customat 0° C
  2. concentrationAfter concentration
  3. additionthe residue was treated with toluene

Sources & evidence

ORD record
ord-c9d76ab5e021469a857b96c088e64955
Source dataset
uspto-grants-2013_08
Patent number
US08513252B2

Reaction notes

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