Cesium carbonate → Dimethyl 4-benzyloxy-1-[cyano(phenyl)methyl]-1H-pyrazole-3,5-dicarboxylate

HRID 1453825

Reaction equation

HRID 1453825 reaction equation
[CH2:1]([O:8][C:9]1[C:10]([C:18]([O:20][CH3:21])=[O:19])=[N:11][NH:12][C:13]=1[C:14]([O:16][CH3:17])=[O:15])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Br[CH:23]([C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)[C:24]#[N:25].C([O-])([O-])=O.[Cs+].[Cs+]>CN(C=O)C>[CH2:1]([O:8][C:9]1[C:13]([C:14]([O:16][CH3:17])=[O:15])=[N:12][N:11]([CH:23]([C:24]#[N:25])[C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[C:10]=1[C:18]([O:20][CH3:21])=[O:19])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 10796Cesium carbonateHCID 22044Bromobenzyl CyanideHCID 57528491dimethyl 4-benzyloxy-1H-pyrazole-3,5-dicarboxylate

Product 1

HCID 68953781Dimethyl 4-benzyloxy-1-[cyano(phenyl)methyl]-1H-pyrazole-3,5-dicarboxylate

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A solution of dimethyl 4-benzyloxy-1H-pyrazole-3,5-dicarboxylate (1.0 g, 3.45 mmol) and bromo(phenyl)acetonitrile (810 mg, 4.13 mmol) in anhydrous DMF was treated with Cs2CO3 (1.46 g, 4.48 mmol) and stirred at room temperature for 3 days. The solvent was removed in vacuo and the residue was partitioned between EtOAc and water. The aqueous layer was extracted with EtOAc several times, and the combined organic layers were dried over Na2SO4 and concentrated in vacuo. The resulting residue was purified by flash column chromatography on silica gel using a gradient elution of 0-20% EtOAc/hexanes. Collection and concentration of the appropriate fractions yielded the title product as a yellow oil. 1H NMR (400 MHz, d6-DMSO) δ 7.70 (s, 1H), 7.50-7.45 (m, 3H), 7.43-7.29 (m, 7H), 5.08 (s, 2H), 3.86 (s, 3H), 3.81 (s, 3H); ES MS (M+1)=406.

Workup

  1. customThe solvent was removed in vacuo
  2. customthe residue was partitioned between EtOAc and water
  3. extractionThe aqueous layer was extracted with EtOAc several times
  4. dry with materialthe combined organic layers were dried over Na2SO4
  5. concentrationconcentrated in vacuo
  6. customThe resulting residue was purified by flash column chromatography on silica gel using
  7. washa gradient elution of 0-20% EtOAc/hexanes
  8. customCollection and concentration of the appropriate fractions

Sources & evidence

ORD record
ord-051401307b164482b4af2cae00ad380f
Source dataset
uspto-grants-2009_01
Patent number
US07476666B2

Linked notes

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