Ethyl bromoacetate → ethyl 2-(4-cyano-1H-pyrazol-1-yl)acetate

HRID 526401Notes

Reaction equation

HRID 526401 reaction equation
[NH:1]1[CH:5]=[C:4]([C:6]#[N:7])[CH:3]=[N:2]1.C(=O)([O-])[O-].[K+].[K+].Br[CH2:15][C:16]([O:18][CH2:19][CH3:20])=[O:17]>CC(C)=O.CCCCCCC>[C:6]([C:4]1[CH:5]=[N:1][N:2]([CH2:15][C:16]([O:18][CH2:19][CH3:20])=[O:17])[CH:3]=1)#[N:7]

Participants

6

Reactant 3

HCID 7748Ethyl bromoacetateHCID 11430Potassium CarbonateHCID 5644491H-Pyrazole-4-carbonitrile

Product 1

HCID 117600226ethyl 2-(4-cyano-1H-pyrazol-1-yl)acetateYield 51.9%

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 8900HeptaneSolvent

Procedure

Combined 1H-pyrazole-4-carbonitrile (0.432 g, 4.64 mmol) in acetone (9.28 mL), potassium carbonate (1.924 g, 13.92 mmol) and ethyl 2-bromoacetate (1.027 mL, 9.28 mmol). The reaction mixture was stirred at room temperature overnight, then concentrated in vacuo, diluted with EtOAc (10 mL), washed with water (10 mL), dried (MgSO4) and concentrated in vacuo to give a residue. The residue was purified using flash column chromatography on silica gel (EtOAc in heptane, 10-50% gradient) to give a white solid. The solid was suspended in heptane and then filtered and dried to give the title compound (0.4314 g, 51.9% yield) as a white solid. 1H NMR (400 MHz, DMSO-d6) δ ppm 1.21 (t, J=7.20 Hz, 3H) 4.17 (q, J=7.07 Hz, 2H) 5.19 (s, 2H) 8.11 (s, 1H) 8.57 (s, 1H). MS m/z [M+H]+ 180.

Workup

  1. concentrationconcentrated in vacuo
  2. additiondiluted with EtOAc (10 mL)
  3. washwashed with water (10 mL)
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated in vacuo
  6. customto give a residue
  7. customThe residue was purified
  8. customto give a white solid
  9. filtrationfiltered
  10. customdried

Sources & evidence

ORD record
ord-5ab0affdf85f48a191238daf0f0634c6
Source dataset
uspto-grants-2016_05
Patent number
US09345713B2

Reaction notes

Loading…