Isopropenyl chloroformate → 1-Methylethenyl N-[3-(2-fluorophenyl)-1-methyl-1H-pyrazol-5-yl]carbamate

HRID 1930334Notes

Reaction equation

HRID 1930334 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1[CH:12]=[C:11]([NH2:13])[N:10]([CH3:14])[N:9]=1.[C:15]([O:18][C:19](Cl)=[O:20])([CH3:17])=[CH2:16]>C(OCC)(=O)C.C([O-])(O)=O.[Na+]>[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1[CH:12]=[C:11]([NH:13][C:19](=[O:20])[O:18][C:15]([CH3:17])=[CH2:16])[N:10]([CH3:14])[N:9]=1

Participants

5

Reactant 2

HCID 93846Isopropenyl chloroformateHCID 33783247HCID 33783247, compound

Product 1

HCID 690385111-Methylethenyl N-[3-(2-fluorophenyl)-1-methyl-1H-pyrazol-5-yl]carbamateYield 82%

Reagents, catalysts & solvents 2

HCID 8857Ethyl AcetateSolventHCID 516892Sodium BicarbonateSolvent

Procedure

To a biphasic solution of 3-(2-fluorophenyl)-1-methyl-1H-pyrazol-5-amine (1.19 g, 6.22 mmol) in ethyl acetate (30 mL) and NaHCO3 solution (30 mL) was added isopropenylchloroformate (1.28 g, 10.6 mmol) and mixture was stirred at RT for 24 h. Both layers were separated; the aqueous layer was extracted with ethyl acetate (1×30 mL) and the combined organic layers were washed with brine, dried (Na2SO4) and concentrated to afford crude product which was purified by chromatography (ethyl acetate/hexane) to afford prop-1-en-2-yl 3-(2-fluorophenyl)-1-methyl-1H-pyrazol-5-ylcarbamate (1.15 g, 82% yield) as a pasty mass. 1H NMR (400 MHz, DMSO-d6): δ 10.09 (brs, 1H), 7.90 (td, J=8.0 Hz, 1.6 Hz, 1H), 7.38-7.22 (m, 3H), 6.54 (d, J=3.6 Hz, 1H), 4.79-4.77 (m, 2H), 3.76 (s, 3H), 1.96 (s, 3H); MS (ESI) m/z: 276.0 (M+H+).

Workup

  1. customBoth layers were separated
  2. extractionthe aqueous layer was extracted with ethyl acetate (1×30 mL)
  3. washthe combined organic layers were washed with brine
  4. dry with materialdried (Na2SO4)
  5. concentrationconcentrated
  6. customto afford crude product which
  7. customwas purified by chromatography (ethyl acetate/hexane)

Sources & evidence

ORD record
ord-3614083dd70340fabdee82caa0765732
Source dataset
uspto-grants-2012_05
Patent number
US08188113B2

Reaction notes

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