Water → 2,2,2-Trichloroethyl 3-tert-butyl-1-P-tolyl-1H-pyrazol-5-ylcarbamate

HRID 2182008Notes

Reaction equation

HRID 2182008 reaction equation
Cl.[NH2:2][C:3]1[N:7]([C:8]2[CH:13]=[CH:12][C:11]([CH3:14])=[CH:10][CH:9]=2)[N:6]=[C:5]([C:15]([CH3:18])([CH3:17])[CH3:16])[CH:4]=1.O.[OH-].[Na+].Cl[C:23]([O:25][CH2:26][C:27]([Cl:30])([Cl:29])[Cl:28])=[O:24]>CCOC(C)=O>[Cl:28][C:27]([Cl:30])([Cl:29])[CH2:26][O:25][C:23]([NH:2][C:3]1[N:7]([C:8]2[CH:13]=[CH:12][C:11]([CH3:14])=[CH:10][CH:9]=2)[N:6]=[C:5]([C:15]([CH3:18])([CH3:17])[CH3:16])[CH:4]=1)=[O:24]

Participants

6

Reactant 4

HCID 962WaterHCID 14798Sodium HydroxideHCID 870632,2,2-Trichloroethyl chloroformateHCID 119912003-(tert-Butyl)-1-(p-tolyl)-1H-pyrazol-5-amine hydrochloride

Product 1

HCID 99310942,2,2-Trichloroethyl 3-tert-butyl-1-P-tolyl-1H-pyrazol-5-ylcarbamate

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
10 °C

Procedure

A mixture of 5-amino-3-t-butyl-1-p-tolylpyrazole hydrochloride (300 g, 1.13 mol), water (0.9 L), EtOAc (2.1 L) and NaOH (117 g, 2.84 mol) was stirred between 5-15° C. for 30 min. To this mixture, 2,2,2-trichloroethyl chloroformate (342 g, 1.58 mol) was added over 1 h between 5-15° C. The mixture was stirred at room temperature for 2 h, and then the aqueous layer was separated from the EtOAc layer. The EtOAc layer was washed with brine (2×0.9 L) and dried over MgSO4 (60 g). The EtOAc layer was collected by filtration. To this solution, heptane was added. A part of the solution was removed by distillation. The product was crystallized from the solution, collected by filtration and dried in vacuum oven to constant weight. Yield: 409 g, 90%. 1H NMR (CDCl3) δ 7.40 (d, 2H), 7.30 (d, 2H), 6.40 (s, 1H), 4.80 (s, 2H), 2.40 (s, 3H), 1.40 (s, 9H). MS (EI) m/z 404 (M+).

Workup

  1. stirringThe mixture was stirred at room temperature for 2 h
  2. customthe aqueous layer was separated from the EtOAc layer
  3. washThe EtOAc layer was washed with brine (2×0.9 L)
  4. dry with materialdried over MgSO4 (60 g)
  5. filtrationThe EtOAc layer was collected by filtration
  6. additionTo this solution, heptane was added
  7. customA part of the solution was removed by distillation
  8. customThe product was crystallized from the solution
  9. filtrationcollected by filtration
  10. customdried in vacuum oven to constant weight

Sources & evidence

ORD record
ord-f811ac78d1de4b37b4ce7299574f5763
Source dataset
uspto-grants-2005_05
Patent number
US06894173B2

Reaction notes

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