Ethyl chloroformate → 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-[N-ethoxycarbonyl-N-(3-ethylthiopropyl)amino]-4-trifluoromethylsulfonylpyrazole

HRID 2109917Notes

Reaction equation

HRID 2109917 reaction equation
[H-].[Na+].[Cl:3][C:4]1[CH:9]=[C:8]([C:10]([F:13])([F:12])[F:11])[CH:7]=[C:6]([Cl:14])[C:5]=1[N:15]1[C:19]([NH:20][CH2:21][CH2:22][CH2:23][S:24][CH2:25][CH3:26])=[C:18]([S:27]([C:30]([F:33])([F:32])[F:31])(=[O:29])=[O:28])[C:17]([C:34]#[N:35])=[N:16]1.Cl[C:37]([O:39][CH2:40][CH3:41])=[O:38].[Cl-].[NH4+]>O1CCCC1.C(OCC)(=O)C>[Cl:14][C:6]1[CH:7]=[C:8]([C:10]([F:13])([F:12])[F:11])[CH:9]=[C:4]([Cl:3])[C:5]=1[N:15]1[C:19]([N:20]([C:37]([O:39][CH2:40][CH3:41])=[O:38])[CH2:21][CH2:22][CH2:23][S:24][CH2:25][CH3:26])=[C:18]([S:27]([C:30]([F:33])([F:32])[F:31])(=[O:28])=[O:29])[C:17]([C:34]#[N:35])=[N:16]1

Participants

7

Reactant 4

HCID 10928Ethyl chloroformateHCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 866002281-(2,6-Dichloro-4-trifluoromethylphenyl)-3-cyano-5-(3-ethylthiopropylamino)-4-trifluoromethylsulfonylpyrazole

Product 1

HCID 866002311-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-[N-ethoxycarbonyl-N-(3-ethylthiopropyl)amino]-4-trifluoromethylsulfonylpyrazoleYield 81%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
20 °C

Procedure

Sodium hydride (0.032 g, 60%, 0.8 mmol) was added to a solution of 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-(3-ethylthiopropylamino)-4-trifluoromethylsulfonylpyrazole (0.3 g, 0.54 mmol) in tetrahydrofuran 20° C. under nitrogen. The mixture was stirred at 20° C. for one hour then ethyl chloroformate (0.121 g, 1.1 mmol) was added. The mixture was stirred at 20° C. for 5 hours, then poured into saturated ammonium chloride and ethyl acetate. The organic layer was washed with water and brine, dried (sodium sulfate), evaporated to provide and purified by chromatography on silica gel eluting with heptane-ethyl acetate (4:1) to give 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-[N-ethoxycarbonyl-N-(3-ethylthiopropyl)amino]-4-trifluoromethylsulfonylpyrazole as an oil (Compound number 3-14, 0.278 g, 81% yield), 19F: −63.9; −77.9.

Workup

  1. stirringThe mixture was stirred at 20° C. for 5 hours
  2. washThe organic layer was washed with water and brine
  3. dry with materialdried (sodium sulfate)
  4. customevaporated
  5. customto provide
  6. custompurified by chromatography on silica gel eluting with heptane-ethyl acetate (4:1)

Sources & evidence

ORD record
ord-a67d097e7a6d4a7fb5c4e4a815b0eeeb
Source dataset
uspto-grants-2009_04
Patent number
US07517877B2

Reaction notes

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