Potassium Carbonate → N-[4-Chloro-3-(cyclopropylcarbamoyl)phenyl]-1-methyl-3-(pentafluoroethyl)-4-ethenyl-1H-pyrazol-5-carboxamide

HRID 1843060Notes

Reaction equation

HRID 1843060 reaction equation
C(=O)([O-])[O-].[K+].[K+].B1(C=C)OB([CH:13]=[CH2:14])OB(C=C)O1.C1C=CN=CC=1.[Cl:25][C:26]1[CH:31]=[CH:30][C:29]([NH:32][C:33]([C:35]2[N:39]([CH3:40])[N:38]=[C:37]([C:41]([F:47])([F:46])[C:42]([F:45])([F:44])[F:43])[C:36]=2I)=[O:34])=[CH:28][C:27]=1[C:49](=[O:54])[NH:50][CH:51]1[CH2:53][CH2:52]1>O.C(COC)OC.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Cl:25][C:26]1[CH:31]=[CH:30][C:29]([NH:32][C:33]([C:35]2[N:39]([CH3:40])[N:38]=[C:37]([C:41]([F:47])([F:46])[C:42]([F:45])([F:44])[F:43])[C:36]=2[CH:13]=[CH2:14])=[O:34])=[CH:28][C:27]=1[C:49](=[O:54])[NH:50][CH:51]1[CH2:53][CH2:52]1

Participants

7

Reactant 3

HCID 11430Potassium CarbonateHCID 27348062,4,6-Trivinylboroxin-Pyridine ComplexHCID 46219667N-[4-chloro-3-(cyclopropylcarbamoyl)phenyl]-1-methyl-3-(pentafluoroethyl)-4-iodo-1H-pyrazole-5-carboxamide

Product 1

HCID 86660084N-[4-Chloro-3-(cyclopropylcarbamoyl)phenyl]-1-methyl-3-(pentafluoroethyl)-4-ethenyl-1H-pyrazol-5-carboxamide

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolvent

Procedure

In succession, 18.5 mg (0.016 mmol) of tetrakis(triphenylphosphine)palladium, 0.044 g (0.320 mmol) of potassium carbonate in 1 ml of water, and 0.077 g (320 μmol of 2,4,6-trivinylcyclotriboroxane pyridine complex are added to a solution of 180 mg (0.32 mmol) of N-[4-chloro-3-(cyclopropylcarbamoyl)phenyl]-1-methyl-3-(pentafluoroethyl)-4-iodo-1H-pyrazole-5-carboxamide from Example Ik-4 in 3 ml of dimethoxyethane, and the reaction mixture is heated under reflux for 20 hours. The solvent is completely distilled off at reduced pressure on a rotary evaporator and the residue is purified by means of flash chromatography on silica gel (eluent: cyclohexane/ethyl acetate; gradient: 2 hours, from 0% to 100% ethyl acetate). This gives 0.107 g of N-[4-chloro-3-(cyclopropylcarbamoyl)phenyl]-1-methyl-3-(pentafluoroethyl)-4-ethenyl-1H-pyrazole-5-carboxamide (70%) as an oil.

Workup

  1. temperaturethe reaction mixture is heated
  2. temperatureunder reflux for 20 hours
  3. distillationThe solvent is completely distilled off at reduced pressure on a rotary evaporator
  4. customthe residue is purified by means of flash chromatography on silica gel (eluent: cyclohexane/ethyl acetate; gradient: 2 hours, from 0% to 100% ethyl acetate)

Sources & evidence

ORD record
ord-eb6efcff2e234a22a742015eb9404b77
Source dataset
uspto-grants-2015_02
Patent number
US08946234B2

Reaction notes

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