Methyl chloroformate → HCID 59355399, compound

HRID 887720Notes

Reaction equation

HRID 887720 reaction equation
[Cl:1][C:2]1[N:7]=[C:6]([C:8]([N:10]([CH2:12][CH3:13])[NH2:11])=[O:9])[C:5]([NH:14][C:15]([C:17]2[N:18]([C:23]3[C:28]([Cl:29])=[CH:27][CH:26]=[CH:25][N:24]=3)[N:19]=[C:20]([Br:22])[CH:21]=2)=[O:16])=[C:4]([CH3:30])[CH:3]=1.Cl[C:32]([O:34][CH3:35])=[O:33]>N1C=CC=CC=1>[CH3:35][O:34][C:32]([NH:11][N:10]([C:8]([C:6]1[C:5]([NH:14][C:15]([C:17]2[N:18]([C:23]3[C:28]([Cl:29])=[CH:27][CH:26]=[CH:25][N:24]=3)[N:19]=[C:20]([Br:22])[CH:21]=2)=[O:16])=[C:4]([CH3:30])[CH:3]=[C:2]([Cl:1])[N:7]=1)=[O:9])[CH2:12][CH3:13])=[O:33]

Participants

4

Reactant 2

HCID 6586Methyl chloroformate2×HCID 59355508HCID 59355508, compound

Product 1

HCID 59355399HCID 59355399, compound

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [6-chloro-2-(N-ethyl-hydrazinocarbonyl)-4-methyl-pyridin-3-yl]-amide (11-a) (177 mg) was dissolved in pyridine (2 mL), methyl chloroformate (100 μL) was added and the reaction mixture was stirred at room temperature. After 30 min, 1 h and 1.5 h, methyl chloroformate (each 50 μL) was added. After 14 h stirring at room temperature, the reaction mixture was quenched with water and 3× co-evaporated with toluene. The residue was dissolved in water and ethyl acetate, the layers were separated and the aqueous layer was extracted 2× with ethyl acetate. The combined organic layer was washed with brine, dried over magnesium sulfate and concentrated in vacuum. The residue was purified by column chromatography (silica 60, chloroform/ethyl acetate=3:1, Rf=0.10) to afford 135 mg of the title compound (11) of the present invention of the formula

Workup

  1. stirringAfter 14 h stirring at room temperature
  2. customthe reaction mixture was quenched with water and 3× co-evaporated with toluene
  3. dissolutionThe residue was dissolved in water
  4. customethyl acetate, the layers were separated
  5. extractionthe aqueous layer was extracted 2× with ethyl acetate
  6. washThe combined organic layer was washed with brine
  7. dry with materialdried over magnesium sulfate
  8. concentrationconcentrated in vacuum
  9. customThe residue was purified by column chromatography (silica 60, chloroform/ethyl acetate=3:1, Rf=0.10)

Sources & evidence

ORD record
ord-1b016443ea5d4e4e8f8ef1d27e0f7492
Source dataset
uspto-grants-2012_08
Patent number
US08247431B2

Reaction notes

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