Pyridine → HCID 59398571, compound

HRID 2070043Notes

Reaction equation

HRID 2070043 reaction equation
[CH3:1][C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[CH:4][C:3]=1[C:9]([F:12])([F:11])[F:10].N1C=CC=CC=1.Cl[C:20]([O:22][CH2:23][C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)=[O:21].[Br:30]N1C(=O)CCC1=O>C(Cl)Cl>[CH2:23]([O:22][C:20](=[O:21])[NH:6][C:5]1[CH:7]=[CH:8][C:2]([CH2:1][Br:30])=[C:3]([C:9]([F:10])([F:11])[F:12])[CH:4]=1)[C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1

Participants

6

Reactant 4

HCID 1049PyridineHCID 10387Benzyl chloroformateHCID 67184N-bromobutanimideHCID 27377154-Methyl-3-(trifluoromethyl)aniline

Product 1

HCID 59398571HCID 59398571, compoundYield 27%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

4-Methyl-3-(trifluoromethyl)aniline (1.75 g, 10.0 mmol) was dissolved in DCM (10 mL), and pyridine (970 μL, 12.0 mmol) and then benzyl chloroformate (2 mL, 14.0 mmol) were dropwise added thereto. The resulting mixture was stirred at 0° C. for 0.5 hours. The organic layer was washed with a saturated sodium bicarbonate solution and saturated brine, sequentially, and then concentrated under reduced pressure. The residue was dissolved in 15 mL of carbon tetrachloride, and N-bromosuccinimide (2.67 g, 15.0 mmol) and 2,2-azobisisobutyronitrile (250 mg, 1.52 mmol) were added thereto. The resulting mixture was refluxed under heating for 1 hour. Insoluble substance was removed by filtration, and the filtrate was concentrated. The residue was purified by silica-gel column chromatography (n-hexane:ethyl acetate 20:1) to give [4-bromomethyl-3-(trifluoromethyl)phenyl]carbamic acid benzyl ester (1.04 g, 27%) as a light-yellow oil.

Workup

  1. washThe organic layer was washed with a saturated sodium bicarbonate solution and saturated brine
  2. concentrationsequentially, and then concentrated under reduced pressure
  3. dissolutionThe residue was dissolved in 15 mL of carbon tetrachloride
  4. temperatureThe resulting mixture was refluxed
  5. temperatureunder heating for 1 hour
  6. customInsoluble substance was removed by filtration
  7. concentrationthe filtrate was concentrated
  8. customThe residue was purified by silica-gel column chromatography (n-hexane:ethyl acetate 20:1)

Sources & evidence

ORD record
ord-6da22f7ffbfa481dad4a75a82c31b4a5
Source dataset
uspto-grants-2012_10
Patent number
US08299252B2

Reaction notes

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