Potassium Carbonate → Ethyl 3-bromo-4-[(3-methyl-2-buten-1-yl)(trifluoroacetyl)amino]-5-nitrobenzoate

HRID 852609Notes

Reaction equation

HRID 852609 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:10]=[C:11]([N+:20]([O-:22])=[O:21])[C:12]=1[NH:13][C:14](=[O:19])[C:15]([F:18])([F:17])[F:16])[C:5]([O:7][CH2:8][CH3:9])=[O:6].C([O-])([O-])=O.[K+].[K+].Br[CH2:30][CH:31]=[C:32]([CH3:34])[CH3:33]>CC#N>[Br:1][C:2]1[CH:3]=[C:4]([CH:10]=[C:11]([N+:20]([O-:22])=[O:21])[C:12]=1[N:13]([CH2:30][CH:31]=[C:32]([CH3:34])[CH3:33])[C:14](=[O:19])[C:15]([F:17])([F:18])[F:16])[C:5]([O:7][CH2:8][CH3:9])=[O:6]

Participants

5

Reactant 3

HCID 11430Potassium CarbonateHCID 700922-Butene, 1-bromo-3-methyl-HCID 86602878Ethyl 3-bromo-5-nitro-4-[(trifluoroacetyl)amino]benzoate

Product 1

HCID 86602879Ethyl 3-bromo-4-[(3-methyl-2-buten-1-yl)(trifluoroacetyl)amino]-5-nitrobenzoateYield 91%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a solution of ethyl 3-bromo-5-nitro-4-[(trifluoroacetyl)amino]benzoate (D214) (12.0 g, 31.3 mmol, 1 equiv) in CH3CN (100 ml) was added K2CO3 (5.6 g, 40 mmol, 1.3 equiv) and 1-bromo-3-methyl-2-butene (5.1 ml, 43.8 mmol, 1.4 equiv) and the resulting mixture was refluxed for 1 h then cooled to room temperature. The precipitate formed was filtered off through a pad of celite and washed with CH3CN. The combined organic layers were concentrated in vacuo and the residue diluted with AcOEt. The organic layer was washed with brine, dried over MgSO4 and concentrated in vacuo. Purification of the residue by flash chromatography on silica gel (iso-hexane/AcOEt: 9/1 to 4/1) gave ethyl 3-bromo-4-[(3-methyl-2-buten-1-yl)(trifluoroacetyl)amino]-5-nitrobenzoate (D215) (12.9 g, 91%) as an orange oil.

Workup

  1. temperaturethe resulting mixture was refluxed for 1 h
  2. customThe precipitate formed
  3. filtrationwas filtered off through a pad of celite
  4. washwashed with CH3CN
  5. concentrationThe combined organic layers were concentrated in vacuo
  6. additionthe residue diluted with AcOEt
  7. washThe organic layer was washed with brine
  8. dry with materialdried over MgSO4
  9. concentrationconcentrated in vacuo
  10. customPurification of the residue by flash chromatography on silica gel (iso-hexane/AcOEt: 9/1 to 4/1)

Sources & evidence

ORD record
ord-c19dcd530b5b463095d079276e551606
Source dataset
uspto-grants-2007_08
Patent number
US07253198B2

Reaction notes

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