Potassium Carbonate → 4-Bromo-1-but-3-ynyloxy-2-nitro-benzene

HRID 886069Notes

Reaction equation

HRID 886069 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5](F)=[C:4]([N+:9]([O-:11])=[O:10])[CH:3]=1.[CH2:12]([OH:16])[CH2:13][C:14]#[CH:15].C(=O)([O-])[O-].[K+].[K+]>CN(C=O)C.O>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([O:16][CH2:12][CH2:13][C:14]#[CH:15])=[C:4]([N+:9]([O-:11])=[O:10])[CH:3]=1

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 135663-Butyn-1-OLHCID 27363284-Bromo-1-fluoro-2-nitrobenzene

Product 1

HCID 582050294-Bromo-1-but-3-ynyloxy-2-nitro-benzeneYield 71.4%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

A mixture of 4-bromo-1-fluoro-2-nitrobenzene (20.0 g, 90 mmol), 3-butyn-1-ol (7.0 g, 99.8 mmol) and potassium carbonate (13.8 g, 99.8 mmol) in dry DMF (20 mL) was heated with 4 Å molecular sieves for 43 h. The mixture was cooled, diluted with water to approximately 500 mL and extracted three times with ethyl acetate. The combined organic extracts were washed with water and then brine, dried and concentrated in vacuo. The resultant residue was subjected to flash chromatography (SiO2, gradient 5 to 10% ethyl acetate in cyclohexane) to give 4-Bromo-1-but-3-ynyloxy-2-nitro-benzene as a yellow solid (17.35 g, 71%). NMR showed an impurity (19%) which was not removed at this stage. LCMS: RT=4.41 min, [M+Na]+=292/294.

Workup

  1. temperaturewas heated with 4 Å molecular sieves for 43 h
  2. temperatureThe mixture was cooled
  3. extractionextracted three times with ethyl acetate
  4. washThe combined organic extracts were washed with water
  5. dry with materialbrine, dried
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-9d0981d0a49e4cbbb9370baba2499fdd
Source dataset
uspto-grants-2012_08
Patent number
US08242104B2

Reaction notes

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