Cesium carbonate → HCID 58976277, compound

HRID 601014Notes

Reaction equation

HRID 601014 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([OH:11])[C:7]([OH:10])=[CH:8][CH:9]=1)([O-:3])=[O:2].Cl[C:13]([F:19])([F:18])C(OC)=O.C(=O)([O-])[O-].[Cs+].[Cs+]>CN(C=O)C>[F:18][CH:13]([F:19])[O:10][C:7]1[CH:8]=[CH:9][C:4]([N+:1]([O-:3])=[O:2])=[CH:5][C:6]=1[OH:11]

Participants

5

Reactant 3

HCID 10796Cesium carbonateHCID 73935Methyl chlorodifluoroacetateHCID 35051094-Nitrocatechol

Product 1

HCID 58976277HCID 58976277, compoundYield 27%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A solution of 4-nitrobenzene-1,2-diol (4.18 g, 27.1 mmol), methyl chlorodifluoroacetate (3.0 mL, 28.5 mmol) and cesium carbonate (11.05 g, 33.9 mmol) in DMF (75 mL) was heated at 90° C. for 24 h. The reaction was cooled, evaporated and diluted with ethyl acetate. Product was extracted twice into 1N NaOH, the combined aqueous phase was acidified, extracted with ethyl acetate (twice) and the organic layers were washed with water (twice) and brine, dried (sodium sulfate) and evaporated. Purification by flash chromatography (SiO2) eluted with 2:8 ethyl acetate:hexanes provided 2-difluoromethoxy-5-nitro-phenol (1.50 g, 27% yield) as a bright yellow solid. 1H-NMR (DMSO-d6, 500 MHz) 10.9 (s, 1H), 7.76 (d, 1H), 7.73 (dd, 1H), 7.36 (d, 1H), 7.28 (t, 1H) ppm; MS (FIA) 204.1 (M−H); HPLC (Method A) 3.307 min.

Workup

  1. temperatureThe reaction was cooled
  2. customevaporated
  3. additiondiluted with ethyl acetate
  4. extractionProduct was extracted twice into 1N NaOH
  5. extractionextracted with ethyl acetate (twice) and the organic layers
  6. washwere washed with water (twice) and brine
  7. dry with materialdried (sodium sulfate)
  8. customevaporated
  9. customPurification by flash chromatography (SiO2)
  10. washeluted with 2:8 ethyl acetate

Sources & evidence

ORD record
ord-5d022342e38c424ea1f372c9ca10a146
Source dataset
uspto-grants-2011_03
Patent number
US07902239B2

Reaction notes

Loading…