Acetic Anhydride → Acetic acid 3-(2-nitrovinyl)-phenyl ester

HRID 20345Notes

Reaction equation

HRID 20345 reaction equation
O[CH:2]([C:7]1[CH:8]=[C:9]([OH:13])[CH:10]=[CH:11][CH:12]=1)[CH2:3][N+:4]([O-:6])=[O:5].[CH2:14]1OCCOCCOCCOCCOCC[O:16][CH2:15]1.[F-].[K+].C(OC(=O)C)(=O)C>>[N+:4]([CH:3]=[CH:2][C:7]1[CH:8]=[C:9]([O:13][C:15](=[O:16])[CH3:14])[CH:10]=[CH:11][CH:12]=1)([O-:6])=[O:5]

Participants

5

Reactant 4

HCID 7918Acetic AnhydrideHCID 2855718-Crown-6HCID 522689Potassium FluorideHCID 444780213-(1-Hydroxy-2-nitroethyl)-phenol

Product 1

HCID 275789Acetic acid 3-(2-nitrovinyl)-phenyl esterYield 987%

Procedure

Add 3-(1-hydroxy-2-nitroethyl)-phenol (22.3 g, 121.8 mmol), 18-Crown-6 (3.3 g, 12.5 mmol), potassium fluoride (spray-dried) (7.1 g, 141 mmol) to acetic anhydride (115 mL, 1.218 mol). Stir for 1 hour. Cool in an ice bath and pour into ice water (400 mL) and stir for 15 minutes. Decant and extract the aqueous with ethyl acetate (twice). Combine extracts with the solid, wash with water (twice), saturated aqueous sodium chloride (twice), dry (magnesium sulfate), filter, concentrate and purify (silica gel chromatography, eluting with 25:75 hexanes:dichloromethane to 100% dichloromethane) to give the desired compound as an orange oil (25.56 g, 91%).

Workup

  1. temperatureCool in an ice bath
  2. stirringstir for 15 minutes
  3. customDecant
  4. extractionextract the aqueous with ethyl acetate (twice)
  5. washCombine extracts with the solid, wash with water (twice), saturated aqueous sodium chloride (twice),
  6. dry with materialdry (magnesium sulfate)
  7. filtrationfilter
  8. concentrationconcentrate
  9. custompurify
  10. wash(silica gel chromatography, eluting with 25:75 hexanes:dichloromethane to 100% dichloromethane)

Sources & evidence

ORD record
ord-4a2bce4c587d41989a6cb6280a4f6160
Source dataset
uspto-grants-2010_06
Patent number
US07745438B2

Reaction notes

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