Nitric Acid → 4-Formyl-2-methoxy-3-nitrophenyl acetate

HRID 1259492Notes

Reaction equation

HRID 1259492 reaction equation
[C:1]([OH:4])(=[O:3])[CH3:2].[O:5]=[CH:6][C:7]1[CH:15]=[CH:14][C:12](O)=[C:9]([O:10][CH3:11])[CH:8]=1.[N+:16]([O-])([OH:18])=[O:17]>>[C:1]([O:4][C:12]1[CH:14]=[CH:15][C:7]([CH:6]=[O:5])=[C:8]([N+:16]([O-:18])=[O:17])[C:9]=1[O:10][CH3:11])(=[O:3])[CH3:2]

Participants

3

Reactant 2

HCID 944Nitric AcidHCID 20405942HCID 20405942, compound

Product 1

HCID 2463194-Formyl-2-methoxy-3-nitrophenyl acetateYield 41%

Procedure

Fuming nitric acid (2200 mL) under nitrogen was cooled to 0° C. at which time vanillin acetate (528 g, 2.7 mol) was added portionwise, keeping the internal temperature below 10° C. After 2 h the resulting mixture was poured over ice with stirring. The slurry was filtered and the resulting solids were washed with water (3×100 mL) and air-dried. After 2 days the solids were heated in DCM (3000 mL) until complete dissolution. The solution was allowed to cool to room temperature while hexanes (3000 mL) was added dropwise. The solids were filtered, washed with hexanes (500 mL) and air dried to give the desired product (269 g, 41%): 1H NMR, (DMSO-d6) δ: 9.90 (s, 1H), 7.94 (d, 1H), 7.75 (d, 1H), 3.87 (s, 3H), 2.40 (s, 3H).

Workup

  1. additionwas added portionwise
  2. customthe internal temperature below 10° C
  3. additionAfter 2 h the resulting mixture was poured over ice
  4. filtrationThe slurry was filtered
  5. washthe resulting solids were washed with water (3×100 mL)
  6. customair-dried
  7. temperatureAfter 2 days the solids were heated in DCM (3000 mL) until complete dissolution
  8. additionwas added dropwise
  9. filtrationThe solids were filtered
  10. washwashed with hexanes (500 mL) and air
  11. customdried

Sources & evidence

ORD record
ord-96fc6b9fc238431b91d0615df8b28a6b
Source dataset
uspto-grants-2013_06
Patent number
US08466283B2

Reaction notes

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