Nitromethane → (E)-Benzyl 2-fluoro-3-(2-nitrovinyl)phenylcarbamate

HRID 2361328Notes

Reaction equation

HRID 2361328 reaction equation
[F:1][C:2]1[C:7]([CH:8]=O)=[CH:6][CH:5]=[CH:4][C:3]=1[NH:10][C:11](=[O:20])[O:12][CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1.[N+:21]([CH3:24])([O-:23])=[O:22]>C(O)(=O)C>[F:1][C:2]1[C:7](/[CH:8]=[CH:24]/[N+:21]([O-:23])=[O:22])=[CH:6][CH:5]=[CH:4][C:3]=1[NH:10][C:11](=[O:20])[O:12][CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1

Participants

4

Reactant 2

HCID 6375Nitromethane2×HCID 86681522Benzyl 2-fluoro-3-formylphenylcarbamate

Product 1

HCID 70651607(E)-Benzyl 2-fluoro-3-(2-nitrovinyl)phenylcarbamateYield 68.4%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

A solution of benzyl 2-fluoro-3-formylphenylcarbamate (4.0253 g, 14.73 mmol), nitromethane (1.98 mL, 36.8 mmol) and nitromethane (1.979 mL, 36.8 mmol) in acetic acid (49.1 mL) under nitrogen was heated at 90° C. After 2 hr, the reaction was cooled to room temperature and concentrated in vacuo. The residue was dissolved in CH2Cl2 (75 mL) and water (75 mL), and Na2CO3 (s) was added until pH basic by litmus paper. After separation of layers, the aqueous layer was extracted with CH2Cl2 (3×75 mL). The organic layers were combined and washed with brine (50 mL), dried over MgSO4, and concentrated in vacuo to give the desired product (4.251 g, 10.08 mmol, 68.4% yield) as a burgundy oil.

Workup

  1. concentrationconcentrated in vacuo
  2. dissolutionThe residue was dissolved in CH2Cl2 (75 mL)
  3. additionwater (75 mL), and Na2CO3 (s) was added until pH basic by litmus paper
  4. customAfter separation of layers
  5. extractionthe aqueous layer was extracted with CH2Cl2 (3×75 mL)
  6. washwashed with brine (50 mL)
  7. dry with materialdried over MgSO4
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-9bd2afb22c0e404b94ad67c5ef414342
Source dataset
uspto-grants-2014_04
Patent number
US08685969B2

Reaction notes

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