Sulfuric Acid → Methyl p-nitrophenylacetate

HRID 1955264Notes

Reaction equation

HRID 1955264 reaction equation
[H-].[Na+].[N+:3]([C:6]1[CH:11]=[CH:10][C:9]([CH2:12][C:13]([OH:15])=[O:14])=[CH:8][CH:7]=1)([O-:5])=[O:4].OS(O)(=O)=O.Br[CH2:22][CH2:23][CH2:24]Br.[H-].CN([CH:30]=[O:31])C>O.CO>[N+:3]([C:6]1[CH:7]=[CH:8][C:9]([CH2:12][C:13]([O:15][CH3:22])=[O:14])=[CH:10][CH:11]=1)([O-:5])=[O:4].[N+:3]([C:6]1[CH:7]=[CH:8][C:9]([C:12]2([C:13]([O:31][CH3:30])=[O:15])[CH2:24][CH2:23][CH2:22]2)=[CH:10][CH:11]=1)([O-:5])=[O:4]

Participants

10

Reactant 6

HCID 1118Sulfuric AcidHCID 4661(4-Nitrophenyl)acetic acidHCID 6228Dimethylformamide3×HCID 80011,3-DibromopropaneHCID 24758Sodium hydrideHCID 166653Hydride

Product 2

HCID 270191Methyl p-nitrophenylacetateHCID 23295037HCID 23295037, compound

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent2×

Procedure

NaH (80% dispersion in mineral oil, 0.26 mol) was suspended in DMF under nitrogen atmosphere. Methyl 4-nitrophenylacetate (0.13 mol), that was prepared by refluxing 4-nitrophenylacetic acid (0.2 mol) with MeOH (100 mL) and conc. H2SO4 (1 mL) for 24 h, dissolved in DMF was added dropwise followed by 1,3-dibromopropane (0.13 mol) in DMF. stirring was continued at room temperature for 1.5 h. Excess hydride was then decomposed by the cautious addion of H2O. More H2O was added and extracted with toluene. The organic layer was washed with H2O, dried (MgSO4) and concentrated to give methyl 1-(4-nitrophenyl)-cyclobutanecarboxylate that was stirred with 0.5 M NaOH (128 mL) in THF overnight. THF was evaporated, the residue was dissolved in H2O and extracted with EtOAc. The aqueous layer was acidified and extracted with EtOAc. The organic layer was dried (MgSO4) and concentrated to give the desired product that was washed with EtOH/H2O. The yield was 0.7 g (12%); 1H NMR (CDCl3) δ 1.90 (m, 1H), 2.05-2.20 (m, 1H), 2.50-2.60 (m, 2H), 2.90 (m, 2H), 7.52 (d, 2H), 8.2 (d, 2H).

Workup

  1. additionwas added dropwise
  2. extractionextracted with toluene
  3. washThe organic layer was washed with H2O
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated

Sources & evidence

ORD record
ord-3a3636fae7b94c31b723a575f2238169
Source dataset
uspto-grants-2000_09
Patent number
US06124354

Reaction notes

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