Acetic Acid → 4′-Methyl-2-(2-nitroethenyl)-1,1′-biphenyl

HRID 653901Notes

Reaction equation

HRID 653901 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:9]([CH:14]=O)=[CH:10][CH:11]=[CH:12][CH:13]=2)=[CH:4][CH:3]=1.C([O-])(=O)C.[NH4+].C(O)(=O)C.[N+:25]([CH3:28])([O-:27])=[O:26]>>[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=2[CH:14]=[CH:28][N+:25]([O-:27])=[O:26])=[CH:4][CH:3]=1

Participants

5

Reactant 4

HCID 176Acetic AcidHCID 6375Nitromethane2×HCID 517165Ammonium Acetate2×HCID 13940094'-Methyl[1,1'-biphenyl]-2-carbaldehyde

Product 1

HCID 540658724′-Methyl-2-(2-nitroethenyl)-1,1′-biphenyl

Procedure

4'-Methylbiphenyl-2-carboxaldehyde (13.21 g, δ.3 mmol (1.0 eq, nitromethane (4.74 mL, 87.5 mmol, 1.3 eq), ammonium acetate (2.07 g, 2.60 mmol, 0.4 eq) and glacial acetic acid (30 mL) were mixed and refluxed for 2 days, at which time more nitromethane (4.74 mL) and ammonium acetate (2.07 g) were added and the reaction was refluxed for an additional 5 hours. The reaction mixture was poured into ice water (300 mL) and extracted with ethyl acetate (300 mL). The ethyl acetate layer was washed with water (3×200 mL), the organic layer dried (MgSO4), the solvent removed in vacuo and the residue chromatographed in 1:1 hexane/toluene to yield 11.22 g of a light yellow oil which crystallized. The product was recrystallized from methylcyclohexane to yield 8.47 g of yellow crystals; m.p. 64.0°-65.0°. NMR (200 MHz, CDCl3) δ 8.04 (d, 1H, J=13Hz); 7.69 (d, 1H, J=9Hz) 7.59-7.37 (m 4H); 7.50 (d, 1H, J=13Hz); 7.27 (d, 2H, J=7Hz); 7.19 (d, 2H, J=7Hz); 2.41 (s, 3H). Anal. Calcd. for C15H13NO2 : C, 75.30; H, 5.48; N, 5.85. Found: C, 75.32; H, 5.56; N, 5.58.

Workup

  1. additionwere added
  2. temperaturethe reaction was refluxed for an additional 5 hours
  3. extractionextracted with ethyl acetate (300 mL)
  4. washThe ethyl acetate layer was washed with water (3×200 mL)
  5. dry with materialthe organic layer dried (MgSO4)
  6. customthe solvent removed in vacuo
  7. customthe residue chromatographed in 1:1 hexane/toluene

Sources & evidence

ORD record
ord-db75e15fba2a450da92f00f3ec2931ac
Source dataset
uspto-grants-1992_07
Patent number
US05128355

Reaction notes

Loading…