Methyl Acrylate → Trimethyl 1-(2-fluoro-4-nitrophenyl)propane-1,1,3-tricarboxylate

HRID 1192864Notes

Reaction equation

HRID 1192864 reaction equation
[F:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[CH:11]([C:16]([O:18][CH3:19])=[O:17])[C:12]([O:14][CH3:15])=[O:13].[C:20]([O:24][CH3:25])(=[O:23])[CH:21]=[CH2:22].C[O-].[Na+]>CO.ClCCl>[F:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[C:11]([C:16]([O:18][CH3:19])=[O:17])([C:12]([O:14][CH3:15])=[O:13])[CH2:22][CH2:21][C:20]([O:24][CH3:25])=[O:23]

Participants

6

Reactant 3

HCID 7294Methyl AcrylateHCID 10942334Sodium MethoxideHCID 53429620Dimethyl 2-(2-fluoro-4-nitrophenyl)malonate

Product 1

HCID 68733963Trimethyl 1-(2-fluoro-4-nitrophenyl)propane-1,1,3-tricarboxylateYield 85%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6344DichloromethaneSolvent

Procedure

To a solution of the nitro diester, Dimethyl 2-(2-fluoro-4-nitrophenyl)malonate (86) (0.44 g, 1.62 mmol) and methyl acrylate (0.22 mL, 2.43 mmol) in absolute methanol (5 mL) was added a catalytic amount of sodium methoxide at 21° C. under argon. The reaction mixture was stirred for 40 h at the same temperature and then diluted with dichloromethane (50 mL). The resulting mixture was washed with water, brine and dried. The residue obtained upon evaporation of the solvents was purified on a silica gel (hexane:ethyl acetate, 8:1) to give Trimethyl 1-(2-fluoro-4-nitrophenyl)propane-1,1,3-tricarboxylate (85) (0.49 g, 85%): 1H NMR δ 8.04 (dd, 1H, J=8.7, 2.3 Hz), 7.95 (dd, 1H, J=10.9, 2.3 Hz), 7.57 (dd, 1H, J=8.7, 7.5 Hz), 3.81 (s, 6H), 3.62 (s, 3H), 2.64-2.69 (m, 2H), 2.35-2.40 (m, 2H).

Workup

  1. washThe resulting mixture was washed with water, brine
  2. customdried
  3. customThe residue obtained upon evaporation of the solvents
  4. customwas purified on a silica gel (hexane:ethyl acetate, 8:1)

Sources & evidence

ORD record
ord-4300c22183b3445caf8fb5ac1021dd27
Source dataset
uspto-grants-2014_03
Patent number
US08680291B2

Reaction notes

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