Acrylonitrile → Dimethyl 2-(2-cyanoethyl)-2-(2-fluoro-4-nitrophenyl)malonate

HRID 1192875Notes

Reaction equation

HRID 1192875 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](#[N:23])[CH:21]=[CH2:22].C[O-].[Na+]>CO.ClCCl>[C:20]([CH2:21][CH2:22][C:11]([C:3]1[CH:4]=[CH:5][C:6]([N+:8]([O-:10])=[O:9])=[CH:7][C:2]=1[F:1])([C:16]([O:18][CH3:19])=[O:17])[C:12]([O:14][CH3:15])=[O:13])#[N:23]

Participants

6

Reactant 3

HCID 7855AcrylonitrileHCID 10942334Sodium MethoxideHCID 53429620Dimethyl 2-(2-fluoro-4-nitrophenyl)malonate

Product 1

HCID 86630008Dimethyl 2-(2-cyanoethyl)-2-(2-fluoro-4-nitrophenyl)malonateYield 52.4%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6344DichloromethaneSolvent

Procedure

To a solution of the nitro diester, Dimethyl 2-(2-fluoro-4-nitrophenyl)malonate (86) (0.4 g, 1.47 mmol) and acrylonitrile (0.11 mL, 1.62 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 Dimethyl 2-(2-cyanoethyl)-2-(2-fluoro-4-nitrophenyl)malonate (73) (0.25 g, 52%): 1H NMR δ 8.07 (dd, 1H, J=8.7, 2.3 Hz), 7.99 (dd, 1H, J=10.9, 2.3 Hz), 7.47 (dd, 1H, J=8.7, 7.3 Hz), 3.85 (s, 6H), 2.65-2.70 (m, 2H), 2.47-2.51 (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-d7a87548317d4d01acc6c819988c0cdb
Source dataset
uspto-grants-2014_03
Patent number
US08680291B2

Reaction notes

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