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

HRID 1192875ノート

反応式

HRID 1192875 の反応式
[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]

参加物

6

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 887Methanol溶媒HCID 6344Dichloromethane溶媒

実験手順

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).

後処理

  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)

出典と根拠

ORDレコード
ord-d7a87548317d4d01acc6c819988c0cdb
出典データセット
uspto-grants-2014_03
特許番号
US08680291B2

反応ノート

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