Hydrochloric Acid → (E)-N,N-diisopropyl-3-(2-methoxy-5-methoxycarbonylphenyl)acrylamide

HRID 1766379

反応式

HRID 1766379 の反応式
CN(C)CC(O)=O.C([O-])(=O)C.[Na+].Br[C:14]1[CH:15]=[C:16]([CH:21]=[CH:22][C:23]=1[O:24][CH3:25])[C:17]([O:19][CH3:20])=[O:18].[CH:26]([N:29]([CH:34]([CH3:36])[CH3:35])[C:30](=[O:33])[CH:31]=[CH2:32])([CH3:28])[CH3:27].Cl>ClCCl.CN1CCCC1=O>[CH:34]([N:29]([CH:26]([CH3:28])[CH3:27])[C:30](=[O:33])/[CH:31]=[CH:32]/[C:14]1[CH:15]=[C:16]([C:17]([O:19][CH3:20])=[O:18])[CH:21]=[CH:22][C:23]=1[O:24][CH3:25])([CH3:36])[CH3:35]

参加物

8

反応物 5

HCID 313Hydrochloric AcidHCID 673N,N-DimethylglycineHCID 517045Sodium AcetateHCID 559397N,N-Diisopropylacrylamide2 回HCID 611662Methyl 3-bromo-4-methoxybenzoate2 回

生成物 1

HCID 22735209(E)-N,N-diisopropyl-3-(2-methoxy-5-methoxycarbonylphenyl)acrylamide収率 69%

試薬・触媒・溶媒 2

HCID 6344Dichloromethane溶媒HCID 13387N-methyl-2-pyrrolidone溶媒

反応条件

温度
130 °C

実験手順

A stirred suspension consisting of N,N-dimethylglycine (6.0 mmol), anhydrous sodium acetate (40 mmol), methyl 3-bromo-4-methoxybenzoate (20 mmol, 4.90 g), N,N-diisopropylacrylamide (24 mmol, 3.72 g), bis-(benzonitrile)-palladium-II chloride (1.5 mol %), and 20 ml of N-methyl-2-pyrrolidinone was heated at 130° C. until no starting material could be detected by tlc (starting material methyl 3-bromo-4-methoxybenzoate: Rf 0.73; N,N-diisopropylacrylamide: Rf 0.46; solvent system (1)). After cooling to room temperature 50 ml of an aqueous 2N HCl solution was added. The reaction was diluted with dichloromethane (50 ml) and the precipitated grey palladium metal was filtered off. The organic phase was washed with five portions (50 ml each) of 2N aqueous hydrochloric acid, dried (MgSO4) and evaporated to dryness. The remaining off-white solid was recrystallized from ethyl acetate/n-hexane to give 4.40 g (E)-N,N-diisopropyl-3-(2-methoxy-5-methoxycarbonylphenyl)-acrylamide in 69% yield, m.p. 139-140° C., tlc: (1) Rf 0.40. NMR (CD2Cl2): 21.22, 22.10, 46.39, 48.87, 52.59, 56.61, 111.42, 123.39, 123.78, 125.54, 130.32, 132.53, 35.07. MS (EI, DI, 105° C.): 319 (M+., 22), 304 (6%), 276 (8%), 219 (100%), 187 (18%), 160 (7%).

後処理

  1. additionwas added
  2. filtrationthe precipitated grey palladium metal was filtered off
  3. washThe organic phase was washed with five portions (50 ml each) of 2N aqueous hydrochloric acid
  4. dry with materialdried (MgSO4)
  5. customevaporated to dryness
  6. customThe remaining off-white solid was recrystallized from ethyl acetate/n-hexane

出典と根拠

ORDレコード
ord-9ac5fe1bf5874a69bdfb29d1380c0b11
出典データセット
uspto-grants-2007_06
特許番号
US07230030B2

関連ノート

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