Water → Diethyl [2,3,4-trifluoro[(1S)-2-hydroxy-1-methylethyl]anilino]methylenemalonate

HRID 8474

反応式

HRID 8474 の反応式
[OH-].[K+].[F:3][C:4]1[C:14]([F:15])=[C:13]([F:16])[CH:12]=[CH:11][C:5]=1[NH:6][C@@H:7]([CH3:10])[CH2:8][OH:9].[CH2:17]([O:19][C:20](=[O:31])[C:21](=[CH:27]OCC)[C:22]([O:24][CH2:25][CH3:26])=[O:23])[CH3:18].O>S([O-])(O)(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC.CN(C=O)C>[F:3][C:4]1[C:14]([F:15])=[C:13]([F:16])[CH:12]=[CH:11][C:5]=1[N:6]([CH:27]=[C:21]([C:20]([O:19][CH2:17][CH3:18])=[O:31])[C:22]([O:24][CH2:25][CH3:26])=[O:23])[C@@H:7]([CH3:10])[CH2:8][OH:9]

参加物

7

反応物 4

HCID 962WaterHCID 6871Diethyl (ethoxymethylene)malonateHCID 14797Potassium HydroxideHCID 11401466(2S)-2-(2,3,4-Trifluoroanilino)propanol

生成物 1

HCID 11485652Diethyl [2,3,4-trifluoro[(1S)-2-hydroxy-1-methylethyl]anilino]methylenemalonate収率 90.2%

試薬・触媒・溶媒 2

HCID 94433Tetrabutylammonium hydrogen sulfate触媒HCID 6228Dimethylformamide溶媒2 回

反応条件

温度
0 °C

実験手順

At room temperature, potassium hydroxide (330 mg) and tetrabutylammonium hydrogensulfate (82.7 mg) were dissolved in DMF (15 ml). After adding a solution (5 ml) of (2S)-2-(2,3,4-trifluoroanilino)propanol (1 g, 99.8% ee) and diethylethoxymethylenemalonate (2.09 g) in DMF, the resultant mixture was stirred for 1 hour. After adding water, the liquid reaction mixture was extracted with a solvent mixture of ethyl acetate and n-hexane (3:2). The organic layer was washed with water and dried over anhydrous magnesium sulfate. After evaporating the solvent, IPE was added to the obtained residue and the mixture was stirred at 0° C. for 1 hour. The crystals thus precipitated were collected by filtration and the moist product thus obtained was dried under reduced pressure. Thus, the title compound (1.65 g, 99. 8% ee) was obtained as colorless crystals. The 1H-NMR and IR spectral data of this product was identical with those of the compound obtained in Example 63.

後処理

  1. customthe liquid reaction mixture
  2. extractionwas extracted with a solvent mixture of ethyl acetate and n-hexane (3:2)
  3. washThe organic layer was washed with water
  4. dry with materialdried over anhydrous magnesium sulfate
  5. customAfter evaporating the solvent, IPE
  6. additionwas added to the obtained residue
  7. customThe crystals thus precipitated
  8. filtrationwere collected by filtration
  9. customthe moist product thus obtained
  10. customwas dried under reduced pressure

出典と根拠

ORDレコード
ord-b70b5d96668a4a3a90823c7b62b9d362
出典データセット
uspto-grants-2006_08
特許番号
US07087778B2

関連ノート

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