2-Propenoic acid, 2-cyano-3-ethoxy-, ethyl ester → HCID 178470003、化合物

HRID 12890

反応式

HRID 12890 の反応式
Cl.[NH:2]([C:4]1(O)[CH2:9][CH2:8][CH2:7][CH2:6][CH2:5]1)[NH2:3].C(O[CH:14]=[C:15]([C:21]#[N:22])[C:16]([O:18][CH2:19][CH3:20])=[O:17])C.[C:23]([O-:26])(=[O:25])[CH3:24].[Na+]>C(O)C>[CH2:19]([O:18][C:16]([C:15]1[CH:14]=[N:3][N:2]([C@H:4]2[CH2:9][CH2:8][C@@H:7]([OH:25])[CH2:6][CH2:5]2)[C:21]=1[NH2:22])=[O:17])[CH3:20].[CH2:19]([O:18][C:16]([C:15]1[CH:14]=[N:3][N:2]([C@H:4]2[CH2:9][CH2:24][C@H:23]([OH:26])[CH2:6][CH2:5]2)[C:21]=1[NH2:22])=[O:17])[CH3:20]

参加物

6

反応物 3

HCID 789432-Propenoic acid, 2-cyano-3-ethoxy-, ethyl esterHCID 517045Sodium AcetateHCID 67020953Hydrazino-cyclohexanol hydrochloride

生成物 2

HCID 178470002HCID 178470002、化合物HCID 178470003HCID 178470003、化合物収率 28%

試薬・触媒・溶媒 1

HCID 702Ethanol溶媒

反応条件

温度
70 °C

実験手順

Hydrazino-cyclohexanol hydrochloride (1.920 g, 9.79 mmol) was dissolved in hot ethanol and then cooled slightly. Ethyl (ethoxymethylene)-cyanoacetate (1.520 g, 8.98 mmol) and anhydrous sodium acetate (2.013 g, 24.54 mmol) were added and the mixture was heated at 70° C. for 15 hours. After cooling to room temperature, the mixture was partitioned between methylene chloride and water. The aqueous phase was washed with a second portion of methylene chloride. The two organic phases were combined, washed with brine, dried over sodium sulfate and concentrated. Flash chromatography, eluting with a 0-20% methanol/ethyl acetate gradient, separated a large portion of the cis-trans mixture of isomers. After chromatography, pure fractions of each isomer were combined and crystallized from EtOAc-hexanes to give 5-amino-1-(cis-4-hydroxy-cyclohexyl)-1H-pyrazole-4-carboxylic acid ethyl ester (0.511 g, 23% (crop 1); 0.121 g, 5% (crop 2)) and 5-amino-1-(trans-4-hydroxy-cyclohexyl)-1H-pyrazole-4-carboxylic acid ethyl ester (0.625 g, 28%).

後処理

  1. temperaturecooled slightly
  2. temperatureAfter cooling to room temperature
  3. customthe mixture was partitioned between methylene chloride and water
  4. washThe aqueous phase was washed with a second portion of methylene chloride
  5. washwashed with brine
  6. dry with materialdried over sodium sulfate
  7. concentrationconcentrated
  8. washFlash chromatography, eluting with a 0-20% methanol/ethyl acetate gradient
  9. customseparated
  10. additiona large portion of the cis-trans mixture of isomers
  11. customcrystallized from EtOAc-hexanes

出典と根拠

ORDレコード
ord-b0eb15d1b2804e658d0348c324e84c96
出典データセット
uspto-grants-2010_06
特許番号
US07728029B2

関連ノート

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