Glyoxylic Acid → 3-(2-Nitrobenzoyl)acrylic acid

HRID 362350

反応式

HRID 362350 の反応式
S(=O)(=O)(O)O.[N+:6]([C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=1[C:15](=[O:17])[CH3:16])([O-:8])=[O:7].[C:18]([OH:22])(=[O:21])[CH:19]=O>>[N+:6]([C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=1[C:15]([CH:16]=[CH:19][C:18]([OH:22])=[O:21])=[O:17])([O-:8])=[O:7]

参加物

4

反応物 3

HCID 760Glyoxylic AcidHCID 1118Sulfuric AcidHCID 113462'-Nitroacetophenone

生成物 1

HCID 30672423-(2-Nitrobenzoyl)acrylic acid収率 30.3%

反応条件

温度
100 °C

実験手順

To a solution of 225 ml of glacial acid and 8.5 ml of concentrated sulfuric acid is added 49.54 g (0.30 mol) of 2'-nitroacetophenone and 47.02 g (0.50 mol) of glyoxylic acid (hydrated). The mixture is heated at 100° C. 16 hours. The mixture is cooled and poured over crushed ice. After the ice melts, the mixture is filtered and the solid washed with cold water. The solid is dried and recrystallized from dichloromethane-hexane to give 20.1 g of 3-(2-nitrobenzoyl)acrylic acid as white crystals, m.p. 153°-158° C. A solution of the preceding compound (9.0 g) in 80 ml of ethanol and 1.6 g of palladium-on-carbon is hydrogenated in a Parr hydrogenator under 30 pounds per square inch of hydrogen for 20 hours. The mixture is filtered through diatomaceous earth and the solvent is removed. The residue (7.0 g) is chromatographed on silica gel with hexane-ethyl acetate (1:1) as solvent to give 4.0 g of 3-(2-aminobenzoyl)acrylic acid as an orange solid, m.p. 103°-107° C. A 0.50 g sample of the preceding compound, 0.36 ml of triethylamine and 0.43 ml of diethoxyphosphinyl cyanide in 20 ml of dichloromethane is stirred at room temperature for 5 days. The solvent is removed, ethyl acetate is added and the mixture washed with water, 2N citric acid, 1M NaHCO3, brine and dried (Na2SO4). The solvent is removed and the residue purified by chromatography over silica gel with ethyl acetate-hexane (1:1) as solvent to give 0.190 g of light brown crystals, m.p. 168°-170° C.

後処理

  1. custom16 hours
  2. temperatureThe mixture is cooled
  3. additionpoured
  4. customover crushed ice
  5. filtrationthe mixture is filtered
  6. washthe solid washed with cold water
  7. customThe solid is dried
  8. customrecrystallized from dichloromethane-hexane

出典と根拠

ORDレコード
ord-a9d6a855211e48f28d0f03245b8b2dc2
出典データセット
uspto-grants-1999_02
特許番号
US05869483

関連ノート

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