Methyl Acrylate → 4-(m-Chlorocinnamyl)-4-phenyl-5-oxo-7-(p-chlorophenyl)-6-heptenoic Acid

HRID 1076315ノート

反応式

HRID 1076315 の反応式
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]=[CH:9][C:10](=[O:28])[CH:11]([C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)[CH2:12][CH:13]=[CH:14][C:15]2[CH:20]=[CH:19][CH:18]=[C:17]([Cl:21])[CH:16]=2)=[CH:4][CH:3]=1.[C:29]([O:33]C)(=[O:32])[CH:30]=[CH2:31]>CO.C(COC)OC>[Cl:21][C:17]1[CH:16]=[C:15]([CH:20]=[CH:19][CH:18]=1)[CH:14]=[CH:13][CH2:12][C:11]([C:22]1[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=1)([C:10](=[O:28])[CH:9]=[CH:8][C:5]1[CH:6]=[CH:7][C:2]([Cl:1])=[CH:3][CH:4]=1)[CH2:31][CH2:30][C:29]([OH:33])=[O:32]

参加物

5

反応物 2

HCID 7294Methyl AcrylateHCID 543508231-(p-Chlorophenyl)-4-phenyl-7-(m-chlorophenyl)-1,6-heptadien-3-one

生成物 1

HCID 536366224-(m-Chlorocinnamyl)-4-phenyl-5-oxo-7-(p-chlorophenyl)-6-heptenoic Acid

試薬・触媒・溶媒 2

HCID 887Methanol溶媒HCID 80711,2-Dimethoxyethane溶媒2 回

実験手順

Triton B (1.5 ml., 40% in MeOH) is added to a stirred solution of 1-(p-chlorophenyl)-4-phenyl-7-(m-chlorophenyl)-1,6-heptadien-3-one (22.8 g., 0.056 mole) in glyme (175 ml.), followed by addition of methyl acrylate (5.76 g., 0.067 mole) in glyme (25 ml.). After stirring for 20 hours, the solvent is removed in vacuo and water (600 ml.) and dilute hydrochloric acid (25 ml.) are added to the residue. The organic material is extracted into ether and these extracts are washed with water, saturated brine and dried (Na2SO4). After removal of the solvent the residue is heated on a steam bath with a solution of 20% sodium hydroxide (25 ml.) in methanol (300 ml.) for 48 hours. The methanol is removed in vacuo and the residue is dissolved in water (1200 ml.). Extraction with ether removes unreacted ketone. Ether is expelled from the aqueous phase by warming. The solution is cooled in an ice bath, acidified with dilute hydrochloric acid (30 ml.), and the sticky yellow solid which precipitates is collected and air-dried, yield 4.5 g., m.p. 65°-105°C. Recrystallization from benzene-petroleum ether (30°-60°C.) followed by several recrystallizations from n-butyl chloride gives material with m.p. 150°-151°C.

後処理

  1. customthe solvent is removed in vacuo and water (600 ml.) and dilute hydrochloric acid (25 ml.)
  2. additionare added to the residue
  3. extractionThe organic material is extracted into ether
  4. washthese extracts are washed with water, saturated brine
  5. dry with materialdried (Na2SO4)
  6. customAfter removal of the solvent the residue
  7. temperatureis heated on a steam bath with a solution of 20% sodium hydroxide (25 ml.) in methanol (300 ml.) for 48 hours
  8. customThe methanol is removed in vacuo
  9. dissolutionthe residue is dissolved in water (1200 ml.)
  10. extractionExtraction with ether
  11. customremoves unreacted ketone
  12. temperatureby warming
  13. temperatureThe solution is cooled in an ice bath
  14. customthe sticky yellow solid which precipitates
  15. customis collected
  16. customair-dried
  17. customRecrystallization from benzene-petroleum ether (30°-60°C.)
  18. customfollowed by several recrystallizations from n-butyl chloride
  19. customgives material with m.p. 150°-151°C.

出典と根拠

ORDレコード
ord-3a8f5f0560e14bc3801d2ea2dd9c3f3f
出典データセット
uspto-grants-1976_05
特許番号
US03956374

反応ノート

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