Ethyl Acetoacetate → Ethyl 2-acetyl-5-chlorohex-4-enoate

HRID 1449131

反応式

HRID 1449131 の反応式
[Na].[C:2]([O:8][CH2:9][CH3:10])(=[O:7])[CH2:3][C:4]([CH3:6])=[O:5].Cl[CH2:12][CH:13]=[C:14]([Cl:16])[CH3:15]>C(O)C>[C:2]([CH:3]([CH2:12][CH:13]=[C:14]([Cl:16])[CH3:15])[C:4](=[O:5])[CH3:6])([O:8][CH2:9][CH3:10])=[O:7]

参加物

5

反応物 3

HCID 8868Ethyl Acetoacetate2 回HCID 135561,3-Dichloro-2-buteneHCID 5360545Sodium

生成物 1

HCID 53723570Ethyl 2-acetyl-5-chlorohex-4-enoate

試薬・触媒・溶媒 1

HCID 702Ethanol溶媒

実験手順

To a solution of 46 g sodium (2 g atom) in 500 ml ethanol at reflux, in a 2-liter flask equipped with mechanical stirrer, and addition funnel, was added 325 g ethyl acetoacetate (2.5 mole) over 30 minutes. The resulting solution of enolate was refluxed for 15 minutes, and then 250 g (2.0 mole) 1,3-dichlorobut-2-ene (nD20 1.4675) was added dropwise at such a rate as to maintain reflux with gentle heating towards the end of the addition. After addition, refluxing and stirring were maintained for 4 hours, the condenser converted for distillation, and ethanol removed as 500 ml distillate. The residual product was cooled, water and 1.2 N hydrochloric acid were added and the organic layer separated. The aqueous portion was extracted with ether, the organic layers combined, washed with water and brine, filtered through sodium sulfate and evaporated in vacuo to give 485 g. dark yellow oil (96%, based on dichlorobutene). Vpc showed 73% of trans plus cis product, together with 20% ethyl acetoacetate and other volatiles, and 7% dialkylated product at long retention time. A small sample was purified by TLC on silica gel (1:3 ethyl acetate:pentane) Rf 0.27, followed by distillation at 100° C./0.1 mm. 3-Carboethoxy-6-chlorohept-5-en-2-one was obtained as a colorless oil, nD20 1.4640.

後処理

  1. customequipped with mechanical stirrer, and addition funnel
  2. temperatureto maintain
  3. temperaturereflux
  4. temperaturewith gentle heating towards the end of the addition
  5. additionAfter addition
  6. temperaturerefluxing
  7. temperaturewere maintained for 4 hours
  8. distillationthe condenser converted for distillation, and ethanol
  9. customremoved as 500 ml distillate
  10. temperatureThe residual product was cooled
  11. additionwater and 1.2 N hydrochloric acid were added
  12. customthe organic layer separated
  13. extractionThe aqueous portion was extracted with ether
  14. washwashed with water and brine
  15. filtrationfiltered through sodium sulfate
  16. customevaporated in vacuo
  17. customto give 485 g
  18. customA small sample was purified by TLC on silica gel (1:3 ethyl acetate:pentane) Rf 0.27
  19. distillationfollowed by distillation at 100° C./0.1 mm

出典と根拠

ORDレコード
ord-b6d8b32d71784c90804bd51924f3995a
出典データセット
uspto-grants-1980_02
特許番号
US04189431

関連ノート

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