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

HRID 973201

반응식

HRID 973201 반응식
[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]

참가 물질

5

반응물 3

HCID 8868Ethyl Acetoacetate2회HCID 135561,3-Dichloro-2-buteneHCID 5360545Sodium

생성물 1

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

시약·촉매·용매 1

HCID 702Ethanol용매

실험 절차

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 layer 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 layyer 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.

후처리

  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 layyer 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

출처 및 근거

ORD 기록
ord-b4daba7621fc42b28b79ae2e07f65137
출처 데이터셋
uspto-grants-1977_10
특허 번호
US04055603

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