Methyl cyanoacetate → 3,6-Dimethyl-2,4-dioxocyclohexanecarbonitrile

HRID 262937

반응식

HRID 262937 반응식
C[O-].[Na+].CO[C:6](=[O:10])[CH2:7][C:8]#[N:9].[CH3:11][CH:12]=[CH:13][C:14](=[O:17])[CH2:15][CH3:16]>CO>[CH3:16][CH:15]1[C:14](=[O:17])[CH2:13][CH:12]([CH3:11])[CH:7]([C:8]#[N:9])[C:6]1=[O:10]

참가 물질

5

반응물 3

HCID 7747Methyl cyanoacetateHCID 17244Hex-4-en-3-oneHCID 10942334Sodium Methoxide

생성물 1

HCID 204735953,6-Dimethyl-2,4-dioxocyclohexanecarbonitrile수율 68.3%

시약·촉매·용매 1

HCID 887Methanol용매2회

실험 절차

To a solution of sodium methoxide (162 grams, 3 moles) in 400 mls of anhydrous methanol is added, dropwise, 276 grams (3.2 moles) of methylcyanoacetate over a period of 1 hour at 60° C. with stirring. The resulting slurry is stirred at 60° C. for 10 minutes, whereupon 288 grams (3.0 moles) of 2-hexen-4-one is added over a 20 minute period. The resulting reaction mixture is stirred and heated at reflux for six hours, whereupon a distillation take-off condenser is affixed to the reaction flask and 240 mls of methanol are removed under reduced pressure (65 mm Hg). The reaction mixture is then cooled to room temperature and poured into 2 liters of water. Toluene (500 ml) is added and the mixture is transferred to a separatory funnel. The aqueous layer is removed and again extracted with toluene (500 mls). To the aqueous solution, 500 mls of 18% HCl are added with external cooling at 25° C., whereupon a solid material precipitates. The solid is filtered, dried and recrystallized from aqueous methanol to afford colorless needles of 3,6-dimethyl-2,4-dioxocyclohexanecarbonitrile (338 grams, 68.3% yield based on 2-hexen-4-one); m.p. 178°-179° C. The resulting product is represented by the following equilibrium mixture: ##STR21##

후처리

  1. additionis added over a 20 minute period
  2. customThe resulting reaction mixture
  3. temperatureheated
  4. temperatureat reflux for six hours, whereupon a distillation take-off condenser
  5. customare removed under reduced pressure (65 mm Hg)
  6. additionpoured into 2 liters of water
  7. additionToluene (500 ml) is added
  8. customthe mixture is transferred to a separatory funnel
  9. customThe aqueous layer is removed
  10. extractionagain extracted with toluene (500 mls)
  11. additionTo the aqueous solution, 500 mls of 18% HCl are added
  12. temperaturewith external cooling at 25° C., whereupon a solid material
  13. customprecipitates
  14. filtrationThe solid is filtered
  15. customdried
  16. customrecrystallized from aqueous methanol

출처 및 근거

ORD 기록
ord-98807ecd473444949d99f55644118e99
출처 데이터셋
uspto-grants-1979_05
특허 번호
US04155867

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