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

HRID 1764155

反応式

HRID 1764155 の反応式
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]

参加物

5

反応物 3

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

生成物 1

HCID 204735953,6-Dimethyl-2,4-dioxocyclohexanecarbonitrile収率 68.3%

試薬・触媒・溶媒 1

HCID 887Methanol溶媒2 回

実験手順

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-hexen4-one is added over a 20 minute period. The resulting reaction mixture is stirred and heated at reflux for 6 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: ##STR26##

後処理

  1. additionis added over a 20 minute period
  2. customThe resulting reaction mixture
  3. temperatureheated
  4. temperatureat reflux for 6 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

出典と根拠

ORDレコード
ord-35d231623c514e9a8bc6997b241244f3
出典データセット
uspto-grants-1978_09
特許番号
US04115431

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