Sulfuric Acid → 4-Methoxycinnamate methyl ester

HRID 327913

반응식

HRID 327913 반응식
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6](N)=[CH:5][CH:4]=1.S(=O)(=O)(O)O.N([O-])=O.[Na+].N(O)=O.[C:22]([O:26][CH3:27])(=[O:25])[CH:23]=[CH2:24]>C(O)(=O)C.[Pd].C(N)(C)(C)C.O>[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([CH:24]=[CH:23][C:22]([O:26][CH3:27])=[O:25])=[CH:5][CH:4]=1

참가 물질

10

반응물 5

HCID 1118Sulfuric AcidHCID 7294Methyl AcrylateHCID 7732P-AnisidineHCID 24529Nitrous AcidHCID 23668193Sodium Nitrite

생성물 1

HCID 928414-Methoxycinnamate methyl ester수율 99%

시약·촉매·용매 4

HCID 6385Tert-Butylamine촉매HCID 23938Palladium촉매HCID 176Acetic Acid용매HCID 962Water용매

실험 절차

p-Anisidine (12.3 g) was dissolved in 55 ml acetic acid and 15 ml water and cooled to 10° C. 98% Sulfuric acid (15 g) was added slowly with agitation while cooling the reaction vessel, a 500 ml three necked round bottom flask equipped with stirrer, thermometer, dropping funnel and cooling bath. Sodium nitrite (6.9 g dissolved in 20 ml water) was then added at 0°-2° C. over one hour while stirring. Excess nitrous acid was then neutralized by the addition of 0.05 g t-butylamine. After 10 minutes, palladium (O) dibenzylidene acetone (Pd(dba)2, 0.15 g) was added followed by methyl acrylate (12.9 g) and butylated hydroxytoluene (0.03 g). The cooling bath was then removed and the temperature allowed to slowly reach ambient conditions (25° C.). After 22 hours of stirring, the acid was neutralized with excess 10% sodium hydroxide solution (aqueous) and the mixture allowed to separate. The aqueous layer was separated and extracted twice with 20 ml portions of ethyl ether. The ether layers were combined with the organic phase, concentrated on a rotary evaporator to remove the ether and distilled to give 19.0 g of methyl p-methoxycinnamate (99% yield, purity 95% by GC).

후처리

  1. temperaturewhile cooling the reaction vessel
  2. temperaturecooling bath
  3. customThe cooling bath was then removed
  4. customallowed to slowly reach ambient conditions (25° C.)
  5. stirringAfter 22 hours of stirring
  6. customto separate
  7. customThe aqueous layer was separated
  8. extractionextracted twice with 20 ml portions of ethyl ether
  9. concentrationconcentrated on a rotary evaporator
  10. customto remove the ether
  11. distillationdistilled

출처 및 근거

ORD 기록
ord-8fc3a731fdda41889dde40611fcea14d
출처 데이터셋
uspto-grants-1993_12
특허 번호
US05274171

연결된 노트

불러오는 중…