Tetrafluoroboric acid → [(E)-3-(4-formyl-3,5-dimethylphenyl)-allyl]-phosphonic acid diethyl ester

HRID 1515047노트

반응식

HRID 1515047 반응식
N[C:2]1[CH:9]=[C:8]([CH3:10])[C:5]([CH:6]=[O:7])=[C:4]([CH3:11])[CH:3]=1.[H+].[B-](F)(F)(F)F.N([O-])=O.[Na+].[CH2:22]([P:25](=[O:32])([O:29][CH2:30][CH3:31])[O:26][CH2:27][CH3:28])[CH:23]=[CH2:24]>O.CC([O-])=O.CC([O-])=O.[Pd+2].CO>[CH2:30]([O:29][P:25]([CH2:22]/[CH:23]=[CH:24]/[C:2]1[CH:9]=[C:8]([CH3:10])[C:5]([CH:6]=[O:7])=[C:4]([CH3:11])[CH:3]=1)(=[O:32])[O:26][CH2:27][CH3:28])[CH3:31]

참가 물질

8

반응물 4

HCID 28118Tetrafluoroboric acidHCID 573014Diethyl allylphosphonateHCID 123812354-Amino-2,6-dimethylbenzaldehydeHCID 23668193Sodium Nitrite

생성물 1

HCID 86632823[(E)-3-(4-formyl-3,5-dimethylphenyl)-allyl]-phosphonic acid diethyl ester

시약·촉매·용매 3

HCID 167845palladium(II) acetate촉매HCID 887Methanol용매HCID 962Water용매

반응 조건

온도
0 °C

실험 절차

4-Amino-2,6-dimethylbenzaldehyde (3.0 g, 20.1 mmol) was taken up in enough 42% HBF4 until the suspension stirred well and then was cooled to 0° C. To this was added a solution of NaNO2 (1.39 g, 20.1 mmol) in water (10 mL) slowly. After 30 min at 0° C., MeOH (50 mL) was added followed by Pd(OAc)2 (677 mg) and diethyl allylphosphonate (5.38 g, 30.2 mmol). The reaction mixture was heated to 80° C. for 30 min and the suspension was filtered through Celite, washed with CH2Cl2, and the filtrate was extracted with CH2Cl2. The combined organic layers were washed with water, brine, dried with MgSO4, and filtered. The solvent was removed under reduced pressure and the residue was purified by flash chromatography using a gradient of heptane/EtOAc (10:1 to 5:1 then followed by 100% EtOAc) to give [(E)-3-(4-formyl-3,5-dimethylphenyl)-allyl]-phosphonic acid diethyl ester as a light yellow oil.

후처리

  1. temperatureThe reaction mixture was heated to 80° C. for 30 min
  2. filtrationthe suspension was filtered through Celite
  3. washwashed with CH2Cl2
  4. extractionthe filtrate was extracted with CH2Cl2
  5. washThe combined organic layers were washed with water, brine
  6. dry with materialdried with MgSO4
  7. filtrationfiltered
  8. customThe solvent was removed under reduced pressure
  9. customthe residue was purified by flash chromatography

출처 및 근거

ORD 기록
ord-daf75626f57b4616bfac6bb36bbc315b
출처 데이터셋
uspto-grants-2012_07
특허 번호
US08222248B2

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