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

HRID 1513279

반응식

HRID 1513279 반응식
CO[C:3](=O)[CH2:4][CH2:5][C:6]1[CH:11]=[C:10]([CH3:12])[C:9]([C:13]2NC3C=C(C4OC(NC5C=CC(OC)=CC=5)=NN=4)C=CC=3N=2)=[C:8]([CH3:36])[CH:7]=1.N([O-])=O.[Na+].C[OH:43].C([P:47](=[O:54])([O:51][CH2:52][CH3:53])[O:48][CH2:49][CH3:50])C=C>[H+].[B-](F)(F)(F)F.O.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH2:49]([O:48][P:47]([CH2:3]/[CH:4]=[CH:5]/[C:6]1[CH:7]=[C:8]([CH3:36])[C:9]([CH:13]=[O:43])=[C:10]([CH3:12])[CH:11]=1)(=[O:54])[O:51][CH2:52][CH3:53])[CH3:50]

참가 물질

8

반응물 4

HCID 887MethanolHCID 573014Diethyl allylphosphonateHCID 23668193Sodium NitriteHCID 669668163-(4-{6-[5-(4-Methoxy-phenylamino)-[1,3,4]oxadiazol-2-yl]-1H-benzoimidazol-2-yl}-3,5-dimethyl-phenyl)-propionic acid methyl ester

생성물 1

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

시약·촉매·용매 3

HCID 167845palladium(II) acetate촉매HCID 962Water용매HCID 28118Tetrafluoroboric acid용매

반응 조건

온도
0 °C

실험 절차

To a suspension of 4-amino-2,6-dimethylbenzaldehyde (3.0 g, 20.1 mmol) (Example 1-60, step B) in enough 42% HBF4 to be stirred at 0° C. 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 and followed by Pd(OAc)2 (677 mg) and diethyl allylphosphonate (5.38 g, 30.2 mmol). The reaction mixture was heated at 80° C. for 30 min and the suspension was filtered through Celite, washed with CH2Cl2. The filtrate was extracted with CH2Cl2 and 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 the title compound as a light yellow oil. MS: m/z 311 (M+1).

후처리

  1. temperatureThe reaction mixture was heated at 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-ed3a586aa409478691b6ceb4b1ec4953
출처 데이터셋
uspto-grants-2012_07
특허 번호
US08217065B2

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