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

HRID 1513279

Reaktionsgleichung

Reaktionsgleichung von HRID 1513279
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]

Komponenten

8

Edukt 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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 167845palladium(II) acetateKatalysatorHCID 962WaterLösungsmittelHCID 28118Tetrafluoroboric acidLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

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).

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-ed3a586aa409478691b6ceb4b1ec4953
Quelldatensatz
uspto-grants-2012_07
Patentnummer
US08217065B2

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