Phosphonic acid, P-(chloromethyl)-, diethyl ester → Diethyl[(6-methoxy-5-nitropyridin-2-yl)methyl]phosphonate

HRID 511528

Reaktionsgleichung

Reaktionsgleichung von HRID 511528
[CH3:1][O:2][C:3]1[C:8]([N+:9]([O-:11])=[O:10])=[CH:7][CH:6]=[CH:5][N:4]=1.Cl[CH2:13][P:14](=[O:21])([O:18][CH2:19][CH3:20])[O:15][CH2:16][CH3:17].CC(C)([O-])C.[K+]>CS(C)=O>[CH3:1][O:2][C:3]1[N:4]=[C:5]([CH2:13][P:14](=[O:21])([O:18][CH2:19][CH3:20])[O:15][CH2:16][CH3:17])[CH:6]=[CH:7][C:8]=1[N+:9]([O-:11])=[O:10]

Komponenten

5

Edukt 3

HCID 76633Phosphonic acid, P-(chloromethyl)-, diethyl esterHCID 2532192-Methoxy-3-nitropyridineHCID 23665647Potassium tert-butoxide

Produkt 1

HCID 86654057Diethyl[(6-methoxy-5-nitropyridin-2-yl)methyl]phosphonateAusbeute 5,5 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 679Dimethyl SulfoxideLösungsmittel2×

Versuchsvorschrift

A solution of 2-methoxy-3-nitropyridine (6.92 g, 44.9 mmol) and diethyl chloromethylphosphonate (7.00 mL, 44.9 mmol) in 40 mL DMSO was added drop wise to a stirred mixture of potassium tert-butoxide (15.1 g, 134.6 mmol) and 40 mL DMSO. The mixture was stirred at room temperature for 30 minutes, after which, it was poured into a 1N HCl/ice mixture and extracted with methylene chloride. The combined organic layers were washed with water, brine, dried over anhydrous sodium sulfate, filtered, concentrated and purified by column chromatography (DCM:EtOAc1:1). The slower eluting regioisomer was collected and confirmed to be the desired product (750 mg, 5.5% yield). MS (ES+): m/z 305.16 (100) [MH+]; HPLC: tR=1.16 min (UPLC, Analytical).

Aufarbeitung

  1. extractionextracted with methylene chloride
  2. washThe combined organic layers were washed with water, brine
  3. dry with materialdried over anhydrous sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. custompurified by column chromatography (DCM:EtOAc1:1)
  7. washThe slower eluting regioisomer
  8. customwas collected

Quellen und Nachweise

ORD-Eintrag
ord-3e15dcb503f74ebdb062b7c0cbe04f65
Quelldatensatz
uspto-grants-2015_08
Patentnummer
US09096624B2

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