Hydrochloric Acid → Diethyl[(6-amino-5-methoxypyridin-3-yl)methyl]phosphonate

HRID 1948121

Reaktionsgleichung

Reaktionsgleichung von HRID 1948121
[N+:1]([C:4]1[C:9]([O:10][CH3:11])=[CH:8][CH:7]=[CH:6][N:5]=1)([O-])=O.Cl[CH2:13][P:14](=[O:21])([O:18][CH2:19][CH3:20])[O:15][CH2:16][CH3:17].C(O[Na])(C)(C)C.Cl>CS(C)=O>[CH2:16]([O:15][P:14]([CH2:13][C:7]1[CH:6]=[N:5][C:4]([NH2:1])=[C:9]([O:10][CH3:11])[CH:8]=1)(=[O:21])[O:18][CH2:19][CH3:20])[CH3:17]

Komponenten

6

Edukt 4

HCID 313Hydrochloric AcidHCID 76633Phosphonic acid, P-(chloromethyl)-, diethyl esterHCID 5560633-Methoxy-2-nitropyridineHCID 178418730sodium 2-methylpropan-2-olate

Produkt 1

HCID 86654065Diethyl[(6-amino-5-methoxypyridin-3-yl)methyl]phosphonateAusbeute 19,2 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 679Dimethyl SulfoxideLösungsmittel2×

Versuchsvorschrift

A solution of 2-nitro-3-methoxypyridine (300 mg, 1.95 mmol) and diethyl chloromethylphosphonate (363 mg, 1.95 mmol) in DMSO (4 mL) was added dropwise to vigorously stirred solution of t-BuONa (0.561 g, 5.84 mmol) in DMSO (4 mL) at room temperature. The reaction mixture turned to deep orange immediately. Stirring was continued for 30 min, then the mixture was poured into 1 M HCl (aq) (10 mL). The product was extracted into ether (3×30 mL), dried over MgSO4, concentrated, and purified by silica gel chromatography (3% MeOH in DCM) to afford 102.6 mg of diethyl[(6-amino-5-methoxypyridin-3-yl)methyl]phosphonate (yield: 17%). 1H NMR (CD3OD, 400 MHz): δ=1.30 (t, J=6.8 Hz, 6H), 3.45 (d, J=22.4 Hz, 2H), 4.00 (s, 3H), 4.09-4.17 (m, 4H), 7.79 (t, J=2.4 Hz, 1H), 7.97 (t, J=2.4 Hz, 1H). MS (ES+): m/z 305.07 [MH+]. HPLC: tR=1.17 min (UPLC TOF, polar—3 min).

Aufarbeitung

  1. extractionThe product was extracted into ether (3×30 mL)
  2. dry with materialdried over MgSO4
  3. concentrationconcentrated
  4. custompurified by silica gel chromatography (3% MeOH in DCM)

Quellen und Nachweise

ORD-Eintrag
ord-38df4a388e804322a0c06b393ec59d54
Quelldatensatz
uspto-grants-2013_03
Patentnummer
US08399433B2

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