Methyl chlorodifluoroacetate → 6-Methoxy-3-nitro-2-(trifluoromethyl)pyridine

HRID 1297286Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1297286
Cl[C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][CH:5]=[C:4]([O:11][CH3:12])[N:3]=1.[F-:13].[K+].Cl[C:16]([F:22])([F:21])C(OC)=O.[NH4+].[OH-].[NH4+].[Cl-]>CN(C=O)C>[CH3:12][O:11][C:4]1[N:3]=[C:2]([C:16]([F:22])([F:13])[F:21])[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][CH:5]=1

Komponenten

6

Edukt 4

HCID 73935Methyl chlorodifluoroacetateHCID 522689Potassium FluorideHCID 27950292-Chloro-6-methoxy-3-nitropyridineHCID 21863491Ammonium chloride ammonium hydroxide

Produkt 1

HCID 282423586-Methoxy-3-nitro-2-(trifluoromethyl)pyridine

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6228DimethylformamideLösungsmittel

Versuchsvorschrift

2-Chloro-6-methoxy-3-nitropyridine (5 g) was heated with Cul (6.05 g), KF(anhydrous, 3.0 g), methyl 2-chloro-2,2-difluoroacetate(6.8 ml) in DMF (28 ml) at 130° C. for 8 hrs. After cooling, it was poured into 1:9 mixture of NH4OH/NH4Cl(100 ml), stirred until homogeneous and extracted with Ethyl acetate. The organic layer were combined, washed with brine and dried (MgSO4), The flash column chromatography (SiO2, 1˜3% EtOAc in heptane) yielded 3.90 g (65%). 1H NMR (CDCl3) δ 4.02, 6.96, 8.10; IR (liq.) 2389 (w), 2254 (w), 2196 (w), 2163 (w), 2017 (w), 1605 (s), 1586 (s), 1538 (s), 1482 (s), 1340 (s), 1290 (s), 1261 (s), 1205 (s), 1180 (s), 1155 (s) cm−1 Anal. Calcd for C7H5F3N2O3: C, 37.85; H, 2.27; N, 12.61; F, 25.66. Found: C, 37.68; H, 2.29; N, 12.30.

Aufarbeitung

  1. temperatureAfter cooling
  2. extractionextracted with Ethyl acetate
  3. washwashed with brine
  4. dry with materialdried (MgSO4)
  5. customThe flash column chromatography (SiO2, 1˜3% EtOAc in heptane) yielded 3.90 g (65%)

Quellen und Nachweise

ORD-Eintrag
ord-1b7d9a390d2241da95e621f9b5b54104
Quelldatensatz
uspto-grants-2007_07
Patentnummer
US07250418B2

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