Water → Methyl 6-(difluoromethoxy)picolinate

HRID 594303Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 594303
[O:1]=[C:2]1[NH:7][C:6]([C:8]([O:10][CH3:11])=[O:9])=[CH:5][CH:4]=[CH:3]1.[H-].[Na+].FS([C:18](C(O)=O)([F:20])[F:19])(=O)=O.O>CC#N>[F:19][CH:18]([F:20])[O:1][C:2]1[N:7]=[C:6]([C:8]([O:10][CH3:11])=[O:9])[CH:5]=[CH:4][CH:3]=1

Komponenten

6

Edukt 4

HCID 962WaterHCID 24758Sodium hydrideHCID 27375162,2-Difluoro-2-(fluorosulfonyl)acetic acidHCID 12342664Methyl 6-oxo-1,6-dihydropyridine-2-carboxylate

Produkt 1

HCID 69081734Methyl 6-(difluoromethoxy)picolinate

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6342AcetonitrileLösungsmittel

Versuchsvorschrift

A mixture of methyl 6-oxo-1,6-dihydropyridine-2-carboxylate (3.074 g; 20.07 mmol) in anh. MeCN (310 ml) was treated portionwise with NaH (60% dispersion in mineral oil; 2.167 g; 54.19 mmol), and stirring at rt, under nitrogen, was continued for 30 min. FSO2CF2CO2H (6.077 g; 34.12 mmol) was then added dropwise, and the resulting heterogeneous mixture was further stirred at rt, under nitrogen, for 30 min. Water (25 ml) was slowly added, and MeCN was removed under reduced pressure. Water (150 ml) and AcOEt (150 ml) were added, and the separated aq. layer was further extracted with AcOEt (2×100 ml). The mixed organic layers were washed with brine (100 ml), dried over anh. MgSO4, filtered, and concentrated to dryness under reduced pressure. Purification by FC (DCM) afforded methyl 6-(difluoromethoxy)picolinate as a yellow solid. LC-MS (conditions D): tR=0.89 min.; no ionisation.

Aufarbeitung

  1. stirringthe resulting heterogeneous mixture was further stirred at rt, under nitrogen, for 30 min
  2. customMeCN was removed under reduced pressure
  3. additionWater (150 ml) and AcOEt (150 ml) were added
  4. extractionthe separated aq. layer was further extracted with AcOEt (2×100 ml)
  5. washThe mixed organic layers were washed with brine (100 ml)
  6. dry with materialdried over anh. MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated to dryness under reduced pressure
  9. customPurification by FC (DCM)

Quellen und Nachweise

ORD-Eintrag
ord-dd258f89f22641828a2e81c1feaa1d25
Quelldatensatz
uspto-grants-2016_01
Patentnummer
US09242970B2

Notizen zur Reaktion

Wird geladen…