Water → Methyl 6-(difluoromethoxy)picolinate

HRID 594303ノート

反応式

HRID 594303 の反応式
[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

参加物

6

反応物 4

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

生成物 1

HCID 69081734Methyl 6-(difluoromethoxy)picolinate

試薬・触媒・溶媒 1

HCID 6342Acetonitrile溶媒

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-dd258f89f22641828a2e81c1feaa1d25
出典データセット
uspto-grants-2016_01
特許番号
US09242970B2

反応ノート

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