Dimethylformamide → 3-Fluoro-2-pyridinecarboxaldehyde

HRID 1823288Notes

Reaction equation

HRID 1823288 reaction equation
C([Li])CCC.N12CCN(CC1)CC2.[F:14][C:15]1[CH:16]=[N:17][CH:18]=[CH:19][CH:20]=1.CN(C)[CH:23]=[O:24]>C(OCC)C.O>[F:14][C:15]1[C:16]([CH:23]=[O:24])=[N:17][CH:18]=[CH:19][CH:20]=1

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 9237DabcoHCID 677943-FluoropyridineHCID 178418339Butyllithium

Product 1

HCID 113440173-Fluoro-2-pyridinecarboxaldehydeYield 49%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 3283Diethyl EtherSolvent

Conditions

Temperature
-70 °C

Procedure

Add a solution of n-butyl lithium (34.4 mL, 0.055 mol, 1.6 M in hexanes) to a mixture of 1,4-diazabicyclo-[2.2.2]octane (6.16, 0.055 mol) in diethyl ether (250 mL) at −10 to−20° C. under a nitrogen atmosphere. Stir for 1 h and cool to −70° C. Add 3-fluoropyridine (4.29 mL, 0.05 mol) dropwise and stir for 2.5 hours at this temperature. Add N,N-dimethylformamide (7.75 mL, 0.10 mol) dropwise via syringe and stir for 1 hour near −70° C. Add water (200 mL) when the mixture warms near −20° C. and extract with ethyl acetate. Dry over sodium sulfate and concentrate in vacuo. Elute over silica gel with dichloromethane to give the desired aldehyde (3.06 g, 49%) as a dark solid. MS(ES): (M+1)+ 126.0 m/z.

Workup

  1. customwarms near −20° C.
  2. extractionextract with ethyl acetate
  3. dry with materialDry over sodium sulfate
  4. concentrationconcentrate in vacuo
  5. washElute over silica gel with dichloromethane

Sources & evidence

ORD record
ord-e8815700676546b28dd81f629807c1eb
Source dataset
uspto-grants-2006_05
Patent number
US07037921B2

Reaction notes

Loading…