Dimethylformamide → 6-Phenylsulfanyl-pyridine-3-carbaldehyde

HRID 78083Notes

Reaction equation

HRID 78083 reaction equation
[O:1]1[CH2:5][CH2:4][CH2:3][CH2:2]1.BrC1C=C[C:10]([S:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)=[N:11][CH:12]=1.C([Li])CCC.CN(C)C=O>O>[C:14]1([S:13][C:10]2[N:11]=[CH:12][C:4]([CH:5]=[O:1])=[CH:3][CH:2]=2)[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 8028TetrahydrofuranHCID 221806675-bromo-2-(phenylthio)pyridineHCID 178418339Butyllithium

Product 1

HCID 542168266-Phenylsulfanyl-pyridine-3-carbaldehydeYield 32%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

To a tetrahydrofuran (40 mL) solution of 5-bromo-2-phenylsulfanyl-pyridine (2.24 g, 8.42 mmol) described in Manufacturing Example 97-1-1 was added n-butyl lithium (6.35 mL, 1.6 M hexane solution, 10.1 mmol) under nitrogen atmosphere at −78° C., which was stirred for 45 minutes at −78°. Next, N,N-dimethylformamide (848 μL, 10.9 mmol) was added to this reaction mixture, and stirred for 35 minutes as the temperature was gradually raised to room temperature. Water was added to the reaction solution at room temperature, which was then extracted with ethyl acetate. The organic layer was separated, washed with saturated aqueous sodium chloride, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under a reduced pressure, and the residue was purified by silica gel column chromatography (heptane: ethyl acetate=2:1) to obtain the title compound (583 mg, 32%).

Workup

  1. stirringstirred for 35 minutes as the temperature
  2. extractionwhich was then extracted with ethyl acetate
  3. customThe organic layer was separated
  4. washwashed with saturated aqueous sodium chloride
  5. dry with materialdried over anhydrous magnesium sulfate
  6. filtrationfiltered
  7. concentrationThe filtrate was concentrated under a reduced pressure
  8. customthe residue was purified by silica gel column chromatography (heptane: ethyl acetate=2:1)

Sources & evidence

ORD record
ord-774833b3bffc42b3839e7d25c8bac208
Source dataset
uspto-grants-2014_09
Patent number
US08841327B2

Reaction notes

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