2,4-Dimethylnicotinaldehyde → (5-Chloro-3-nitro-pyridin-2-yl)-(2,4-dimethyl-pyridin-3-yl)-methanol

HRID 1438542Notes

Reaction equation

HRID 1438542 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([N+:9]([O-:11])=[O:10])[C:5](I)=[N:6][CH:7]=1.C1([Mg]Cl)C=CC=CC=1.[CH3:20][C:21]1[C:26]([CH:27]=[O:28])=[C:25]([CH3:29])[CH:24]=[CH:23][N:22]=1>C1COCC1>[Cl:1][C:2]1[CH:3]=[C:4]([N+:9]([O-:11])=[O:10])[C:5]([CH:27]([C:26]2[C:21]([CH3:20])=[N:22][CH:23]=[CH:24][C:25]=2[CH3:29])[OH:28])=[N:6][CH:7]=1

Participants

5

Reactant 3

HCID 104417552,4-DimethylnicotinaldehydeHCID 579421085-Chloro-2-iodo-3-nitropyridineHCID 178478979HCID 178478979, compound

Product 1

HCID 57942234(5-Chloro-3-nitro-pyridin-2-yl)-(2,4-dimethyl-pyridin-3-yl)-methanol

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a stirred solution of 5-Chloro-2-iodo-3-nitro-pyridine (2.5 g, 8.77 mmol) in anhydrous THF (20 mL) at −78° C. was added 2 M phenylmagnesiumchloride in THF (4.8 mL, 9.6 mmol) and stirred at the same temperature for 30 minutes and then 2,4-Dimethyl-pyridine-3-carbaldehyde (1.82 g, 13.15 mmol) was added in one portion and the progress of the reaction was followed by LCMS. The reaction mixture was warmed to room temperature and stirred overnight (18 h). It was then quenched with saturated aqueous NH4Cl (10 mL), and extracted with EtOAc. The combined extracts were washed with aqueous NaHCO3, brine, and then dried (Na2SO4), filtered and concentrated under reduced pressure. The residue was purified by flash column chromatography to (5-Chloro-3-nitro-pyridin-2-yl)-(2,4-dimethyl-pyridin-3-yl)-methanol. Mass spectrum m/z: 294.4 (M+H).

Workup

  1. stirringstirred overnight (18 h)
  2. customIt was then quenched with saturated aqueous NH4Cl (10 mL)
  3. extractionextracted with EtOAc
  4. washThe combined extracts were washed with aqueous NaHCO3, brine
  5. dry with materialdried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customThe residue was purified by flash column chromatography to (5-Chloro-3-nitro-pyridin-2-yl)-(2,4-dimethyl-pyridin-3-yl)-methanol

Sources & evidence

ORD record
ord-ce37de5088e14603a6c1ba2094c60643
Source dataset
uspto-grants-2009_11
Patent number
US07622583B2

Reaction notes

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