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

HRID 419099Notes

Reaction equation

HRID 419099 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-94da1ba8c1934521b74045d7a0bda19b
Source dataset
uspto-grants-2012_01
Patent number
US08093247B2

Reaction notes

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