Ethyl Acetate → HCID 90425921, compound

HRID 2278905Notes

Reaction equation

HRID 2278905 reaction equation
[I:1][C:2]1[N:7]=[C:6]([CH3:8])[C:5]([OH:9])=[C:4]([CH3:10])[CH:3]=1.[Cl:11][C:12]1[CH:17]=[C:16](Cl)[CH:15]=[CH:14][N:13]=1.C([O-])([O-])=O.[K+].[K+].CCOC(C)=O>CC(N(C)C)=O.O>[Cl:11][C:12]1[CH:17]=[C:16]([O:9][C:5]2[C:6]([CH3:8])=[N:7][C:2]([I:1])=[CH:3][C:4]=2[CH3:10])[CH:15]=[CH:14][N:13]=1

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 11430Potassium CarbonateHCID 335152,4-DichloropyridineHCID 58570265HCID 58570265, compound

Product 1

HCID 90425921HCID 90425921, compoundYield 20%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 31374DimethylacetamideSolvent

Conditions

Temperature
105 °C

Procedure

A solution of 6-iodo-2,4-dimethylpyridin-3-ol (5.10 g, 20.48 mmol) in DMA (60 mL) was sparged with Ar, treated with 2,4-dichloropyridine (3.94 g, 26.60 mmol) and K2CO3 (3.40 g, 24.57 mmol) and heated at 105° C. overnight. The mixture was cooled to RT, treated with EtOAc and water, filtered to remove solids, then treated with charcoal, warmed to reflux, cooled to RT and filtered through diatomaceous earth. The layers of the filtrate were separated, the aqueous layer extracted with additional EtOAc (1×) and the combined organics were washed with brine, dried over Na2SO4, concentrated to dryness and purified via silica gel chromatography (EtOAc/Hex) to afford 3-((2-chloropyridin-4-yl)oxy)-6-iodo-2,4-dimethylpyridine (1.476 g, 20%). 1H NMR (400 MHz, DMSO-d6): δ 8.27 (d, J=5.8 Hz, 1 H), 7.75 (s, 1 H), 7.05 (d, J=2.3 Hz, 1 H), 6.89 (dd, J=5.8, 2.3 Hz, 1 H), 2.20 (s, 3 H), 2.02 (s, 3 H); MS (ESI) m/z: 361.0 (M+H+).

Workup

  1. temperatureThe mixture was cooled to RT
  2. filtrationfiltered
  3. customto remove solids
  4. additiontreated with charcoal
  5. temperaturewarmed
  6. temperatureto reflux
  7. temperaturecooled to RT
  8. filtrationfiltered through diatomaceous earth
  9. customThe layers of the filtrate were separated
  10. extractionthe aqueous layer extracted with additional EtOAc (1×)
  11. washthe combined organics were washed with brine
  12. dry with materialdried over Na2SO4
  13. concentrationconcentrated to dryness
  14. custompurified via silica gel chromatography (EtOAc/Hex)

Sources & evidence

ORD record
ord-c2f0eae1f8e44b40bf3df395d206b9f6
Source dataset
uspto-grants-2015_09
Patent number
US09133183B2

Reaction notes

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