2-Pyridinamine, N-methyl- → HCID 66628284, compound

HRID 495248

Reaction equation

HRID 495248 reaction equation
[CH3:1][NH:2][C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][N:4]=1.Br[C:10]1[CH:15]=[CH:14][CH:13]=[C:12]([CH3:16])[N:11]=1.CC(C)([O-])C.[Na+]>C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].C1(C)C=CC=CC=1>[CH3:1][N:2]([C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][N:4]=1)[C:10]1[CH:15]=[CH:14][CH:13]=[C:12]([CH3:16])[N:11]=1

Participants

6

Reactant 3

HCID 207272-Pyridinamine, N-methyl-HCID 792052-Bromo-6-methylpyridineHCID 23676156Sodium t-butoxide

Product 1

HCID 66628284HCID 66628284, compoundYield 95%

Reagents, catalysts & solvents 2

HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 1140TolueneSolvent

Procedure

To a flask were added 0.75 g 2-(methylamino)pyridine, 1.0 g 2-bromo-6-methylpyridine, 0.95 g sodium tert-butoxide, 0.16 g 1,1′-bis(diphenylphosphino)ferrocene and 50 ml toluene. The mixture was purged thoroughly with nitrogen and 0.14 g of tris(dibenzylideneacetone)d2-propanollladium(0) was added and the mixture was heated to 80 C under nitrogen for 16 hours. After cooling to 22 C and quenching with 50 ml water, the product was extracted twice with ethyl acetate and washed twice with water. After filtration and solvent removal, the product was purified by silica gel chromatography using 35% ethyl acetate in hexane resulting in an orange oil. This was dissolved in 75 ml tert-butyl methyl ether and extracted into 75 ml 1M hydrochloric acid. After basification with 3M sodium hydroxide solution, the product was extracted with 75 ml tert-butyl methyl ether. Following removal of solvent, 1.1 g of a yellow oil was obtained.

Workup

  1. customThe mixture was purged thoroughly with nitrogen and 0.14 g of tris(dibenzylideneacetone)d2-propanollladium(0)
  2. additionwas added
  3. temperaturethe mixture was heated to 80 C under nitrogen for 16 hours
  4. temperatureAfter cooling to 22 C
  5. customquenching with 50 ml water
  6. extractionthe product was extracted twice with ethyl acetate
  7. washwashed twice with water
  8. filtrationAfter filtration and solvent removal
  9. customthe product was purified by silica gel chromatography
  10. dissolutionThis was dissolved in 75 ml tert-butyl methyl ether
  11. extractionextracted into 75 ml 1M hydrochloric acid
  12. extractionAfter basification with 3M sodium hydroxide solution, the product was extracted with 75 ml tert-butyl methyl ether
  13. customremoval of solvent

Sources & evidence

ORD record
ord-8cdd455ac79545c2934bfa00fdc9fee5
Source dataset
uspto-grants-2009_05
Patent number
US07538931B2

Linked notes

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