2-Bromopyridine → 6-methyl-N-phenyl-N-pyridin-2-ylpyridin-2-amine

HRID 495268

Reaction equation

HRID 495268 reaction equation
[CH3:1][C:2]1[N:7]=[C:6]([NH:8][C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)[CH:5]=[CH:4][CH:3]=1.Br[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][N:17]=1.CC(C)([O-])C.[Na+]>C1(C)C=CC=CC=1>[CH3:1][C:2]1[N:7]=[C:6]([N:8]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)[C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][N:17]=2)[CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 79732-BromopyridineHCID 219935396-methyl-N-phenylpyridin-2-amineHCID 23676156Sodium t-butoxide

Product 1

HCID 666281216-methyl-N-phenyl-N-pyridin-2-ylpyridin-2-amineYield 80.5%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a flask were added 18.4 g of 6-methyl-N-phenylpyridin-2-amine, 15.8 g of 2-bromopyridine, 11.5 g of sodium tert-butoxide, and 250 ml toluene. The mixture was purged thoroughly with nitrogen and 270 mg of 1,1′-bis(diphenylphosphino)ferrocene and 110 mg of palladium acetate were added. The reaction mixture was heated to 90 C for 6 hours, and then cooled to 22 C. After quenching with 100 ml water, the product was extracted with 75 ml ethyl acetate. The product was extracted with 50 ml of 1M hydrochloric acid, and then basified with sodium hydroxide. The mixture was cooled to 5 C, and the crude product was filtered and washed with water. The product was dissolved in 100 ml hot 2-propanol and treated with 0.4 g activated carbon. After hot filtration through a bed of celite, 150 ml of water was added slowly and the mixture was seeded to induce crystallization. After cooling to 5 C, the product was filtered and washed with 50 ml of 33% 2-propanol in water. The product was dried resulting in 21 g of a light tan solid.

Workup

  1. customThe mixture was purged thoroughly with nitrogen and 270 mg of 1,1′-bis(diphenylphosphino)ferrocene and 110 mg of palladium acetate
  2. additionwere added
  3. temperatureThe reaction mixture was heated to 90 C for 6 hours
  4. temperaturecooled to 22 C
  5. customAfter quenching with 100 ml water
  6. extractionthe product was extracted with 75 ml ethyl acetate
  7. extractionThe product was extracted with 50 ml of 1M hydrochloric acid
  8. temperatureThe mixture was cooled to 5 C
  9. filtrationthe crude product was filtered
  10. washwashed with water
  11. dissolutionThe product was dissolved in 100 ml hot 2-propanol
  12. additiontreated with 0.4 g
  13. filtrationAfter hot filtration through a bed of celite, 150 ml of water
  14. additionwas added slowly
  15. customcrystallization
  16. temperatureAfter cooling to 5 C
  17. filtrationthe product was filtered
  18. washwashed with 50 ml of 33% 2-propanol in water
  19. customThe product was dried

Sources & evidence

ORD record
ord-df629a918ba84ee0a963ce5204f882ac
Source dataset
uspto-grants-2009_05
Patent number
US07538931B2

Linked notes

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