Acetone → 5-bromo-2-chloro-N-(propan-2-yl)pyridin-3-amine

HRID 2077532Notes

Reaction equation

HRID 2077532 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([NH2:9])[C:5]([Cl:8])=[N:6][CH:7]=1.[CH3:10][C:11]([CH3:13])=O.FC(F)(F)C(O)=O.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>C(OC(C)C)(=O)C>[Br:1][C:2]1[CH:3]=[C:4]([NH:9][CH:11]([CH3:13])[CH3:10])[C:5]([Cl:8])=[N:6][CH:7]=1

Participants

6

Reactant 4

HCID 180AcetoneHCID 6422Trifluoroacetic acidHCID 5049666Sodium triacetoxyborohydrideHCID 218583543-Amino-5-bromo-2-chloropyridine

Product 1

HCID 575849795-bromo-2-chloro-N-(propan-2-yl)pyridin-3-amineYield 102.6%

Reagents, catalysts & solvents 1

HCID 7915Isopropyl AcetateSolvent

Procedure

5-bromo-2-chloropyridin-3-amine (1.889 g, 9.1 mmol) was dissolved in isopropyl acetate (20 ml) and acetone (0.81 ml, 11 mmol), trifluoroacetic acid (1.40 ml, 18 mmol), and sodium triacetoxyborohydride (2.34 g, 11 mmol) were added. The reaction was stirred under nitrogen at room temperature for almost 4.5 hours and then quenched with 10% sodium hydroxide in water (˜20 ml) to raise the pH to about 9. The layers were separated, and the aqueous phase was extracted with EtOAc. The organic extracts were combined, dried over sodium sulfate, filtered, concentrated, and dried under high vacuum to afford 5-bromo-2-chloro-N-isopropylpyridin-3-amine (2.33 g, 89% purity, 100% yield). MS (ESI pos. ion) m/z: 249 (MH+, 79Br), 251 (MH+, 81Br). Calculated exact mass for C8H10BrClN2 248 (79Br), 250 (81Br).

Workup

  1. customquenched with 10% sodium hydroxide in water (˜20 ml)
  2. temperatureto raise the pH to about 9
  3. customThe layers were separated
  4. extractionthe aqueous phase was extracted with EtOAc
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customdried under high vacuum

Sources & evidence

ORD record
ord-a53b221b2cf048c497be4529d728db6e
Source dataset
uspto-grants-2011_04
Patent number
US07928140B2

Reaction notes

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