Ammonia → [2,2'-Bipyridin]-6-amine

HRID 1908984Notes

Reaction equation

HRID 1908984 reaction equation
Br[C:2]1[N:7]=[C:6]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][N:9]=2)[CH:5]=[CH:4][CH:3]=1.O.[NH3:15]>>[N:7]1[C:2]([NH2:15])=[CH:3][CH:4]=[CH:5][C:6]=1[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][N:9]=1

Participants

4

Reactant 3

HCID 222Ammonia2×HCID 962WaterHCID 117911522-Bromo-6-(pyridin-2-yl)pyridine

Product 1

HCID 14964570[2,2'-Bipyridin]-6-amineYield 85%

Procedure

To a mixture of 6-bromo-2,2′-bipyridine (3.0 mmol, 705 mg) and Cu2O (0.01 mmol, 1.0 mg) in glycol in autoclave NH3 was feed. The reaction was maintained under 10 atm of NH3 at 110° C. for 24 h. After cooling to room temperature, water was added and the aqueous phase was extracted with DCM. The combined organic layers were washed with brine and dried over MgSO4. After solvent evaporation, the crude product was purified by column chromatography on silica gel (Hexanes:ethyl acetate=1:1 as eluent) to afford a white solid (437 mg, 85% yield). 1H NMR (500 MHz, CDCl3, ppm): 8.65 (s, 1H), 8.25 (d, 1H, J=7.9 Hz), 7.79-7.76 (m, 1H), 7.71-7.70 (m, 1H), 7.57 (t, 1H, J=7.1 Hz), 7.26 (t, 1H, J=7.1 Hz), 6.65 (d, 1H, J=7.9 Hz), 4.53 (br, 2H). 13C NMR (125 MHz, CDCl3, ppm): 157.97, 156.38, 154.57, 149.11, 138.58, 136.73, 123.31, 120.94, 111.59, 108.87.

Workup

  1. extractionthe aqueous phase was extracted with DCM
  2. washThe combined organic layers were washed with brine
  3. dry with materialdried over MgSO4
  4. customAfter solvent evaporation
  5. customthe crude product was purified by column chromatography on silica gel (Hexanes:ethyl acetate=1:1 as eluent)

Sources & evidence

ORD record
ord-a4ba18500ba5406f81a1b87d08965963
Source dataset
uspto-grants-2013_12
Patent number
US08598351B2

Reaction notes

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