2-(Tributylstannyl)pyridine → 2-(2,5-Dimethyl-4-nitrophenyl)pyridine

HRID 536345Notes

Reaction equation

HRID 536345 reaction equation
Br[C:2]1[CH:7]=[C:6]([CH3:8])[C:5]([N+:9]([O-:11])=[O:10])=[CH:4][C:3]=1[CH3:12].C([Sn](CCCC)(CCCC)[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][N:19]=1)CCC>CN(C=O)C.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:12][C:3]1[CH:4]=[C:5]([N+:9]([O-:11])=[O:10])[C:6]([CH3:8])=[CH:7][C:2]=1[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][N:19]=1

Participants

5

Reactant 2

HCID 6077842-(Tributylstannyl)pyridineHCID 8258081-Bromo-2,5-dimethyl-4-nitrobenzene

Product 1

HCID 671553762-(2,5-Dimethyl-4-nitrophenyl)pyridine

Reagents, catalysts & solvents 2

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
120 °C

Procedure

To a mixture of 1-bromo-2,5-dimethyl-4-nitrobenzene (185 mg, 1 mmol) and 2-(tributylstannyl)pyridine (202 mg, 1.1 mmol) in DMF (4 mL) was added tetrakis(triphenylphosphine) palladium (0) (58 mg, 5% mmol). The reaction tube was sealed, the mixture was purged with N2 for 3 min and then heated at 120° C. under N2 for overnight. The reaction was cooled to room temperature and poured into saturated aqueous ammonia chloride solution. The crude reaction mixture was extracted with ethyl acetate (3×15 mL). The organic extracts were combined, washed with brine and concentrated. The crude product was purified with silica gel column chromatography (60% ethyl acetate in hexanes) to afford 2-(2,5-dimethyl-4-nitrophenyl)pyridine as a white solid. The obtained solid was dissolved in acetic acid/TFA (15 mL/200 uL). To this solution was added PtO2 (10% w/w). The reaction mixture was degassed and purged with H2 for several times and stirred under 1 atm. hydrogen gas overnight. The mixture was filtered and concentrated to afford 2,5-Dimethyl-4-(piperidin-2-yl)aniline as a yellow oil. ESMS m/z 205 (M+H+).

Workup

  1. customThe reaction tube was sealed
  2. customthe mixture was purged with N2 for 3 min
  3. temperatureThe reaction was cooled to room temperature
  4. additionpoured into saturated aqueous ammonia chloride solution
  5. customThe crude reaction mixture
  6. extractionwas extracted with ethyl acetate (3×15 mL)
  7. washwashed with brine
  8. concentrationconcentrated
  9. customThe crude product was purified with silica gel column chromatography (60% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-55783f3fd7b6465bab035f68c72ffc15
Source dataset
uspto-grants-2014_10
Patent number
US08859574B2

Reaction notes

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