Sodium Carbonate → 5-Nitro-3,3'-bipyridin-4-amine

HRID 68923Notes

Reaction equation

HRID 68923 reaction equation
Br[C:2]1[CH:3]=[N:4][CH:5]=[C:6]([N+:9]([O-:11])=[O:10])[C:7]=1[NH2:8].[N:12]1[CH:17]=[CH:16][CH:15]=[C:14](B(O)O)[CH:13]=1.C([O-])([O-])=O.[Na+].[Na+]>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O1CCOCC1>[N+:9]([C:6]1[C:7]([NH2:8])=[C:2]([C:14]2[CH:13]=[N:12][CH:17]=[CH:16][CH:15]=2)[CH:3]=[N:4][CH:5]=1)([O-:11])=[O:10]

Participants

6

Reactant 3

HCID 10340Sodium CarbonateHCID 27343783-Pyridinylboronic acidHCID 49975884-Amino-3-bromo-5-nitropyridine

Product 1

HCID 581355295-Nitro-3,3'-bipyridin-4-amineYield 88.8%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 312751,4-DioxaneSolvent

Procedure

A solution of 3-bromo-5-nitropyridin-4-amine (XIII) (6 g, 26 mmol), pyridin-3-ylboronic acid (3.54 g, 29 mmol), 1 N Na2CO3 solution (78 ml) and 1,4-dioxane (150 mL) was degassed with argon thrice. Pd(PPh3)2Cl2 (927 mg, 5 mmol %) was added to the reaction and the solution was refluxed for 15 h until TLC showed the reaction was complete. The reaction was passed through a pad of Celite and then concentrated under reduced pressure. The reaction mixture was concentrated and the residue was taken up in ethyl acetate. The organic extract was washed with water, dried and concentrated under vacuum. The crude product was purified on a silica gel column (100% EtOAc→2:98 MeOH:DCM) to give 5-nitro-3,3′-bipyridin-4-amine (XIV) as a yellow solid (5 g, 23.1 mmol, 87% yield). 1H NMR (CDCl3, 400 MHz), δ ppm 9.31 (s, 1H), 8.80-8.79 (m, 1H), 8.70 (s, 1H), 8.23 (s, 1H), 7.80-7.73 (m, 1H), 7.52-7.48 (m, 1H). ESIMS found C10H8N4O2 m/z 216.95 (M+H).

Workup

  1. temperaturethe solution was refluxed for 15 h until TLC
  2. concentrationconcentrated under reduced pressure
  3. concentrationThe reaction mixture was concentrated
  4. extractionThe organic extract
  5. washwas washed with water
  6. customdried
  7. concentrationconcentrated under vacuum
  8. customThe crude product was purified on a silica gel column (100% EtOAc→2:98 MeOH:DCM)

Sources & evidence

ORD record
ord-1768a09aeda84dda81064ca28bb645dc
Source dataset
uspto-grants-2014_09
Patent number
US08822478B2

Reaction notes

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