Triphenylphosphine → [4,4'-Bipyridin]-3-amine

HRID 524945Notes

Reaction equation

HRID 524945 reaction equation
Cl[C:2]1[CH:7]=[CH:6][N:5]=[CH:4][C:3]=1[N+:8]([O-])=O.[N:11]1[CH:16]=[CH:15][C:14](B(O)O)=[CH:13][CH:12]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[O-]P([O-])([O-])=O.[K+].[K+].[K+]>O1CCOCC1.[Pd]>[N:5]1[CH:6]=[CH:7][C:2]([C:14]2[CH:15]=[CH:16][N:11]=[CH:12][CH:13]=2)=[C:3]([NH2:8])[CH:4]=1

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 62657Potassium Phosphate, TribasicHCID 2734379(Pyridin-4-yl)boronic acidHCID 27357814-Chloro-3-nitropyridine

Product 1

HCID 13636635[4,4'-Bipyridin]-3-amine

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalyst2×HCID 312751,4-DioxaneSolvent

Procedure

4-chloro-3-nitro-pyridine (100 mg, 0.6307 mmol), 4-pyridylboronic acid (77.52 mg, 0.6307 mmol), palladium; triphenylphosphane (36.45 mg, 0.03154 mmol), K3PO4 (946.0 μL, of 2 M, 1.892 mmol) in dioxane (3 mL) was heated at 130° C. for 30 min in a microwave. The mixture was loaded on a SCX column, washed with MeOH. The product was eluted with a 2M NH3 in MeOH. The filtrate was concentrated in vacuo. The residue was dissolved in MeOH (20 mL), Pd/C 10% (42.04 mg, 0.3950 mmol) was added and the mixture was hydrogenated (H2 balloon) overnight. The catalyst was filtered off and the filtrate was concentrated in vacuo yielding [4,4′-bipyridin]-3-amine that was used in next step without further purification. MS (ES+) 172.1.

Workup

  1. washwashed with MeOH
  2. washThe product was eluted with a 2M NH3 in MeOH
  3. concentrationThe filtrate was concentrated in vacuo
  4. dissolutionThe residue was dissolved in MeOH (20 mL)
  5. custom(H2 balloon) overnight
  6. filtrationThe catalyst was filtered off
  7. concentrationthe filtrate was concentrated in vacuo

Sources & evidence

ORD record
ord-34c50f3443984d639c3a0ac94e8225ed
Source dataset
uspto-grants-2016_05
Patent number
US09340546B2

Reaction notes

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