Pentapotassium Triphosphate → 4-Chloro-2-[(2,5-dichloro-4-pyridinyl)amino]benzonitrile

HRID 62530

Reaction equation

HRID 62530 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6](I)[C:5]([Cl:9])=[CH:4][N:3]=1.[NH2:10][C:11]1[CH:18]=[C:17]([Cl:19])[CH:16]=[CH:15][C:12]=1[C:13]#[N:14].[O-]P(OP(OP([O-])([O-])=O)([O-])=O)(=O)[O-].[K+].[K+].[K+].[K+].[K+].C1C=CC(P(C2C(OC3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=CC=3)=CC=CC=2)C2C=CC=CC=2)=CC=1>O1CCOCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[Cl:19][C:17]1[CH:16]=[CH:15][C:12]([C:13]#[N:14])=[C:11]([NH:10][C:6]2[C:5]([Cl:9])=[CH:4][N:3]=[C:2]([Cl:1])[CH:7]=2)[CH:18]=1

Participants

7

Reactant 4

HCID 61695Pentapotassium TriphosphateHCID 170059Benzonitrile, 2-amino-4-chloro-HCID 4285986Bis[2-(diphenylphosphino)phenyl] etherHCID 534009652,5-Dichloro-4-iodopyridine

Product 1

HCID 575169164-Chloro-2-[(2,5-dichloro-4-pyridinyl)amino]benzonitrileYield 57.1%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 312751,4-DioxaneSolvent

Procedure

To a degassed solution of 2,5-dichloro-4-iodopyridine (4.5 g, 16.43 mmol), 2-amino-4-chlorobenzonitrile (2.507 g, 16.43 mmol) and potassium triphosphate (10.46 g, 49.3 mmol) in 1,4-dioxane (60 ml) stirred under nitrogen at the room temperature was added DPEPhos (0.708 g, 1.314 mmol) and palladium acetate (0.148 g, 0.657 mmol). The reaction mixture was stirred at the reflux for 18 hr. The reaction mixture was filtered. The solution was evaporated. Ether (50 ml) was added and the formed solid was filtered. 4-chloro-2-[(2,5-dichloro-4-pyridinyl)amino]benzonitrile (2.8 g, 9.38 mmol, 57.1% yield) was isolated as an orange solid. 1H NMR (400 MHz, DMSO-d6) ppm 6.70 (s, 1 H) 7.53 (dd, J=8.34, 2.02 Hz, 1 H) 7.65 (d, J=2.02 Hz, 1 H) 7.95 (d, J=8.34 Hz, 1 H) 8.28 (s, 1 H) 9.12 (br. s., 1 H); HPLC Rt=3.50 min, MS (ESI): 298.0, 300.0 [M+H]+.

Workup

  1. temperaturereflux for 18 hr
  2. filtrationThe reaction mixture was filtered
  3. customThe solution was evaporated
  4. additionEther (50 ml) was added
  5. filtrationthe formed solid was filtered

Sources & evidence

ORD record
ord-26a121a17bbd42c3bb2d5e1864966d8f
Source dataset
uspto-grants-2016_09
Patent number
US09446034B2

Linked notes

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