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

HRID 1472579Notes

Reaction equation

HRID 1472579 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]=[CH:17][C:16]([Cl:19])=[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:16]1[CH:17]=[CH:18][C:11]([NH:10][C:6]2[C:5]([Cl:9])=[CH:4][N:3]=[C:2]([Cl:1])[CH:7]=2)=[C:12]([CH:15]=1)[C:13]#[N:14]

Participants

7

Reactant 4

HCID 61695Pentapotassium TriphosphateHCID 800192-Amino-5-chlorobenzonitrileHCID 4285986Bis[2-(diphenylphosphino)phenyl] etherHCID 534009652,5-Dichloro-4-iodopyridine

Product 1

HCID 575169175-Chloro-2-[(2,5-dichloro-4-pyridinyl)amino]benzonitrileYield 33%

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-5-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 reflux for 18 hr. The reaction mixture was filtered. The reaction mixture was evaporated. Ether (50 ml) was added and the solid was filtered. 5-chloro-2-[(2,5-dichloro-4-pyridinyl)amino]benzonitrile (1.8 g, 5.43 mmol, 33.0% yield) was isolated as orange solid. 1H NMR (400 MHz, DMSO-d6) ppm 6.63 (s, 1 H) 7.52 (d, J=8.59 Hz, 1 H) 7.81 (dd, J=8.59, 2.53 Hz, 1 H) 8.09 (d, J=2.53 Hz, 1 H) 8.24 (s, 1 H) 9.06 (br. s., 1 H); HPLC Rt=3.53 min, MS (ESI): 298.0, 299.9 [M+H]+.

Workup

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

Sources & evidence

ORD record
ord-57d09e4e255d40ec898f52c23eb112ae
Source dataset
uspto-grants-2015_04
Patent number
US09012479B2

Reaction notes

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