Water → 4-{4-[(4-Aminoanilino)carbonyl]anilino}-1-methylpyridinium chloride

HRID 1711344Notes

Reaction equation

HRID 1711344 reaction equation
[Cl-:1].[CH3:2][N+:3]1[CH:8]=[CH:7][C:6]([NH:9][C:10]2[CH:15]=[CH:14][C:13]([C:16]([NH:18][C:19]3[CH:24]=[CH:23][C:22]([N+:25]([O-])=O)=[CH:21][CH:20]=3)=[O:17])=[CH:12][CH:11]=2)=[CH:5][CH:4]=1.O>CCO.[Fe]>[Cl-:1].[NH2:25][C:22]1[CH:23]=[CH:24][C:19]([NH:18][C:16]([C:13]2[CH:14]=[CH:15][C:10]([NH:9][C:6]3[CH:5]=[CH:4][N+:3]([CH3:2])=[CH:8][CH:7]=3)=[CH:11][CH:12]=2)=[O:17])=[CH:20][CH:21]=1

Participants

5

Reactant 2

HCID 962WaterHCID 671999221-Methyl-4-{4-[(4-nitroanilino)carbonyl]anilino}pyridinium chloride

Product 1

HCID 672001654-{4-[(4-Aminoanilino)carbonyl]anilino}-1-methylpyridinium chlorideYield 80%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 702EthanolSolvent

Procedure

Compound D4 (295 mg, 0.77 mmol) was dissolved in ˜5:1 EtOH:H2O (12 mL), and Fe dust (209 mg) was added. The mixture was vigorously stirred and refluxed for 4 h, and then filtered hot through a pad of Celite. The Celite was washed with boiling EtOH, and EtOH fractions were combined and evaporated to dryness. The residue was extracted into hot water, and filtered through Celite, and then evaporated to dryness. The residue was azeotroped with MeOH (3×20 mL), and then dissolved in MeOH (10 mL). Methanolic HCl (1.25 M, 5 mL) was added, and the solution stirred for 10 min. Solvent was removed under reduced pressure, and the residue was crystallized from MeOH/EtOAc to give D5 (218 mg, 80%); mp (MeOH/EtOAc); 1H NMR [(CD3)2SO] δ 11.13 (s, 1H, NH), 10.44 (s, 1H, NH), 9.88 (br, 2H, NH2), 8.36 (d, J=7.5 Hz, 2H, ArH), 8.12 (d, J=8.6 Hz, 2H, ArH), 7.86 (d, J=8.8 Hz, 2H, ArH), 7.50 (d, J=8.8 Hz, 2H, ArH), 7.32 (d, J=8.6 Hz, 2H, ArH), 7.32 (d, J=7.5 Hz, 2H, ArH), 7.30 (d, J=8.7 Hz, 2 H, ArH), 4.00 (s, 3H, N+CH3); LCMS 319+ve

Workup

  1. temperaturerefluxed for 4 h
  2. filtrationfiltered hot through a pad of Celite
  3. washThe Celite was washed with boiling EtOH, and EtOH fractions
  4. customevaporated to dryness
  5. extractionThe residue was extracted into hot water
  6. filtrationfiltered through Celite
  7. customevaporated to dryness
  8. customThe residue was azeotroped with MeOH (3×20 mL)
  9. dissolutiondissolved in MeOH (10 mL)
  10. additionMethanolic HCl (1.25 M, 5 mL) was added
  11. stirringthe solution stirred for 10 min
  12. customSolvent was removed under reduced pressure
  13. customthe residue was crystallized from MeOH/EtOAc

Sources & evidence

ORD record
ord-c00f77d2f45441718414ab2385df7ce1
Source dataset
uspto-grants-2010_09
Patent number
US07790746B2

Reaction notes

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