Ammonium Chloride → 6-Amino-4-(3-bromo-phenylamino)-[1,8]naphthyridine-3-carbonitrile

HRID 1266258Notes

Reaction equation

HRID 1266258 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([NH:8][C:9]2[C:18]3[C:13](=[N:14][CH:15]=[C:16]([N+:19]([O-])=O)[CH:17]=3)[N:12]=[CH:11][C:10]=2[C:22]#[N:23])[CH:5]=[CH:6][CH:7]=1.[Cl-].[NH4+]>O.CO.[Fe]>[NH2:19][C:16]1[CH:17]=[C:18]2[C:13](=[N:14][CH:15]=1)[N:12]=[CH:11][C:10]([C:22]#[N:23])=[C:9]2[NH:8][C:4]1[CH:5]=[CH:6][CH:7]=[C:2]([Br:1])[CH:3]=1

Participants

6

Reactant 2

HCID 25517Ammonium ChlorideHCID 99292724-(3-Bromo-phenylamino)-6-nitro-[1,8]naphthyridine-3-carbonitrile

Product 1

HCID 99498136-Amino-4-(3-bromo-phenylamino)-[1,8]naphthyridine-3-carbonitrileYield 78%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 887MethanolSolventHCID 962WaterSolvent

Procedure

A mixture of 11.2 g (30.3 mmol) of 4-(3-bromo-phenylamino)-6-nitro-[1.8]naphthyridine-3-carbonitrile, 5.1 g (90.8 mmol) of powdered iron, and 8.1 g (151 mmol) of ammonium chloride was mechanically stirred at reflux in a mixture of 330 ml water and 560 ml methanol for 40 min. The liquid layer was decanted from the solids and diluted with ethyl acetate, saturated sodium bicarbonate, and brine. This mixture was extract multiple times with ethyl acetate (final volume 3500 ml). The combined extracts were dried with magnesium sulfate and filter through a short column of silica gel. The solvent was removed and the residue was stirred with ether. The solid was collected and dried give 8.04 g of the title compound as an orange solid: mass spectrum (electrospray, m/e): M+H 340, 342.1.

Workup

  1. customThe liquid layer was decanted from the solids
  2. additiondiluted with ethyl acetate, saturated sodium bicarbonate, and brine
  3. extractionThis mixture was extract multiple times with ethyl acetate (final volume 3500 ml)
  4. dry with materialThe combined extracts were dried with magnesium sulfate
  5. filtrationfilter through a short column of silica gel
  6. customThe solvent was removed
  7. stirringthe residue was stirred with ether
  8. customThe solid was collected
  9. customdried

Sources & evidence

ORD record
ord-cb89444d222e46d9b73226c17b803f5d
Source dataset
uspto-grants-2003_04
Patent number
US06548496B2

Reaction notes

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