Ammonium Chloride → 3,5-Dichloro-4-(6-methyl-quinolin-3-yloxy)-phenylamine

HRID 1819772Notes

Reaction equation

HRID 1819772 reaction equation
[Cl:1][C:2]1[CH:19]=[C:18]([N+:20]([O-])=O)[CH:17]=[C:16]([Cl:23])[C:3]=1[O:4][C:5]1[CH:6]=[N:7][C:8]2[C:13]([CH:14]=1)=[CH:12][C:11]([CH3:15])=[CH:10][CH:9]=2.[NH4+].[Cl-]>CCO.C1COCC1.O.[Fe]>[Cl:1][C:2]1[CH:19]=[C:18]([NH2:20])[CH:17]=[C:16]([Cl:23])[C:3]=1[O:4][C:5]1[CH:6]=[N:7][C:8]2[C:13]([CH:14]=1)=[CH:12][C:11]([CH3:15])=[CH:10][CH:9]=2

Participants

5

Reactant 2

HCID 25517Ammonium ChlorideHCID 221488743-(2,6-Dichloro-4-nitro-phenoxy)-6-methyl-quinoline

Product 1

HCID 221488173,5-Dichloro-4-(6-methyl-quinolin-3-yloxy)-phenylamineYield 99.6%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 18504229Ethanol tetrahydrofuran waterSolvent

Procedure

To a solution of 3-(2,6-Dichloro-4-nitro-phenoxy)-6-methyl-quinoline (93) (1.30 g, 3.71 mmol) and NH4Cl (992 mg, 18.55 mmol) in EtOH/THF/H2O=12 mL/2 mL/3 mL, was added iron powder (1.04 g, 18.55 mmol). The mixture was refluxed for 4 h. Insoluble materials were removed by Celite filtration. The filtrate was concentrated and sat NaHCO3 was added to the residue, which was then extracted twice with AcOEt. Organic layer was washed with brine, dried over anhydrous MgSO4, and concentrated to afford compound 100 (1.18 g, 98%). 1H NMR (300 MHz, DMSO-d6) δ 2.44 (3H, s), 5.75 (2H, br s), 6.77 (2H, s), 7.27 (1H, d, J=2.8 Hz), 7.48 (1H, d, J=8.6 Hz), 7.67 (1H, s), 7.89 (1H, d, J=8.6 Hz), 8.74 (1H, d, J=2.8 Hz).

Workup

  1. temperatureThe mixture was refluxed for 4 h
  2. customInsoluble materials were removed by Celite filtration
  3. concentrationThe filtrate was concentrated
  4. additionwas added to the residue, which
  5. extractionwas then extracted twice with AcOEt
  6. washOrganic layer was washed with brine
  7. dry with materialdried over anhydrous MgSO4
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-00fae868adfc4a82b7cf6e4955912751
Source dataset
uspto-grants-2009_10
Patent number
US07601841B2

Reaction notes

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