Potassium Carbonate → 4-(4-Amino-2,3-dichlorophenoxy)-3-nitropyridin-2-amine

HRID 1427412Notes

Reaction equation

HRID 1427412 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[C:4]([Cl:9])[C:3]=1[Cl:10].C([O-])([O-])=O.[K+].[K+].Cl[C:18]1[CH:23]=[CH:22][N:21]=[C:20]([NH2:24])[C:19]=1[N+:25]([O-:27])=[O:26]>CN(C=O)C>[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([O:8][C:18]2[CH:23]=[CH:22][N:21]=[C:20]([NH2:24])[C:19]=2[N+:25]([O-:27])=[O:26])=[C:4]([Cl:9])[C:3]=1[Cl:10]

Participants

5

Reactant 3

HCID 11430Potassium CarbonateHCID 40716944-Chloro-3-nitropyridin-2-amineHCID 98775294-Amino-2,3-dichlorophenol

Product 1

HCID 680017114-(4-Amino-2,3-dichlorophenoxy)-3-nitropyridin-2-amineYield 72.3%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

To a stirred solution of 4-amino-2,3-dichlorophenol (1.00 g, 5.62 mmol) in dry DMF (20 mL) under N2 was added K2CO3 (854 mg, 6.18 mmol) and the mixture kept at RT for 10 min and then treated with a solution of 4-chloro-3-nitropyridin-2-amine (1.024 g, 5.90 mmol) in dry DMF (5.0 mL) in a single portion. The reaction mixture was maintained at RT for 19 hr and was then partitioned between EtOAc (100 mL) and water (100 mL). The aq layer was separated and was extracted with EtOAc (4×70 mL) and the combined organic extracts were dried and evaporated in vacuo. The residue was purified by flash column chromatography (SiO2, 80 g, EtOAc in isohexane, 0-70%, gradient elution) to afford 4-(4-amino-2,3-dichlorophenoxy)-3-nitropyridin-2-amine as a dark solid (1.28 g, 70%); Rt 1.85 min (Method 2); m/z 315 (M+H)+ (ES+).

Workup

  1. customwas then partitioned between EtOAc (100 mL) and water (100 mL)
  2. customThe aq layer was separated
  3. extractionwas extracted with EtOAc (4×70 mL)
  4. customthe combined organic extracts were dried
  5. customevaporated in vacuo
  6. customThe residue was purified by flash column chromatography (SiO2, 80 g, EtOAc in isohexane, 0-70%, gradient elution)

Sources & evidence

ORD record
ord-2e2d8c3ca8ce44b6abdc0621059ba965
Source dataset
uspto-grants-2015_01
Patent number
US08933228B2

Reaction notes

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