Hydrochloric Acid → 5,6-difluoro-N1-(2-fluoro-4-iodophenyl)-3-methoxybenzene-1,2-diamine

HRID 1914868Notes

Reaction equation

HRID 1914868 reaction equation
Cl.[F:2][C:3]1[C:8]([F:9])=[CH:7][C:6]([O:10][CH3:11])=[C:5]([N+:12]([O-])=O)[C:4]=1[NH:15][C:16]1[CH:21]=[CH:20][C:19]([I:22])=[CH:18][C:17]=1[F:23].C(OCC)(=O)C>C1COCC1.CCCCCC.[Zn]>[F:2][C:3]1[C:8]([F:9])=[CH:7][C:6]([O:10][CH3:11])=[C:5]([NH2:12])[C:4]=1[NH:15][C:16]1[CH:21]=[CH:20][C:19]([I:22])=[CH:18][C:17]=1[F:23]

Participants

7

Reactant 3

HCID 313Hydrochloric AcidHCID 8857Ethyl AcetateHCID 593863122,3-Difluoro-N-(2-fluoro-4-iodophenyl)-5-methoxy-6-nitroaniline

Product 1

HCID 532609665,6-difluoro-N1-(2-fluoro-4-iodophenyl)-3-methoxybenzene-1,2-diamineYield 94%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Procedure

Concentrated HCl (20 mL) was added to a solution of (2,3-difluoro-5-methoxy-6-nitro-phenyl)-(2-fluoro-4-iodo-phenyl)-amine (I-3a: 8.0 g, 17 mmol) in THF (160 mL) and the resulting mixture was stirred for 5 minutes. This was followed by portion wise addition of zinc powder (6.8 g, 103 mmol) over a period of 30 minutes and stirring was continued for a further 30 min at room temperature. The reaction was monitored by TLC (20% ethyl acetate in hexane). The reaction mixture was concentrated and the concentrate was quenched with water and extracted with ethyl acetate. The organic layer was washed with brine and concentrated. The crude product was triturated with ether and filtered. The residue was dried to afford 6.3 g of the product (85% yield).

Workup

  1. stirringstirring
  2. waitwas continued for a further 30 min at room temperature
  3. concentrationThe reaction mixture was concentrated
  4. customthe concentrate was quenched with water
  5. extractionextracted with ethyl acetate
  6. washThe organic layer was washed with brine
  7. concentrationconcentrated
  8. customThe crude product was triturated with ether
  9. filtrationfiltered
  10. customThe residue was dried

Sources & evidence

ORD record
ord-5845b69065fa497ebab23fc0413b7da9
Source dataset
uspto-grants-2013_12
Patent number
US08614239B2

Reaction notes

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