3-Iodo-5-nitroaniline → 1-Fluoro-3-iodo-5-nitrobenzene

HRID 1939549Notes

Reaction equation

HRID 1939549 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([N+:21]([O-:23])=[O:22])[CH:5]=[C:6](C2C=C3C(=CC=2)NC(C)(C)C=C3C)[CH:7]=1.FC1C=CC=C([N+]([O-])=O)C=1[I:34].IC1C=C(C=C([N+]([O-])=O)C=1)N>C(Cl)Cl>[F:1][C:2]1[CH:3]=[C:4]([N+:21]([O-:23])=[O:22])[CH:5]=[C:6]([I:34])[CH:7]=1

Participants

5

Reactant 3

HCID 252253-Iodo-5-nitroanilineHCID 108050526-(3-Fluoro-5-nitrophenyl)-2,2,4-trimethyl-1,2-dihydroquinoline2×HCID 234335971-Fluoro-2-iodo-3-nitrobenzene

Product 1

HCID 2590861-Fluoro-3-iodo-5-nitrobenzeneYield 50%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

6-(5-Fluoro-3-nitrophenyl)-1,2-dihydro-2,2,4-trimethylquinoline (Compound 280, structure 4 of Scheme II, where R1 =5-fluoro-3-nitrophenyl) 1-Fluoro-3-nitroiodobenzene To a 25 mL round-bottom flask equivuipped with a magnetic stir bar 3-iodo-5-nitroaniline (543.3 mg, 2.06 mmol) and methylene chloride (10 mL) were added under nitrogen. Nitrogen was bubbled through the colorless solution for 15 min. The solution was cooled to 0° C. in an ice bath. At that point approximately 500 mg nitrosonium tetrafluoroborate was added in one portion making a cloudy precipitate. The reaction was allowed to continue stirring for 2 hours. The mixture was kept under nitrogen as 10 mL dry, deoxygenated ortho-dichlorobenzene was added. A distillation apparatus was fitted to the reaction flask. The flask was placed in an oil bath and was heated until the material had completely distilled over. The crude product was isolated by washing the residue through a short column (74 mL silica, hexane). Purification by silica gel chromatography (74 mL silica, hexane) afforded 279.4 mg (50%) of 5-fluoro-3-nitroiodobenzene. Data for 5-fluoro-3-nitroiodobenzene: 1H NMR (400 MHz, acetone-d6) 8.36 (s, 1 H), 8.00 (m, 2 H).

Workup

  1. customNitrogen was bubbled through the colorless solution for 15 min
  2. additionAt that point approximately 500 mg nitrosonium tetrafluoroborate was added in one portion
  3. customdry
  4. customdeoxygenated ortho-dichlorobenzene
  5. additionwas added
  6. customA distillation apparatus was fitted to the reaction flask
  7. customThe flask was placed in an oil bath
  8. temperaturewas heated until the material
  9. distillationhad completely distilled over
  10. customThe crude product was isolated
  11. washby washing the residue through a short column (74 mL silica, hexane)
  12. customPurification by silica gel chromatography (74 mL silica, hexane)

Sources & evidence

ORD record
ord-b50920869ae047adbc14160d1727957d
Source dataset
uspto-grants-1997_12
Patent number
US05696133

Reaction notes

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