Potassium Iodide → 2-Chloro-1-iodo-4-(trifluoromethoxy)benzene

HRID 1824723Notes

Reaction equation

HRID 1824723 reaction equation
[Cl:1][C:2]1[CH:8]=[C:7]([O:9][C:10]([F:13])([F:12])[F:11])[CH:6]=[CH:5][C:3]=1N.N([O-])=O.[Na+].[I-:18].[K+]>Cl.C1CCCCC1.ClCCl>[Cl:1][C:2]1[CH:8]=[C:7]([O:9][C:10]([F:13])([F:12])[F:11])[CH:6]=[CH:5][C:3]=1[I:18]

Participants

7

Reactant 3

HCID 4875Potassium IodideHCID 27340842-Chloro-4-(trifluoromethoxy)anilineHCID 23668193Sodium Nitrite

Product 1

HCID 269854362-Chloro-1-iodo-4-(trifluoromethoxy)benzeneYield 78%

Reagents, catalysts & solvents 3

HCID 313Hydrochloric AcidSolventHCID 6344DichloromethaneSolventHCID 8078CyclohexaneSolvent

Procedure

Part B. A solution of the aniline from Part A (17.97 g, 84.9 mmol) in concentrated hydrochloric acid (50 mL) was cooled to −5° C., and treated with a saturated aqueous solution of sodium nitrite (6.45 g, 93.5 mmol) After stirring for 30 min., the solution was diluted with 50 mL cyclohexane and 50 mL dichloromethane, and the resulting mixture was stirred vigorously while a saturated aqueous solution of potassium iodide (28.2 g, 170 mmol) was added dropwise. The resulting solution was allowed to stir for 12 h, then was partitioned between water and dichloromethane. The organic phase was washed with 1 N aqueous sodium bisulfite solution and brine. The three aqueous phases were back-extracted in sequence with dichloromethane, and the organic phases were combined, dried over anhydrous magnesium sulfate, filtered and evaporated. The product was purified by distillation to afford the product, 3-chloro-4-iodo-trifluoroanisole (21.38 g, 66.3 mmol, 78%). b.p. 60-70° C./l mm Hg (bulb-to-bulb). 1H NMR (300 MHz, CDCl3): Δ 7.87 (1H, d, J=8.8 Hz), 7.35 (1H, d, J=2.5 Hz), 6.87 (1H, J=ddd, J=8.8 Hz, 2.5H, 0.7 Hz). MS (H2O-GC/MS): m/e 324 (31), 323 (10), 322 (100).

Workup

  1. additionwas added dropwise
  2. stirringto stir for 12 h
  3. customwas partitioned between water and dichloromethane
  4. washThe organic phase was washed with 1 N aqueous sodium bisulfite solution and brine
  5. extractionThe three aqueous phases were back-extracted in sequence with dichloromethane
  6. dry with materialdried over anhydrous magnesium sulfate
  7. filtrationfiltered
  8. customevaporated
  9. distillationThe product was purified by distillation

Sources & evidence

ORD record
ord-63bc8d32cb814df599af25eb4e00f5df
Source dataset
uspto-grants-2006_05
Patent number
US07045529B2

Reaction notes

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