Hydrochloric Acid → HCID 68808682, compound

HRID 2249369Notes

Reaction equation

HRID 2249369 reaction equation
C(N[C:8]1[CH:13]=[CH:12][C:11]([Cl:14])=[C:10]([O:15][CH3:16])[C:9]=1[Br:17])(=O)C(C)(C)C.Cl.[Na].N([O-])=O.[Na+].[I-:24].[Na+]>O1CCOCC1.O.C(Cl)Cl>[Br:17][C:9]1[C:10]([O:15][CH3:16])=[C:11]([Cl:14])[CH:12]=[CH:13][C:8]=1[I:24]

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 5238Sodium IodideHCID 5360545SodiumHCID 23668193Sodium NitriteHCID 68810143HCID 68810143, compound

Product 1

HCID 68808682HCID 68808682, compoundYield 50%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 312751,4-DioxaneSolvent

Procedure

A solution of N-pivaloyl-2-bromo-4-chloro-3-methoxyaniline (3.7 g, 1.2 mmol) in dioxane (35 mL) was treated with concentrated hydrochloric acid (35 mL) and the solution heated under reflux for 2 hours. After the solution was cooled the pH was adjusted to 10 by addition of sodium hyrdroxide (50% solution) and extracted with ethyl ether (2×50 mL). The combined extracts were washed with brine, dried (sodium sulfate) and concentrated. The crude aniline was dissolved in 2N hydrochloric acid and sodium nitrite (750 mg, 11 mmol) was added and the solution stirred for 20 minutes. This solution was poured into a vigorously stirred solution of sodium iodide (3.3 g, 22 mmol) in water (20 mL) and methylene chloride (30 mL) and stirred for 20 minutes. The solution was then extracted with methylene chloride (2×25 mL) and the combined extracts washed with brine, dried (sodium sulfate) and concentrated. The residue was purified by chromatography (hexanes) to give 2-bromo-4-chloro-1-iodo-3-methoxybenzene (1.5 g, 0.6 mmol): LC/MS (m/z=267).

Workup

  1. temperaturethe solution heated
  2. temperatureunder reflux for 2 hours
  3. temperatureAfter the solution was cooled the pH
  4. extractionextracted with ethyl ether (2×50 mL)
  5. washThe combined extracts were washed with brine
  6. dry with materialdried (sodium sulfate)
  7. concentrationconcentrated
  8. dissolutionThe crude aniline was dissolved in 2N hydrochloric acid
  9. stirringstirred for 20 minutes
  10. extractionThe solution was then extracted with methylene chloride (2×25 mL)
  11. washthe combined extracts washed with brine
  12. dry with materialdried (sodium sulfate)
  13. concentrationconcentrated
  14. customThe residue was purified by chromatography (hexanes)

Sources & evidence

ORD record
ord-e77bd6e4348644ffa6801d78f3d60ee4
Source dataset
uspto-grants-2008_01
Patent number
US07314849B2

Reaction notes

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