Hydrochloric Acid → 2-Chloro-1-iodo-4-(methylsulfonyl)benzene

HRID 239858Notes

Reaction equation

HRID 239858 reaction equation
[Cl:1][C:2]1[CH:8]=[C:7]([S:9]([CH3:12])(=[O:11])=[O:10])[CH:6]=[CH:5][C:3]=1N.Cl.N([O-])=O.[Na+].[I-:18].[K+]>O.C(O)(=O)C>[Cl:1][C:2]1[CH:8]=[C:7]([S:9]([CH3:12])(=[O:11])=[O:10])[CH:6]=[CH:5][C:3]=1[I:18]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 4875Potassium IodideHCID 25801Benzenamine, 2-chloro-4-(methylsulfonyl)-HCID 23668193Sodium Nitrite

Product 1

HCID 593508192-Chloro-1-iodo-4-(methylsulfonyl)benzene

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 962WaterSolvent3×

Conditions

Temperature
5 °C

Procedure

2-Chloro-4-Methylsulfonylaniline in a 1:1:3 mixture (0.4 M) of Acetic Acid, Hydrochloric Acid, 37% and Water was cooled to 0° C. and slowly treated with a 4 M solution of sodium nitrite in water. The reaction was stirred at 5° C. for 30 minutes then treated dropwise with a 2M solution of potassium iodide in water. The reaction evolved a gas and turned brown. The reaction was stirred 15 minutes at 0° C., 40 minutes at rt and 1 h at 60° C. The brown solid was filtered, dissolved in ethyl acetate and the solution washed with acidified sodium thiosulfate and then brine. The organic phase was dried over magnesium sulfate and concentrated under reduced pressure. During evaporation, a precipitate appeared and was filtered. The mother liquors were evaporated further and 2 more crops were collected. The last mother liquor was transferred with diethyl ether and upon evaporation yields more products.

Workup

  1. stirringThe reaction was stirred 15 minutes at 0° C., 40 minutes at rt and 1 h at 60° C
  2. filtrationThe brown solid was filtered
  3. dissolutiondissolved in ethyl acetate
  4. washthe solution washed with acidified sodium thiosulfate
  5. dry with materialThe organic phase was dried over magnesium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customDuring evaporation
  8. filtrationwas filtered
  9. customThe mother liquors were evaporated further
  10. custom2 more crops were collected
  11. customThe last mother liquor was transferred with diethyl ether and upon evaporation
  12. customyields more products

Sources & evidence

ORD record
ord-ccb7f8216303491c84585e7787bdf140
Source dataset
uspto-grants-2014_02
Patent number
US08642799B2

Reaction notes

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