Chlorobenzene → Bis(4-chlorophenyl)iodonium trifluoromethanesulfonate

HRID 376048

Reaction equation

HRID 376048 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.I([O-])(=O)=O.[K+].[OH:13][S:14]([C:17]([F:20])([F:19])[F:18])(=[O:16])=[O:15].[O-]S(C(F)(F)F)(=O)=O.ClC1C=CC=CC=1[I+:36][C:37]1[CH:42]=[CH:41][C:40]([Cl:43])=[CH:39][CH:38]=1>C(OC(=O)C)(=O)C.C(Cl)Cl.O>[F:18][C:17]([F:20])([F:19])[S:14]([O-:16])(=[O:15])=[O:13].[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([I+:36][C:37]2[CH:42]=[CH:41][C:40]([Cl:43])=[CH:39][CH:38]=2)=[CH:4][CH:3]=1

Participants

8

Reactant 4

HCID 7964ChlorobenzeneHCID 62406Trifluoromethanesulfonic acidHCID 19708102HCID 19708102, compoundHCID 23665710Potassium Iodate

Product 1

HCID 22389797Bis(4-chlorophenyl)iodonium trifluoromethanesulfonateYield 8.6%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6344DichloromethaneSolvent2×HCID 7918Acetic AnhydrideSolvent

Conditions

Temperature
0 °C

Procedure

To a mixture of 20.0 grams (178 mmol, 1 eq) of chlorobenzene in 30 mL of acetic anhydride and 19.0 grams (88.8 mmol, 0.5 eq) of potassium iodate cooled to 0° C. was added 26.7 grams (15.7 mL, 178 mmol, 1.0 eq) of triflic acid at such a rate that the reaction temperature did not exceed 0° C. The mixture was allowed to warm to room temperature slowly and stirred for 14 hours. Approximately 45 mL of water was added to the reaction mixture at 0°-20° C. followed by methylene chloride. The precipitate dissolved in the methylene chloride and the organic phase was washed with water, aqueous sodium bicarbonate, and water, and concentrated in vacuo. This material was recrystallized from a mixture of 20 mL of isopropanol and 35 mL of hexane to give 7.62 grams (8.6% yield). A second crop was obtained from the mother liquor, 2.5 grams (total yield 11.4%). The product contains less than 7% of the isomeric 2-chlorophenyl-4-chlorophenyliodonium triflate and a small amount of uncharacterized impurity.

Workup

  1. customdid not exceed 0° C
  2. temperatureto warm to room temperature slowly
  3. washthe organic phase was washed with water, aqueous sodium bicarbonate, and water
  4. concentrationconcentrated in vacuo
  5. customThis material was recrystallized from a mixture of 20 mL of isopropanol and 35 mL of hexane
  6. customto give 7.62 grams (8.6% yield)
  7. customA second crop was obtained from the mother liquor, 2.5 grams (total yield 11.4%)

Sources & evidence

ORD record
ord-c637bad955cd4ae5bb05e77022d53f32
Source dataset
uspto-grants-1996_01
Patent number
US05488147

Linked notes

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