Hydrogen Peroxide → 2-Iodo-4'-methyl-1,1'-biphenyl

HRID 1779437Notes

Reaction equation

HRID 1779437 reaction equation
I[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[I:8].C(=O)([O-])[O-].[Na+].[Na+].[CH3:15][C:16]1[CH:21]=[CH:20][C:19](B(O)O)=[CH:18][CH:17]=1.OO.[Cl-].[Na+]>C1(C)C=CC=CC=1.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[I:8][C:3]1[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=1[C:19]1[CH:20]=[CH:21][C:16]([CH3:15])=[CH:17][CH:18]=1

Participants

9

Reactant 5

HCID 784Hydrogen PeroxideHCID 5234Sodium ChlorideHCID 10340Sodium CarbonateHCID 119941,2-DiiodobenzeneHCID 79799Tolylboronic acid

Product 1

HCID 124946642-Iodo-4'-methyl-1,1'-biphenylYield 44.2%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

A mixture of 1,2-diiodobenzene (6.6 g) and tetrakis(triphenylphosphine)palladium(0) (0.34 g) in AR toluene (100 ml) was stirred under a nitrogen atmosphere at ambient temperature. A solution of sodium carbonate (2 g) in water (15 ml) was added. The resulting orange mixture was stirred and heated under reflux while a solution of 4-methylbenzeneboronic acid (1.36 g) in industrial methylated spirit (40 ml) was added dropwise over a period of 40 minutes. The mixture obtained was heated under reflux for an additional 4 hours, then cooled to ambient temperature. Aqueous hydrogen peroxide (30%; 1 ml) was added and the resulting mixture was stirred for 1 hour at ambient temperature. Saturated aqueous sodium chloride solution (50 ml) was then added and the organic phase was separated. The aqueous phase was extracted with ethyl acetate (2×50 ml) and the combined organic phases were washed with saturated aqueous sodium chloride solution (1×70 ml), dried over magnesium sulphate and evaporated to give an orange oil. This oil was triturated with petroleum ether (b.p. 40°-60° C.) (200 ml) to give a gum which was partially purified by flash chromatography on silica gel (eluting with petroleum ether (b.p. 40°-60° C.): ethyl acetate (4:1)) then further purified by high performance liquid chromatography on a silica column (eluting with petroleum ether (b.p. 60°-80° C.) at 200 ml/minute), to give the intermediate compound 2'-iodo-4-methylbiphenyl as a colourless oil (1.3 g).

Workup

  1. stirringThe resulting orange mixture was stirred
  2. temperatureheated
  3. additionwas added dropwise over a period of 40 minutes
  4. customThe mixture obtained
  5. temperaturewas heated
  6. temperatureunder reflux for an additional 4 hours
  7. temperaturecooled to ambient temperature
  8. stirringthe resulting mixture was stirred for 1 hour at ambient temperature
  9. customthe organic phase was separated
  10. extractionThe aqueous phase was extracted with ethyl acetate (2×50 ml)
  11. washthe combined organic phases were washed with saturated aqueous sodium chloride solution (1×70 ml)
  12. dry with materialdried over magnesium sulphate
  13. customevaporated
  14. customto give an orange oil
  15. customThis oil was triturated with petroleum ether (b.p. 40°-60° C.) (200 ml)
  16. customto give a gum which
  17. customwas partially purified by flash chromatography on silica gel (eluting with petroleum ether (b.p. 40°-60° C.): ethyl acetate (4:1))
  18. customthen further purified by high performance liquid chromatography on a silica column (eluting with petroleum ether (b.p. 60°-80° C.) at 200 ml/minute)

Sources & evidence

ORD record
ord-f6c9a68aaf054b1faf15aa66c0a07b09
Source dataset
uspto-grants-1997_05
Patent number
US05627191

Reaction notes

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