1-Bromo-2-iodobenzene → HCID 58239429, compound

HRID 1909440Notes

Reaction equation

HRID 1909440 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1I.C([Mg]Cl)(C)C.[CH3:14][C:15]1[CH:16]=[C:17]([P:24]([C:26]2[CH:31]=[C:30]([CH3:32])[C:29]([O:33][CH3:34])=[C:28]([CH3:35])[CH:27]=2)Cl)[CH:18]=[C:19]([CH3:23])[C:20]=1[O:21][CH3:22]>C1COCC1.CC(OC)(C)C>[Br:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[P:24]([C:26]1[CH:31]=[C:30]([CH3:32])[C:29]([O:33][CH3:34])=[C:28]([CH3:35])[CH:27]=1)[C:17]1[CH:16]=[C:15]([CH3:14])[C:20]([O:21][CH3:22])=[C:19]([CH3:23])[CH:18]=1

Participants

6

Reactant 3

HCID 114151-Bromo-2-iodobenzeneHCID 4368797BIS(3,5-DIMETHYL-4-METHOXYPHENYL)CHLOROPHOSPHINEHCID 178418918HCID 178418918, compound

Product 1

HCID 58239429HCID 58239429, compoundYield 76%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 15413tert-Butyl methyl etherSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of 9.67 g (34.2 mmol) of 1-bromo-2-iodobenzene in 30 ml of THF are added dropwise, at −78° C., 17.6 ml (37.6 mmol) of an isopropylmagnesium chloride solution (2 molar in THF). The mixture is stirred at a temperature between −30° C. and −40° C. for a further 1 hour, then cooled again to −78° C., and a solution of 12.66 g (37.6 mmol) of bis(3,5-dimethyl-4-methoxyphenyl)chlorophosphine in 10 ml of THF and 10 ml of TBME is added. The cooling is removed and the reaction mixture is stirred at room temperature overnight. The resulting solution is admixed with 50 ml of water and extracted with water/TBME. The organic phases are collected and dried over sodium sulphate, and the solvent is distilled off under reduced pressure on a rotary evaporator. The crude product is purified by chromatography (silica gel 60; eluent=1:1 heptane/ethyl acetate). The desired product is obtained in the form of white crystals in a yield of 76%.

Workup

  1. customThe cooling is removed
  2. stirringthe reaction mixture is stirred at room temperature overnight
  3. extractionextracted with water/TBME
  4. customThe organic phases are collected
  5. dry with materialdried over sodium sulphate
  6. distillationthe solvent is distilled off under reduced pressure on a rotary evaporator
  7. customThe crude product is purified by chromatography (silica gel 60; eluent=1:1 heptane/ethyl acetate)

Sources & evidence

ORD record
ord-d67493bbd25f4f9ea0fda69e7ad3fea6
Source dataset
uspto-grants-2013_12
Patent number
US08598371B2

Reaction notes

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