2,4-Dimethoxy-1-nitrobenzene → 1,5-Dimethoxy-2-iodo-4-nitrobenzene

HRID 990848Notes

Reaction equation

HRID 990848 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[C:7]([O:9][CH3:10])[CH:6]=[CH:5][C:4]=1[N+:11]([O-:13])=[O:12].[I:14](Cl)(=O)=O.I(Cl)(=O)=O.C([N+](C)(C)C)C1C=CC=CC=1>C(O)(=O)C.[Cl-].[Zn+2].[Cl-]>[I:14][C:6]1[CH:5]=[C:4]([N+:11]([O-:13])=[O:12])[C:3]([O:2][CH3:1])=[CH:8][C:7]=1[O:9][CH3:10]

Participants

5

Reactant 2

HCID 786332,4-Dimethoxy-1-nitrobenzeneHCID 56924451Trimethylbenzylammonium Dichloroiodate2×

Product 1

HCID 185429691,5-Dimethoxy-2-iodo-4-nitrobenzene

Reagents, catalysts & solvents 2

HCID 3007855ZincchlorideCatalyst2×HCID 176Acetic AcidSolvent2×

Procedure

To a solution of 2,4-dimethoxy-nitrobenzene (1.0 g) in glacial acetic acid (30 mL) is added benzyltrimethylammonium dichloroiodate (1.90 g) and anhydrous zinc chloride (1.0 g) and the mixture is stirred at room temperature under an atmosphere of argon. Additional benzyltrimethylammonium dichloroiodate (0.4 g) is added after 5 hours and again after 24 hours. Additional zinc chloride (0.5 g) and glacial acetic acid (15 mL) is added after 24 hours. The mixture is permitted to stir at room temperature for 3 days and is then filtered, diluted with 5% aqueous sodium bisulfite, and extracted three times with ethyl acetate. These pooled organic extracts are washed successively with 5% aqueous sodium bisulfite, saturated aqueous sodium chloride, then dried over anhydrous magnesium sulfate. After removal of the solvent under reduced pressure the residue is triturated with hexanes to provide the desired product as a pale yellow solid.

Workup

  1. stirringto stir at room temperature for 3 days
  2. filtrationis then filtered
  3. additiondiluted with 5% aqueous sodium bisulfite
  4. extractionextracted three times with ethyl acetate
  5. washThese pooled organic extracts are washed successively with 5% aqueous sodium bisulfite, saturated aqueous sodium chloride
  6. dry with materialdried over anhydrous magnesium sulfate
  7. customAfter removal of the solvent under reduced pressure the residue
  8. customis triturated with hexanes

Sources & evidence

ORD record
ord-46f8c127467c4a0b8606de3f28b75751
Source dataset
uspto-grants-2002_10
Patent number
US06462055B2

Reaction notes

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