Diethyl Ether → 2-Bromo-4-iodo-1-methylbenzene

HRID 1591496Notes

Reaction equation

HRID 1591496 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:6]=[CH:7][C:8]=1[CH3:9])N.N([O-])=O.[Na+].[I-:14].[K+].CCOCC>Cl.O>[Br:1][C:2]1[CH:3]=[C:4]([I:14])[CH:6]=[CH:7][C:8]=1[CH3:9]

Participants

7

Reactant 4

HCID 3283Diethyl EtherHCID 4875Potassium IodideHCID 82187Benzenamine, 3-bromo-4-methyl-HCID 23668193Sodium Nitrite

Product 1

HCID 215600382-Bromo-4-iodo-1-methylbenzeneYield 53%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 962WaterSolvent

Procedure

A well stirred solution of 18.6 g (0.10 mol) of 3-bromo-p-toluidine in 80 mL of 6N HCl at 0° C. was treated with a solution of 7.35 g (0.11 mol) of sodium nitrite in 15 mL of water at a rate that maintained the temperature <10° C. The mixture was stirred for 45 minutes then cautiously treated with 33.2 g (0.20 mol) of potassium iodide at 0° C. The mixture was treated with 300 mL of ether and washed (3×) with saturated aqueous sodium bisulfite. The organic layer was separated, dried over magnesium sulfate, filtered and concentrated under vacuum. The residue was redissolved in 50 mL of hexane, filtered through 30 g of silica and concentrated under vacuum to afford 15.6 g (0.053 mol,53%) of the product which was determined to be 65% pure by 1H NMR. 1H NMR (200 MHz,CDCl3): 2.33 (s,3H), 6.97 (d,8 Hz,1H), 7.51 (dd;2,8 Hz,1H), 7.86 (d,2 Hz,1H).

Workup

  1. temperaturemaintained the temperature <10° C
  2. washwashed (3×) with saturated aqueous sodium bisulfite
  3. customThe organic layer was separated
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated under vacuum
  7. dissolutionThe residue was redissolved in 50 mL of hexane
  8. filtrationfiltered through 30 g of silica
  9. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-fff0e9e2487e479b8c19e87d996d6cb5
Source dataset
uspto-grants-1993_04
Patent number
US05206235

Reaction notes

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