Methyl iodide → 4-Bromo-2-chloro-1-methanesulfonylbenzene

HRID 859698Notes

Reaction equation

HRID 859698 reaction equation
O.NN.[Br:4][C:5]1[CH:10]=[CH:9][C:8]([S:11](Cl)(=[O:13])=[O:12])=[C:7]([Cl:15])[CH:6]=1.[C:16]([O-])(=O)C.[Na+].CI>C1COCC1.CCO>[Br:4][C:5]1[CH:10]=[CH:9][C:8]([S:11]([CH3:16])(=[O:13])=[O:12])=[C:7]([Cl:15])[CH:6]=1

Participants

7

Reactant 4

HCID 6328Methyl iodideHCID 24654Hydrazine hydrate (1:1)HCID 517045Sodium AcetateHCID 27347664-Bromo-2-chlorobenzenesulfonyl chloride

Product 1

HCID 230930614-Bromo-2-chloro-1-methanesulfonylbenzeneYield 32.4%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

Hydrazine monohydrate (1.51 mL, 48 mmol) was added to a cooled 0° C. solution of 4-bromo-2-chlorobenzenesulfonyl chloride (5 g, 17.2 mmol) dissolved in THF (50 mL). The reaction was stirred at room temperature for 2 hours and then the solvent was removed in vacuo to give a white solid. The solid was dissolved in EtOH (100 mL) and treated with sodium acetate (6.56 g, 80 mmol) followed by methyl iodide (4.9 mL, 79 mmol). The reaction mixture was refluxed for 18 hours. The solvent was removed in vacuo to give a residue that was partitioned between 1 N HCl and EtOAc. The organic layer was dried over MgSO4 and concentrated. The crude mixture was purified by flash column chromatography to give the product (1.5 g, 32%). 1H NMR (300 MHz, CDCl3): δ 3.26 (s, 3 H), 7.63 (dd, J=8.5, 1.9 Hz, 2 H), 7.74 (d, J=1.9 Hz, 1 H), 8.02 (d, J=8.5 Hz, 1 H).

Workup

  1. customthe solvent was removed in vacuo
  2. customto give a white solid
  3. temperatureThe reaction mixture was refluxed for 18 hours
  4. customThe solvent was removed in vacuo
  5. customto give a residue that
  6. customwas partitioned between 1 N HCl and EtOAc
  7. dry with materialThe organic layer was dried over MgSO4
  8. concentrationconcentrated
  9. customThe crude mixture was purified by flash column chromatography

Sources & evidence

ORD record
ord-dea5459c89034b29a8ef6b3c3fdfb9d9
Source dataset
uspto-grants-2006_12
Patent number
US07151105B2

Reaction notes

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