1-bromo-4-chloro-2-methylsulfanylbenzene

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-Bromo-5-chloroaniline (85.2 g, 0.41 mol) was dissolved in 1 L of acetonitrile followed by the addition of dimethydisulfide (30.0 mL, 0.33 mol). The flask was immersed in a water bath warmed to 60° C., equipped with a reflux condenser, and tert-butyl nitrite (54.0, 0.45 mol) was added in portions over 15 minutes. Once the addition was complete, the reaction was refluxed for 2 hours. After cooling to room temperature, the acetonitrile was evaporated, followed by re-dissolving in dichloromethane and subsequent concentration to remove remaining acetonitrile. The residue was re-dissolved in a minimal amount of dichloromethane and diluted with hexanes until precipitation was initiated. The mixture was filtered through a plug of silica and washed with hexanes. The filtrate was then concentrated in vacuo and crystallized upon cooling. 1-Bromo-4-chloro-2-methylsulfanylbenzene (52.0 g, 53%) was isolated via suction filtration. The flask was immersed in a water bath equipped with a reflux condenser Once the addition the reaction was refluxed for 2 hours After cooling to room temperature the acetonitrile was evaporated by re-dissolving in dichloromethane subsequent concentration to remove The residue was re-dissolved in a minimal amount of dichloromethane diluted with hexanes until precipitation The mixture was filtered through a plug of silica washed with hexanes The filtrate was then concentrated in vacuo crystallized upon cooling