Tert-Butyl nitrite → HCID 58026158, compound

Temperature

60 °C

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.

1. customThe flask was immersed in a water bath
2. customequipped with a reflux condenser
3. additionOnce the addition
4. temperaturethe reaction was refluxed for 2 hours
5. temperatureAfter cooling to room temperature
6. customthe acetonitrile was evaporated
7. dissolutionby re-dissolving in dichloromethane
8. concentrationsubsequent concentration
9. customto remove
10. dissolutionThe residue was re-dissolved in a minimal amount of dichloromethane
11. additiondiluted with hexanes until precipitation
12. filtrationThe mixture was filtered through a plug of silica
13. washwashed with hexanes
14. concentrationThe filtrate was then concentrated in vacuo
15. customcrystallized
16. temperatureupon cooling

ORD record

ord-24a8babfa98f4e5a9c4c2d30e8c19f6f

Source dataset

uspto-grants-2012_09

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08268859B2