Hydrogen Bromide → 5-Bromo-1,3-dichloro-2-methylbenzene

Suspend the 3,5-dichloro-4-methylaniline in 48% HBr (5 mL) and water (5 mL) and heat with a heat gun until the mixture is near the boiling point. Cool the slurry to room temperature and then cool to 0° C. with an ice/brine bath. Add a solution of sodium nitrite (109 mg, 1.58 mmol) in water (2 mL) dropwise. After the addition is complete, stir the reaction an additional 15 min in the cold bath. Add a solution of CuBr (1.08 g, 7.53 mmol) in 48% HBr (2 mL) and heat the rapidly stirring reaction to 50° C. for 1 hour. Cool the reaction to room temperature, dilute the reaction with ethyl acetate and discard the aqueous layer. Wash the organic layer with water and brine, dry with MgSO4, filter through celite and concentrate to an orange residue. Purify the residue by silica gel chromatography eluting with hexanes to afford 164 mg (45%) of the product as a yellow solid.

1. temperatureheat with a heat gun until the mixture
2. temperaturecool to 0° C. with an ice/brine bath
3. additionAfter the addition
4. customthe reaction an additional 15 min in the cold bath
5. temperatureheat the
6. stirringrapidly stirring
7. customreaction to 50° C. for 1 hour
8. temperatureCool
9. customthe reaction to room temperature
10. additiondilute
11. washWash the organic layer with water and brine
12. dry with materialdry with MgSO4
13. filtrationfilter through celite
14. concentrationconcentrate to an orange residue
15. customPurify the residue by silica gel chromatography
16. washeluting with hexanes

ORDレコード

ord-21e693eafa8a43cbb7892bcea51d876b

出典データセット

uspto-grants-2011_06

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US07968585B2