Dichloromethane → 7-Bromo-1-chloronaphthalene

A mixture of the product from Step C (6.0 g, 30 mmol) and 6 M HCl (13.4 ml) was stirred at room temperature until a solid formed. The mixture was cooled to 0° C. and a solution of sodium nitrite (1.9 g, 30 mmol) in water (5.6 ml) was slowly added keeping the temperature below 5° C. The resulting brown slurry was stirred at 0° C. for 15 minutes and then a solution of copper(I) chloride (3.3 g, 30 mmol) in 6 M HCl (15.4 ml) was added. The mixture was stirred at 0° C. for 10 minutes, then warmed to room temperature and stirred at 60° C. for 30 minutes. After cooling to room temperature, dichloromethane was added. The mixture was filtered through diatomaceous earth and the filtrate was extracted with dichloromethane three times. The combined organic layers were washed with water and dried over magnesium sulfate to give 7-bromo-1-chloronaphthalene (2.8 g, 43%) after chromatography (100% hexanes): 1H NMR (300 MHz, DMSO-d6) δ 8.30 (d, J=1.8 Hz, 1H), 7.96-8.02 (m, 2H), 7.74-7.78 (m, 2H), 7.55 (t, J=7.8 Hz, 1H).

1. customformed
2. temperatureThe mixture was cooled to 0° C.
3. customthe temperature below 5° C
4. stirringThe resulting brown slurry was stirred at 0° C. for 15 minutes
5. stirringThe mixture was stirred at 0° C. for 10 minutes
6. temperaturewarmed to room temperature
7. stirringstirred at 60° C. for 30 minutes
8. temperatureAfter cooling to room temperature
9. filtrationThe mixture was filtered through diatomaceous earth
10. extractionthe filtrate was extracted with dichloromethane three times
11. washThe combined organic layers were washed with water
12. dry with materialdried over magnesium sulfate

ORD record

ord-58da1d25fc9b4cbaa8f2a0f16af9cf88

Source dataset

uspto-grants-2012_08

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08236796B2