Sodium Cyanide → 2-Bromo-4-methylbenzonitrile

Temperature

0 °C

To a solution of 2-bromo-4-methylaniline (558 mg, 3.0 mmol) in 30 mL of acetbnitrile was added tetrafluoroborate (600 μL of a 54% solution in Et2O, 4.35 mmol). The solution was cooled to about 0° C. and t-butyl nitrite (55 uL, 4.62 mmol) was added. After stirring for about 45 minutes, the solution was transferred to a solution of CuCN (800 mg, 8.93 mmol) and NaCN (1.47 g, 30 mmol) in 30 mL, of water cooled to 0° C. via cannula. The cold bath was removed. After stirring overnight, the aqueous solution was extracted with Et2O (2×). The combined organic solutions were washed with 1 M HCl, saturated sodium bicarbonate, water and brine, and then dried (Na2SO4), filtered and concentrated. The material was adsorbed onto 3 g of silica gel and purified by silica gel flash chromatography (4×15 cm column, 5-20 Et2O/pentane, over 48 min at 35 mL/min) to afford about 320 mg (1.63 mmol, 54%) of 2-bromo-4-methyl-benzonitrile as a colorless oil. GC/MS (EI): 195.

1. temperaturecooled to 0° C. via cannula
2. customThe cold bath was removed
3. stirringAfter stirring overnight
4. extractionthe aqueous solution was extracted with Et2O (2×)
5. washThe combined organic solutions were washed with 1 M HCl, saturated sodium bicarbonate, water and brine
6. dry with materialdried (Na2SO4)
7. filtrationfiltered
8. concentrationconcentrated
9. custompurified by silica gel flash chromatography (4×15 cm column, 5-20 Et2O/pentane, over 48 min at 35 mL/min)

ORD record

ord-5e7fd79f621443a0a4c1e6774ac3875f

Source dataset

uspto-grants-2007_11

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07291619B2