Sodium Bromide → 4-Bromo-3-iodotoluene

To a mixture of 2-iodo-4-methylaniline (50 g, 214.55 mmol) in HOAc (250 mL), H2SO4 (10 mL), and H2O (40 mL) was added a solution of NaNO2 (14.5 g) in H2O (80 mL) at 0° C. The solution was stirred for 1.5 h. This was defined as mixture A. In another round bottom flask, a mixture of NaBr (107 g), CuSO4 (32.2 g), Cu (38.9 g), H2SO4 (39 mL), and H2O (25 mL) was refluxed for 1.5 h. To this mixture was added mixture A, and the solution was then refluxed for 3 h. The solution was treated with water and extracted with EA (500 mL×3). The combined organic layers were washed with brine, dried over Na2SO4, and then concentrated in vacuo. Purification by column chromatography over silica gel eluted with PE afforded the product as colorless oil (43 g, yield 68%). 1H NMR (300 MHz, CDCl3): δ 7.69 (m, 1H), 7.47 (d, J=8.1 Hz, 1H), 7.00 (m, 1H), 2.26 (s, 3H) ppm.

1. temperaturewas refluxed for 1.5 h
2. additionTo this mixture was added mixture A, and the solution
3. temperaturewas then refluxed for 3 h
4. extractionextracted with EA (500 mL×3)
5. washThe combined organic layers were washed with brine
6. dry with materialdried over Na2SO4
7. concentrationconcentrated in vacuo
8. customPurification by column chromatography over silica gel
9. washeluted with PE

ORD-Eintrag

ord-23e9a92d80b94a9291ad91d23aea90ee

Quelldatensatz

uspto-grants-2015_10

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US09156860B2