2-Iodo-4-nitroaniline → 1-Fluoro-2-iodo-4-nitrobenzene

Temperatur

0 °C

A solution of nitrosonium tetrafluoroborate (24 g, 0.21 mol) in dichloromethane (200 mL) at 0° C. was treated with a solution of 2-iodo-4-nitroaniline (50 g, 0.19 mol) in dichloromethane (350 mL) and stirred at 0° C. for 1 h. The dichloromethane was concentrated to about half volume and the reaction mixture was treated with 1,2-dichlorobenzene (300 mL). The remaining dichloromethane was further concentrated in vacuo. The resultant 1,2-dichlorobenzene suspension was heated at 110° C. for 1 h, cooled to 20° C., and treated with water (200 mL) and dichloromethane (500 mL). The reaction mixture was filtered over celite and the celite was washed with dichloromethane and water. The aqueous layer of the filtrate was separated and extracted with dichloromethane (2×). The combined organic layers were washed with 20% sodium thiosulfate and brine, dried over anhydrous sodium sulfate, and filtered. The dichloromethane was removed under standard conditions while the 1,2-dichlorobenzene was removed via vacuum distillation to give a crude dark oil. This material was purified by distillation to give the desired product (19 g, 38%) as a solid.

1. concentrationThe dichloromethane was concentrated to about half volume
2. additionthe reaction mixture was treated with 1,2-dichlorobenzene (300 mL)
3. concentrationThe remaining dichloromethane was further concentrated in vacuo
4. temperatureThe resultant 1,2-dichlorobenzene suspension was heated at 110° C. for 1 h
5. temperaturecooled to 20° C.
6. additiontreated with water (200 mL) and dichloromethane (500 mL)
7. filtrationThe reaction mixture was filtered over celite
8. washthe celite was washed with dichloromethane and water
9. customThe aqueous layer of the filtrate was separated
10. extractionextracted with dichloromethane (2×)
11. washThe combined organic layers were washed with 20% sodium thiosulfate and brine
12. dry with materialdried over anhydrous sodium sulfate
13. filtrationfiltered
14. customThe dichloromethane was removed under standard conditions while the 1,2-dichlorobenzene
15. customwas removed via vacuum distillation
16. customto give a crude dark oil
17. distillationThis material was purified by distillation

ORD-Eintrag

ord-837a55d8d67b4df4970587f1e6089a35

Quelldatensatz

uspto-grants-2014_10

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US08871753B2