Iodine → HCID 11078407, compound

Temperature

60 °C

Under argon, 1 mol of Mg turnings and a spatula tip of iodine in a mixture of 100 ml of tetrahydrofuran and 100 ml of toluene were heated to 60° C. Over the course of 10 minutes, 200 g of 5-bromo-2-chloroanisole in a mixture of 200 ml of tetrahydrofuran and 200 ml of toluene were added dropwise. During the dropwise addition, the internal temperature was maintained at 60° C. by cooling. When the dropwise addition was complete, the reaction mixture was heated to reflux temperature and after-stirred for 30 minutes at this temperature. The mixture was then cooled to 0° C. and 236.8 g of diphenylphosphinic chloride were added dropwise over the course of 45 minutes. The internal temperature was maintained during this operation between 0 and 5° C. The reaction mixture was after-stirred for 5 minutes at 0° C., the cooling was switched off, and the mixture was stirred for a further 2 hours. For work-up, the reaction mixture was poured onto 1.6 liter of iced water, the organic phase was separated off, and the aqueous phase was washed again with 2×400 ml of toluene. The combined organic phases were washed with 400 ml of 2.5% strength by weight aqueous soda solution and then with 400 ml of water, and then concentrated on a rotary evaporator to a volume of 200 ml. Then, with stirring, 300 ml of n-pentane were added dropwise. The solid that precipitated out overnight was filtered off with suction, washed with n-pentane, and dried. This gave 203.5 g of a white solid. The yield was 82% and the purity was 94%.

1. additionwere added dropwise
2. additionDuring the dropwise addition
3. temperaturethe internal temperature was maintained at 60° C.
4. temperatureby cooling
5. additionWhen the dropwise addition
6. temperaturethe reaction mixture was heated
7. temperatureto reflux temperature
8. temperatureThe mixture was then cooled to 0° C.
9. temperatureThe internal temperature was maintained during this operation between 0 and 5° C
10. stirringThe reaction mixture was after-stirred for 5 minutes at 0° C.
11. stirringthe mixture was stirred for a further 2 hours
12. customthe organic phase was separated off
13. washthe aqueous phase was washed again with 2×400 ml of toluene
14. washThe combined organic phases were washed with 400 ml of 2.5% strength by weight aqueous soda solution
15. concentrationwith 400 ml of water, and then concentrated on a rotary evaporator to a volume of 200 ml
16. stirringThen, with stirring
17. addition300 ml of n-pentane were added dropwise
18. customThe solid that precipitated out overnight
19. filtrationwas filtered off with suction
20. washwashed with n-pentane
21. customdried

ORD record

ord-380af7ce6ce24665a0fead5b56cfc843

Source dataset

uspto-grants-2002_12

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06489513B2