Allyl bromide → HCID 11116577, compound

Temperature

150 °C

A 100 mL flask containing copper(I) cyanide (0.85 g, 9.54 mmol) and lithium chloride (0.81 g, 19.08 mmol) was placed under vacuum and heated to 150° C. for 90 minutes, and then cooled to room temperature. A 500 mL flask containing a solution of methyl 4-iodobenzoate (12.5 g, 47.7 mmol) in tetrahydrofuran (75 mL) under argon was cooled to −25° C. and isopropylmagnesium chloride—lithium chloride complex (49.1 mL, 1 M, 49.1 mmol) was added over 16 minutes while the internal temperature was maintained at below −20° C. After 45 minutes, the copper(I) cyanide and lithium chloride were dissolved in tetrahydrofuran (20 mL) with sonication, and the resulting solution was transferred to the clear, orange reaction mixture via cannula. After an additional 25 minutes, allyl bromide (4.13 mL, 47.7 mmol) was added over 10 min while the reaction temperature was kept below −15° C., and then the reaction was kept at −5° C. for 24 hours. 60 mL of 9:1 NH4Cl(sat):NH3(sat) was then added, followed by 50 mL of water and 200 mL dichloromethane. The layers were separated, and the aqueous layer was extracted with dichloromethane (2×100 mL). The combined organic layers were washed with 100 mL water and then diluted with 100 mL dichloromethane and 100 mL chloroform. The organic layer was washed with 150 mL brine, dried over MgSO4 and Na2SO4, filtered, and concentrated to yield an oil and a solid. The oil was filtered through a cotton plug and the entire flask was then rinsed with hexanes (4×2 mL); these rinses were combined with the oil after filtering through cotton. Concentration of this solution yielded the title compound. 1H NMR (600 MHz, DMSO): δ 7.86 (d, J=8.2Hz, 2H), 7.31 (d, J=8.5Hz, 2H), 5.93 (m, 1 H), 5.07 (m, 1H), 5.05 (m, 1H), 3.79 (s, 3H), 3.41 (d, J=6.7Hz, 1H).

1. temperaturecooled to room temperature
2. temperaturewas cooled to −25° C.
3. additionisopropylmagnesium chloride—lithium chloride complex (49.1 mL, 1 M, 49.1 mmol) was added over 16 minutes while the internal temperature
4. temperaturewas maintained at below −20° C
5. waitAfter an additional 25 minutes
6. customwas kept below −15° C.
7. waitthe reaction was kept at −5° C. for 24 hours
8. customThe layers were separated
9. extractionthe aqueous layer was extracted with dichloromethane (2×100 mL)
10. washThe combined organic layers were washed with 100 mL water
11. additiondiluted with 100 mL dichloromethane and 100 mL chloroform
12. washThe organic layer was washed with 150 mL brine
13. dry with materialdried over MgSO4 and Na2SO4
14. filtrationfiltered
15. concentrationconcentrated
16. customto yield an oil
17. filtrationThe oil was filtered through a cotton plug
18. washthe entire flask was then rinsed with hexanes (4×2 mL)
19. filtrationafter filtering through cotton

ORD record

ord-f4383b30cc0e4372b2965833b49dd46a

Source dataset

uspto-grants-2013_01

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08344144B2