Allyl bromide → HCID 21842666, compound

To 14 g (0.35 mole) of 60% sodium hydride/mineral oil dispersion in a two liter flask was added 500 ml of hexane. The mixture was swirled briefly, the solid allowed to settle and the supernatant liquid decanted. DMF (800 ml) was added, followed by a solution of 47 g (0.30 mole) of 5-chlorosalicylaldehyde in 50 ml of DMF. The mixture was stirred at room temperature under nitrogen for 30 minutes, then 54.5 g (0.45 mole) of allyl bromide was added. The mixture was heated at 65° C. under nitrogen for 18 hours. The solvent was then removed in vacuum and replaced with one liter of methylene chloride. This solution was washed with water and with saturated brine and dried over sodium sulfate. It was then filtered and 150 g (0.50-0.75 mole) of 57-86% m-chloroperoxybenzoic acid added and the mixture stirred at room temperature overnight. The reaction was filtered and the filtrate washed with three 400 ml portions of saturated aqueous sodium bicarbonate and with saturated brine, dried over sodium sulfate, filtered and concentrated in vacuum. The residue was dissolved in 750 ml of methanol and stirred with 150 g of basic alumina for 15 hr. The mixture was then filtered and evaporated in vacuum and the crude product partitioned between 500 ml each of 1N NaOH (aq) and methylene chloride. The organic phase was extracted with an additional 500 ml of base, and the combined basic extracts back-washed with 500 ml of methylene chloride. Finally, the basic extracts were carefully acidified with concentrated HCl and extracted with two 400 ml portions of methylene chloride. The combined organic extracts were washed with saturated brine, dried over sodium sulfate, filtered and concentrated in vacuum to give 37.3 g of the title compound as a yellow oil. 1H (CDCl3) singlet, 6.90δ(1 H); quartet, 6.70δ(2 H); singlet, 6.20δ(1 H, OH);.multiplet, 5.97δ(1 H); quartet, 5.25δ(2 H); doublet, 4.50δ(2 H).

1. customthe supernatant liquid decanted
2. additionDMF (800 ml) was added
3. temperatureThe mixture was heated at 65° C. under nitrogen for 18 hours
4. customThe solvent was then removed in vacuum
5. washThis solution was washed with water and with saturated brine
6. dry with materialdried over sodium sulfate
7. filtrationIt was then filtered
8. stirringthe mixture stirred at room temperature overnight
9. filtrationThe reaction was filtered
10. washthe filtrate washed with three 400 ml portions of saturated aqueous sodium bicarbonate and with saturated brine
11. dry with materialdried over sodium sulfate
12. filtrationfiltered
13. concentrationconcentrated in vacuum
14. dissolutionThe residue was dissolved in 750 ml of methanol
15. stirringstirred with 150 g of basic alumina for 15 hr
16. filtrationThe mixture was then filtered
17. customevaporated in vacuum
18. customthe crude product partitioned between 500 ml each of 1N NaOH (aq) and methylene chloride
19. extractionThe organic phase was extracted with an additional 500 ml of base
20. washthe combined basic extracts back-washed with 500 ml of methylene chloride
21. extractionextracted with two 400 ml portions of methylene chloride
22. washThe combined organic extracts were washed with saturated brine
23. dry with materialdried over sodium sulfate
24. filtrationfiltered
25. concentrationconcentrated in vacuum

ORD record

ord-3befaad1c463464497c9e93864a4cc13

Source dataset

uspto-grants-1998_05

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05756532