1-Bromo-4-iodobenzene → 3-(4-Bromophenyl)oxetan-3-ol

1-Bromo-4-iodobenzene (0.65 g, 2.3 mmol, Lancaster) was stirred in pentane (7 mL) and then n-BuLi (1.6 M in hexane, 1.4 mL, 2.3 mmol) was added dropwise at rt. The mixture was and the stirred for 1 h. A white precipitate formed and the precipitate was allowed to settled. The pentane was removed by pipette. The mixture was diluted with pentane (7 mL) back up to the original volume. The mixture was then added to a solution of 3-oxetanone (0.315 g, 4.37 mmol) in THF (7 mL) that was cooled in an ice bath. The mixture was then allowed to come to rt and stirred for about 2 h. The mixture was quenched by the addition of saturated NH4Cl (10 mL) and allowed to stir overnight. EtOAc (15 mL) was added and the layers separated. The aqueous layer was then extracted with EtOAc (5 mL). The combined organic layers were washed with brine (5 mL), dried over MgSO4, filtered, and concentrated in vacuo. The solid was purified by flash column chromatography (40 g Silicycle™ column) eluting with 20-50% EtOAc/heptane. The solid was recrystallized by dissolving in a mixture of heptane and DCM and concentrating under reduced pressure until a precipitate had formed. The solid was collected by filtration and washed with heptane (10 mL) to provide 3-(4-bromophenyl)oxetan-3-ol (0.333 g, 63%): 1H NMR (400 MHz, DMSO) δ 7.65-7.43 (m, 4H), 6.42 (s, 1H), 4.68 (dd, J=50.6, 6.8, 4H).

1. customA white precipitate formed
2. customThe pentane was removed by pipette
3. additionThe mixture was diluted with pentane (7 mL) back up to the original volume
4. temperaturewas cooled in an ice bath
5. customto come to rt
6. stirringstirred for about 2 h
7. customThe mixture was quenched by the addition of saturated NH4Cl (10 mL)
8. stirringto stir overnight
9. additionEtOAc (15 mL) was added
10. customthe layers separated
11. extractionThe aqueous layer was then extracted with EtOAc (5 mL)
12. washThe combined organic layers were washed with brine (5 mL)
13. dry with materialdried over MgSO4
14. filtrationfiltered
15. concentrationconcentrated in vacuo
16. customThe solid was purified by flash column chromatography (40 g Silicycle™ column)
17. washeluting with 20-50% EtOAc/heptane
18. customThe solid was recrystallized
19. dissolutionby dissolving in a mixture of heptane and DCM
20. concentrationconcentrating under reduced pressure until a precipitate
21. customhad formed
22. filtrationThe solid was collected by filtration
23. washwashed with heptane (10 mL)

ORD record

ord-e51f70b7d5214395bd097a53a7d387b0

Source dataset

uspto-grants-2014_07

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08785639B2