反应详情

To a solution of [(4-bromophenyl)oxy]acetonitrile (3.07 g; 14.5 mmol; step 1 above) in anhyd THF (10 mL) at 0° C. was added BH3.DMS (18.1 mL of a 2M solution in THF; 36.2 mmol), dropwise over 5 min. The mixture was heated under reflux for 1.5 h, cooled, and 2M HCl (ca. 50 mL) was slowly added. The acidic mixture was extracted with Et2O (×2) and the extracts set aside. NaOH pellets were added to the aqueous residue until ca. pH 14, and the whole was extracted with Et2O (×3). Combined extracts of the basic mixture were washed (brine), dried over Na2SO4, and concentrated in vacuo, affording the first batch of title compound as a pale yellow liquid. The reserved Et2O extracts (from acidic mixture) were concentrated in vacuo, the residue was heated at near reflux in 15 wt % NaOH (aq) for 15 min, cooled, and extracted with CH2Cl2 (×3). Combined organics were washed (brine) and concentrated in vacuo. The residue was slurried in 4M HCl and insoluble material was removed by filtration. The filtrate was extracted with Et2O (×2), pH was adjusted to ca. pH 14 by addition of NaOH pellets and extracted with Et2O (×5). Combined extracts from the basic mixture were washed (brine), dried over Na2SO4, filtered and concentrated in vacuo, affording a second batch of the title compound, which was combined with the first batch. LC/MS (method D) 1.15 min, m/z 216 (M+H, 79Br), 218 (M+H, 81Br).

1. temperatureThe mixture was heated
2. temperatureunder reflux for 1.5 h
3. temperaturecooled
4. extractionThe acidic mixture was extracted with Et2O (×2)
5. additionNaOH pellets were added to the aqueous residue until ca. pH 14
6. extractionthe whole was extracted with Et2O (×3)
7. washCombined extracts of the basic mixture were washed (brine)
8. dry with materialdried over Na2SO4
9. concentrationconcentrated in vacuo