4-Bromodiphenyl Ether → 4-Phenoxyphenylboronic acid

温度

-78 °C

To a solution of 4-phenoxybromobenzene (98.2 g, 0.39 mol) in dry THF (800 mL) under nitrogen at −78° C. was added n-BuLi (2.5M solution in hexanes) (172 mL, 0.43 mol) dropwise. A temperature rise to −65° C. was observed. On complete addition, the mixture was allowed to stir at −78° C. for 15 min. Triisopropylborate (109.2 mL, 0.473 mol) was added dropwise over 30 min. On complete addition, a suspension was observed. The mixture was allowed to warm to 0° C. over 1 hr, stirred at 0° C. for 4 hrs. The reaction was quenched by the dropwise addition of water (300 mL) such that the internal temperature<20° C. (ice-cooling required). The mixture was allowed to warm to room temperature overnight then evaporated to dryness. The residue was suspended in water (600 mL) and acidified by the cautious addition of conc. HCl. The resulting precipitate was collected by filtration and dried in vacuo at 45° C. The solid was ground to a fine powder and triturated with petroleum ether (40-60° C.). The pale solid was filtered and dried to give 4-phenoxyphenylboronic acid (68.8 g, 83%). 1H NMR (250 MHz, d6-DMSO):7.99 (1H, m), 7.91 (1H, t), 7.83 (1H, d), 7.4 (2H, m), 7.14 (1H, m), 6.92-7.07 (5H, m). Microanalysis:Req. C(71.4%), H(5.45%), Found C(70.25%), H(4.7%).

1. customto −65° C.
2. additionOn complete addition
3. additionOn complete addition
4. temperatureto warm to 0° C. over 1 hr
5. stirringstirred at 0° C. for 4 hrs
6. customThe reaction was quenched by the dropwise addition of water (300 mL) such that
7. temperaturethe internal temperature<20° C. (ice-cooling required)
8. temperatureto warm to room temperature overnight
9. customthen evaporated to dryness
10. additionacidified by the cautious addition of conc. HCl
11. filtrationThe resulting precipitate was collected by filtration
12. customdried in vacuo at 45° C
13. customtriturated with petroleum ether (40-60° C.)
14. filtrationThe pale solid was filtered
15. customdried

ORDレコード

ord-cc40fd7a44f64a7ba351bd141582bd7a

出典データセット

uspto-grants-2003_12

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US06660744B1