3-Bromodiphenyl ether → (4-Hydroxy-4-(3-phenoxyphenyl)cyclohexane-1,1-diyl)bis(methylene) bis(4-methylbenzenesulfonate)

Temperature

-78 °C

To a solution of 1-bromo-3-phenoxybenzene (0.320 g, 1.29 mmol) in anhydrous THF (10 mL) at −78° C. was added n-BuLi (0.804 mL of a 1.6 M solution in hexanes; 1.286 mmol). The reaction was stirred at −78° C. for 0.5 h and a solution of (4-oxocyclohexane-1,1-diyl)bis(methylene) bis(4-methylbenzenesulfonate) (0.5 g, 1.07 mmol) in THF (5 mL) was then added dropwise. The reaction mixture was slowly warmed to rt and stirred overnight. The reaction was quenched with sat′d aq NH4Cl and diluted with water. The mixture was extracted with EtOAc. The organic layer was dried (Na2SO4) and concentrated in vacuo. The crude oil was purified by flash chromatography on SiO2 (0 to 50% EtOAc:hexanes) to afford the title compound (0.39 g, 57% yield) as a white foam. 1H NMR (500 MHz, CDCl3) δ 7.78 (t, J=8.6 Hz, 4H), 7.41-7.33 (m, 6H), 7.29 (dd, J=11.4, 5.0 Hz, 1H), 7.16-7.10 (m, 1H), 7.08-6.99 (m, 4H), 6.89-6.84 (m, 1H), 4.01 (s, 2H), 3.81 (s, 2H), 2.49 (s, 3H), 2.45 (s, 3H), 1.75-1.47 (m, 8H).

1. temperatureThe reaction mixture was slowly warmed to rt
2. stirringstirred overnight
3. customThe reaction was quenched with sat′d aq NH4Cl
4. additiondiluted with water
5. extractionThe mixture was extracted with EtOAc
6. dry with materialThe organic layer was dried (Na2SO4)
7. concentrationconcentrated in vacuo
8. customThe crude oil was purified by flash chromatography on SiO2 (0 to 50% EtOAc:hexanes)

ORD record

ord-26e28c72872a4cc8bcce3e416754266f

Source dataset

uspto-grants-2015_02

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08962660B2