Aluminium lithium hydride → 2-(2-Bromo-4-nitrophenyl)-2-methylpropane-1,3-diol

To a solution of diethyl 2-(2-bromo-4-nitrophenyl)-2-methylmalonate (7.5 g, 20.0 mmol) in anhydrous tetrahydrofuran (80 mL) was slowly added a solution of lithium aluminum hydride (22 mL, 22.0 mmol, 1.0 M in THF) at 0° C. under an atmosphere of nitrogen. After stirring for 10 minutes the reaction was completed. The reaction mixture was quenched by the slow addition of methanol at 0° C. The reaction mixture was then partitioned between dichloromethane and 1 N hydrochloric acid. The layers were separated and the aqueous layer was extracted three times with dichloromethane. The combined organic layers were dried over anhydrous Na2SO4 and evaporated under vacuum to give crude product, which was purified by silica gel column chromatography (petroleum ether/EtOAc 2:1) to give 2-(2-bromo-4-nitrophenyl)-2-methylpropane-1,3-diol (1.4 g, 24%) as a red solid. 1H NMR (400 MHz, DMSO-d6) δ 8.31 (d, J=2.4 Hz, 1H), 8.13 (dd, J=2.4, 8.8 Hz, 1H), 7.74 (d, J=8.8 Hz, 1H), 4.74 (t, J=5.2 Hz, 2H), 3.93 (q, J=5.2 Hz, 2H), 3.79 (m, q, J=5.2 Hz, 2H), 1.38 (s, 3H).

1. customThe reaction mixture was quenched by the slow addition of methanol at 0° C
2. customThe reaction mixture was then partitioned between dichloromethane and 1 N hydrochloric acid
3. customThe layers were separated
4. extractionthe aqueous layer was extracted three times with dichloromethane
5. dry with materialThe combined organic layers were dried over anhydrous Na2SO4
6. customevaporated under vacuum
7. customto give crude product, which
8. customwas purified by silica gel column chromatography (petroleum ether/EtOAc 2:1)

ORD record

ord-8d90491a52f3494b960b0aa4df2d7b50

Source dataset

uspto-grants-2014_08

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08802700B2