Methyl iodide → 1,3-Diethyl 2-(4-bromophenyl)-2-methylpropanedioate

HRID 2242748Notes

Reaction equation

[Br:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]([C:14]([O:16][CH2:17][CH3:18])=[O:15])[C:9]([O:11][CH2:12][CH3:13])=[O:10])=[CH:4][CH:3]=1.[H-].[Na+].I[CH3:22]>C1COCC1>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([CH3:22])([C:9]([O:11][CH2:12][CH3:13])=[O:10])[C:14]([O:16][CH2:17][CH3:18])=[O:15])=[CH:4][CH:3]=1

Participants

Conditions

Temperature: 0 °C

Procedure

To a solution of diethyl 2-(4-bromophenyl)malonate (1.5 g, 4.8 mmol) in dry THF (5 mL) at 0° C. was added sodium hydride (380 mg, 9.5 mmol). After stirring for 30 minutes at 0° C., iodomethane (600 μL, 9.5 mmol) was added and the reaction was allowed to warm to room temperature. After stirring for 12 h at room temperature, the reaction was quenched with water (3 mL). The mixture was partitioned between 1 N HCl (10 mL) and dichloromethane (10 mL), and the organic layer was separated. The organic layer was washed with 1 N HCl (10 mL), dried over Na2SO4 and evaporated. The crude material was purified by silica gel chromatography, eluting with 0-20% ethyl acetate in hexanes, to give diethyl 2-(4-bromophenyl)-2-methylmalonate (850 mg, 55%) 1H NMR (400 MHz, DMSO-d6) δ7.59-7.55 (m, 2H), 7.31-7.27 (m, 2H), 4.21-4.14 (m, 4H), 1.75 (s, 3H), 1.19-1.16 (m, 6H).

Workup

temperatureto warm to room temperature
stirringAfter stirring for 12 h at room temperature
customthe reaction was quenched with water (3 mL)
customThe mixture was partitioned between 1 N HCl (10 mL) and dichloromethane (10 mL)
customthe organic layer was separated
washThe organic layer was washed with 1 N HCl (10 mL)
dry with materialdried over Na2SO4
customevaporated
customThe crude material was purified by silica gel chromatography
washeluting with 0-20% ethyl acetate in hexanes

Sources & evidence

ORD record: ord-597f472cb66f4c579e45d5fbaedce374
Source dataset: uspto-grants-2010_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07671221B2

Reaction notes

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