Diethyl Malonate → HCID 594682, compound

HRID 131116Notes

Reaction equation

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

Participants

Conditions

Temperature: 0 °C

Procedure

A mixture of sodium hydride (60% in mineral oil, 435 mg, 10.87 mmol, 1.1 eq) in DMF (20 mL) was treated dropwise with diethyl malonate (1.5 mL, 9.88 mmol, 1.0 eq). The reaction mixture was then cooled to 0° C. and 4-bromo-1-butene (1.0 mL, 9.88 mmol, 1 eq) was added dropwise. The reaction mixture was warmed to rt, stirred for 3 days and then partitioned between ether and water. The layers were separated, the aqueous layer was extracted with ether (2×50 mL) and the combined organic phases were washed with water (2×) and brine, dried over MgSO4 and concentrated. Column chromatography (SiO2, 5% ether/heptane) gave C8.1 (1.51 g, 71% yield) as a colorless oil. 1H NMR (400 MHz, DMSO-d6): δ 5.77 (m, 1 H), 5.00 (m, 2 H), 4.13 (q, J=7.1 Hz, 4 H), 3.43 (t, J=7.4 Hz, 1 H), 2.02 (m, 2 H), 1.84 (m, 2 H), 1.17 (t, J=7.1 Hz, 6 H).

Workup

temperatureThe reaction mixture was warmed to rt
custompartitioned between ether and water
customThe layers were separated
extractionthe aqueous layer was extracted with ether (2×50 mL)
washthe combined organic phases were washed with water (2×) and brine
dry with materialdried over MgSO4
concentrationconcentrated
customColumn chromatography (SiO2, 5% ether/heptane) gave C8.1 (1.51 g, 71% yield) as a colorless oil

Sources & evidence

ORD record: ord-13ca2e55ae2c4f71b3b1daa42aa7af65
Source dataset: uspto-grants-2008_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07384937B2

Reaction notes

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