Diethyl 2-(ethoxymethylidene)-3-oxobutanedioate → Triethyl 1,6-dihydro-6-oxo-2,3,5-pyridinetricarboxylate

HRID 1734468Notes

Reaction equation

C([CH:3]([C:7]([NH2:9])=[O:8])[C:4]([O-:6])=[O:5])C.C(O[CH:13]=[C:14]([C:20]([C:22]([O:24][CH2:25][CH3:26])=[O:23])=O)[C:15]([O:17][CH2:18][CH3:19])=[O:16])C.[C:27]([O-])(=O)[CH3:28].[Na+]>C(O)C>[CH2:25]([O:24][C:22]([C:20]1[NH:9][C:7](=[O:8])[C:3]([C:4]([O:6][CH2:27][CH3:28])=[O:5])=[CH:13][C:14]=1[C:15]([O:17][CH2:18][CH3:19])=[O:16])=[O:23])[CH3:26]

Participants

Conditions

Temperature: 0 °C

Procedure

A solution of ethylmalonamate (23.6 g, 0.18 mol) in absolute ethanol (300 mL) is added to a stirred solution of diethyl ethoxymethyleneoxalacetate (44.0 g, 0.18 mol) in ethanol (200 mL) at 0° C., followed by the addition, of solid sodium acetate (14.72 g, 0.18 mol). After stirring for ten minutes at 0° C., the mixture is heated to reflux and stirred for 13.5 hours. After cooling, the ethanol is removed under vacuum, and the residue diluted with water and acidified to pH 2 with concentrated hydrochloric acid. The aqueous solution is extracted with methylene chloride (2×200 mL) and the organic layer washed with 300 mL saturated sodium chloride, then dried over anhydrous magnesium sulfate and concentrated in vacuum to give 45.0 g of the title product as an orange oil.

Workup

temperaturethe mixture is heated
temperatureto reflux
stirringstirred for 13.5 hours
temperatureAfter cooling
customthe ethanol is removed under vacuum
additionthe residue diluted with water
extractionThe aqueous solution is extracted with methylene chloride (2×200 mL)
washthe organic layer washed with 300 mL saturated sodium chloride
dry with materialdried over anhydrous magnesium sulfate
concentrationconcentrated in vacuum

Sources & evidence

ORD record: ord-b88d7281d6254e95b13da4305a72b0c4
Source dataset: uspto-grants-1996_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05534483

Reaction notes

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