Diethyl Malonate → Acetamidomalonic acid diethyl ester

HRID 343633Notes

Reaction equation

[O:1]1CCO[CH2:3][CH2:2]1.[C:7]([O:15][CH2:16][CH3:17])(=[O:14])[CH2:8][C:9]([O:11][CH2:12][CH3:13])=[O:10].[N:18]([O-])=O.[Na+]>C(O)(=O)C.O>[NH:18]([CH:8]([C:9]([O:11][CH2:12][CH3:13])=[O:10])[C:7]([O:15][CH2:16][CH3:17])=[O:14])[C:2]([CH3:3])=[O:1]

Participants

Conditions

Temperature: 35 °C

Procedure

A mixture of 1,4-dioxane, acetic acid and water, obtained from a previous reaction mixture by taking a low-boiling cut, was metered into a stirred mixture of 320.4 g (2.0 mol) of diethyl malonate and 160 g (2.3 mol) of sodium nitrite (technical grade), maintained at 35° C. 12.0 g of water were then metered in and 166 g (207. mol) of acetic acid (96%) were added dropwise over 2 hours. The mixture was allowed to continue reacting for 2 hours at 40° C. and was worked up as described in Example 4. There remained 425 g of light yellow oil, which, after catalytic hydrogenation and recrystallization of the crude product, gave diethyl acetaminomalonate at a yield of 86% of theory, based on the diethyl malonate employed, and with a purity of >99.8 FID area percent.

Workup

customobtained from a previous reaction mixture
additionwere added dropwise over 2 hours
customafter catalytic hydrogenation and recrystallization of the crude product

Sources & evidence

ORD record: ord-4bda829e630e4901b637a5febcf58af6
Source dataset: uspto-grants-1999_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05861533

Reaction notes

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