Acetamidomalonic acid diethyl ester → HCID 14482015, compound

HRID 1742748Notes

Reaction equation

HRID 1742748 reaction equation
[Na].[C:2]([NH:5][CH:6]([C:12]([O:14][CH2:15][CH3:16])=[O:13])[C:7]([O:9][CH2:10][CH3:11])=[O:8])(=[O:4])[CH3:3].[CH:17](=[O:23])/[CH:18]=[CH:19]/[CH2:20][CH2:21][CH3:22]>C(O)C>[C:2]([N:5]1[CH:17]([OH:23])[CH2:18][CH:19]([CH2:20][CH2:21][CH3:22])[C:6]1([C:12]([O:14][CH2:15][CH3:16])=[O:13])[C:7]([O:9][CH2:10][CH3:11])=[O:8])(=[O:4])[CH3:3]

Participants

5

Reactant 3

HCID 14041Acetamidomalonic acid diethyl esterHCID 5281168trans-2-HexenalHCID 5360545Sodium

Product 1

HCID 14482015HCID 14482015, compoundYield 93%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
0 °C

Procedure

Sodium metal (3.48 g, 0.15 mol) was dissolved in a stirred solution of diethyl acetamidomalonate (201.6 g, 0.93 mol) in anhydrous ethanol (1200 mL) at room temperature under nitrogen. The reaction mixture was cooled to 0° C. and trans-2-hexenal (100.0 g, 1.02 mol) was then added dropwise. The resulting mixture was allowed to warm to room temperature. After stirring for 3 hours at 23° C., the reaction was quenched with 24 mL of acetic acid. The solution was concentrated in vacuo and the resulting residue was taken up in ethyl acetate and washed with saturated aqueous NaHCO3 (2×) and brine. Dried over anhydrous magnesium sulfate, concentation and recrystallization of the residue from EtOAc/Hexane gave 271.4 g (93% yield) of the title compound as fine needles, mp 105°-106° C. TLC, Rf =0.43 (9:1 CHCl3 /MeOH). MS(CI) m/e 316 (M+1)+, 298 (MH-H2O)+ . 1H NMR (CD3OD, 300 MHz) δ0.94 (t, J=7.2 Hz, 3H), 1.47-1.11 (m, 9H), 1.90-1.78 (m, 1H), 1.94 (dd, J=12.8, 5.2 Hz, 1H), 2.08 (dd, J=12.8, 6.4 Hz, 1H), 2.21 (s, 3H), 2.83 (m, 1H), 4.10-4.26 (m, 4H), 5.64 (d, J=5.2 Hz, 1H). IR (CDCl3) 3460, 1750, 1665 cm-1. Anal. calcd. for C15H25NO6 : C, 57.13; H, 7.99; N, 4.44. Found: C, 57.28; H, 8.08; N, 4.42.

Workup

  1. temperatureto warm to room temperature
  2. customthe reaction was quenched with 24 mL of acetic acid
  3. concentrationThe solution was concentrated in vacuo
  4. washwashed with saturated aqueous NaHCO3 (2×) and brine
  5. dry with materialDried over anhydrous magnesium sulfate, concentation and recrystallization of the residue from EtOAc/Hexane

Sources & evidence

ORD record
ord-d231089b85dd4abdb048d864219e5c13
Source dataset
uspto-grants-1994_08
Patent number
US05340802

Reaction notes

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