Propanal → Diethyl 2-(propylamino)malonate

HRID 1648278Notes

Reaction equation

HRID 1648278 reaction equation
[NH2:1][CH:2]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[C:3]([O:5][CH2:6][CH3:7])=[O:4].[O-]CC.[Na+].[CH:17](=O)[CH2:18][CH3:19].C([BH3-])#N.[Na+]>C(O)C>[CH2:17]([NH:1][CH:2]([C:3]([O:5][CH2:6][CH3:7])=[O:4])[C:8]([O:10][CH2:11][CH3:12])=[O:9])[CH2:18][CH3:19]

Participants

6

Reactant 4

HCID 527Propanal2×HCID 81272Propanedioic acid, 2-amino-, 1,3-diethyl esterHCID 2723922Sodium ethoxideHCID 5003444Sodium cyanoborohydride2×

Product 1

HCID 15122388Diethyl 2-(propylamino)malonateYield 115.5%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Procedure

Diethyl aminomalonate (21.1 g, 0.1 mol) was dissolved in ethanol and sodium ethoxide in ethanol (50 mL of I M) was added. Propionaldehyde (6.6 g, 0.11 mol) and sodium cyanoborohydride (3.6 g, 0.058 mol) were added to the stirred solution. After 30 minutes additional propionaldehyde (6.0 g) and sodium cyanoborohydride (2.6 g) were added to complete the reaction. The solution was evaporated, and the residue was partitioned between ethyl acetate and water. Evaporation of the ethyl acetate gave 25.1 g of diethyl (propylamino)malonate. This was mixed with di t-butyl dicarbonate (34 g, 0.156 mol) and the mixture was heated at 100° C. for 1 hour. The crude product was chromatographed on silica gel using ethyl acetate:hexane as the eluant to give 21.2 g of diethyl (N-(1,1-dimethylethoxycarbonyl)propylamino)malonate as an oil.

Workup

  1. customthe reaction
  2. customThe solution was evaporated
  3. customthe residue was partitioned between ethyl acetate and water
  4. customEvaporation of the ethyl acetate

Sources & evidence

ORD record
ord-e836971056f440ae9d10b77a44ebee76
Source dataset
uspto-grants-1995_07
Patent number
US05436240

Reaction notes

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