Ethanol → Diethyl (3-oxopropyl)malonate

HRID 426983

Reaction equation

HRID 426983 reaction equation
[CH:1]([CH:3]=[CH2:4])=[O:2].Br[CH:6]([C:12]([O:14][CH2:15][CH3:16])=[O:13])[C:7]([O:9][CH2:10][CH3:11])=[O:8].C(N(CCCC)CCCC)CCC.C(O)C>C(O)(=O)C>[C:7]([CH:6]([C:12]([O:14][CH2:15][CH3:16])=[O:13])[CH2:4][CH2:3][CH:1]=[O:2])([O:9][CH2:10][CH3:11])=[O:8]

Participants

6

Reactant 4

HCID 702EthanolHCID 7622Tributylamine2×HCID 7847Acrolein2×HCID 69637Diethyl bromomalonate

Product 1

HCID 88096Diethyl (3-oxopropyl)malonate

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

First, 100 ml acrolein was added to a solution of 180 g diethyl bromomalonate, 14 g tributylamine, and 600 ml ethanol while cooling in an ice bath. After 2-3 hours, an additional 1.5 g tributylamine and 20 ml acrolein was added. The stirring was continued for an additional 1 to 2 hours without additional cooling. The reaction mixture was neutralized with 7 ml glacial acetic acid and the ethanol and unreacted acrolein were removed on a rotary evaporator. The residue was diluted with 500 ml benzene and washed with 3×100 ml H2O and 2×100 ml saturated NaCl solution. The benzene solution was dried over CaSO4 and rotary evaporated to yield 207 g of yellow oil which was indicated to be 48% product by glc.

Workup

  1. temperaturewhile cooling in an ice bath
  2. waitThe stirring was continued for an additional 1 to 2 hours without additional cooling
  3. customthe ethanol and unreacted acrolein were removed on a rotary evaporator
  4. additionThe residue was diluted with 500 ml benzene
  5. washwashed with 3×100 ml H2O and 2×100 ml saturated NaCl solution
  6. dry with materialThe benzene solution was dried over CaSO4
  7. customrotary evaporated

Sources & evidence

ORD record
ord-5caeb267308d4b75b89501a9b9f34d9e
Source dataset
uspto-grants-1979_10
Patent number
US04172208

Linked notes

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