Ethanol → ethyl 2-acetyl-3-ethoxybut-2-enoate

HRID 2178752Notes

Reaction equation

HRID 2178752 reaction equation
[C:1]([O:7][CH2:8][CH3:9])(=[O:6])[CH2:2][C:3]([CH3:5])=[O:4].[CH2:10]([O:12][C:13](OCC)=[CH2:14])[CH3:11].CCO>[O-]CC.[Na+].CCOC(C)=O>[C:3]([C:2](=[C:10]([O:12][CH2:13][CH3:14])[CH3:11])[C:1]([O:7][CH2:8][CH3:9])=[O:6])(=[O:4])[CH3:5]

Participants

6

Reactant 3

HCID 702EthanolHCID 8868Ethyl AcetoacetateHCID 1376731,1-Diethoxyethene

Product 1

HCID 231474ethyl 2-acetyl-3-ethoxybut-2-enoateYield 89%

Reagents, catalysts & solvents 2

HCID 2723922Sodium ethoxideCatalystHCID 8857Ethyl AcetateSolvent

Procedure

A 5 L 4-neck flask equipped with a mechanical stirrer, condenser, thermowell, addition funnel and N2 inlet was charged with ethyl acetoacetate (493.1 g, 483 mL, 3.7931 mol, 1.0 equiv) and sodium ethoxide (3.1 g, 0.046 mol, 1.2 mol %). Ketene diethylacetal (880.0 g, 1000 mL, 7.5862 mol, 2.0 equiv) was added over 1 hr maintaining the reaction temperature at <22° C. by external cooling. When addition was complete, the reaction mixture was heated at 85° C.±5° C. for 7.5 hr. The yellow brown reaction mixture was cooled to room temperature and stirred overnight. Much of the lower boiling components [EtOH, EtOAc, Me(OEt)3] were stripped on a roto-evaporator (bath temperature ˜65° C.). The residual yellow-orange oil was distilled, collecting the fraction with bp 100-107° C. (1.8-2.1 Torr) to give 675.2 g (89%) of product as a yellow liquid.

Workup

  1. customA 5 L 4-neck flask equipped with a mechanical stirrer, condenser
  2. additionthermowell, addition funnel and N2 inlet
  3. temperaturemaintaining the reaction temperature at <22° C. by external cooling
  4. additionWhen addition
  5. temperaturethe reaction mixture was heated at 85° C.±5° C. for 7.5 hr
  6. customwere stripped on a roto-evaporator (bath temperature ˜65° C.)
  7. distillationThe residual yellow-orange oil was distilled
  8. customcollecting the fraction with bp 100-107° C. (1.8-2.1 Torr)

Sources & evidence

ORD record
ord-5f5f82ec29a9484ebf51e25907de1c90
Source dataset
uspto-grants-2015_06
Patent number
US09067921B2

Reaction notes

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