Malic Acid → bis(2-methylpropyl) 2-hydroxybutanedioate

HRID 840954Notes

Reaction equation

HRID 840954 reaction equation
[C:1]([OH:9])(=[O:8])[CH:2]([CH2:4][C:5]([OH:7])=[O:6])[OH:3].[CH3:10][CH:11]([CH3:14])[CH2:12]O>>[CH2:10]([O:8][C:1](=[O:9])[CH:2]([CH2:4][C:5]([O:7][CH2:10][CH:11]([CH3:14])[CH3:12])=[O:6])[OH:3])[CH:11]([CH3:14])[CH3:12]

Participants

3

Reactant 2

HCID 525Malic Acid2×HCID 6560Isobutanol2×

Product 1

HCID 225819bis(2-methylpropyl) 2-hydroxybutanedioate

Conditions

Temperature
108 °C

Procedure

Diisobutyl-DL-malate was prepared by esterification of DL-malic acid with isobutyl alcohol. To a three-neck 1 L round-bottomed flask equipped with a reflux condenser, Dean-Stark trap, septum, thermocouple and mechanical stirrer, were added DL-malic acid (75.91 g), 2-methyl-1-propanol (210 mL) and Amberlyst® 15 ion exchange resin (10 g). The mixture was placed under nitrogen and heated to reflux. At 106° C., two phases started to collect in the Dean-Stark trap. The reaction temperature was maintained at 108° C. for 2 hr 15 min and the water was continuously removed via the Dean-Stark trap. As collection in the Dean-Stark trap slowed, the reaction temperature was increased to 115° C. and fresh alcohol (50 mL) was added to the reaction. The reaction was heated to 120° C. and more alcohol (50 mL) was added. At this point, no more water collected in the Dean-Stark trap. The product was separated from the catalyst via filtration. The crude yellow liquid was purified via vacuum distillation. Diisobutyl-DL-malate was obtained as a low viscosity, clear, colorless liquid with a slight pleasant odor (120.4 g, 86.3% yield).

Workup

  1. customTo a three-neck 1 L round-bottomed flask equipped with a reflux condenser
  2. temperatureheated to reflux
  3. customAt 106° C.
  4. customto collect in the Dean-Stark trap
  5. customthe water was continuously removed via the Dean-Stark trap
  6. customAs collection in the Dean-Stark trap
  7. temperaturethe reaction temperature was increased to 115° C.
  8. additionfresh alcohol (50 mL) was added to the reaction
  9. temperatureThe reaction was heated to 120° C.
  10. additionmore alcohol (50 mL) was added
  11. customAt this point, no more water collected in the Dean-Stark trap
  12. customThe product was separated from the catalyst via filtration
  13. distillationThe crude yellow liquid was purified via vacuum distillation

Sources & evidence

ORD record
ord-ac3fdc1e39dd4afcabc78e3a9ce4826c
Source dataset
uspto-grants-2002_04
Patent number
US06369146B1

Reaction notes

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