Malic Acid → Di-sec-butyl-DL-malate

HRID 840955Notes

Reaction equation

HRID 840955 reaction equation
[C:1]([OH:9])(=[O:8])[CH:2]([CH2:4][C:5]([OH:7])=[O:6])[OH:3].[CH3:10][CH:11](O)[CH2:12][CH3:13]>>[CH:11]([O:8][C:1](=[O:9])[CH:2]([CH2:4][C:5]([O:7][CH:2]([CH2:4][CH3:5])[CH3:1])=[O:6])[OH:3])([CH2:12][CH3:13])[CH3:10]

Participants

3

Reactant 2

HCID 525Malic AcidHCID 6568(+-)-2-Butanol

Product 1

HCID 245378Di-sec-butyl-DL-malate

Conditions

Temperature
102 °C

Procedure

Di-sec-butyl-DL-malate was prepared using a procedure similar to Example 3. This compound was isolated as a bottoms product. To the reaction flask, DL-malic acid (80.23 g), 2-butanol (220 mL) and Amberlyst® 15 ion exchange resin (11.2 g) were added. The mixture was placed under nitrogen and heated to reflux. At 102° C., one phase started to collect in the Dean-Stark trap. The reaction was maintained at 102° C. for 4 hr. During this time, the water/alcohol azeotrope was removed as fresh alcohol was added. The product was dissolved in diethyl ether, separated from the catalyst via filtration over a bed of silica, washed with saturated sodium bicarbonate a number of times, washed once with water, and dried over magnesium sulfate. Diethyl ether was removed via rotary evaporation. Di-sec-butyl-DL-malate was obtained as a low viscosity, clear light yellow liquid with no detectable odor (46 g, 31% yield) after pumping on the sample in vacuo to remove residual 2-butanol.

Workup

  1. customDi-sec-butyl-DL-malate was prepared
  2. customThis compound was isolated as a bottoms product
  3. temperatureheated to reflux
  4. customAt 102° C.
  5. customto collect in the Dean-Stark trap
  6. customDuring this time, the water/alcohol azeotrope was removed as fresh alcohol
  7. additionwas added
  8. dissolutionThe product was dissolved in diethyl ether
  9. customseparated from the catalyst via filtration over a bed of silica
  10. washwashed with saturated sodium bicarbonate a number of times
  11. washwashed once with water
  12. dry with materialdried over magnesium sulfate
  13. customDiethyl ether was removed via rotary evaporation

Sources & evidence

ORD record
ord-a9382240e28d4ed48a6a9e71dcd10e43
Source dataset
uspto-grants-2002_04
Patent number
US06369146B1

Reaction notes

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