Benzyl Alcohol → Dibenzyl 2-hydroxybutanedioate

HRID 1064525Notes

Reaction equation

HRID 1064525 reaction equation
[C:1]([OH:9])(=[O:8])[CH:2]([CH2:4][C:5]([OH:7])=[O:6])[OH:3].[CH2:10](O)[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.[C:18]1([CH3:28])[CH:23]=[CH:22][C:21](S(O)(=O)=O)=[CH:20][CH:19]=1>C1(C)C=CC=CC=1>[CH2:10]([O:8][C:1](=[O:9])[CH:2]([CH2:4][C:5]([O:7][CH2:28][C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)=[O:6])[OH:3])[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1

Participants

5

Reactant 3

HCID 244Benzyl AlcoholHCID 525Malic AcidHCID 6101p-Toluenesulfonic acid

Product 1

HCID 13511133Dibenzyl 2-hydroxybutanedioateYield 28%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
105 °C

Procedure

Dibenzyl-DL-malate was prepared using the method of Lee et al, J. Chem. Soc. Perkin Trans. I, 1995, 2877. To a three-neck 1 L round-bottomed flask equipped with a reflux condenser, Dean-Stark trap, thermocouple and mechanical stirrer, were added DL-malic acid (81.96 g), benzyl alcohol (132.0 g), toluene (620 mL) and p-toluenesulfonic acid (1.165 g). The mixture was placed under nitrogen and heated to reflux. At 100° C., two phases started to collect in the Dean-Stark trap. After 2 hr, the reaction temperature was increased to 105° C. for 1.5 hr. The crude product was neutralized with saturated sodium bicarbonate and poured into a separatory funnel. The organic layer was washed with saturated sodium bicarbonate twice, washed once with water, and dried over magnesium sulfate. The toluene was removed via rotary evaporation. Two-thirds of the crude product were purified via column chromatography (20% ethyl acetate in hexane eluent). Residual benzyl alcohol was removed via vacuum distillation to give a low viscosity, clear, colorless oil with no detectable odor (49.9 g, 28% yield).

Workup

  1. customTo a three-neck 1 L round-bottomed flask equipped with a reflux condenser
  2. temperatureheated to reflux
  3. customAt 100° C.
  4. customto collect in the Dean-Stark trap
  5. additionpoured into a separatory funnel
  6. washThe organic layer was washed with saturated sodium bicarbonate twice
  7. washwashed once with water
  8. dry with materialdried over magnesium sulfate
  9. customThe toluene was removed via rotary evaporation
  10. customTwo-thirds of the crude product were purified via column chromatography (20% ethyl acetate in hexane eluent)
  11. customResidual benzyl alcohol was removed via vacuum distillation
  12. customto give a low viscosity

Sources & evidence

ORD record
ord-7630427b08d84da79a06c97586e88426
Source dataset
uspto-grants-2005_11
Patent number
US06969738B2

Reaction notes

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