Itaconic acid → Di-tert-butyl 2-methylidenebutanedioate

HRID 1486872Notes

Reaction equation

HRID 1486872 reaction equation
[CH3:1][C:2]([CH3:4])=[CH2:3].[CH2:5]=[C:6]([CH2:10][C:11]([OH:13])=[O:12])[C:7]([OH:9])=[O:8].S(=O)(=O)(O)O>>[CH2:5]=[C:6]([CH2:10][C:11]([O:13][C:2]([CH3:4])([CH3:3])[CH3:1])=[O:12])[C:7]([O:9][C:2]([CH3:4])([CH3:1])[CH3:3])=[O:8]

Participants

4

Reactant 3

HCID 811Itaconic acidHCID 1118Sulfuric AcidHCID 8255Isobutylene

Product 1

HCID 54559210Di-tert-butyl 2-methylidenebutanedioate

Procedure

2-Methylprop-1-ene (50.3 mL) was added to 2-methylenesuccinic acid (10.0 g) at −78 C, then sulfuric acid (0.819 mL) was added dropwise at −78 C, and then, the obtained mixture was stirred at room temperature at 4.5 to 3.5 atm for 22 hours in a sealed tube. After removal of 2-methylprop-1-ene at room temperature, the reaction mixture was diluted with ethyl acetate (100 mL) and added to a saturated aqueous solution of sodium bicarbonate (100 mL) at 0 C, followed by extraction with ethyl acetate. The extract was washed with brine and dried over anhydrous magnesium sulfate, and then, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate/hexane) to obtain the title compound (12.8 g).

Workup

  1. customAfter removal of 2-methylprop-1-ene at room temperature
  2. additionthe reaction mixture was diluted with ethyl acetate (100 mL)
  3. additionadded to a saturated aqueous solution of sodium bicarbonate (100 mL) at 0 C
  4. extractionfollowed by extraction with ethyl acetate
  5. washThe extract was washed with brine
  6. dry with materialdried over anhydrous magnesium sulfate
  7. distillationthe solvent was distilled off under reduced pressure
  8. customThe residue was purified by silica gel column chromatography (ethyl acetate/hexane)

Sources & evidence

ORD record
ord-e13b5f7919094445bc4e65b35e7b7a43
Source dataset
uspto-grants-2016_08
Patent number
US09428470B2

Reaction notes

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