Succinic Acid → Di-tert-butyl succinate

HRID 1416687Notes

Reaction equation

HRID 1416687 reaction equation
[C:1]([OH:8])(=[O:7])[CH2:2][CH2:3][C:4]([OH:6])=[O:5].[C:9](O)([CH3:12])([CH3:11])[CH3:10].[CH2:14]=[C:15]([CH3:17])[CH3:16].S(=O)(=O)(O)O.[OH-].[Na+]>>[C:1]([O:8][C:15]([CH3:17])([CH3:16])[CH3:14])(=[O:7])[CH2:2][CH2:3][C:4]([O:6][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:5]

Participants

6

Reactant 5

HCID 1110Succinic AcidHCID 1118Sulfuric AcidHCID 6386tert-ButanolHCID 8255IsobutyleneHCID 14798Sodium Hydroxide

Product 1

HCID 10966312Di-tert-butyl succinateYield 79.4%

Conditions

Temperature
276.5 K

Procedure

An autoclave is charged with 212.5 g (1.80 mol) of succinic acid and 166.8 g (2.25 mol) of tert-butanol and then 808 g (14.40 mol) of isobutene are forced in at 263 K jacket temperature. After the addition is complete, 108.1 g (1.08 mol) of 98% sulfuric acid are pumped in over 70 minutes at a temperature of 268 to 275 K in the vessel. The reaction mixture is then stirred for 30 minutes at a temperature of 275 to 278 K in the vessel and, after increasing the temperature to 293 to 295 K, it is stirred for another 14 hours at that temperature and at a pressure from (4×105) to (5×105) Pa. The reaction mixture is then forced into an agitated mixture consisting of 1000 g of ice and 300 ml (3 mol) of 30% sodium hydroxide solution and the autoclave is then flushed with 200-300 ml of petroleum ether which is also added to the mixture of ice/sodium hydroxide solution. The mixture is warmed to room temperature and the organic phase is separated. The aqueous phase is extracted 3 times with 100-150 ml of petroleum ether each and the organic phases are then combined. The organic phases are concentrated in a rotary evaporator at a bath temperature of 323 K and (3×103) Pa (final value). To purify the crude product it is fractionally distilled, with addition of about 0.5 g of magnesium oxide, via a 30 cm packed column (Raschig rings 5×5 mm) under vacuum. The ester content of the individual fractions is determined by gas chromatography. Fractions having ester contents of <97% by weight are distilled again. After a total of 3 distillations, 329.3 g (79.4% of theory) of di-tert-butyl succinate are obtained having a 97.2% purity (percent per area), determined by gas chromatography, corresponding to 7.2% of theory a 100%.

Workup

  1. customare forced in at 263 K jacket temperature
  2. additionAfter the addition
  3. customare pumped in over 70 minutes at a temperature of 268 to 275 K in the vessel
  4. temperatureafter increasing the temperature to 293 to 295 K
  5. stirringit is stirred for another 14 hours at that temperature and at a pressure from (4×105) to (5×105) Pa
  6. customthe autoclave is then flushed with 200-300 ml of petroleum ether which
  7. additionis also added to the mixture of ice/sodium hydroxide solution
  8. temperatureThe mixture is warmed to room temperature
  9. customthe organic phase is separated
  10. extractionThe aqueous phase is extracted 3 times with 100-150 ml of petroleum ether each and the organic phases
  11. concentrationThe organic phases are concentrated in a rotary evaporator at a bath temperature of 323 K and (3×103) Pa (final value)
  12. customTo purify the crude product it
  13. distillationis fractionally distilled, with addition of about 0.5 g of magnesium oxide, via a 30 cm
  14. distillationare distilled again

Sources & evidence

ORD record
ord-966a6a6fb3bf4862a268ad3bb904838c
Source dataset
uspto-grants-1999_06
Patent number
US05914426

Reaction notes

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