tert-Butanol → Tert-butyl acetoacetate

HRID 1031231Notes

Reaction equation

HRID 1031231 reaction equation
[C:1]([OH:5])([CH3:4])([CH3:3])[CH3:2].C([O-])(=O)C.[Na+].[CH2:11]=[C:12]1[O:16][C:14](=[O:15])[CH2:13]1>>[O:16]=[C:12]([CH3:11])[CH2:13][C:14]([O:5][C:1]([CH3:4])([CH3:3])[CH3:2])=[O:15]

Participants

4

Reactant 3

HCID 6386tert-ButanolHCID 12661Diketene2×HCID 517045Sodium Acetate

Product 1

HCID 15538Tert-butyl acetoacetate

Procedure

To tert-butyl alcohol [79 g (1.07 mol.)] heated at 80° to 85° C. was added, while stirring, anhydrous sodium acetate [0.4 g (4.8 mmol.)]. To the mixture was then added dropwise diketene [96 g (1.14 mol.)] in the course of 2.5 hours. During the initial 15 minutes, the addition was carried out at 60° to 70° C., then while heating up to 110° to 115° C. After the dropwise addition of diketene, the resulting blackish brown reaction mixture was stirred for further 30 minutes, immediately followed by distillation under reduced pressure to afford tert-butyl 3-oxobutyrate, b.p. 85° C./20mmHg. The yield was 135 g (80%).

Workup

  1. additionwas added
  2. additionDuring the initial 15 minutes, the addition
  3. customwas carried out at 60° to 70° C.
  4. temperaturewhile heating up to 110° to 115° C
  5. stirringthe resulting blackish brown reaction mixture was stirred for further 30 minutes
  6. distillationimmediately followed by distillation under reduced pressure

Sources & evidence

ORD record
ord-cc7478c0dc1c408393536c5977072057
Source dataset
uspto-grants-1992_04
Patent number
US05109131

Reaction notes

Loading…