tert-Butanol → Tert-butyl 3-chloropivaloate

HRID 2167892Notes

Reaction equation

HRID 2167892 reaction equation
[Cl:1][CH2:2][C:3]([CH3:8])([CH3:7])[C:4]([OH:6])=[O:5].[C:9](O)([CH3:12])([CH3:11])[CH3:10].C1CCN2C(=NCCC2)CC1.C([O-])(O)=O.[Na+]>CN(C=O)C>[C:9]([O:5][C:4](=[O:6])[C:3]([CH3:8])([CH3:7])[CH2:2][Cl:1])([CH3:12])([CH3:11])[CH3:10]

Participants

6

Reactant 4

HCID 6386tert-ButanolHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 83542beta-Chloropivalic acidHCID 516892Sodium Bicarbonate

Product 1

HCID 22590969Tert-butyl 3-chloropivaloateYield 47.4%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
40 °C

Procedure

prepared as follows: To a solution of 3-chloro-2,2-dimethylpropionic acid (5.00 g; 36.6 mmol) in DMF (25 mL) was added N,N′-carbonyldiimidazole (5.94 g; 36.6 mmol) and the resulting mixture was stirred for 1 hour at 40° C. Subsequently, tert-butyl alcohol (7.1 mL; 73 mmol) and DBU (5.5 mL; 36.6 mmol) were added and the mixture stirred overnight at 40° C. After cooling to RT, 5% aqueous NaHCO3 solution (50 mL) was added to the mixture and stirred for another 15 minutes. The reaction mixture was extracted with EtOAc. The organic layer was dried (Na2SO4), concentrated in vacuo and purified by column chromatography (SiO2, Et2O:hexanes 1:1) to afford 3-chloro-2,2-dimethyl-propionic acid tert-butyl ester (3.34 g).

Workup

  1. customprepared
  2. stirringthe mixture stirred overnight at 40° C
  3. temperatureAfter cooling to RT
  4. stirringstirred for another 15 minutes
  5. extractionThe reaction mixture was extracted with EtOAc
  6. dry with materialThe organic layer was dried (Na2SO4)
  7. concentrationconcentrated in vacuo
  8. custompurified by column chromatography (SiO2, Et2O:hexanes 1:1)

Sources & evidence

ORD record
ord-ec386ed62e59422c9e8cfbd7b6562bdb
Source dataset
uspto-grants-2015_06
Patent number
US09045441B2

Reaction notes

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