3-Chlorobenzoic Acid → Tert-butylperoxy 3-chlorobenzoate

HRID 398259Notes

Reaction equation

HRID 398259 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:8]=[CH:9][CH:10]=1)[C:5]([OH:7])=[O:6].[OH-].[Na+].ClC(OC(CC)C)=O.[CH3:21][C:22]([O:25][OH:26])([CH3:24])[CH3:23]>C(OCC)C.O>[Cl:1][C:2]1[CH:3]=[C:4]([CH:8]=[CH:9][CH:10]=1)[C:5]([O:7][O:26][O:25][C:22]([CH3:24])([CH3:23])[CH3:21])=[O:6]

Participants

7

Reactant 4

HCID 4473-Chlorobenzoic AcidHCID 6410tert-Butyl hydroperoxideHCID 14798Sodium Hydroxide2×HCID 11829505sec-Butyl chloroformate

Product 1

HCID 23002557Tert-butylperoxy 3-chlorobenzoateYield 80%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 3283Diethyl EtherSolvent

Conditions

Temperature
5 °C

Procedure

To a well-stirred reaction vessel equipped with a thermometer and a pH-electrode were added 39 g of water and 0.20 g of Arquad CB50 at 5° C. After the addition of 0.05 mole of 3-chlorobenzoic acid the pH was adjusted to 6 using a 10 wt % aqueous NaOH solution. Then, 0.05 mole of sec-butyl chloroformate was dosed within 5 min at 5° C. During this time and a post-reaction time of 165 min at 5° C. the pH was kept at a value between 6 and 9. After the post-reaction, 8.1 g of TBHP were added (0.063 mole), and using a 33 wt % aqueous NaOH solution the pH was adjusted to 13 within 5 min while keeping the temperature at 5° C. During a post-reaction time of 75 min at 5° C. the pH was maintained at 13. Then, 25 g of diethyl ether were added, and the reaction mixture was allowed to separate. After separation of the water layer, the organic layer was washed, twice with 40 g of a 15 wt % aqueous NaCl solution. The ether layer was dried over MgSO4, and the diethyl ether was removed under vacuum. As a result, 9.4 g of tert-butylperoxy 3-chlorobenzoate having a content of 95.4% were obtained in a yield of 80% based on 3-chlorobenzoic acid. The molar ratio of tert-butylperoxy 3-chlorobenzoate to tert-butylperoxy 1-methyl-1-propylcarbonate was calculated to be 97.6:2.4.

Workup

  1. customTo a well-stirred reaction vessel
  2. customequipped with a thermometer
  3. customa post-reaction time of 165 min
  4. customat 5° C.
  5. additionwere added (0.063 mole)
  6. customat 5° C
  7. customto separate
  8. customAfter separation of the water layer
  9. washthe organic layer was washed, twice with 40 g of a 15 wt % aqueous NaCl solution
  10. dry with materialThe ether layer was dried over MgSO4
  11. customthe diethyl ether was removed under vacuum

Sources & evidence

ORD record
ord-09b63d7a191a4ab991a836e3f9ba3a69
Source dataset
uspto-grants-2003_08
Patent number
US06610880B1

Reaction notes

Loading…