Methyl chloroformate → Carbonic acid, 2-bromo-4-fluorophenyl methyl ester

HRID 619884Notes

Reaction equation

HRID 619884 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[CH:4][CH:3]=1.[Br:9]Br.Cl[C:12]([O:14][CH3:15])=[O:13].[OH-].[Na+]>O1CCOCC1>[C:12](=[O:13])([O:14][CH3:15])[O:8][C:5]1[CH:6]=[CH:7][C:2]([F:1])=[CH:3][C:4]=1[Br:9]

Participants

6

Reactant 4

HCID 6586Methyl chloroformateHCID 97324-FluorophenolHCID 14798Sodium HydroxideHCID 24408Bromine

Product 1

HCID 13268177Carbonic acid, 2-bromo-4-fluorophenyl methyl esterYield 97.3%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

A stirred solution of 561 g (5.0 moles) of 4-fluorophenol in 600 mL of dioxane was cooled in an ice-water bath and 831 g (5.2 moles) of bromine was added dropwise. The complete addition required 1.5 hours, during which the reaction mixture temperature was maintained at 14°-25° C. Following the addition, the ice-water bath was removed, and the reaction mixture temperature rose to 35° C. The reaction mixture was stirred for two hours, then 600 mL of water, followed by 420 mL of 10.8N aqueous sodium hydroxide were added dropwise over 30 minutes and 1 hour respectively. Upon complete addition, the reaction mixture was cooled to 0°-10° C., and 591 g (6.15 moles) of methyl chloroformate was added dropwise over four hours. Upon complete addition, the reaction mixture was allowed to warm to ambient temperature and was stirred for 17 hours. After this time, 450 g of aqueous 50% sodium hydroxide was added to neutralize the reaction mixture. The resultant solid was collected by filtration, and the filter cake washed with two 500 mL portions of water. The solid was dried under reduced pressure to give 1211 g of 2-bromo-4-fluorophenyl methyl carbonate; m.p. 75°-78° C.

Workup

  1. additionThe complete addition required 1.5 hours
  2. temperatureduring which the reaction mixture temperature was maintained at 14°-25° C
  3. additionthe addition
  4. customthe ice-water bath was removed
  5. customrose to 35° C
  6. additionwere added dropwise over 30 minutes and 1 hour respectively
  7. additionUpon complete addition
  8. temperaturethe reaction mixture was cooled to 0°-10° C.
  9. additionUpon complete addition
  10. stirringwas stirred for 17 hours
  11. filtrationThe resultant solid was collected by filtration
  12. washthe filter cake washed with two 500 mL portions of water
  13. customThe solid was dried under reduced pressure

Sources & evidence

ORD record
ord-0ce2d03c444743b9a4a62ddab5bce405
Source dataset
uspto-grants-1989_04
Patent number
US04818276

Reaction notes

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