Pyridine → Dimethyl 5-[[(Trifluoromethyl)sulfonyl]oxy]isophthalate

HRID 498155Notes

Reaction equation

HRID 498155 reaction equation
[OH:1][C:2]1[CH:3]=[C:4]([C:12]([O:14][CH3:15])=[O:13])[CH:5]=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8].N1C=CC=CC=1.[F:22][C:23]([F:29])([F:28])[S:24](O)(=[O:26])=[O:25]>C1(C)C=CC=CC=1>[F:22][C:23]([F:29])([F:28])[S:24]([O:1][C:2]1[CH:11]=[C:6]([C:7]([O:9][CH3:10])=[O:8])[CH:5]=[C:4]([CH:3]=1)[C:12]([O:14][CH3:15])=[O:13])(=[O:26])=[O:25]

Participants

5

Reactant 3

HCID 1049PyridineHCID 62406Trifluoromethanesulfonic acidHCID 830651,3-Benzenedicarboxylic acid, 5-hydroxy-, 1,3-dimethyl ester

Product 1

HCID 10617248Dimethyl 5-[[(Trifluoromethyl)sulfonyl]oxy]isophthalateYield 95%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

Into a 5 liter four-necked flask equipped with a thermometer, a Dimroth condenser, a calcium chloride tube and a stirrer, 190.0 g (0.904 moles) of dimethyl 5-hydroxyisophthalate, 3 liters of dehydrated toluene and 214.7 g (2.718 moles) of dehydrated pyridine were placed and the resultant mixture was cooled at −30° C. under stirring. To the cooled mixture, 510.2 g (1.808 moles) of anhydrous trifluoromethanesulfonic acid was slowly added dropwise with sufficient care so that the temperature did not exceed −25° C. It took 1 hour to complete the addition. After the addition was completed, the temperature of the reaction was elevated at 0° C. and the reaction was allowed to proceed for 1 hour. Then, the temperature was elevated to the room temperature and the reaction was allowed to proceed for 5 hours. The obtained reaction mixture was poured into 4 liters of ice water and separated into an aqueous layer and an organic layer. The aqueous layer was treated twice by extraction with 500 ml of toluene and the extract was combined with the organic layer. The obtained organic layer was washed twice with 3 liters of water and dried with 100 g of anhydrous magnesium sulfate. From the resultant mixture, anhydrous magnesium sulfate was removed by filtration and toluene was removed by distillation using a rotary evaporator. After drying under a reduced pressure, 294.0 g of dimethyl 5-trifluoromethanesulfonyloxyisophthalate was obtained as a light yellow solid substance (the yield: 95%). The crude product obtained above was recrystallized from hexane and white needle crystals were obtained. The obtained crystals were used for the next reaction.

Workup

  1. customInto a 5 liter four-necked flask equipped with a thermometer
  2. customdid not exceed −25° C
  3. additionthe addition
  4. additionAfter the addition
  5. customwas elevated at 0° C.
  6. waitto proceed for 1 hour
  7. customwas elevated to the room temperature
  8. waitto proceed for 5 hours
  9. customThe obtained reaction mixture
  10. customseparated into an aqueous layer
  11. additionThe aqueous layer was treated twice by extraction with 500 ml of toluene
  12. washThe obtained organic layer was washed twice with 3 liters of water
  13. dry with materialdried with 100 g of anhydrous magnesium sulfate
  14. customFrom the resultant mixture, anhydrous magnesium sulfate was removed by filtration and toluene
  15. customwas removed by distillation
  16. customa rotary evaporator
  17. customAfter drying under a reduced pressure

Sources & evidence

ORD record
ord-67494726feb2441c87dd347d365eff7b
Source dataset
uspto-grants-2005_09
Patent number
US06949674B2

Reaction notes

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