Hydrochloric Acid → Bis(2,4,6-trichlorophenyl) 2-[3-(trifluoromethyl)phenyl]propanedioate

HRID 341125Notes

Reaction equation

HRID 341125 reaction equation
[F:1][C:2]([F:19])([F:18])[C:3]1[CH:4]=[C:5]([CH:9]([C:14]([O:16][CH3:17])=[O:15])[C:10]([O:12][CH3:13])=[O:11])[CH:6]=[CH:7][CH:8]=1.[OH-].[Na+].[ClH:22].[Cl:23][C:24]1[CH:29]=[C:28]([Cl:30])[CH:27]=[C:26]([Cl:31])C=1O>O>[F:1][C:2]([F:18])([F:19])[C:3]1[CH:4]=[C:5]([CH:9]([C:10]([O:12][C:13]2[C:26]([Cl:31])=[CH:27][C:28]([Cl:30])=[CH:29][C:24]=2[Cl:23])=[O:11])[C:14]([O:16][C:17]2[C:24]([Cl:22])=[CH:29][C:28]([Cl:30])=[CH:27][C:26]=2[Cl:31])=[O:15])[CH:6]=[CH:7][CH:8]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 69142,4,6-TrichlorophenolHCID 14798Sodium HydroxideHCID 57348216Dimethyl-(3-(trifluoromethyl)-phenyl)-malonate

Product 1

HCID 86690526Bis(2,4,6-trichlorophenyl) 2-[3-(trifluoromethyl)phenyl]propanedioateYield 50.43%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
60 °C

Procedure

The product of Step C was added to a solution of NaOH (25 g) in water (75 mL), and the reaction mixture was vigorously stirred under a nitrogen atmosphere at 60° C. for 8 minutes. The reaction mixture was then added to ice (100 g), and aqueous 6 N HCl was added until a pH of 1 was reached. The solution was extracted with ethyl acetate (3×100 mL), and the combined organic extracts were dried over magnesium sulfate, filtered, and concentrated under reduced pressure. Dichloromethane (200 mL) was added to the resulting white solid, followed by the addition of oxalyl chloride (5 mL) and N,N-dimethylformamide (0.5 mL). The reaction mixture was stirred at room temperature for 2 hours, followed by the addition of 2,4,6-trichlorophenol (10.528 g, 53.32 mmol). After stirring overnight at room temperature, the reaction mixture was concentrated under reduced pressure. Methanol was added to the resulting residue, and a solid slowly precipitated from the solution. The solid was collected by filtration to provide 8.161 g (50.43%) of the title product as a solid. 1H NMR (CDCl3) δ 7.91 (s, 1H), 7.83 (d, 1H), 7.70 (d, 1H), 7.59 (t, 1H), 7.37 (s, 4H), 5.38 (s, 1H).

Workup

  1. additionwas added until a pH of 1
  2. extractionThe solution was extracted with ethyl acetate (3×100 mL)
  3. dry with materialthe combined organic extracts were dried over magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure
  6. additionDichloromethane (200 mL) was added to the resulting white solid
  7. additionfollowed by the addition of oxalyl chloride (5 mL) and N,N-dimethylformamide (0.5 mL)
  8. stirringThe reaction mixture was stirred at room temperature for 2 hours
  9. stirringAfter stirring overnight at room temperature
  10. concentrationthe reaction mixture was concentrated under reduced pressure
  11. additionMethanol was added to the resulting residue
  12. customa solid slowly precipitated from the solution
  13. filtrationThe solid was collected by filtration

Sources & evidence

ORD record
ord-d743822888014dd5b072fb23035577f2
Source dataset
uspto-grants-2014_11
Patent number
US08895738B2

Reaction notes

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