Acrylic Acid → 3-{[4-(Ethoxycarbonyl)-2,5-dimethylphenyl]sulfanyl}propanoic acid

HRID 1275448Notes

Reaction equation

HRID 1275448 reaction equation
[SH-:1].[Na+].[CH2:3]([O:5][C:6](=[O:16])[C:7]1[CH:12]=[C:11]([CH3:13])[C:10](Br)=[CH:9][C:8]=1[CH3:15])[CH3:4].[C:17]([OH:21])(=[O:20])[CH:18]=[CH2:19].C(N(CC)CC)C>O.CN(C)C=O.C1(C)C=CC=CC=1>[CH2:3]([O:5][C:6]([C:7]1[C:8]([CH3:15])=[CH:9][C:10]([S:1][CH2:19][CH2:18][C:17]([OH:21])=[O:20])=[C:11]([CH3:13])[CH:12]=1)=[O:16])[CH3:4]

Participants

8

Reactant 4

HCID 6581Acrylic AcidHCID 8471TriethylamineHCID 28015Sodium hydrosulfideHCID 22118385HCID 22118385, compound

Product 1

HCID 221184403-{[4-(Ethoxycarbonyl)-2,5-dimethylphenyl]sulfanyl}propanoic acidYield 58%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 1140TolueneSolventHCID 6228DimethylformamideSolvent

Procedure

47 Grams (607 mmol) of a 70 wt % sodium hydrosulfide and 200 ml of toluene were added to 400 ml of N,N-dimethylformamide, and while the mixture was refluxed under heat for 2 hours, water was distilled off from the reaction system. When the temperature of the reaction mixture was decreased to about 100° C. while the reaction mixture was allowed to cool, 54 g (210 mmol) of ethyl-4-bromo-2,5-dimethylbenzoate was added, and the mixture was allowed to react at the same temperature for 6 hours. The reaction mixture was cooled to room temperature, 42 ml (607 mmol) of acrylic acid was dropwise added, then 84 ml (607 mmol) of triethylamine was added, and then the mixture was stirred at room temperature for about 1 day. The above procedures were all conducted under nitrogen atmosphere. The reaction mixture was diluted with water, and washed with ethyl acetate four times and with n-hexane once, and an aqueous layer was acidified with a 12N hydrochloric acid aqueous solution. A precipitated solid was collected by filtration under reduced pressure, washed with water, dissolved in ethyl acetate, washed with a saturated sodium chloride aqueous solution and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to give 34.3 g (yield 58%) of the titled compound.

Workup

  1. temperaturewhile the mixture was refluxed
  2. temperatureunder heat for 2 hours
  3. distillationwater was distilled off from the reaction system
  4. customwas decreased to about 100° C. while the reaction mixture
  5. temperatureto cool
  6. customto react at the same temperature for 6 hours
  7. washwashed with ethyl acetate four times and with n-hexane once
  8. filtrationA precipitated solid was collected by filtration under reduced pressure
  9. washwashed with water
  10. dissolutiondissolved in ethyl acetate
  11. washwashed with a saturated sodium chloride aqueous solution
  12. dry with materialdried over anhydrous sodium sulfate
  13. distillationThe solvent was distilled off under reduced pressure

Sources & evidence

ORD record
ord-00acf4a987fe4422bfe66ff7c56b9137
Source dataset
uspto-grants-2000_12
Patent number
US06159904

Reaction notes

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