Methane → 2-sulfoterephthalic Acid

HRID 2211192Notes

Reaction equation

HRID 2211192 reaction equation
[O-:1][S:2]([O-:5])(=O)=[O:3].[Ca+2].[C:7]([OH:18])(=[O:17])[C:8]1[CH:16]=[CH:15][C:11]([C:12]([OH:14])=[O:13])=[CH:10][CH:9]=1.OS(O)(=O)=O.O=S(=O)=O.C>O.[Hg]>[S:2]([C:15]1[CH:16]=[C:8]([C:7]([OH:18])=[O:17])[CH:9]=[CH:10][C:11]=1[C:12]([OH:14])=[O:13])([OH:5])(=[O:3])=[O:1]

Participants

7

Reactant 4

HCID 297MethaneHCID 7489Terephthalic AcidHCID 24497Calcium SulfateHCID 24681Fuming sulfuric acid

Product 1

HCID 98785022-sulfoterephthalic Acid

Reagents, catalysts & solvents 2

HCID 23931MercuryCatalystHCID 962WaterSolvent

Procedure

A 500 ml 3-neck flask equipped with an air condenser (connected to Drierite tube), stirrer and thermometer, was charged with terephthalic acid (100 g), oleum (190 g, 3.76 mol of 27-33%) and mercury (2.7 g). The light brown solution was stirred at 255°-260° C. for 7 hours. The color of the mixture changed to dark brown. The reaction mixture was cooled overnight to room temperature, a precipitate had formed. The mixture was then poured very slowly and portionwise into a beaker of ice cold water, (132 ml), whereupon a homogenous solution was formed. Upon cooling, a precipitate formed and the whole was allowed to stand for 2 hours. The precipitate was filtered. The solid acid thus obtained was dissolved in 750 ml of hot H2O, charcoal was added and the mixture allowed to reflux for 35 minutes. It was then filtered hot, passed through a pad of celite, and the filtrate was cooled in an ice bath. The solution was saturated with gaseous hydrogen chloride (1 hour) and the product precipitated out. The precipitate was collected by filtration, dried over P2O5 in a vacuum dessicator for 48 hours (79 g, 53%), and recrystallized 3 times from acetic acid. Further purification was carried out as follows. The material was dissolved in 200 ml of hot acetic acid and allowed to reflux for 30 minutes. It was then filtered hot and the filtrate was stored in a refrigerator overnight. The precipitate which resulted was filtered and dried at room temperature for several hours and then under high vacuum. The dry pale yellow product (61 g, 41%) melted at 244°-249° C. (Lit 254°-258° C.); Rf=0.35 (1 ml acetic acid: 1 ml H2O: 1.5 ml n-BuOH).

Workup

  1. temperatureThe reaction mixture was cooled overnight to room temperature
  2. customa precipitate had formed
  3. customwas formed
  4. temperatureUpon cooling
  5. customa precipitate formed
  6. waitto stand for 2 hours
  7. filtrationThe precipitate was filtered
  8. customThe solid acid thus obtained
  9. temperatureto reflux for 35 minutes
  10. filtrationIt was then filtered hot
  11. temperaturethe filtrate was cooled in an ice bath
  12. customwas saturated with gaseous hydrogen chloride (1 hour)
  13. customthe product precipitated out
  14. filtrationThe precipitate was collected by filtration
  15. dry with materialdried over P2O5 in a vacuum dessicator for 48 hours (79 g, 53%)
  16. customrecrystallized 3 times from acetic acid
  17. customFurther purification
  18. dissolutionThe material was dissolved in 200 ml of hot acetic acid
  19. temperatureto reflux for 30 minutes
  20. filtrationIt was then filtered hot
  21. customwas stored in a refrigerator overnight
  22. customThe precipitate which resulted
  23. filtrationwas filtered
  24. customdried at room temperature for several hours
  25. customThe dry pale yellow product (61 g, 41%) melted at 244°-249° C. (Lit 254°-258° C.)

Sources & evidence

ORD record
ord-474944d250df4df68cc45c03ea39decd
Source dataset
uspto-grants-1995_10
Patent number
US05462991

Reaction notes

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