4-Hydroxybenzoic Acid → (1,1'-Biphenyl)-2,3'-diol

HRID 1845792Notes

Reaction equation

HRID 1845792 reaction equation
[OH:1][C:2]1C=C[C:5]([C:6](O)=O)=[CH:4][CH:3]=1.[C:11]1(O)[C:12](=[CH:14][C:15](=[CH:17][CH:18]=1)[OH:16])[CH3:13].O.C1(C)C=CC(S(O)(=O)=O)=CC=1.CC1C=CC=CC=1C>C(OCC)(=O)C.C1(C)C=CC=CC=1>[CH:5]1[CH:6]=[C:13]([C:12]2[CH:11]=[CH:18][CH:17]=[C:15]([OH:16])[CH:14]=2)[C:2]([OH:1])=[CH:3][CH:4]=1

Participants

7

Reactant 4

HCID 1354-Hydroxybenzoic AcidHCID 7237O-XyleneHCID 7253MethylhydroquinoneHCID 521998p-Toluenesulfonic acid monohydrate

Product 1

HCID 33665(1,1'-Biphenyl)-2,3'-diol

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
178 °C

Procedure

A mixture consisting of 276.24 g 4-hydroxybenzoic acid, 124.12 g toluhydroquinone, 20.00 g p-toluenesulfonic acid monohydrate and 1800 ml o-xylene in a chemical reactor equipped with stirrer, thermometer and separator for the azeotropic removal of water under reflux is heated to reflux in an oil bath of 178° C. Refluxing and separation of water starts at a vapour temperature of ca. 137° C. and is continued for a total of 18 hours with ca. 35 ml of water separated. A beige, slightly viscous suspension is formed. It is cooled to 65° C. and 1250 ml of toluene are added. After further cooling to 25° C. the mixture is stirred for 30 minutes at this temperature and then filtered. The crystalline filter residue is washed with toluene to yield a beige solid. The orange filtrates are discarded. The solid is suspended in 1250 ml ethyl acetate and stirred for 1 hour at 45° C. The suspension is cooled to 6° C., filtered, the filter residue washed with ca. 800 ml of ice-cold ethyl acetate and dried in vacuum at 50° C. to constant weight to yield 341.60 g nearly colourless diphenol (XIV). HPLC purity is 99 area %

Workup

  1. customequipped with stirrer
  2. customthermometer and separator for the azeotropic removal of water
  3. temperatureunder reflux
  4. temperatureis heated
  5. temperatureRefluxing
  6. customseparation of water
  7. customstarts at a vapour temperature of ca. 137° C.
  8. customis continued for a total of 18 hours with ca. 35 ml of water
  9. customseparated
  10. customA beige, slightly viscous suspension is formed
  11. temperatureIt is cooled to 65° C.
  12. temperatureAfter further cooling to 25° C. the mixture
  13. filtrationfiltered
  14. washThe crystalline filter residue is washed with toluene
  15. customto yield a beige solid
  16. stirringstirred for 1 hour at 45° C
  17. temperatureThe suspension is cooled to 6° C.
  18. filtrationfiltered
  19. washthe filter residue washed with ca. 800 ml of ice-cold ethyl acetate
  20. customdried in vacuum at 50° C. to constant weight

Sources & evidence

ORD record
ord-e5bfe65051ad406aab8ced1554ae45bf
Source dataset
uspto-grants-2015_02
Patent number
US08951616B2

Reaction notes

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