Sodium Bromide → [1,1'-Biphenyl]-2,3,4,5-tetracarboxylic acid

HRID 1090412Notes

Reaction equation

HRID 1090412 reaction equation
Cl[C:2]1[CH:3]=[C:4]([C:12]([O:14]C)=[O:13])[C:5]([C:8]([O:10]C)=[O:9])=[CH:6][CH:7]=1.[Na+].[Br-]>[Zn].Cl[Ni]Cl.CC(N(C)C)=O>[C:2]1([C:4]2[CH:3]=[CH:2][CH:7]=[CH:6][CH:5]=2)[CH:7]=[C:6]([C:12]([OH:14])=[O:13])[C:5]([C:8]([OH:10])=[O:9])=[C:4]([C:12]([OH:14])=[O:13])[C:3]=1[C:8]([OH:10])=[O:9]

Participants

6

Reactant 2

HCID 253881Sodium BromideHCID 607564Dimethyl 4-chlorophthalate

Product 1

HCID 19935321[1,1'-Biphenyl]-2,3,4,5-tetracarboxylic acidYield 97%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 24385Nickel DichlorideCatalystHCID 31374DimethylacetamideSolvent

Procedure

Into a nitrogen-flushed reaction flask, under N2 atmosphere, was added 4.50 g (20 mmol) of dimethyl 4-chloro-benzenedicarboxylate (CBDM) 5.2 g (20 mmol) of anhydrous NaBr, 2.68 g (40 mmol) zinc powder and 0.52 g (0.8 mmol) (Ph3P)2.NiCl2. The mixture was maintained under a nitrogen atmosphere while 30 ml of DMAC, dried over molecular sieves was added. The mixture was heated with stirring to 80.C in one hour. The color of the solution turned from bluish-green to brown in 0 5 hours. After 4 hours, the solution was cooled, filtered and the solvent was removed on a rotary evaporator. Chloroform was added and the solution filtered again. The filtrate was washed three times with saturated aqueous NaCl. CHCl3 was removed. 50 ml of 20% NaOH solution was added to the residue and and the mixtures was heated to reflux for 4 hours. The mixture was filtered and the filtrate was acidified with concentrated hydrochloric acid. A white precipitate formed, was filtered, washed with H2O several times, and dried in an oven at 100° C. to afford 3.2 g of biphenyltetracarboxylic acid (97% yield). The tetra acid was heated slowly to 210°-220° C. to dehydrate and afford biphenyldianhydride, m.p. 299°-302° C.

Workup

  1. customInto a nitrogen-flushed
  2. customreaction flask
  3. customdried over molecular sieves
  4. additionwas added
  5. temperatureThe mixture was heated
  6. custombrown in 0 5 hours
  7. waitAfter 4 hours
  8. temperaturethe solution was cooled
  9. filtrationfiltered
  10. customthe solvent was removed on a rotary evaporator
  11. additionChloroform was added
  12. filtrationthe solution filtered again
  13. washThe filtrate was washed three times with saturated aqueous NaCl
  14. customCHCl3 was removed
  15. addition50 ml of 20% NaOH solution was added to the residue
  16. temperaturethe mixtures was heated
  17. temperatureto reflux for 4 hours
  18. filtrationThe mixture was filtered
  19. customA white precipitate formed
  20. filtrationwas filtered
  21. washwashed with H2O several times
  22. customdried in an oven at 100° C.

Sources & evidence

ORD record
ord-c2f789889ae34e238e47cf57f88e464e
Source dataset
uspto-grants-1992_01
Patent number
US05081281

Reaction notes

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