Hydrochloric Acid → HCID 17912068, compound

HRID 1402818Notes

Reaction equation

HRID 1402818 reaction equation
[C:1]1([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)[CH:6]=[CH:5][C:4]([CH:7]=O)=[CH:3][CH:2]=1.[C:15]([O:21][CH2:22][CH3:23])(=[O:20])[CH2:16]C(C)=O.[OH-:24].[Na+].Cl>C(O)C.C(Cl)(=O)C.ClCCl>[C:1]1([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)[CH:6]=[CH:5][C:4]([CH:7]2[CH2:16][C:15](=[O:20])[O:21][C:22](=[O:24])[CH2:23]2)=[CH:3][CH:2]=1

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 8868Ethyl AcetoacetateHCID 14798Sodium HydroxideHCID 76689(1,1'-Biphenyl)-4-carboxaldehyde

Product 1

HCID 17912068HCID 17912068, compoundYield 42.9%

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 6344DichloromethaneSolventHCID 6367Acetyl chlorideSolvent

Procedure

To a solution of commercial 4-biphenylcarboxaldehyde (5.37 g) and ethyl acetoacetate (7.68 g) in ethanol (10 ml) piperidine (1 ml) was added with stirring at rt. The yellow solution was kept at rt overnight. The precipitate was collected by suction filtration and washed with ethanol. After drying in vacuo 10.2 g of a faint yellowish solid (the bis-adduct of acetoacetate to the aldehyde) was isolated. The finely divided solid was added in portions to 40% NaOH (120 g) with stirring. The resulting yellow slurry was stirred at reflux for 2 h. After cooling in an ice bath the mixture was acidified by portionwise addition of conc. HCl (110 ml) to give a yellowish precipitate. The solid was collected by suction filtration and washed with water. After drying in vacuo slightly impure 3-(4-biphenyl-4-yl)glutaric acid (8.1 g) was obtained. The suspension of finely divided 3-(4-biphenyl-4-yl)glutaric acid in acetyl chloride (28 ml) was heated to reflux with stirring for 2 h. After cooling to rt precipitation of the product is completed by addition of petrol ether (100 ml). The precipitate is isolated by suction filtration, washed with petrol ether, and dried at the air to give a crude (4.39 g). The crude was dissolved in dichloromethane (110 ml), filtered, and the filtrate concentrated in vacuo to afford 3-(biphenyl-4-yl)glutaric anhydride (3.37 g) as colourless solid.

Workup

  1. filtrationThe precipitate was collected by suction filtration
  2. washwashed with ethanol
  3. dry with materialAfter drying in vacuo 10.2 g of a faint yellowish solid (the bis-adduct of acetoacetate to the aldehyde)
  4. customwas isolated
  5. stirringwith stirring
  6. stirringThe resulting yellow slurry was stirred
  7. temperatureat reflux for 2 h
  8. temperatureAfter cooling in an ice bath the mixture
  9. customto give a yellowish precipitate
  10. filtrationThe solid was collected by suction filtration
  11. washwashed with water
  12. dry with materialAfter drying in vacuo slightly impure 3-(4-biphenyl-4-yl)glutaric acid (8.1 g)
  13. customwas obtained
  14. temperaturewas heated
  15. temperatureto reflux
  16. stirringwith stirring for 2 h
  17. temperatureAfter cooling to rt
  18. customprecipitation of the product
  19. additionis completed by addition of petrol ether (100 ml)
  20. customThe precipitate is isolated by suction filtration
  21. washwashed with petrol ether
  22. customdried at the air
  23. customto give a crude (4.39 g)
  24. filtrationfiltered
  25. concentrationthe filtrate concentrated in vacuo

Sources & evidence

ORD record
ord-513d8ab9cfcd422b89b84a5bcd9bf27f
Source dataset
uspto-grants-2014_12
Patent number
US08912186B2

Reaction notes

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