Hydrochloric Acid → 3-(4-bromophenyl)glutaric anhydride

HRID 1402804Notes

Reaction equation

HRID 1402804 reaction equation
[OH-].[Na+].Cl.[Br:4][C:5]1[CH:10]=[CH:9][C:8]([CH:11]([CH2:16][C:17]([OH:19])=[O:18])[CH2:12][C:13]([OH:15])=O)=[CH:7][CH:6]=1>C(Cl)(=O)C>[Br:4][C:5]1[CH:6]=[CH:7][C:8]([CH:11]2[CH2:12][C:13](=[O:15])[O:19][C:17](=[O:18])[CH2:16]2)=[CH:9][CH:10]=1

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 14798Sodium HydroxideHCID 106846833-(4-bromophenyl)pentanedioic Acid

Product 1

HCID 114927253-(4-bromophenyl)glutaric anhydride

Reagents, catalysts & solvents 1

HCID 6367Acetyl chlorideSolvent

Procedure

To a solution of commercial 4-bromobenzaldehyde (23.4 g) in ethyl acetoacetate (32.9 g) piperidine (3 ml) was added with stirring at rt. The yellowish solution slowly evolves strong heat. Ethanol (40 ml) was added to induce crystallisation and the mixture was kept at rt for 2 h. The precipitate was collected by suction filtration, washed with ethanol, and dried in vacuo to give 29.5 g of a faint yellowish solid (the bis-adduct of acetoacetate to the benzaldehyde). The powdered solid was added in portions to 50% NaOH (500 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 (450 ml) to give a white, partly resinous precipitate. The solid was collected by suction filtration and washed with water. After drying in vacuo 3-(4-bromophenyl)glutaric acid (16.7 g) was obtained. The suspension of finely divided 3-(4-bromophenyl)-glutaric acid in acetyl chloride (20 ml) was heated to reflux with stirring for 1 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 acetyl chloride (2×6 ml) and petrol ether, and dried in vacuo to give 3-(4-bromophenyl)-glutaric anhydride (12.3 g) as colourless crystals.

Workup

  1. stirringThe resulting yellow slurry was stirred
  2. temperatureat reflux for 2 h
  3. temperatureAfter cooling in an ice bath the mixture
  4. customto give a white, partly resinous precipitate
  5. filtrationThe solid was collected by suction filtration
  6. washwashed with water
  7. dry with materialAfter drying in vacuo 3-(4-bromophenyl)glutaric acid (16.7 g)
  8. customwas obtained
  9. temperaturewas heated
  10. temperatureto reflux
  11. stirringwith stirring for 1 h
  12. customprecipitation of the product
  13. additionis completed by addition of petrol ether (100 ml)
  14. customThe precipitate is isolated by suction filtration
  15. washwashed with acetyl chloride (2×6 ml) and petrol ether
  16. customdried in vacuo

Sources & evidence

ORD record
ord-d70d85179d2f492c89df4af089001d36
Source dataset
uspto-grants-2014_12
Patent number
US08912186B2

Reaction notes

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