Copper(I) as a homogeneous catalyst for the Ullmann reaction in aqueous solutions - The transformation of 2-bromobenzoate into salicylate

Magal Saphier, Alexandra Masarwa, Haim Cohen, Dan Meyerstein

Research output: Contribution to journalArticlepeer-review

22 Scopus citations

Abstract

The CuI-catalyzed transformation of 2-bromobenzoic acid (2-Br-BA) into salicylic acid (main product), benzoic acid, and diphenoic acid was studied. The reaction was monitored by UV/Vis spectroscopy, HPLC, and ESR. Up to 25 turnovers were achieved for low CuI concentrations. An intermediate was observed that was assigned to a complex between copper and a follow-up product of the aromatic acid, probably a complex with a copper-carbon σ-bond. The process is probably initiated by the formation of a d-π* complex of CuI with the aromatic ring of 2-Br-BA followed by the reaction with a second CuI ion. The effect of the addition of CH3CN or NH3 on the catalytic process is reported. Both were found to accelerate the process when present at relatively low concentrations and slow it down at higher concentrations. A side product, 2-aminobenzoate was observed in the presence of NH3.

Original languageEnglish
Pages (from-to)1226-1234
Number of pages9
JournalEuropean Journal of Inorganic Chemistry
Issue number5
DOIs
StatePublished - 1 Jan 2002
Externally publishedYes

Keywords

  • Aromatic compounds
  • Catalysis
  • Copper(I)
  • Ullmann reaction

ASJC Scopus subject areas

  • Inorganic Chemistry

Fingerprint

Dive into the research topics of 'Copper(I) as a homogeneous catalyst for the Ullmann reaction in aqueous solutions - The transformation of 2-bromobenzoate into salicylate'. Together they form a unique fingerprint.

Cite this