The Open Organic Chemistry Journal

2009, 3 : 35-41
Published online 2009 April 3. DOI: 10.2174/1874095200903010035
Publisher ID: TOOCJ-3-35

Smiles Rearrangement in the Synthesis of Di- and Triiodinated 5- (Acylamino)-1,3-Benzenedicarboxamides

Pier Lucio Anelli , Marino Brocchetta , Enrico Cappelletti and Veronica Vincenzi
Centro Ricerche Bracco, Bracco Imaging spa, via Ribes 5, 10010 Colleretto Giacosa (TO), Italy

ABSTRACT

Both the number and the position of iodine atoms on the aromatic ring of polyiodinated N,N’-bis(2,3- dihydroxypropyl)-5-[2-methylamino-2-oxoethoxy]-1,3-benzenedicarboxamides are crucial to define the structure of the product obtained by treatment with aqueous NaOH. The 2,6-diiodo and the 2,4,6-triiodo derivatives give the corresponding Smiles rearrangement products in 77 and 96% yields, respectively. Conversely, under the same conditions, the 2,4- diiodo isomer predominantly undergoes hydrolysis of the phenoxyacetamide moiety.

Keywords:

Iodinated X-ray contrast media, Smiles rearrangement, Hydrolysis, Jackson-Meisenheimer intermediates, Computational studies.