Oxidative Cleavage of β-Keto Sulfones via Nitrous Acid. (15th December 2014)

• Record Type: Journal Article
• Authors: Abdel-Aziz, Hatem A.
• Other Names: Portalone Gustavo Academic Editor.
• Is Part Of: Journal of chemistry. Volume 2014(2014)
• Publication Date: 2014-12-15
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1155/2014/524930
• Languages: English
• ISSNs: 2090-9063

Abstract

Abstract : The reaction of nitrous acid with 1-aryl-2-(arylsulfonyl)ethanones 3a –e afforded the unexpected arenecarboxylic acids 12a –e, formic acid 14, and benzene/4-toluenesulfinic acid 15a, b through oxidative cleavage reaction. 4-Chlorobenzoic acid (12a ), [1, 1′-biphenyl]-4-carboxylic acid (12b ), 2-naphthoic acid (12c ), 2-thiophenecarboxylic acid (12d ), and 2-benzofurancarboxylic acid (12e ) were isolated in 72%, 62%, 55%, 58%, and 62% yields, respectively. The reported mechanistic pathways proposed the production of 1-aryl-2-(phenyl/tolylsulfonyl)ethane-1, 2-dione 7 instead of arenecarboxylic acids 12 . A mechanistic pathway to explain the reaction of nitrous acid with 1-aryl-2-(arylsulfonyl)ethanones 3a –e was suggested. In this pathway, the intermediate 1, 2-oxazete 10 lost benzene/4-toluenesulfinic acid 15 to produce 1, 2-oxazet-3-one 11 . Ring cleavage of the latter intermediate afforded the arenecarboxylic acids 12 .