Reaction between phenyliodosoacetate and amides–a kinetic study of the oxidative rearrangement

✍ Scribed by K. Swaminathan; K. Vaidynathan; N. Venkatasubramanian

• Publisher: John Wiley and Sons
• Year: 1974
• Tongue: English
• Weight: 158 KB
• Volume: 6
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550060513

✦ Synopsis

Primary amides are known to be oxidatively rearranged to the corresponding isocyanates when they are treated with lead tetraacetate (LTA) and with phenyliodosoacetate (PIA). The isocyanates can be isolated when the reaction is carried out in nonaqueous solvents [I]. The isocyanates are converted into acylamines in situ by reaction with solvent acetic acid, while in t-butyl alcohol, the t-butyl carbamate is the major product [2,3]. It has been suggested that the reaction takes place through a concerted rearrangement of a lead-amide complex simulating the Hoffman reaction.

Although the preparative aspects of these reactions (particularly with LTA) have been studied extensively, to our knowledge, no kinetic work has been done in this field. We report, in this communication, certain interesting observations in the reaction between benzamide and PIA. In view of the similarities between PIA and LTA, the deductions from this investigation