Effects of N-alkyl substitution on the formation and rate-limiting deprotonation of the spiro-meisenheimer intermediate of smiles' rearrangement of 2-(p-nitrophenoxy) ethylamine.

✍ Scribed by A.C. Knipe; N. Sridhar; J. Lound-Keast

• Book ID: 104237790
• Publisher: Elsevier Science
• Year: 1979
• Tongue: French
• Weight: 180 KB
• Volume: 20
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(01)86343-7

✦ Synopsis

General base catalysis, and N-alkyl group dependence, of the title rearrangement (which approaches a rate limit at high base concentration) has been interpreted: We recently reported (1) that kinetic studies of intramolecular nucleophilic aromatic displacement of alkoxide ion by the amino group in 2-(p-nitrophenoxy)ethylamine (SH) support a mechanism (SCHEME, R=H) whereby, at low base concentration, the rate of Smiles' rearrangement is dependent upon the rate of general base-catalysed deprotonation of a Spiro-Meisenheimer intermediate (MH);