Cyclopropylnitrenium ions and substituent effects

✍ Scribed by J.A. Deyrup; R.B. Greenwald

• Publisher: Elsevier Science
• Year: 1973
• Tongue: French
• Weight: 142 KB
• Volume: 14
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(01)87333-0

✦ Synopsis

Extensive recent investigations have sought to define the role of electron deficient nitrogen atoms in transition states and as intermediates. 1 It now appears certain that significant positive charge does develop on nitrogen in many reactions. We would like to report in this communication our observations concerning the effects of substituents on potential precursors of cyclopropyl nitrenium ions. These obeervations seem to reveal mechanistic types. a not unexpected spectrum of Our interest in N-chlorocyclopropylamines was prompted by our hope that elimination of HCl might provide a simple route to cyclopropanone imines. 4 For this purpose a CHC13 solution of 1 was reacted with 5% NaOCl saturated with Na2C03 at room temperature. 5 Immediate monitoring of the CHC13 layer by nmr spectroscopy revealed a total destruction of the cyclopropane ring hydrogen peaks and the formation of a single new substance. This substance (m.p. 79-80°, 81%) was assigned structure 3 on the basis of analytical and spectral data. 6 Confirmation of this assignment was obtained by hydrolysis of 3 to cinnamadehyde 4.