Electron impact studies. LXXXVI. Ion-molecule reactions of alkyl and aryl cyanides

Abstract

Positive ion-molecule reactions of representative alkyl and aryl cyanides have been studied by ioncyclotron resonance spectroscopy. The major secondary ion produced from alkyl cyanides is an [MH]⁺ species. Neutral alkyl cyanides react preferentially with even-electron ions produced from alkyl cyanide molecular ions by the general process ⁺R¹ + R²CN → R²-C=N+-R¹ but the corresponding aryl cyanides react with both odd- and even-electron ions. The characteristic reaction of acetonitrile,'s2 viz. CH₂CN⁺ + CH₃CN → C₃H₄N⁺ + HCN does not occur for higher homologues, but a mixture of acetonitrile and propionitrile gives the analogous reaction CH₂CN+ + C₂H₅CN → C₄H₆N+ + HCN