Mechanismus der Amin‐eliminierungen bei der Elektronenstoßinduzierten Fragmentierung von 1.3‐Diaminopropanen

Abstract

Abstract-l,3-Diaminopropanes exhibit strong elimination of amines from the molecular ions upon electron-impact. This is followed by secondary reactions in the course of which a substituent from the C-2 of the propane unit is eliminated and also a N-substituent to a smaller degree. Lowering the electron density at only one nitrogen atom by appropriate substituents causes a decrease in the intensity1 of both [M -aminel+' ions. The corresponding fragmentation processes were investigated by means of deuterium labelling. Zusammenfassung-1.3-Diaminopropane spalten beim ElektronenstoOinduzierten

Intramolecular hydrogen transfer in mass spectra. III. Rearrangements involving the loss of small neutral molecules

“…1245 The loss of amine fragments from , , ', '-tetrasubstituted 1,3-diaminopropanes has been shown to involve the loss of the amine group from C-1 together with a hydrogen from C-3; an azetidine ring is postulated as the product of this reaction. 1246 The loss of nitrous acid from the molecular ion of the methyl ester of -nitrobutyric acid occurs to the extent of about 85% by a 1,1-elimination, providing the third example of an elimination of this type. 1247 Previous examples of this type of elimination have been the elimination of HCN from alkyl cyanides1735 and from o-nitrobenzyl cyanide.…”