✍ Scribed by Hans-Friedrich Grützmacher; Doris Pankoke
No coin nor oath required. For personal study only.
The fragmentation reactions of glycidic methyl ester (1) and of its derivatives (26) substituted by one, two and three methyl groups, respectively, at the oxirane ring, of the corresponding glycidols (7-12), and of the glycidyl ethers (13-16) in the 70 eV mass spectra have been studied using isotopic labelling and mass-analysed ion kinetic energy spectrometry. It is shown that the typical reaction of these aliphatic oxirane radical cations carrying a nucleophilic methoxy group and hydroxy group, respectively, at the side chain corresponds under high-energy conditions to a rearrangement by a methoxy group or a hydroxy group migration to the p-carbon atom of the oxirane moiety. This rearrangement is very likely mediated by the isomerization of the molecular ions into distonic ions via C-C bond cleavage within the oxirane ring.
📜 SIMILAR VOLUMES
By ion cyclotron resonance it is found that various substituted cyclopropanes after ionization react with ammonia to give products which allow identification of the degree and kind of substitution on the cyclopropyl ring. For example, cyclopropane reacts to give[CH2NH,]+ (m/e 30), methylcyclopropane
Molecular Orbital Study of the Rearrangement of Seleniranium Ions -[mechanism of phenylselenoetherification of unsaturated alcohols involving seleniranium cationic intermediates]. -(MARKOVIC, Z.; KONSTANTI-