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Isomerization and fragmentation of aliphatic ether radical cations: Interconversion of distonic ions and cyclopropane intermediates

✍ Scribed by Henri Edouard Audier; Georges Sozzi; Arielle Milliet; Steen Hammerum

Publisher: John Wiley and Sons
Year: 1990
Tongue: English
Weight: 596 KB
Volume: 25
Category: Article
ISSN: 1076-5174
DOI: 10.1002/oms.1210250705

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✦ Synopsis

The reactions of propyl ether radical cations close to threshold are initiated by (reversible) formation of ydistonic isomers, R6(H)CH,CH,CH,'. The three methylene groups in these ions lose their positional identity by ring closurelring opening via [ cyclopropane + alcohol] + ' intermediates. Extensive hydrogen exchange occurs within the C,-chain. When R is not methyl the y-distonic isomer undergoes further intramolecular hydrogen atom transfer reactions that lead to formation of a-and /l-distonic ions. The a-distonic isomers expel ethyl and propyl radicals by C -0 bond cleavage.

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✍ Michael J. Polce; Chrys Wesdemiotis 📂 Article 📅 1996 🏛 John Wiley and Sons 🌐 English ⚖ 763 KB

The distonic radical ion 'CH,CH,SCH,' (l"), generated by dissociative electron ionization of 1,4-dithiane or 1,4-thioxane, is identified in the gas phase by its collisionally activated dissociation (CAD), neutralizationreionization ('NR' ) and charge-reversal ('CR-) mass spectra. The unimolecular ch