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Formation of β-distonic oxonium ions: Study of ROCH2CH2OR′ radical cations

✍ Scribed by Arielle Milliet; Georges Sozzi; Henri E. Audier

Publisher
John Wiley and Sons
Year
1992
Tongue
English
Weight
688 KB
Volume
27
Category
Article
ISSN
1076-5174

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✦ Synopsis

Radical cations derived from the ethers ROCH,CH,OR (R, R = H, CH, , C,HJ were studied, since Bdistonic oxonium ions are often prepared from ionized ethers of glycol. The first step in the fragmentation is a 1,Stransfer of an a-hydrogen to oxygen of a terminal alkoxy group leading to a Wistonic oxonium ion. This step is thermoneutral and reversible in the ROCH,CH,OH radical cations and exothermic and irreversible in the dialkyl ether radical cations. Depending on R and R', these Sdistonic oxonium ions fragment by three reactions: the loss of an alcohol or a water molecule, the formation of a /Idistonic oxonium ion 'CH2CH20(H)+R and a 1,QH migration between carbon atoms. Competition between these processes is discussed.

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