A combined time-resolved and stereospecific deuterium labelling study of the elimination of methanol from the molecular ion of methoxycyclohexane

✍ Scribed by Tineke A. Molenaar-Langeveld; Nico M. M. Nibbering

• Publisher: John Wiley and Sons
• Year: 1986
• Tongue: English
• Weight: 791 KB
• Volume: 21
• Category: Article
• ISSN: 1076-5174
• DOI: 10.1002/oms.1210211007

✦ Synopsis

It is shown by field ionization kinetics in combination with both site-specific and stereospecific D-labelling that the loss of a molecule of methanol from the molecular ion of methoxycyclohexane can occur via 1,4-and 1,3-eiiinations. The 1,4-elimination predominates at molecular ion lifetimes of rlO-'O.l s. It is found that -19% of this reaction channel corresponds to a stereospecific &-elimination, whereas the remaining 81% is only site-specific. At molecular ion lifetimes of between 10-l' and lOU9s, a very sudden increase of the 1,Ielimiination is observed at the expense of the 1,4-eliination. A stereospecific loss of methanol, however, is not observed at all for the 1,Ielimination within the limits of error. Possible intermediates and reaction pathways, which can account for the observations made, are discussed.