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Spectrom."],"published-print":{"date-parts":[[2012,4]]},"abstract":"<jats:p>The competition between benzylic cleavage (simple bond fission [SBF]) and retro\u2010ene rearrangement (RER) from ionised <jats:italic>ortho<\/jats:italic>, <jats:italic>meta<\/jats:italic> and <jats:italic>para<\/jats:italic> RC<jats:sub>6<\/jats:sub>H<jats:sub>4<\/jats:sub>OH and RC<jats:sub>6<\/jats:sub>H<jats:sub>4<\/jats:sub>OCH<jats:sub>3<\/jats:sub> (R\u2009=\u2009<jats:italic>n<\/jats:italic>\u2010C<jats:sub>3<\/jats:sub>H<jats:sub>7<\/jats:sub>, <jats:italic>n<\/jats:italic>\u2010C<jats:sub>4<\/jats:sub>H<jats:sub>9<\/jats:sub>, <jats:italic>n<\/jats:italic>\u2010C<jats:sub>5<\/jats:sub>H<jats:sub>11<\/jats:sub>, <jats:italic>n<\/jats:italic>\u2010C<jats:sub>7<\/jats:sub>H<jats:sub>15<\/jats:sub>, <jats:italic>n<\/jats:italic>\u2010C<jats:sub>9<\/jats:sub>H<jats:sub>19<\/jats:sub>, <jats:italic>n<\/jats:italic>\u2010C<jats:sub>15<\/jats:sub>H<jats:sub>31<\/jats:sub>) is examined. It is observed that the SBF\/RER ratio is significantly influenced by the position of the substituent on the aromatic ring. As a rule, phenols and anisoles substituted by an alkyl group in <jats:italic>meta<\/jats:italic> position lead to more abundant methylene\u20102,4\u2010cyclohexadiene cations (RER fragmentation) than their <jats:italic>ortho<\/jats:italic> and <jats:italic>para<\/jats:italic> homologues. This \u2018<jats:italic>meta<\/jats:italic> effect\u2019 is explained on the basis of energetic and kinetic of the two reaction channels. Quantum chemistry computations have been used to provide estimate of the thermochemistry associated with these two fragmentation routes. G3B3 calculation shows that a hydroxy or a methoxy group in the <jats:italic>meta<\/jats:italic> position destabilises the SBF and stabilises the RER product ions. Modelling of the SBF\/RER intensities ratio has been performed assuming two single reaction rates for both fragmentation processes and computing them within the statistical RRKM formalism in the case of <jats:italic>ortho<\/jats:italic>, <jats:italic>meta<\/jats:italic> and <jats:italic>para<\/jats:italic> butyl phenols. It is clearly demonstrated that, combining thermochemistry and kinetics, the inequality (SBF\/RER)<jats:sub>meta<\/jats:sub>\u2009&lt;\u2009(SBF\/RER)<jats:sub>ortho<\/jats:sub>\u2009&lt;\u2009(SBF\/RER)<jats:sub>para<\/jats:sub> holds for the butyl phenols series. It is expected that the \u2018<jats:italic>meta<\/jats:italic> effect\u2019 described in this study enables unequivocal identification of <jats:italic>meta<\/jats:italic> isomers from <jats:italic>ortho<\/jats:italic> and <jats:italic>para<\/jats:italic> isomers not only of alkyl phenols and alkyl anisoles but also in other alkyl benzene series. Copyright \u00a9 2012 John Wiley &amp; Sons, Ltd.<\/jats:p>","DOI":"10.1002\/jms.2977","type":"journal-article","created":{"date-parts":[[2012,6,11]],"date-time":"2012-06-11T07:55:42Z","timestamp":1339401342000},"page":"539-546","source":"Crossref","is-referenced-by-count":5,"title":["A \u2018<i>meta<\/i> effect\u2019 in the fragmentation reactions of ionised alkyl phenols and alkyl anisoles"],"prefix":"10.1002","volume":"47","author":[{"given":"Guy","family":"Bouchoux","sequence":"first","affiliation":[{"name":"Laboratoire des M\u00e9canismes R\u00e9actionnels, Ecole Polytechnique, CNRS  91128 Palaiseau France"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Michel","family":"Sablier","sequence":"additional","affiliation":[{"name":"Laboratoire des M\u00e9canismes R\u00e9actionnels, Ecole Polytechnique, CNRS  91128 Palaiseau France"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Tetsuo","family":"Miyakoshi","sequence":"additional","affiliation":[{"name":"School of Science and Technology Meiji University  Higashi\u2010Mita 1\u20101\u20101 Tama\u2010ku Kawasaki 214\u20108571 Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Takashi","family":"Honda","sequence":"additional","affiliation":[{"name":"School of Science and Technology Meiji University  Higashi\u2010Mita 1\u20101\u20101 Tama\u2010ku Kawasaki 214\u20108571 Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2012,4,12]]},"reference":[{"key":"e_1_2_5_2_1","series-title":"Fundamentals of and Applications to Organic (and Organometallic compounds)","first-page":"396","volume-title":"The Encyclopedia of Mass Spectrometry","author":"Turecek F.","year":"2005"},{"key":"e_1_2_5_2_2","series-title":"Fundamentals of and Applications to Organic (and Organometallic compounds)","first-page":"9","volume-title":"The Encyclopedia of Mass Spectrometry","author":"Baer T.","year":"2005"},{"key":"e_1_2_5_2_3","series-title":"Fundamentals of and Applications to Organic (and Organometallic compounds)","first-page":"97","volume-title":"The Encyclopedia of Mass Spectrometry","author":"Kuck D.","year":"2005"},{"key":"e_1_2_5_2_4","series-title":"Fundamentals of and Applications to Organic (and Organometallic compounds)","first-page":"199","volume-title":"The Encyclopedia of Mass Spectrometry","author":"Kuck D.","year":"2005"},{"key":"e_1_2_5_3_1","doi-asserted-by":"publisher","DOI":"10.1016\/0020-7381(81)80004-6"},{"key":"e_1_2_5_4_1","doi-asserted-by":"publisher","DOI":"10.1016\/0020-7381(81)80026-5"},{"key":"e_1_2_5_5_1","doi-asserted-by":"publisher","DOI":"10.1016\/0020-7381(82)80015-6"},{"issue":"20","key":"e_1_2_5_6_1","doi-asserted-by":"crossref","first-page":"4759","DOI":"10.1021\/j150664a062","article-title":"Competitive two\u2010channel photodissociation of n\u2010butylbenzene ions in the Fourier transform ion cyclotron resonance mass spectrometer","volume":"88","author":"Chen J. 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