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Abstraction Versus Electrophilic Substitution: Metaphosphate-Mediated Reactions in the Gas Phase |
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| Authors: | Malcolm R Banks J I G Cadogan Ian Gosney Philip KG Hodgson David R Rodger |
| Institution: | 1. Department of Chemistry , University of Edinburgh , West Mains Road, Edinburgh, EH9 3JJ, Scotland;2. B.P. Research Centre , Chertsey Road, Sunbury-on-Thames, Middlesex, TW16 7LN, England;3. Department of Chemistry , University of Edinburgh , West Mains Road, Edinburgh, EH9 3JJ, Scotland;4. B.P. Research Centre , Chertsey Road, Sunbury-on-Thames, Middlesex, TW16 7LN, England |
| Abstract: | Abstract Whereas arylmetaphosphates (ArOPO2) tend to cyclise by intramolecular C-H insertion (phosphorylation) when generated in the gas phase, their alkyl-substituted counterparts exhibit non-electrophilic behaviour and give rise to alkenes by an unusual 1,2-methyl shift induced by a combination of hydrogen abstraction with concomitant elimination of metaphosphoric acid (HOPO2). |
| Keywords: | thioalkynes thiophosphorus acid bromoacetylene |