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https://hdl.handle.net/2440/4516
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Type: | Journal article |
Title: | The Gas Phase Payne Rearrangement. Part 2. The Effect of Methyl Substitution |
Author: | Dua, S. Bowie, J. Taylor, M. Buntine, M. |
Citation: | International journal of mass spectrometry and ion processes, 1997; 165-166(November):139-153 |
Publisher: | Elsevier |
Issue Date: | 1997 |
ISSN: | 0168-1176 1873-2798 |
Abstract: | An ab initio study (at G2[MP2]) level shows that deprotonated 2-methyl-3,4-epoxybutan-2-ol (A) and 3-methyl-2,3-epoxybutan-1-ol (B) should interconvert via modest barriers (A → B [47 kJ mol⁻¹]; B → A [33 kJ mol⁻¹]) by three-centre Payne rearrangements. The competing four-centre rearrangements of A and B to deprotonated 2,2-dimethyl-3-hydroxyoxetane (C) have barriers of 117 and 121 kJ mol⁻¹, respectively. The collision-induced mass spectra of (A)–(C) are very similar and the corresponding spectra of a number of ²H- and ¹⁸O-labelled derivatives confirm that isomers A, B and C interconvert on collisional activation, i.e. the three-centre Payne and four-centre ‘oxetane’ cyclisations compete under the reaction conditions. The major cleavages noted in the spectra of A, B and C involve competitive losses of CH₂O and CO: these are both fragmentations of deprotonated 3-methyl-2,3-epoxybutan-2-ol (B). |
Keywords: | Ab initio study Payne rearrangement Isomers |
DOI: | 10.1016/S0168-1176(97)00201-2 |
Description (link): | http://www.sciencedirect.com/science/journal/01681176 |
Published version: | http://dx.doi.org/10.1016/s0168-1176(97)00201-2 |
Appears in Collections: | Aurora harvest 6 Chemistry publications |
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