The Ladenburg rearrangement
| dc.contributor.author | Creamer, L. K. | en |
| dc.date.accessioned | 2014-06-08T23:22:54Z | |
| dc.date.available | 2014-06-08T23:22:54Z | |
| dc.date.issued | 1963 | en |
| dc.description.abstract | Ladenburg found that thermal decomposition of pyridine ethiodide led to both 2- and 4-ethylpyridine. Because no systematic study of this reaction had ever been reported, the present work was undertaken to explore the reaction as a synthetic method, and also, to elucidate the reaction mechanism. To this end a number of alkylpyridine alkiodides have been decomposed and the products identified and analysed quantitatively, Gas chromatography and ion-exchange chromatography were used extensively in the analyses. It was found that the alkyl group entered the pyridine nucleus preferentially at the 2- and the 4- positions. It was also found that alkylpyridine alkiodides rearranged to give, in addition to the nuclear substituted products, substituted in 2- or 4-alkyl sidechains. In the case of the 4-ethylpyridine methiodide rearrangement, 4-iso-propylpyridine is the most important substitution product. Both nuclear and sidechain substitution appear to be intermolecular but while nuclear substitution seems most likely to involve a free radical intermediate, sidechain alkylation appears to involve carbonium ion attack on the deprotonated sidechain of an N-methylalkylpyridinium ion. | en |
| dc.identifier.uri | http://hdl.handle.net/10092/9250 | |
| dc.identifier.uri | http://dx.doi.org/10.26021/8926 | |
| dc.language.iso | en | |
| dc.publisher | University of Canterbury. Chemistry | en |
| dc.relation.isreferencedby | NZCU | en |
| dc.rights | Copyright L. K. Creamer | en |
| dc.rights.uri | https://canterbury.libguides.com/rights/theses | en |
| dc.title | The Ladenburg rearrangement | en |
| dc.type | Theses / Dissertations | |
| thesis.degree.discipline | Chemistry | |
| thesis.degree.grantor | University of Canterbury | en |
| thesis.degree.level | Doctoral | en |
| thesis.degree.name | Doctor of Philosophy | en |
| uc.bibnumber | 348693 | |
| uc.college | Faculty of Science | en |
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