Files in this item
The reactivity of some organophosphorus esters
Item metadata
dc.contributor.advisor | Cadogan, J. I. G. | |
dc.contributor.author | Eastlick, David Thomas | |
dc.coverage.spatial | 221 p. | en_US |
dc.date.accessioned | 2018-07-03T13:16:59Z | |
dc.date.available | 2018-07-03T13:16:59Z | |
dc.date.issued | 1969 | |
dc.identifier.uri | https://hdl.handle.net/10023/14848 | |
dc.description.abstract | Part 1: The occurrence of bimolecular nucleophilic aromatic substitution has been established in the reaction of o-dinitrobenzene with triethyl phosphite and diethyl methylphosphonite in acetonitrile solution. There is a fine balance between the customary deoxygenation and nucleophilic substitution of aromatic nitrocompounds. The role of the o-nitro group in facilitating the nucleophilic substitution has been discussed in terms of "built-in solvation" of the reaction centres. The exclusive formation of ethyl nitrite in the reactions has been shown to be compatible with the dealkylation of a quasi-phosphonium intermediate by nitrite ions. Part 2: A series of alkyl a-hydroxyimino-p-nitrobenzyl alkylphophyl adducts have been synthesised from phosphorus-containing acids and p-nitrobenzonitrile oxide. Their solvolytic behaviour has been examined. Hydrolysis occurred in acid solution at 25°with anchimeric assistance of about 2x10⁷ by the neighbouring oximino group, to yield the alcohol of the ester moiety. Exclusive phosphorus-oxygen fission occurred. P-Nitroaniline was formed in alkaline solution by intramolecular attack by the oximate anion, followed by a Lossen rearrangement. Evidence is presented for the intermediary of pentacovalent intermediates, and the relative reactivities of the adducts are explained by the constraints necessary for pseudo-rotation to allow further reaction to form the products in alkaline solution. The acid hydrolysis of ethyl pinacolyl methylphosphonate was shown to proceed via a unimolecular mechanism with the formation of a carbonium ion in 50% aqueous dioxin at 100 ° | en_US |
dc.language.iso | en | en_US |
dc.publisher | University of St Andrews | |
dc.subject.lcc | QD305.A2E2 | |
dc.subject.lcsh | Esters | en |
dc.title | The reactivity of some organophosphorus esters | en_US |
dc.type | Thesis | en_US |
dc.contributor.sponsor | Science Research Council (Great Britain) | en_US |
dc.type.qualificationlevel | Doctoral | en_US |
dc.type.qualificationname | PhD Doctor of Philosophy | en_US |
dc.publisher.institution | The University of St Andrews | en_US |
This item appears in the following Collection(s)
Items in the St Andrews Research Repository are protected by copyright, with all rights reserved, unless otherwise indicated.