Skip to main content

Thermal rearrangements of some hydroxamic acid derivatives

Ankers, William B. (1973) Thermal rearrangements of some hydroxamic acid derivatives. Doctor of Philosophy (PhD) thesis, University of Kent. (doi:10.22024/UniKent/01.02.94174) (KAR id:94174)

PDF (Optical Character Recognition (OCR) of this thesis enables read aloud functionality of the text.)
Language: English


Download this file
(PDF/74MB)
[thumbnail of Optical Character Recognition (OCR) of this thesis enables read aloud functionality of the text.]
Preview
Official URL:
https://doi.org/10.22024/UniKent/01.02.94174

Abstract

An historical survey of the thermolyses of hydroxamic acids and O-acylated hydroxamic acids is presented, and thermal rearrangements which proceed by [l,3 ]-sigmatropic and free radical shifts are reviewed, together with the phenomenon of chemically induced dynamic nuclear polarisation (CIDNP). N-Methyl hydroxamic acids are found to undergo, on distillation, a novel thermal rearrangement to the isomeric N-methyl-O-acylhydroxylamines, the thermodynamically less stable product. The rearrangement is shown to occur, at least in part, via an intermolecular mechanism involving formation of N-methylhydroxylamine and N-methyl-N,0-diacylhydroxylamine. Various O-thiocarbamoylated N-methyl hydroxamic acids are found to undergo, in solution, a thermal [l,3 ] rearrangement to the isomeric hydrosulphamine derivatives. This rearrangement, which is accompanied by appreciable fragmentation to the corres­ponding N-methyl amide, is shown to proceed largely via a pathway involving caged free radical pairs.

Item Type: Thesis (Doctor of Philosophy (PhD))
Thesis advisor: Bigley, D.B.
DOI/Identification number: 10.22024/UniKent/01.02.94174
Additional information: This thesis has been digitised by EThOS, the British Library digitisation service, for purposes of preservation and dissemination. It was uploaded to KAR on 25 April 2022 in order to hold its content and record within University of Kent systems. It is available Open Access using a Creative Commons Attribution, Non-commercial, No Derivatives (https://creativecommons.org/licenses/by-nc-nd/4.0/) licence so that the thesis and its author, can benefit from opportunities for increased readership and citation. This was done in line with University of Kent policies (https://www.kent.ac.uk/is/strategy/docs/Kent%20Open%20Access%20policy.pdf). If you feel that your rights are compromised by open access to this thesis, or if you would like more information about its availability, please contact us at ResearchSupport@kent.ac.uk and we will seriously consider your claim under the terms of our Take-Down Policy (https://www.kent.ac.uk/is/regulations/library/kar-take-down-policy.html).
Subjects: Q Science
Divisions: Divisions > Division of Natural Sciences > Chemistry and Forensics
SWORD Depositor: SWORD Copy
Depositing User: SWORD Copy
Date Deposited: 27 Sep 2022 15:56 UTC
Last Modified: 27 Sep 2022 15:56 UTC
Resource URI: https://kar.kent.ac.uk/id/eprint/94174 (The current URI for this page, for reference purposes)

University of Kent Author Information

  • Depositors only (login required):

Total unique views for this document in KAR since July 2020. For more details click on the image.