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Phosphinic acid synthesis

Andrew Boyd, E (2021) Phosphinic acid synthesis. Doctor of Philosophy (PhD) thesis, University of Kent. (doi:10.22024/UniKent/01.02.86060) (KAR id:86060)

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Abstract

Chapter 1 gives a background to the importance of phosphinic acids, and a description of their physical properties and chemical reactivity. A review of the more useful methods towards synthesis is given. At the end of the chapter, trivalent silyl phosphonite esters are introduced as potentially useful synthetic reagents. However, only limited work has performed using these species. Chapter 2 introduces the novel addition of bis(trimethylsilyl) phosphonite to c-unsaturated esters under basic silylating conditions. This reaction is optimised and transformed into a useful synthetic method for the preparation of phosphinic acids, named the "triethylammonium phosphinate reaction." Various other electrophiles were used as substrates in this reaction, little success was obtained. Theories are provided to explain side reactions and products, some additional reactions were performed to give evidence to support these theories. A novel reaction between a Nannich base and silyl phosphonite esters, yielding a phosphinic acid, is introduced. The problems of phosphinic acid purification by physical and chemical methods are discussed. Chapter 3 is concerned with the development of the "triethylammonium reaction" to allow addition of silyl phosphonite esters to a,-unsaturated ketones. The novel "sodium phosphinate" reaction was developed but little success was achieved, however excellent yields of phosphinic acids were obtained when a,-unsaturated esters were used as substrates. Chapter 4 is about developing a new reaction to allow phosphinic acid synthesis using vinyl ketones as substrates, under controlled conditions. This mild reaction was then combined with a novel method of purification forming adamantanammonium phosphinate esters. This flexible methodology was established by the preparation of a variety of substituted phosphinic acids and phosphinate esters. In chapter 5 adaption of the reaction discovered in chapter 4 was undertaken which, allows the synthesis of phosphinic acids using alkyl iodides. A useful reaction was developed which gives similar products to the Arbuzov reaction, however it is demonstrated that this new reaction does not proceed by the same mechanism. Chapter 6 gives an account of work undertaken to the phosphinate analogue of platelet activating factor. The original route was unsuccessful, reasons for this are discussed. A shorter alternative route is given, which relies on chemistry developed in this thesis. I have made an attempt to show the utility of the novel methodology contained in this thesis, by giving my ideas on proposed routes to the synthesis of some interesting phosphinate analogues. I consider some of these analogues to be useful biochemical tools.

Item Type: Thesis (Doctor of Philosophy (PhD))
DOI/Identification number: 10.22024/UniKent/01.02.86060
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 09 February 2021 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).
Uncontrolled keywords: Organic chemistry
Subjects: Q Science > QD Chemistry
Divisions: Divisions > Division of Natural Sciences > Chemistry and Forensics
SWORD Depositor: SWORD Copy
Depositing User: SWORD Copy
Date Deposited: 29 Oct 2019 16:26 UTC
Last Modified: 07 Dec 2021 11:03 UTC
Resource URI: https://kar.kent.ac.uk/id/eprint/86060 (The current URI for this page, for reference purposes)
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