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The solution photochemistry of nitroalkenes and nitroketones.

Moles, Peter J. (1978) The solution photochemistry of nitroalkenes and nitroketones. Doctor of Philosophy (PhD) thesis, University of Kent. (doi:10.22024/UniKent/01.02.94535) (KAR id:94535)


The thesis describes an investigation or the solution photochemistry of nitroalkenes and α-nitroketones, The introduction discusses the general concepts of photochemistry and provides a detailed review of the photochemistry of nitroalkenes, nitroalkanes and nitroaromatics and attempts to relate theoretical studios on the nitro group to the observed photochemistry.

Aliphatic α, β-nitroalkenes have been shown to undergo a photoinduced nitro-to-nitrite rearrangement in a variety of solvents, when steric .interactions push the nitro group out of conjugation with the double bond, Nitroalkenes with a secondary or tertiary hydrogen, at the γ-carbon from the nitro group undergo a hydrogen abstraction reaction, which competes with the nitro-to-nitrite rearrangement. Planar nitroalkene3 do not undergo the nitro-to-nitrite rearrangement, but do undergo photoaddition of methanol, when this is used as the solvent.

α, β-unsaturated nitroalkenes photochemically add to a variety of alkenes. The adducts resulting from β-nitrostyrene are the most stable. The photoreaction is regiospecific with the most nucleophilic carbon of the alkene attached to the α-position of the β-substituted nitroalkene, out gives in every case a, mixture of stereoisomers. The mechanism of the photoaddition is either concerted or else involves a short-lived diradical .intermediate.

Secondary acyclic α-nitroketones undergo photoreactions in a variety of solvents to give hydroxyiminoketones, whore the carbon bearing the oxime group formerly bore the nitro group. This reaction can be rationalized in terms of an initial C-N bond cleavage.

Secondary acyclic α-nitroketones on refluxing in alcohols and ethers give hydroxyrminoketones, solvent oxidation products and fragmentation products. This reaction was again rationalised by an initial C-K bond cleavage, 2-Nictocyclohexanone undergoes a ring cleavage reaction on refluxing in alcohols, via a hemi-acetal intermediate.

Item Type: Thesis (Doctor of Philosophy (PhD))
DOI/Identification number: 10.22024/UniKent/01.02.94535
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 ( 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 ( 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 and we will seriously consider your claim under the terms of our Take-Down Policy (
Subjects: Q Science > QD Chemistry
Divisions: Divisions > Division of Natural Sciences > Chemistry and Forensics
SWORD Depositor: SWORD Copy
Depositing User: SWORD Copy
Date Deposited: 14 Jul 2023 15:26 UTC
Last Modified: 14 Jul 2023 15:26 UTC
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