Effect of structure in benzaldehyde oximes on the formation of aldehydes and nitriles under photoinduced electron-transfer conditions
Document Type
Article
Publication Title
Journal of Organic Chemistry
Abstract
(Chemical Equation Presented) The mechanistic aspects of the photosensitized reactions of a series of benzaldehyde oximes (1a-o) were studied by steady-state (product studies) and laser flash photolysis methods. Nanosecond laser flash photolysis studies have shown that the reaction of the oxime with triplet chloranil (3CA) proceeds via an electron-transfer mechanism provided the free energy for electron transfer (ΔGET) is favorable; typically, the oxidation potential of the oxime should be below 2.0 V. Substituted benzaldehyde oximes with oxidation potentials greater than 2.0 V quench 3CA at rates that are independent of the substituent and the oxidation potential. The most likely mechanism under these conditions is a hydrogen atom transfer mechanism as this reaction should be dependent on the O-H bond strength only, which is virtually the same for all oximes. Product studies have shown that aldoximes feact to give both the corresponding aldehyde and the nitrile. The important intermediate in the aldehyde pathway is the iminoxyl radical, which is formed via an electron transfer-proton transfer (ET-PT) sequence (for oximes with low oxidation potentials) or via a hydrogen atom transfer (HAT) pathway (for oximes with larger oxidation potentials). The nitriles are proposed to result from intermediate iminoyl radicals, which can be formed via direct hydrogen atom abstraction or via an electron-transfer-proton- transfer sequence. The experimental data seems to support the direct hydrogen atom abstraction as evidenced by the break in linearity in the plot of the quenching rates against the oxidation potential, which suggests a change in mechanism. The nitrile product is favored when electron-accepting substituents are present on the benzene ring of the benzaldehyde oximes or when the hydroxyl hydrogen atom is unavailable for abstraction. The latter is the case in pyridine-2-carboxaldoxime (2), where a strong intramolecular hydrogen bond is formed. Other molecules that form weaker intramolecular hydrogen bonds such as 2-furaldehyde oxime (3) and thiophene-2-carboxaldoxime (4) tend to yield increasing amounts of aldehyde. © 2006 American Chemical Society.
First Page
7785
Last Page
7792
DOI
10.1021/jo061325m
Publication Date
9-29-2006
Recommended Citation
De Lijser, H. J.Peter; Hsu, Susan; Marquez, Bernadette V.; Park, Adriana; Sanguantrakun, Nawaporn; and Sawyer, Jody R., "Effect of structure in benzaldehyde oximes on the formation of aldehydes and nitriles under photoinduced electron-transfer conditions" (2006). Basic Sciences Faculty Publications. 28.
https://doi.org/10.1021/jo061325m
https://collections.uhsp.edu/basic-sciences_pubs/28