Photochemical Production of MicromolarSuperoxideStandards in Aqueous SolutionT

Superoxide(O2-) is a reactive free radical that rapidly undergoes disproportionation to hydrogen peroxide and oxygen. This property makes preparation of superoxide standard for instrument calibration difficult. McDowell et al. (1983) showed photolysis of ketone and alcohol as a convenient method to generate superoxide through triplet and radical intermediates reacting with molecular oxygen. This study expands on this past work and investigates detailed mechanism of the reaction.

Photochemical degradation of 2,4-D and atrazine in well-defined media

Atrazine and 2,4-D are common herbicides used for crop, lawn, and rangeland management. Photochemical degradation has been proposed as one safe and efficient remediation strategy for both 2,4-D and Atrazine. In the presence of iron(llI) and hydrogen peroxide these herbicides decay by both thermal and light induced oxidation. Past studies have focused primarily on sun light as an energy source. This work provides a mechanistic description of herbicide degradation incorporating intermediate degradation products produced in the dark and under well-defined light conditions.

Photochemical Generation and Intramolecular Chemistry of β-Alkoxycarbenes

The photolytic phenanthrene-based precursors for both β-methoxycarbene and β-ethoxycarbene were synthesized with and without a deuterium label attached to the a carbon. The incorporation of this deuterium label allowed distinction between a 1, 2-H shift and a 1, 2-O shift pathway to the respective alkyl vinyl ether, without the influence of a primary kinetic isotope effect. Photolyses of these precursors gave rearrangement products of the expected β-alkoxycarbenes. In the case of β-methoxycarbene, no methyl vinyl ether was observed due to its volatility. However, the appearance of aldehyde peaks in the NMR spectra, from an apparent further rearrangement to acetaldehyde through an enol intermediate, indicated that a 1,2-H shift had occurred. Ethyl vinyl ether was isolated following the photolysis of the β-ethoxycarbene precursor. Quantification of the two pathways showed less than 2% undergoing an ethoxy shift to the ethyl vinyl ether. Yield experiments on this photolysis demonstrated a maximum yield of β-ethoxycarbene as 43%, though this decreased as the experiment continued. Computational work on the β-ethoxycarbene system indicates that the triplet scate is more stable than the singlet. In addition, the activation energy to the 1.2-H shift pathway is remarkably low and is clearly consistent with the observed overwhelming preference for this pathway in the experiment.