In recent years, the number of pollinators in the world has significantly decreased. A possible reason for this is the toxic effects of agrochemicals reducing the immunity of insects that leads to their increased susceptibility to pathogens. Ascosphaera apis is a dangerous entomopathogenic fungus, afflicting both honeybees and bumblebees. We investigated fungicide activity of cyclic synthetic peroxides against A. apis isolated from Bombus terrestris L. The peroxides exhibited high mycelium growth inhibition of A. apis up to 94–100% at concentration 30 mg/L. EC50 values were determined for the most active peroxides. Two peroxides showed higher antifungal activity against A. apis than the commercial fungicide Triadimefon. The studied peroxides did not reduce the ability of bumblebees to fly and did not lead to the death of bumblebees. A new field of application for peroxides was disclosed.
Organic peroxides are an important class of compounds for organic synthesis, pharmacological chemistry, materials science, and the polymer industry. Here, for the first time, we summarize the main achievements in the synthesis of organic peroxides by the action of Lewis acids and heteropoly acids. This review consists of three parts: (1) metal-based Lewis acids in the synthesis of organic peroxides; (2) the synthesis of organic peroxides promoted by non-metal-based Lewis acids; and (3) the application of heteropoly acids in the synthesis of organic peroxides. The information covered in this review will be useful for specialists in the field of organic synthesis, reactions and processes of oxygen-containing compounds, catalysis, pharmaceuticals, and materials engineering.
The search for new classes of fungicides has long been important in plant protection due to the development of fungal resistance to currently used agrochemicals. Organic peroxides have long been regarded as exotic and unstable compounds. The discovery of the antimalarial activity of the peroxide natural product Artemisinin, an achievement that was recently recognized with the Nobel Prize, has brought organic peroxides into the medicinal and agrochemistry. In this paper, fungicidal activity of synthesized organic peroxides—geminal bishydroperoxide, bridged 1,2,4,5-tetraoxanes, and tricyclic monoperoxides—were tested in vitro against an important species of phytopathogenic fungi (F. culmorum, R. solani, A. solani, P. infestans, C. coccodes). We discovered that substituted bridged 1,2,4,5-tetraoxanes exhibit fungicidal activity comparable or superior to azoxystrobin and superior to geminal bishydroperoxide and tricyclic monoperoxides. The contact mode of action was demonstrated for the bridged 1,2,4,5-tetraoxane.
A breakthrough synthetic approach to geminal unsymmetrical alkylperoxyhydroperoxides has been developed based on CN fragment ozonolysis in a hydroperoxide-containing medium.
Visible-light photocatalysis enables the integration of classical electrophile/nucleophile chemistry with radical species (free radicals, radical cations, and radical anions) and metallocomplexes, significantly expanding the scope of organic transformations. Substrates capable of generating radicals via single-electron transfer (SET) are therefore of high value in this field. Among conventional radical precursors, organic peroxides occupy a distinctive position due to their unique reactivity. They can generate both oxygen-centered and carbon-centered radicals through either oxidative or reductive SET pathways. Furthermore, organic peroxides can act as radical precursors, nucleophiles, and oxidants. The review emphasizes the advancements of visible-light-mediated reactions utilizing the broad potential of organic peroxides for constructing various chemical bonds.