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.
Herein, we report an efficient one-pot synthesis of bridged aminodiperoxides via a three-component reaction of 1,5-diketones with geminal bishydroperoxides and ammonium acetate. The synthesized aminodiperoxides are stable despite containing an unprotected secondary NH-group adjacent to two peroxide functionalities. Under optimal conditions, the reaction affords aminodiperoxides in high yields (up to 88%) with outstanding selectivity and high atom economy, thereby eliminating the need for column chromatographic purification. The synthesized aminodiperoxides exhibit potent cytotoxicity and remarkable selectivity toward Jurkat, K562, and A549 cancer cell lines, and are significantly superior to the clinically used anticancer agent camptothecin. Among all tested compounds, 3ec is the most promising candidate, exhibiting high activity and selectivity toward all tested cell lines (Jurkat: CC50 = 12.9 µM, SI = 67.09; K562: CC50 = 19.6 µM, SI = 44.28; A549: CC50 = 48.2 µM, SI = 17.98). Furthermore, a novel class of fungicidal compounds has been discovered. The aminodiperoxides exhibit fungicidal activity against phytopathogenic fungi, in some cases comparable to the commercial fungicide Triadimefon.