A. O. Terent’ev

General methods for the preparation of 1,2,4,5-tetraoxanes – key structures for the development of peroxidic antimalarial agents

General methods are presented for the preparation of symmetric and asymmetric 1,2,4,5-tetraoxanes, based on peroxidation of carbonyl compounds and their derivatives.

Synthesis of peroxide compounds by the BF3-catalyzed reaction of acetals and enol ethers with H2O2

Aliphatic and alicyclic gem-bis-hydroperoxides and their derivatives, bis(1-hydroperoxycycloalkyl) and bis(1-hydroperoxyalkyl) peroxides, dispiro- and tetraalkyl-1,2,4,5-tetroxanes were synthesized by the reaction of aliphatic and alicyclic acetals and enol ethers with H2O2 in the presence of BF3 in anhydrous Et2O.

Synthesis and Antifungal Activity of Arylthiocyanates

A new method for the synthesis of arylthiocyanates from derivatives of aniline, pyrrole, and indole is described. Products had antimicrobial activity. Dithiocyanates N-methylpyrrole and N-phenylpyrrole were active against Candida albicans, Candida tropicalis, Candida krusei, and Aspergillus niger with activity levels comparable to those of fluconazole and amphotericin.

Synthesis of nine-, ten-, and fifteen-membered alkenolides by the oxidative cleavage of the bridging C=C bond in 2-oxabicycloalkenes

Hydroperoxidation of C=C-bridged 2-oxabicycloalkenes in which the five- or six-membered oxacycle is fused with the five-, six-, or twelve-membered hydrocarbon ring was studied. The Cu(OAc)2-catalyzed decomposition of the resulting hydroperoxides afforded nine-, ten-, or fifteen-membered trans-alkenolides, respectively. The latter compounds were obtained as pairs of regioisomers, with the isomers in which the double bond is more remote from the ether oxygen atom predominating.

Peroxidation of β-diketones and β-keto esters with tert-butyl hydroperoxide in the presence of Cu(ClO4)2/SiO2

Reactions of β-diketones and β-keto esters with tert-butyl hydroperoxide under heterogeneous conditions using SiO2-supported copper(II) perchlorate as a catalyst give rise to α-peroxidation products in 65—82% yields. A possibility to reuse the catalyst was demonstrated.

A new property of geminal bishydroperoxides: Hydrolysis with the removal of hydroperoxide groups to form a ketone

A new property of geminal bishydroperoxide was discovered: the ability to hydrolyze in acid medium in the presence of hydrogen peroxide with the formation of ketones. The most resistant to hydrolysis are the cyclic C6-bishydroperoxydes: at room temperature within one day they are practically not hydrolyzed; less stable is bishydroperoxycycloheptane (C7): in a day its one fifth part is hydrolyzed. Bishydroperoxydes with the cycles of C8 and C12 for the same time hydrolyzed to 80 and 90% respectively. Of the two linear bishydroperoxydes, 2,2-dihydroperoxydecane, with sterically unhindered center, is more resistant to hydrolysis than 6,6-dihydroperoxyundecane.

Synthesis and antimicrobial activity of geminal bis-hydroperoxides

A series of six new geminal bis-hydroperoxides were synthesized based on cyclic ketones. Experiments in vitro show that the synthesized compounds exhibit pronounced antimicrobial properties that are comparable with the effect of some antiseptics and, to a lesser extent, antibiotics. Tests on B. cereus, E. coli, P. aeruginosa, S. aureus, C. albicans, and A. niger showed that bis-hydroperoxides were similar to hydrogen peroxide with respect to both the spectrum of action and the MIC level (0.1, 1.0, and 10 mg/mL), which is evidence for a similar mechanism of antimicrobial action.

Oxidative C-O coupling of benzylmalononitrile with 3-(hydroxyimino)pentane-2,4-dione

Oxidative C-O coupling of benzylmalononitrile with 3-(hydroxyimino)pentane-2,4-dione has been accomplished. This reaction is the first example of oxidative C-O coupling of a malononitrile with an oxime. The best yield (65%) of the coupling product, 2-benzyl-2-[(2,4-dioxopent-3-ylidene)aminooxy]malononitrile, has been achieved with the use of Cu(ClO4)2 · 6 H2O as oxidant. It is believed that the reaction involves intermediate formation of oxygen-centered aminoxyl radical.

Synthesis of peroxides from β,δ-triketones under heterogeneous conditions

Heterogeneous reactions of β,δ-triketones with ethereal hydrogen peroxide in nonpolar solvents, catalyzed by phosphomolybdic acid, afforded mixtures of stereoisomeric ozonides, tricyclic monoperoxides, and bridged tetraoxanes. The trioxolane ring is formed by the carbonyl groups located in the δ-position with respect to each other.

Electrochemical oxidation of 1,1-dihydroxy-4-methylcyclohexane on platinum anode. Synthesis of 3,12-dimethyl-7,8,15,16-tetraoxadispiro[5.2.5.2]hexadecane

The possibility is shown of electrochemical synthesis of 3,12-dimethyl-7,8,15,16-tetraoxadispiro[5.2.5.2]hexadecane that belong to the class of 1,2,4,5-tetraoxanes by oxidation of 1,1-dihydroperoxy-4-methylcyclohexane using a Pt anode.