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The behavior of [1,2-bis(tert-butylperoxy)ethyl]benzene (I) on Pt electrode is studied by means of cyclic voltammetry (CVA). A comparison of the electrochemical properties of I and the properties of previously studied bridge-type 1,2,4,5-tetraoxane ((1,4)-1,4-dimethyl-7-(4-methylbenzyl)-2,3,5,6-tetraoxabicyclo[2.2.1]heptane) (II) shows that the biperoxide studied in this work is reduced on a Pt electrode at lower cathodic potentials and is resistant to electrooxidation.

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.

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.

Oxidative C-O-coupling of N-hydroxyphthalimide (NHPI) with toluene was studied. The reaction occurred in different organic solvents with a wide range of oxidants, such as (NH4)2Ce(NO3)6, PhI(OAc)2, KMnO4, Mn(OAc)3·2H2O, Pb(OAc)4, and Co(OAc)2/O2, to afford N-benzyloxyphthalimide in yield of 11–75%. Phthalimide-N-oxyl radicals, generated under the reaction conditions, could eliminate the hydrogen atom from the benzyl fragment of alkylarene at room temperature. Probably, formation of the product of the oxidative coupling occurred via recombination of benzyl and phthalimide-N-oxyl radicals.

The electrochemical synthesis of 3,12-dimethyl-7,8,15,16-tetraoxadispiro[5.2.5.2]hexadecane (1,2,4,5-tetraoxane) from 1,1-bis-hydroperoxy-4-methylcyclohexane on platinum electrode in a cell with separated and unseparated cathode and anode space in an aprotic solvent is conducted. The kinetics of electrochemical oxidation of 1,1-bis(hydroperoxy)-4-methylcyclohexane is studied. The current yield of the reaction is determined.

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.