Oxidation of organic sulfides and disulfides with a tert-butyl hydroperoxide-aluminum tri-tert-butoxide system

Methyl phenylethynyl and phenyl phenylethynyl sulfides are selectively converted into methyl phenylethynyl and phenyl phenylethynyl sulfones, respectively, under the action of system tert-butyl hydroperoxide-aluminum tri-tert-butoxide in benzene at 20 °C. The analogous oxidation of diphenyl disulfide results in S-phenyl benzenethiosulfonate.     

Synthesis and biological evaluation of colchicine and thiocolchicine derivatives bearing a Michael acceptor moiety in ring A

Russian Chemical Bulletin - A series of colchicine and thiocolchicine derivatives bearing a Michael acceptor moiety in ring A were synthesized. Some of these compounds exhibit cytotoxic activity in...     

Controlled polymerization of styrene in the presence of Blatter’s radicals

Russian Chemical Bulletin - Controlled polymerization of styrene (both self-initiated and initiated with azobisisobutyronitrile) in the presence of Blatter’s radical at 125 °C was...     

p-Quinones in the radical polymerization of styrene

Russian Chemical Bulletin - The polymerization of styrene in the presence of p-quinones of various structures was studied. The polymerization kinetics and molecular weight characteristics of...     

Oxidation of fullerene C<Subscript>60</Subscript> with the system aluminum tri-<Emphasis Type="Italic">tert</Emphasis>-butoxide—<Emphasis Type="Italic">tert</Emphasis>-butyl hydroperoxide

Oxidation of fullerene C₆₀ with the system aluminum tri-tert-butoxide-tert-butyl hydroperoxide, in which electron-excited dioxygen is generated, gave a complex mixture of fullerene oxides C₆₀O _x (x = 1–6). The pathways of their formation were proposed. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 296–300, February, 2008.     

Radical low-temperature oxidation of dibenzyl sulfide with the triphenylbismuth—tert-butyl hydroperoxide system

The reaction of Ph₃Bi with Bu^tOOH in a mole ratio of 1: 3 in hydrocarbon solvents affords the η²-peroxo complex of triphenylbismuth Ph₃Bi(η²O₂) which oxidizes the C-H bonds of the methylene group of dibenzyl sulfide. The reaction proceeds via the radical mechanism with the formation of intermediate unstable sulfur-containing hydroperoxide. Its decomposition is accompanied by the C-S bond cleavage, resulting in benzaldehyde. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1183–1185, June, 2008.     

Electron-excited dioxygen generated by the tri-tert-butoxyaluminum—tert-butyl hydroperoxide system as an efficient oxidant of aniline and some N-substituted anilines

The tri-tert-butoxyaluminum—tert-butyl hydroperoxide system generates molecular oxygen in the electron-excited singlet state (¹O₂), which oxidizes diphenylamine, N-ethylaniline, aniline, and 2,6-diisopropylaniline to form nitroxyl radicals. The latters were identified by ESR at 240—293 K. Oxidation proceeds via the intermediate formation of nitrogen-containing N-peroxide compounds.     

Liquid-phase oxidation of sulfides by an aluminum (and titanium) <Emphasis Type="Italic">tert</Emphasis>-butoxide—<Emphasis Type="Italic">tert</Emphasis>-butyl hydroperoxide system

A system aluminum (and titanium) tert-butoxide—tert-butyl hydroperoxide (1 : 2) under mild conditions (20 °C, 1 h) oxidizes aliphatic and alkylaromatic sulfides and diphenyl sulfide to the corresponding sulfones in yields close to 100%. The oxidation is induced by electron-excited dioxygen formed upon thermal decomposition of intermediate metal-containing peroxy trioxides (ozonides). The latter are formed as a result of the reversible reaction of aluminum or titanium tert-butoxides with tert-butyl hydroperoxide followed by the interaction of di-tert-butoxy-tert-butylperoxyaluminum and tri-tert-butoxy-tert-butylperoxytitanium that formed with another Bu^tOOH molecule. Aluminum-containing peroxide (Bu^tO)₂AlOOBu^t oxidizes sulfides to sulfoxides.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1663–1668, August, 2004.