Maxim M. Platonov

Convenient Synthesis of Geminal Bishydroperoxides by the Reaction of Ketones with Hydrogen Peroxide

Abstract A convenient procedure was developed for the synthesis of geminal bishydroperoxides by the sulfuric acid–catalyzed reaction of ketones with hydrogen peroxide in THF. Gem‐bishydroperoxides were prepared by the reactions of five‐ to seven‐membered cycloalkanones without additional purification in 80–95% yields with a purity of more than 95%; their acyclic analogs were prepared in 43–72% yields.

A new method for the synthesis of bishydroperoxides based on a reaction of ketals with hydrogen peroxide catalyzed by boron trifluoride complexes

Abstract A reaction of cycloalkanone, alkanone and alkyl aryl ketone ketals with H 2 O 2 catalyzed by boron trifluoride etherate and boron trifluoride–methanol complexes was studied. A new versatile method for the synthesis of bishydroperoxides and their derivatives, viz. 1,1′-dihydroperoxyperoxides and 1,2,4,5-tetraoxacyclohexanes, was developed based on this reaction.

Polyelectrolyte sorbents based on aliphatic ionenes for ion chromatography

2-4, 3-4, 2-8, 3-8, 3-6, 4-6, 6-8, 6-10-ionenes (polymers with quaternary nitrogen atoms in the main chain) served as modifiers in synthesizing polyelectrolyte sorbents for ion chromatography. The approaches to the synthesis and their stability are discussed. Cluster analysis was applied to separate aliphatic ionenes to three groups as chromatographic modifiers, namely hydrophilic, hydrophobic, and intermediate. Each group is characterized by a certain selectivity to sulfate, perchlorate, iodide and thiocyanate. The sorbents show high selectivity and efficiency up to 15,000 theoretical plates per meter.

A new oxidation process. Transformation of gem-bishydroperoxides into esters

A new oxidation process has been found where α,ω-dicarboxylic acid esters and ω-hydroxycarboxylic acid esters are formed on heating gem-bishydroperoxides in alcohol in the presence of BF3·Et2O. By addition of H2O2 to this reaction α,ω-dicarboxylic acid esters are formed almost selectively.

Ion-chromatographic selectivity of polyelectrolyte sorbents based on some aliphatic and aromatic ionenes

An aliphatic ionene with hydroxyl group (2HP-8 ionene), mixed aliphatic-aromatic ionenes (3-X and 6-X ionenes), aromatic ionene (Ph-X ionene), and viologen (Dp-X ionene) - polymers with quaternary nitrogen atoms in the main chain served as modifiers in synthesising polyelectrolyte sorbents for ion chromatography. The selectivity of produced and several previously prepared anion exchangers was compared with those of aliphatic ionenes. It was found that aromatic ionenes having a rigid structure of polymer chains are similar to their aliphatic analogues with shorter chains with a high charge density. Polyelectrolyte sorbents based on aromatic ionenes show higher selectivity to aromatic acids (e.g., 1-naphthalenesulfonic acid) as compared with aliphatic ionenes due to specific pi-pi interactions.

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.

Ring contraction of 1,2,4,5,7,8-hexaoxa-3-silonanes by selective reduction of COOSi fragments. Synthesis of new silicon-containing rings, 1,3,5,6-tetraoxa-2-silepanes.

The reducing agents Ph(3)P, (C(8)H(17))(3)P, or NH(2)C(S)NH(2) promote the ring contraction of nine-membered triperoxides, viz., 1,2,4,5,7,8-hexaoxa-3-silonanes, giving rise to seven-membered rings belonging to the previously unknown class of monoperoxides, viz., 1,3,5,6-tetraoxa-2-silepanes, in yields from 67% to 91%. Therefore, the selective reduction of the SiOOC fragments to SiOC in molecules containing simultaneously the COOC fragment was performed for the first time.

Application of the pattern-recognition method for modelling expert estimation of chromatogram quality

A method of nonparametric regression, namely the method of k-nearest neighbours, was applied in chromatography for creating an estimation criterion of chromatogram quality. A training set was constructed using expert estimation of a number of model and real chromatograms, and the method was learned to estimate chromatograms as a single image. The parameters for chromatogram estimation were selected, and their variance weights were determined. The proposed approach is compared with the existing criteria, and its advantages are shown. The method was successfully applied for searching for the optimum conditions for the ion-chromatographic determination of inorganic anions.

Synthesis of 1,1-bishydroperoxydi(cycloalkyl) peroxides by homocoupling of 11-15-membered gem-bis(hydroperoxy)cycloalkanes in the presence of boron trifluoride

A procedure was developed for the synthesis of 1,1′-bishydroperoxydi(C11-C15-cycloalkyl) peroxides based on homocoupling of geminal 11–15-membered bis(hydroperoxy)cycloalkanes in the presence of BF3⋅OEt2.

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.