O. V. Korenchenko

Anodic Doping of Electropolymerized Copper 2,9,16,23-Tetraaminophthalocyanine

Anodic polymerization of 2,9,16,23-tetraamino substituted copper phthalocyanine is studied in 0.1 M Bu4NBF4and Bu4NClO4in dimethylformamide (DMF). The electropolymerization rate in DMF is two to three times that in dimethyl sulfoxide, due to a lesser donor ability of DMF and a weaker blocking of radical cations formed during the oxidation of initial copper phthalocyanine. According to a study of the electrochemical behavior of polymerized copper phthalocyanine in neutral aqueous solutions, the anodic doping of the polymer is accompanied by one redox transition. The two redox transitions, observed in an aqueous solution of acid, are explained by two successive steps of oxidation of an aniline-like structure or by the involvement of two protonated systems in the doping process, specifically, a stacked system (phthalocyanine ligands collected in parallel stacks) and a polyaniline system.

Electrochemical and electrochromic properties of rare-earth metal diphthalocyanine complexes

The electrochemical and spectroelectrochemical properties of several new rare-earth metal diphthalocyanine complexes with different substituents containing both electron-withdrawing and -donating substituents in the phthalocyanine rings were studied. The influence of structural modification of the phthalocyanine complexes (viz., the nature of the central metal atom and substituents in the phthalocyanine rings and the number of phthalocyanine rings in the complexes) on the total number of redox transitions, their potentials, and spectral characteristics of anionic and cationic forms of the complexes was examined. The potentials of the first anodic and cathodic redox transitions of the diphthalocyanine complexes are in a good linear correlation with the ionic radii of lanthanides. The potentials of the observed redox transitions of the complexes under study correlate well with the sums of Hammett constants for the substituents and the minimum molecular electrostatic potential of the benzene rings in the phthalocyanine moiety, which serves as a measure of electron perturbations introduced by the substituents. The revealed regularities allow the prediction of the redox properties and structure of rare-earth element diphthalocyanine complexes, which are redox-active in a specified potential range.

ALKOXYCARBONYLIMINES OF HEXAFLUOROACETONE IN REACTION OF 2+4-CYCLOADDITION

The [2+4]-cycloadditions of alkoxycarbonylimines of hexafluoroacetone to cyclopentadiene andN-nitriles have been studied. Alkoxycarbonylimines of hexafluoroacetone may be considered as both dienophiles and 1,3-heterodienes.

Synthesis of trifluoroalanine derivatives

Abstract Reaction of hexafluoroacetone ethoxycarbonylimine with trimethylphosphite at r.t. results in the formation of fluoroalkenyl carbamate (1)instead of ordinary products of well-known reactions of acylimines of hexafluoroacetone — cyclic phosphoranes (2) (see [1]), and dimethylfluorophosphate. The structure of (1) was established on basis of NMR spectra and next reactions [2]: The new compounds would expected to be biologically active.

Effect of solvent and supporting electrolyte on redox conversions of electropolymerized copper tetraaminophthalocyanine

Electropolymerization of copper tetraaminophthalocyanine in dimethyl sulfoxide (DMSO) is studied, along with redox conversions of this polymer inDMSO and propylene carbonate (PC). At cathodic potentials, redox conversions of the polymer are similar to those of the monomer. At anodic potentials, the polymer exhibits some redox activity in PC and almost none, inDMSO. The redox conversions are attributed to the formation of a common system of conjugated bonds.

2-AIkoxyhexafluoropropyl-2-isocyanates

A convenient preparative method for the synthesis of 2-alkoxyhexafluoropropyl-2-isocyanates is proposed. The reactions of the isocyanates with amines and alcohols are studied.

Reaction of phosphorus-containing cyanoguanidines with hexafluoroacetone imines

Substituted hexafluoroacetone imines react with 1-(2-cyanoguanidino) alkylphosphonates at the C≡N group at −5-0°C, forming [2+4]-cycloaddition products, which are phosphorus-containing 4,4-bis(trifluoromethyl)1,3,5-oxadiazines. The reaction products are readily alkylated by substituted hexafluoroacetone imines at the nitrogen atom of the guanidine fragment. The two reactions are accompanied by tautomeric transformations of the guanidine fragment of the molecules. An NMR spectral analysis was carried out.

Reaction of O-triphenylphosphiminoformylisobutyrohydroximoyl chloride with hexafluoroacetone

O-Triphenylphosphiminoformylisobutyrohydroximoyl chloride reacts with hexafluoroacetone to give the product of a sigmatropic rearrangement, namely,α-(O-isopropylchloroformimino) hexafluoroisopropyl isocyanate.

Reaction of fluorine-containing 1,4,2-oxazaphospholine with OH-nucleophiles

Abstract1,4,2-Oxazaphospholine (I) decomposes upon the action of OH-nucleophiles with the formation of phosphonate esters (II).

Synthesis and properties N-(2-chloroperfluoroisopropyl)carbamates

Abstract N-(2-Chloroperfluoroprop-2-yl) alkyl (aryl) carbamates (1) are synthesized according to Treatment of (1) (or (1) received in situ [1]) with amine bases resulted in 2-alkoxyperfluoroisopropylisocyanates (2) or (and) alkoxycarbonylimines of hexafluoroacetone (3). The direction of the latter one depend on the starting alcohol and reactions conditions. The Arbusovs reaction of (1)with trialkylphosphites yields phosphonates (4) some of which were synthesized earlier [2]. The chemical properties of compounds (2), (3) and physiolgical activity of (4) are discussed.