O. I. Koifman

Synthesis of tetraphenylporphins with active groups in the phenyl rings. 2. Preparation of tetrakis(hydroxyphenyl)porphins

Condensation of p-nitrobenzaldehyde with pyrrole in propionic acid with added acetic anhydride gave tetrakis(4-nitrophenyl)porphin (24%), by the reduction of which tetrakis(4-aminophenyl)porphin, which was also obtained by hydrolysis of tetrakis(4-acetamidophenyl)porphin, was synthesized.

Calix[4]arene-porphyrin molecular receptors for selective binding of ethylenediamines

A new zinc calix[4]arene-bis-porphyrinate was synthesized and its 1 : 1 and 1 : 2 complexation reaction with ehtylenediamine, diethylenediamine, and triethylenediamine in toluene at 298 K was studied by spectrophotometric titration and 1H NMR.

Novel aqueous soluble cobalt(II) phthalocyanines of tetracarboxyl-substituted: Synthesis and catalytic activity on oxidation of sodium diethyldithiocarbamate

Enhancement of the catalytic activity of phthalocyanine catalysts by immobilizing them on polymer matrix has been studied. It has been found that the immobilization of cobalt(II) phthalocyanines on polymers enhances their catalytic activity in the oxidation of sodium diethyldithiocarbamate by air oxygen under mild conditions.

Thermodynamic properties and selectivity of substituted liquid-crystal formylazobenzenes as stationary phases for gas chromatography

The retention of xylene, cresol, methylanisole, and lutidine isomers was studied by gas chromatography using the stationary phases based on mesomorphic 4-butyloxy-4′-formylazobenzene and 4-(3-hydroxypropyloxy)-4′-formylazobenzene. A thermodynamic interpretation of the structural selectivity of the nematic phase of the mesogens was proposed.

Kinetics and mechanism of oxidation of super-reduced cobalamin and cobinamide species by thiosulfate, sulfite and dithionite

We studied the kinetics of reactions of cob(I)alamin and cob(I)inamide with thiosulfate, sulfite, and dithionite by UV-Visible (UV-Vis) and stopped-flow spectroscopy. We found that the two Co(I) species were oxidized by these sulfur-containing compounds to Co(II) forms: oxidation by excess thiosulfate leads to penta-coordinate complexes and oxidation by excess sulfite or dithionite leads to hexa-coordinate Co(II)-SO2(-) complexes. The net scheme involves transfer of three electrons in the case of oxidation by thiosulfate and one electron for oxidation by sulfite and dithionite. On the basis of kinetic data, the nature of the reactive oxidants was suggested, i.e., HS2O3(-) (for oxidation by thiosulfate), S2O5(2-), HSO3(-), and aquated SO2 (for oxidation by sulfite), and S2O4(2-) and SO2(-) (for oxidation by dithionite). No difference was observed in kinetics with cob(i)alamin or cob(i)inamide as reductants.

Stability and catalytic properties of μ-oxo and μ-nitrido dimeric iron tetrasulfophthalocyanines in the oxidation of Orange II by tert-butylhydroperoxide

A study of catalytic activity of μ-nitrido- and μ-oxo-dimeric iron tetrasulfophthalocyanines in the oxidation of Orange II by tert-butylhydroperoxide in aqueous solutions has been performed. It is shown that though in one catalytic cycle activity of μ-oxo-dimer is higher, stability of this complex in oxidative conditions is poor. μ-nitrido-dimer combines relatively good catalytic activity with very high stability in the presence of tert-butylhydroperoxide. The mechanisms of oxidative decomposition of dimers and catalytic oxidation of Orange II have been proposed on the base of kinetic results. The products of catalytic processes are shown to be bio-degradable non-toxic small organic compounds.

Synthesis and coordination properties of the zinc complex of dimeric porphyrin in reactions with imidazole, 2-methylimidazole, and the pyridine in benzene

Dimeric porphyrin(2,6-bis[15′-(3″,5″-di-tert-butylphenol)-3′,7′,13′,17′-tetramethyl-2′,8′,12′,18-tetraethylporphin-5′-yl]-4-tert-buthylphenol) and its binuclear zinc complex were obtained from 4,4′-dimethyl-3,3′-diethyldipyrrolylmethane, 2,6-diformyl-4-tert-butylphenol and 3,5-di-tert-buthylbenzaldehyde. Coordina-tion properties of dimeric zincporphyrin in the intermolecular reaction with nitrogen-containing bases (imidazole, 2-methylimidazole, and pyridine) in benzene were studied. Geometry and electronic structure of the zincporphyrin and its molecular complexes were calculated by a quantum-chemical method. Energy characteristics of the intermolecular reaction of the dimeric zincporphyrin with bases were determined. The calculated energies of the central metal atom interaction with the nitrogen atom of an extra-ligand agree well with the stability of the Zn-porphyrin molecular complexes. The influence of the deformation distortions of the porphyrin ligand on the strength of the metal-extra-ligand σ-bond was established.

Improved method for synthesis of substituted tetraphenylporphins

Condensation of pyrrole with benzaldehydes in a mixture of xylene and chloroacetic acid gives a series of substituted tetraphenylporphins with yields exceeding the yields of porphyrins synthesized according to known preparative methods.

A B3LYP/6-31G(d) study of Diels-Alder reactions between cyclopentadiene and (E)-2-arylnitroethenes

AbstractThe B3LYP/6-31G(d) simulations of competing CDA and HDA reactions between cyclopentadiene and (E)-2-arylnitroethenes prove that regardless of the medium polarity, the processes leading to respective 5-nitro-6-aryl-bicyclo-[2,2,0]-hept-2-enes 3,4 (paths A and B) should be most favoured, and the more electrophilic (E)-2-(p-nitrophenyl)-nitroethene should be more reactive than the less electrophilic (E)-2-(p-methoxyphenyl)-nitroethene. Asymmetry of the transition complexes on the favoured pathways increases with increase of medium polarity, but not sufficiently to enforce the zwitterionic mechanism. Analysis of competing pathways leading to HDA adducts proves that not all these compounds can be formed directly from the adducts. In particular, on the path C, the initially formed 5-nitro-6-aryl-bicyclo-[2,2,0]-hept-2-enes 3 is converted to 2-phenyl-4-aza-5-oxy-bicyclo-[3,4,0]-nona-3,7-diene N-oxides 5 as a result of a [3.3]-sigmatropic shift. On the paths D–F leading to 2-phenyl-4-aza-5-oxy-bicyclo-[3,4,0]-nonadienes N-oxides 6–8, the reaction proceeds according to a one-step mechanism.

Complexation of zinc octaalkylporphyrin with mono-, di-, and triethylenediamines in toluene

The complexation of zinc octaalkylporphyrin with mono-, di-, and triethylenediamines in toluene was studied by spectrophotometry using the molar ratio method and by 1H NMR. The effect of the structure of the two-center organic base on the formation of 1 : 1 or 2 : 1 metal porphyrin-ligand complex was established. The stability constants of the resulting complexes were calculated and the concentration ranges of their existence were determined.