Журнал "Макрогетероциклы"

Behavior of Octa-(benzo-15-crown-5)substituted Metal Phthalocyanines in Polar Media and their Immobilization on Solid Supports

Elena V. Ovsyannikova,^a Nataliya F. Goldshleger,^b Nadezhda M. Kurochkina,^a Vladimir E. Baulin,^a,c Aslan Yu. Tsivadze,^a and Ninel M. Alpatova^a@

^aA.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, 119991 Moscow, Russia

^bInstitute of Problems of Chemical Physics, Russian Academy of Sciences, 142432 Chernogolovka, Russia

^cInstitute of Physiologically Active Compounds, Russian Academy of Sciences, 142432 Chernogolovka, Russia

^@Corresponding author E-mail: alpatova@elchem.ac.ru

Self-organization of phthalocyanines (Pc) as a result of stacking interaction between aromatic rings provides, in particular, their rather low solubility which increases when alkyl, alkylaromatic and polar groups for organic and aqueous media, respectively, are introduced as substituents in macrocycles. The presence of crown ethers groups both enhances solubility of Pc and provides new properties for these macrocyclic compounds: the crown fragments annulated or introduced via oxygen bridges provide self-organization of the Pc molecules involving the guest cation, whose stability depends on the observation of the principle of geometrical conformity and multiplicity of interactions, namely, a growing number of reacting groups. Phthalocyanine molecules comprising eight crown containing substituents, octa-(benzo-15-crown-5)phthalocyanines, to the utmost meet these requirements. Electronic spectroscopy as the most informative method for studying the aggregation of crown-substituted phthalocyaninates of metals in solution was used to study: 1) the behavior of octa-(benzo-15-crown-5)phthalocyaninates of nickel (Nicr8Pc) and cobalt (Cocr8Pc) in mixed solvents and in polar media including water; 2) the formation of related composites on ITO and quartz by the layer by layer deposition method; 3) the embedding of Pc in the tetraalkylammonium bromide matrix. In such conditions crown containing Pc can form a number of structures, for example, ‘sandwich’ heteronuclear complexes if a complex forming cation is larger than the crown ether cavity. It has been shown that complex formation between crown fragments of Mcr8Pc (M = Ni, Co) and cations (Na+, K+ and TBА+) provides such phthalocyanines with solubility in a polar organic medium, namely, propylene carbonate. It was suggested that the possibility of dissolution is due to the presence of both a great number of substituents and an oxygen bridge between a benzo-crown group and a phthalocyanine macrocycle. The presence of a spacer provides crown groups with mobility which makes it possible to obtain identical ‘stack’ structures of Pc involving К+ or ТБА+ cations. For inorganic polar solvent (water), the presence of K+ in solution results in the dissolution of Mcr8Pc (M = Ni, Co) and the formation of stable charged forms of octa-crown-metallophthalocyaninates what allows them to be used in the development of composites consisted of ultra-thin layers of differently charged ions, K+/Mcr8Pc- PSS−.

DFT B3LYP Quantum-Chemical Calculation of Molecular Structures of (6.6.6)Macrotricyclic MII Complexes with (N,N,N,N)-Coordinating Ligand Formed in the MII–Hydrazinomethanethiohydrazide–Propanone Triple Systems

Denis V. Chachkov^b and Oleg V. Mikhailov^a@

^aKazan State Technological University, 420015 Kazan, Russia

^bKazan Branch of Interdepartmental Super-Computer Center of RAS, 420008 Kazan, Russia

^@Corresponding author E-mail: ovm@kstu.ru

Using DFT B3LYP method with 6-31G(d) basis set and the Gaussian 98 program, a calculation of geometric parameters of MnII, FeII, CoII, NiII, CuII and ZnII complexes with the tetradentate ligand – 4,6,6-trimethyl-2,3,7,8-tetraazanonen-3-dithiohydrazide-1,9 with NNNN-coordination of donor centres formed as a result of template processes in the MII–hydrazinomethanethiohydrazide–propanone triple systems, was carried out. The bond lengths and angles between various atoms in each of above-mentioned complexes is presented. It is noted that the additional 6-membered metalchelate cycle formed as a result of template “stitching”, is not planar and is turned round with respect to the two 6-membered cycles on rather considerable angle; moreover, none of the chelate cycles in these complexes is plane.

Crown Ethers in Extraction and Sorption. I. Bromoderivatives of Benzo- and Dibenzocrown Ethers in the Sorption Processes of Elements from Acidic Water Solutions

Victor V. Yakshin,^a@1 Оlga М. Vilkova,^а Sergei М. Pluzhnik-Gladyr,^b and Sergei А. Кotlyar^b@2

^aPublic Company «Leading Research Institute of Chemical Technology», 115409 Moscow, Russia

^bA. V. Bogatsky Physico-Chemical Institute, National Academy of Sciences of Ukraine, 65080 Odessa, Ukraine

^@1Corresponding author E-mail: vyakshin@bk.ru

^@2Corresponding author E-mail: kotlyar_sk@mail.ru

For the first time the reaction ability of bromoderivatives of benzo- and dibenzocrown ethers at sorption of ~30 elements from the water solutions of nitric and muriatic acids was studied. It was found, that an introduction of one (in the case of benzocrown ethers) or two (dibenzocrown ethers) bromine atoms into the phenylene rings of macrocycle increases the sorption properties of the aimed bromides in comparison with the corresponding unsubstituted crown ethers. In this case the properties of dibenzocrown ethers differ rather strongly. So, 4’,4’’,(5’’)-dibromo[3.3]dibenzo-18-crown-6 has low level of activity, but in going from [4.4]dibenzo-24-crown-8 to its 4’,4’’,(5’’)-dibromoderivative the sorption properties when extracting some elements from water solutions of hydrochloric acid increase in hundreds of times. Thus, a new highly selective agent for the extraction and separation of elements from multicomponent mixtures was found. Despite rather close spatial and electronic parameters, the reaction ability of 4’,4’’,(5’’)-dibromo- and 4’,4’’,(5’’)-diiodo[4.4]dibenzo-24-crown-8 differs dramatically because the latter is absolutely unselective and extracts 28 elements of all studied to the same extent. 

Synthesis of 2-Aryl-4,5-diphenyl-1-(N-β-D-glucopyranosyl)-imidazoles

Vijay S. Taile,^a@ Kishor M. Hatzade,^b Vikas D. Umare,^a and Vishwas N. Ingle^a

^aDepartment of Chemistry, Rashtrasant Tukadoji Maharaj Nagpur University, 440033 Nagpur, India

^bDepartment of Chemistry, D.B. Science College, 441614 Gondia, India

^@Corresponding author E-mail: vijaytaile@gmail.com

2-Aryl-4,5-diphenyl-1H-imidazoles (1a-g) were prepared by the reaction between aromatic α-diketone (benzil), ammonium acetate and substituted arylaldehyde. These imidazoles were glucosylated using α-acetobromoglucose to form 2-aryl-4,5-diphenyl-1-(N-β-D-2,3,4,6-tetra-O-acetylglucopyranosyl)imidazoles (2a-g) which were deacetylated by sodium methoxide to afford 2-aryl-4, 5-diphenyl-1-(N-β-D-glucopyranosyl)imidazoles (3a-g). All synthesized compounds were characterized spectroscopically.

Aminomethylation of Chlorophyll a Phorbine Derivatives Using bis(N,N-Dimethylamino)methane

Dmitry V. Belykh,^a@ Irina  S. Tarabukina,^a Ivan V. Gruzdev,^b and Alexander V. Kuchin^a

^aInstitute of Chemistry, Komi Scientific Centre, Ural Division of Russian Academy of Sciences, 167982 Syktyvkar, Russia

^bInstitute of Biology, Komi Scientific Centre, Ural Division of Russian Academy of Sciences, 167982 Syktyvkar, Russia

^@Corresponding author E-mail: belykh-dv@chemi.komisc.ru, belykh-dv@mail.ru

It has been shown that aminomethylation of the vinyl group in Zn complexes of chlorophyll a phorbine derivatives can be accomplished under the action of bis(N,N-dimethylamino)methane in the presence of weak acid (AcOH) at room temperature. The new chlorophyll a phorbine derivatives with two N,N-dimethylaminomethyl substituents in vinyl group were synthesized.