E. A. Luk’yanets

Phthalocyanines and related compounds: XLV. Nucleophilic substitution of chlorine in tetrachlorophthalonitrile: Synthesis of aryloxy-aubstituted phthalonitriles and phthalocyanines derived from them

Nucleophilic substitution of chlorine in tetrachlorophthalonitrile by the reaction with aryloxy anions is studied. Depending on the reactant ratio, the products of substitution of one, two, and/or three chlorine atoms are formed. Their tetramerization gives aryloxychloro-substituted phthalocyanines having the absorption band in the near-IR range.

Phthalocyanines and related compounds: XLIII. Synthesis of poly[phenyl(alkyl)sulfanyl]-substituted phthalonitriles and some phthalocyanines based thereon

Nucleophilic substitution of chlorine atoms in tetrachlorophthalonitrile by benzene- and alkanethiols in the presence of a base was studied at different reactant ratios. The substitution is characterized by complete regioselectivity: the chlorine atom in position 4 of tetrachlorophthalonitrile is replaced first; next follows replacement of the 5-chlorine atom. The reactions of tetrachlorophthalonitrile with nucleophiles at ratios of 1:2 and 1:4 lead to the formation of the corresponding 3,6-dichloro-4,5-bis[phenyl(alkyl)sulfanyl]- and tetrakis[phenyl(alkyl)sulfanyl]phthalonitriles. The latter were converted into metal complexes of [phenyl-(alkyl)sulfanyl]-substituted phthalocyanines which absorb in the red and near-IR regions of the electronic spectra.

Phthalocyanines and related compounds: XLIV. Synthesis of conjugates of phthalocyanines with rhodamines

A series of conjugates of sulfo- and carboxy-substituted phthalocyanines with rhodamines were prepared, and their electronic absorption and luminescence spectra were studied. An intramolecular transfer of the excitation energy from the rhodamine moiety (donor) to the phthalocyanine moiety (acceptor) was revealed.

Phthalocyanines and related compounds: XLVII. Nucleophilic replacement of chlorine atoms in tetrachlorophthalonitrile. Synthesis of phenyl(alkyl)amino-substituted phthalonitriles and some phthalocyanines based thereon

Nucleophilic replacement of chlorine atoms in tetrachlorophthalonitrile by the action of primary and secondary amines was studied. The reactions of tetrachlorophthalonitrile with amines at a ratio of 1: 10 gave with high yields and regioselectivity the corresponding 4,5-diamino-3,6-dichlorophthalonitriles from cyclic secondary amines and 4-amino-3,5,6-trichlorophthalonitriles from primary amines and acyclic secondary amines. 4-Amino-3,5,6-trichlorophthalonitriles were used to synthesize cobalt and zinc phthalocyanine complexes. It was shown that replacement of chlorine atoms in the pyrrolic β-positions of hexadecachlorophthalocyanines by amino groups is not accompanied by red shift of the long-wave absorption band in the electronic spectra.

Phthalocyanines and related compounds: XLVIII. Stepwise nucleophilic substitution in tetrachlorophthalonitrile: Synthesis of polysubstituted phthalonitriles

Chlorine-containing products of incomplete nucleophilic substitution in tetrachlorophthalonitrile were subjected to further reaction with nucleophiles. The nature of the nucleophiles and the order of their introduction into stepwise nucleophilic substitution in tetrachlorophthalonitrile were shown to be of principal importance for selective synthesis on this basis of phthalonitrile derivatives with various substituents.

Zinc phthalocyanine-based water-soluble thiolated photosensitizer and its conjugates with gold nanoparticles: Synthesis and spectral properties

A new photosensitizer, monoconjugate of zinc octa-4,5-carboxy-phthalocyanine with L-cysteine, which is rather readily soluble in water, has been synthesized and characterized. The chemisorption of its molecules on the surface of gold nanoparticles with different sizes has been studied. A comparative analysis of the spectral characteristics of the synthesized conjugates of gold nanoparticles with the photosensitizer has shown that the photosensitizer grafted to gold nanoparticles exhibits rather intense fluorescence. Therefore, such conjugates can be used for photodynamic therapy of tumors.

Phthalocyanines and related compounds: XLII. Synthesis of phenyl-substituted tetraazachlorins and tetraazabacteriochlorins

New oxidation-resistant hexaphenyl-substituted tetramethyltetraazachlorin, its nickel complex, and tetraphenyl-substituted octamethyltetraazabacteriochlorin and octamethyltetraazaisobacteriochlorin nickel complexes were synthesized for the first time by mixed condensation of diphenylm aleonitrile with tetramethylsuccinonitrile in the presence of lithium dimethylaminoethoxide or nickel chloride. The products were characterized by electronic absorption, 1H NMR, and mass spectra. Mixed condensation of diphenylsuccinonitrile with phthalonitrile in the presence of nickel chloride was found to give nickel complexes of phenylsubstituted benzo-fused tetraazaporphyrins rather than their hydrogenated derivatives.

Phthalocyanines and related compounds: XLI. Synthesis of 9,10-diphenylanthracene-2,3-dicarboxylic acid derivatives

Derivatives of 9,10-diphenylanthracene-2,3-dicarboxylic acid were synthesized by the Diels-Alder reaction of 1,3-diphenylisobenzofuran with adducts of furan (or silvan) and the corresponding maleic (fumaric) acid derivative or with trans-cyclohex-4-ene-1,2-dicarbonitrile, followed by aromatization.

Phthalocyanines and related compounds: XLVI. [4+2]-cycloaddition of tetraazaporphine to dienes of the cyclopentadiene series

The [4+2]-cycloaddition reaction of unsubstituted tetraazaporphine as the dienophile with a series of dienes of the cyclopentadiene series gave novel norbornene-condensed tetraazachlorins, tetraazabacteriochlorins, and tetraazaisobacteriochlorins. It was shown that, depending on the type of the diene, the reagent ratio, reaction time, and temperature mono-or bis-adducts are formed. The compounds obtained were characterized by the elemental analyses, electronic absorption spectra, 1H NMR spectra, and mass spectra.

Mesoporous Silica Particles as Nanocontainers for Phthalocyanine Photosensitizers: Estimation of Efficiency in In Vivo Experiments

The template synthesis of mesoporous silica nanoparticles with predetermined size and porous structure is carried out. Water-soluble photosensitizer Photosens is used to study the possibility of applying such particles as containers for photosensitizers of a phthalocyanine series. In vivo experiments have shown that the application of such nanocontainers for the delivery of Photosens to a tumor makes it possible to improve the efficiency of fluorescence diagnostics and the photodynamic therapy of cancer.