The material presented in this review is devoted to scientific research carried out at one of the oldest graduating departments of ISUCT - the Department of Fine Organic Synthesis Technology. For citation: Danilova E.A., Galanin N.E., Islyaikin M.K., Maizlish V.E., Berezina G.R., Rumyantseva T.A., Suvorova Yu.V., Znoiko S.A., Kustova T.V. Achievements in the field of chemistry of macroheterocyclic compounds at the department of technology of fine organic synthesis. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2023. V. 66. N 7. P. 111-119. DOI: 10.6060/ivkkt.20236607. 6826j.

The solubility of 1-imino-2-phenyl-1H-indene-3-amine with fragments of 1,4-phenylenediamine and 1,3,4-, 1,2,4-thiadiazoles in ethanol and DMF in the 298–318 K range of temperatures. Patterns of the dissolution of macroheterocyclic compounds are discussed. The thermodynamic parameters of the dissolution of the synthesized compounds are calculated.

In this work 5,10,15,20-tetrakis(1`-methyl-pyrid-4- and-3-yl)porphin tetratosylates and tetraiodide [H-2(1`-methyl-Py-4- and -3)(4)P](4+) (X-)(4), 5,10,15,20-tetrakis(1'-methyl-pyrid-4- and -3-yl)porphin tetratosylates cobalt [Co-tetrakis(1`-methyl-Py-4- and -3)(4)P](4+) (Ts-)(4) have been synthesized and characterized. These compounds were differed by the isomerism of the meso-substituent of the porphyrin molecule and the nature of the counterion (Ts-, I-). The data of the redox-behavior and efficiency of the use of porphyrin compounds in oxygen reduction reaction (ORR) have been obtained. The electrochemical behavior has been studied by using the cycling voltammetry method. It should be noted that two stages of the electroreduction process were observed in an argon medium for ligands. For the cobalt complexes additional processes was found. The process of the porphyrin macrocycle electroreduction in the potential region of -0.78 ... -1.36 V and the Co3+<-> Co2+, oxidation (reduction) process localized on the metal atom at E-red/ox = 0.19 V were found. The N-substitution of the pyridyl fragment of porphyrins leads to a small increase in their reducing ability, in comparison with unsubstituted tetrapyridylporphyrins [H-2(Py-4- and -3)(4)P]. The possibility of using water-soluble porphyrins in the ORR electrocatalysis has been considered. It has been shown that the nature of the metal cation has a significant effect on the electrocatalytic activity of compounds in the molecular oxygen ionization reaction of in an aqueous-alkaline media. The activity of Co-complexes was increased by similar to 50-90 mV compared with ligands and a system without a catalyst at similar to 140-160 mV.

The solubilities of compounds based on 1-imino-2-phenyl-1H-indene-3-amine with 1,4-diaminonaphthalene and 1,4-diaminonaphthalene-5-sulfonic acid fragments in DMF and ethanol at 298–318 K are studied via isothermal saturation with spectrophotometric monitoring of their concentrations. Patterns of the dissolution of 1 : 2, 2 : 1, and 2 : 2 products of condensation in DMF and ethanol are discussed. The thermodynamic parameters of the dissolution of the synthesized compounds were calculated.

Методом изотермического насыщения со спектрофотометрическим контролем концентрации изучена растворимость соединений на основе 1-имино-2-фенил-1H-инден-3-амина с фрагментами 3,5-диамино-1,2,4- и 2,5-диамино-1,3,4-тиадиазолов в ДМФА и этаноле в интервале температур 298-318 К. Обсуждены закономерности растворения продуктов конденсации состава 1:2, 2:1 и 2:2 в индивидуальных растворителях. Рассчитаны термодинамические параметры растворения синтезированных соединений.

By the reaction of 1-imino-2-phenyl-1H-indene-3-amine with 1,4-naphthylenediamine and 1,4-diaminonaphthalenesulfonic acid linear products of 1 : 2 and 2 : 1 condensation as well as macrocyclic compounds were synthesized.

The present communication is a continuation of the systematic studies of the authors in the field of synthesis and studying the properties of macroheterocyclic compounds, as large as possible structural modifications allow currently to synthesize macroheterocyclic compounds, differing in composition, the nature of their constituent heteroatoms and make this class of compounds promising from the point of view of directed synthesis to obtain materials with valuable practical properties. Condensation products and macroheterocyclic compounds of a symmetrical structure are synthesized by the interaction of diimine 2-methylindandione-1,3 with 2,4-diaminobenzenesulfonic acid and 3,5-diamino-1,2,4-thiadiazole in a molar ratio of 2:1. Condensation products constitute a powdery substance with different shades of red color, soluble in water and organic solvents of different nature. Macroheterocyclic compounds were synthesized with two ways. The first method is cyclization of compounds of structure 2:1 in a symmetric structure, and the second in a molar ratio of the starting materials. A purification was performed by column chromatography on alumina of II degree of activity by Brockmann eluent acetone - chloroform, 1:1 by volume. An identification of the synthesis products was performed by thin-layer chromatography on plates Silufol UV-254 (eluent – acetone - chloroform, 1:1 by volume). The compounds were characterized by data of IR, electronic and 1H NMR spectroscopy. Electronic absorption spectra were measured on instrument Hitachi U-2010 in quartz cuvettes at 20 °C. IR spectra were obtained on the device Avatar 360 FT-IR ESP in KBr. 1H NMR spectra of solutions of samples in acetone – D6 were recorded on device "AMD Brucker 500" with an internal standard of TMS. The data of elemental analysis obtained on the instrument CHNS-O Analyzer FlashEA 1112 Series. A hypsochromic shift of the absorption bands was observed upon closure in a cycle. The widened absorption bands in the visible part of the electron spectrum indicate that the molecules of synthesized compounds have a flat structure and the absorption due to individual fragments, which are part of molecules and single-chain pairing of the synthesized structures.Forcitation:Berezina G.R., Nikolaeva K.A. Synthesis and properties of macrocyclic compounds with fragment of methylindandone. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 6. P. 29-34

The reactions of 1-imino-2-phenyl-1 H -inden-3-amine with 3,5-diamino-1,2,4- and 2,5-diamino-1,3,4- thiadiazoles were used to synthesize linear 1: 2 and 2: 1 condensation products, as well as symmetrical macroheterocyclic compounds. The synthesized compounds were characterized by IR, UV, and 1 Н NMR spectroscopy.

The dissolution of compounds based on 1-imino-2-phenyl-1H-inden-3-amine with fragments of 3,5-diamino-1,2,4- and 2,5-diamino-1,3,4-thiadiazoles in DMF and ethanol is investigated by means of isothermal saturation with spectrophotometric concentration monitoring in the temperature range of 298–318 K. Characteristics of the dissolution of the products of condensation with compositions 1 : 2, 2 : 1, and 2 : 2 in individual solvents are presented. Thermodynamic parameters of the dissolution of the synthesized compounds are calculated.

New sulfo and alkylsulfamoyl substituted 2,9,16,23-tetrakis(1-benzotriazolyl) 3,10,17,24-tetrakis(4-cyclohexylphenoxy) phthalocyanines and their Cu(II) complexes were synthesized. Their physicochemical properties such as electronic absorption, solubility in organic solvents, thermostability and mesomorphism were investigated. It was established that introduction of sulfo group into cyclohexylphenoxy fragment of the studied phthalocyanines causes bathochromic shift of long wave band s in both DMF and concentrated sulfuric acid solutions. In contrast, introduction of octadecylsulfamoyl substituentsdoes not influence the position of Q band in DMF, but shifts this band hypsochromically. The performed synthesis revealed that introduction of bulky fragments into ortho-position with respect to the oxygen atom of aryloxy group excludes manifestation of liquid crystalline properties. While substitution by the same substituent in para-position leads to formation of mesophase. This fact can be connected with the sterical hindrance of liquid crystalline molecular packing. Thus, it was established that the presence of donor and acceptor fragments in mix-substituted phthalocyanines is important but not determining factor for their mesophase formation. The forecast data on the absence of mesomorphism of new phthalocyanine derivatives with sulfo and alkylsulfamoyl groups are in a good agreement with the experimental data, which is the evidence of the applicability of the method used to identify mesogen / non-mesogen structures for this class of compounds.

The solubility of substituted copper tetraantraquinonoporphyrazines is studied in the temperature interval of 288–308 K. The regularities of the dissolution of complexes in alkaline water solutions as a function of different substituents located at the periphery of the molecule are discussed. The thermodynamic parameters of the dissolution of synthesized metal complexes are calculated.

Reaction of 2-methylindan-1,3-dione diimine with diaminobiphenyl (3,3′-dichloro-, 3,3′-dimethoxy-, and 2,2′-disulfo-) derivatives afforded the 2: 1 cyclization products and symmetric macrocyclic compounds. Structures of compounds were confirmed by IR, UV, and NMR spectroscopy data.

Linear condensation products and macrocyclic compounds of symmetric structure were synthesized by reacting of aminoimino-2-phenylindandione with biphenyl-4,4′-diamine, 4,4′-sulfandiyldianiline, and 4,4′-oxydianiline. The obtained compounds were characterized by IR, UV, and 1H NMR spectroscopy.

Phenylendiamines and based on its macroheterocyclic compounds were synthesized by interaction indandione-1,3 with 2,4-diaminesulfonis acid and 2,4-diaminophenol. Data of infrared and electronic spectra were presented.

Reaction of 1-imino-2-phenyl-1 H -inden-3-amine with 3,3′-dichloro-, 2,2′-disulfo-, and 2,2′-dinitrobiphenyl-4,4′-diamines gave 2 : 1 and 1 : 2 linear condensation products and symmetrical macroheterocycles. The products were characterized by the IR, UV, and 1H NMR data.

The theoretical generalization of the experiments results on oxidative ammonolysis of 4-phenyl- and 4-brom-o-xylenes was carried out. It has been established, that owing to electronic factor of both phenyl group, and bromine atom, in both cases the para-methyl group is activated the first and meta-methyl group is activated the second. The electronic effect of both substituents was shown to influence only on activation of para- methyl group, and as a result, the corresponding intermediate mono nitril is formed in the first place, which in turn is converted into the target dinitril.

Indandione reacts with m-phenylenediaminosulfonic acid or 2,4-diaminophenol to form compounds with phenylenediamine fragment. Complexes of these compounds with copper, cobalt, and zinc were synthesized. IR and UV spectroscopic data are presenred.