Porphyrazines of symmetric and unsymmetrical structure with fused fragments of 1,4-bis(2-phenoxyethoxy)benzene and 5,6-diphenylpyrazine. Synthesis and spectral characteristics

By alkylation of 3,6-dihydroxyphthalonitrile with 1-bromo-2-phenoxyethane 3,6-bis(2-phenoxyethoxy) phthalonitrile was obtained. A random condensation of the nitrile with 2,3-dicyano-5,6-diphenylpyrazine in 1-butanol in the presence of lithium 1-butanolate porphyrazines were synthesized of symmetric and unsymmetrical structure, and their spectral characteristics were investigated.     

Cobalt Porphyrazines with Heterocyclic Substituents

Reactions of 4,5-diaminophthalodinitrile with thionyl chloride, sodium nitrite in concentrated sulfuric acid, and phenanthrenequinone gave, respectively, 5,6-dicyano-2,1,3-benzothiadiazole, 5,6-dicyano- 1H-benzotriazole, and 6,7-dicyano-2,3-(9,10-phenanthro)quinoxaline, from which the corresponding cobalt porphyrazines were prepared. The effect of the heterocyclic moiety on the physicochemical and spectral properties of porphyrazines was elucidated.     

Unsymmetrical Pentoxy-Substituted Porphyrazines

The reactions of 3,6-dipentoxyphthalonitrile (A) in the 1-pentanol - magnesium pentylate medium with phthalonitrile, 2,3-di(methylsulfanyl)-2-butenedinitrile, and 2,3-dihydro-1,4-dithiin-5,6-dicarbonitrile (B) were performed. Unsymmetrically substituted porphyrazines A₃B were prepared and studied. The influence of the structure of fragment B on the spectral characteristics of the porphyrazines was examined.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 3, 2005, pp. 504–508.Original Russian Text Copyright © 2005 by Nikolaev, Kudrik, Kulinich, Shaposhnikov.     

Bis(dimethylamino)porphyrazines: synthetic, structural, and spectroscopic investigations

The synthesis and isolation of unsymmetrical porphyrazines bearing two, four, and six bis-(dimethylamino) functionalities has been achieved via the base-catalyzed cross-condensation of 1,2-dicyanobenzene 8 and bis(dimethylamino)maleonitrile 7. In addition, the benzo-fused hexaaminoporphyrazine dimer 10 was prepared from condensation of dinitrile 7 (in excess) with benzenebis(1,3-diiminopyrroline) 9. Electrochemical studies reveal that all porphyrazines may be readily oxidized. The X-ray structures of porphyrazines 2b and 5a and the cis isomer 3a are presented. The latter is the first structure of a porphyrazine having a cis-type substitution pattern. The extended pi-conjugation in dimer 10 causes a approximately 100 nm red-shifted Q-band in the electronic absorption spectrum.     

2-(2-Furyl)-5,6-dihydro-1(3)H-acenaphtho[4,5-d]imidazole. Synthesis and electrophilic substitution reactions

2-(2-Furyl)-5,6-dihydro-1(3)H-acenaphtho[4,5-d]imidazole was synthesized by the Weidenhagen reaction of acenaphthene-4,5-diamine with furfural. Alkylation of the title compound with methyl iodide in KOH-DMSO gave isomeric 1- and 3-methyl derivative, the latter being the major product. 2-(2-Furyl)-3-methyl-5,6-dihydro-3H-acenaphtho[4,5-d]imidazole was subjected to electrophilic substitution reactions (bromination, nitration, formylation, acylation, and sulfonation. Depending on the conditions, electrophilic attack was directed at the furan ring or acenaphthene fragment or both these.     

Synthesis and some transformations of 2-(2-thienyl)-1(3)H-imidazo[4,5-f] quinoline

2-(2-Thienyl)-1(3)H-imidazo{cm[4,5-f]}quinoline was synthesized by the Weidenhagen reaction of quinoline-5,6-diamine with thiophene-2-carbaldehyde. Its methylation in the system KOH-DMSO gave isomeric 1-methyl-2-(2-thienyl)-1H- and 3-methyl-2-(2-thienyl)-3H-imidazo{cm[4,5-f]}quinolines, the latter being the major product. The 3-methyl derivative was subjected to electrophilic substitution reactions (bromination, nitration, formylation, acylation, sulfonation). Depending on the conditions, electrophilic attack was directed at the thiophene or quinoline fragment or both these.     

四(4-硝基苯基)卟啉和四(4-氨基苯基)卟啉的合成

四（４氨基苯基）卟啉（ＴＡＰＰ）是含有４个反应活性基团的卟啉衍生物,可在模拟某些生物过程或氧化还原反应的树枝状或簇状分子中作为富电子中心,也可直接用来制备光电器件或作为光电功能聚合物的功能单体和交联剂,因此,ＴＡＰＰ的合成研究具有重要意义［１］．...     

Synthesis and Characterisation of Unsymmetrical Porphyrazines Containing Bis(hydroxyethylthio) Substituents

Summary. Unsymmetrical porphyrazines bearing a single peripheral bis(hydroxyethylthio) moiety were synthesised by mixed condensation of bis(2-hydroxyethylthio)maleonitrile and phthalonitrile. Complexation of the thioether groups of metal-free porphyrazine with PdCl₂ further lowered the intensity of the Q-band absorption of the porphyrazine core. The new compounds were characterised by elemental analyses, IR, ¹H NMR, UV-Vis, and mass spectra.     

Synthesis and Some Properties of Transition Metal Complexes with Octa(sulfophenyl)tetrapyrazinoporphyrazine

Sulfonation of metal complexes of octaphenyltetrapyrazinoporphyrazine gave water-soluble octasulfoderivatives. The complexes synthesized were studied by EPR, ¹H NMR, electronic, and IR spectroscopy. It was found that, unlike complexes of other porphyrins and porphyrazines, this nickel complex is paramagnetic, whereas the cobalt complex gives no EPR signal. The cobalt complex can reversibly bind an oxygen molecule.__________Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 5, 2005, pp. 545–549.Original Russian Text Copyright © 2005 by Shishkin, Kudrik, Shaposhnikov.     

Synthesis,Structures and Room Temperature Phosphorescence of 2-(2-Methoxynaphthyl)-1H-imidazo[4,5-f][1,10]-(1)phenanthroline-Cu(I) Complexes

A new ligand, 2-(2-methoxynaphthyl)-1H-imidazo[4,5-f][1,10]phenanthroline(mnipH), was synthesized by the condensation of 2-methoxy-1-naphthaldehyde and 5,6-diamino-1,10-phenanthroline. Then three ionic copper(I) complexes were obtained through the reactions of [Cu(MeCN)_4]ClO_4, mnipH and the chelating diphosphine ligands with a molar ratio of 1:1:1. The photoluminescence and the corresponding luminescent mechanism of all copper(I) complexes in the solid state were investigated at room temperature.     

Synthesis and Characterisation of Unsymmetrical Porphyrazines Containing Bis(hydroxyethylthio) Substituents

Unsymmetrical porphyrazines bearing a single peripheral bis(hydroxyethylthio) moiety were synthesised by mixed condensation of bis(2-hydroxyethylthio)maleonitrile and phthalonitrile. Complexation of the thioether groups of metal-free porphyrazine with PdCl₂ further lowered the intensity of the Q-band absorption of the porphyrazine core. The new compounds were characterised by elemental analyses, IR, ¹H NMR, UV-Vis, and mass spectra.     

Octakis(ferrocene)-substituted porphyrazines

Metal-free porphyrazine and metal porphyrazinates (M = Mg, Cu, Co or Zn) substituted with eight ferrocene moieties on the periphery through flexible alkylthio-bridges have been synthesised in a multi-step reaction sequence. The new compounds have been characterised by elemental analyses, i.r., ¹H- and ¹³C-n.m.r., u.v.–vis. and mass spectra. The electrochemical investigation of porphyrazines indicates that all the ferrocene moieties are oxidised at the same potential, confirming the lack of any interaction among ferrocene groups or between ferrocenes and the porphyrazine core.     

Electrochemical Investigation of Metal-Free and Nickel-Containing Porphyrazines Carrying Eight Tosylaminoethylthia Groups

 In this study, the electrochemical properties of metal-free and nickel-containing porphyrazines with eight tosylaminoethylthia groups were investigated using cyclic voltammetry, double potential step chronoamperometry, double potential step chronocoulometry, and controlled potential coulometry. Cyclic voltammetry measurements showed that both compounds exhibit two quasi-reversible and an irreversible reduction waves. The first electron transfer reaction was followed by an irreversible chemical reaction, the second one by a reversible chemical reaction for both species. The electrode processes of metal-free and nickel-containing porphyrazines are diffusion controlled, but the double potential step chronocoulometry measurements indicated that the nickel porphyrazine is adsorbed at the electrode. However, a small adsorption current has no significant effect on the mass transport mechanism of the system. Diffusion coefficients of both compounds were determined by both cyclic voltammetric and chronocoulometric measurements. The diffusion coefficients of the reduced forms of the porphyrazines were found to be smaller than those of the neutral forms.     

2-(2-Furyl)-1(3)H-imidazo[4,5-f]quinoline. Synthesis and electrophilic substitution reactions

2-(2-Furyl)-1(3)H-imidazo[4,5-f]quinoline was synthesized by the Weidenhagen reaction of quinoline-5,6-diamine with furfural. Its alkylation with methyl iodide in the system KOH-DMSO gave two isomeric N-methyl derivatives, 2-(2-furyl)-1-methyl-1H- and 2-(2-furyl)-3-methyl-3H-imidazo[4,5-f]quinolines, the latter prevailing. 2-(2-Furyl)-3-methyl-3H-imidazo[4,5-f]quinoline was brought into electrophilic substitution reactions: bromination, nitration, formylation, acylation, sulfonation. Depending on the reaction conditions, electrophilic attack could be directed at both furan ring and quinoline fragment.     

Indole derivatives. 128. Synthesis and properties of 5,6- and 4,5-ethylenedioxyindoles

Reaction of 3,4-ethylenedioxyphenyldiazonium chloride with ethyl 2-methylacetoacetate and subsequent cyclization of the 3,4-ethylenedioxyphenylhydrazone of ethyl pyruvate gives a 14 mixture of 4,5- and 5,6-ethylenedioxy-2-ethoxycarbonylindoles, respectively, from which 4,5- and 5,6-ethylenedioxyindoles are formed by subsequent hydrolysis and decarboxylation. Mannich and Vilsmeyer reactions as well as acetylation and azo coupling have been studied for 5,6-ethylenedioxyindole.For Communication 127, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1624–1628, December, 1986.     

Copper,cobalt, and nickel complexes with unsymmetrical porphyrazines based on 3,6-di(hexadecyloxy)phthalonitrile and anthraquinone-2,3-dicarboxylic imide. Synthesis and spectral properties

Copper, cobalt, and nickel complexes with А3В, ААВВ и АВАВ unsymmetrical porphyrazines have been synthesized via the reaction between 3,6-di(hexadecyloxy)phthalonitrile (component А), anthraquinone-2,3-dicarboxylic imide (component В), and the corresponding metal acetate in the presence of urea. Spectral properties of the synthesized compounds have been studied.     

5,6-Dihydropyridin-2(1H)-ones and 5,6-dihydropyridine-2(1H)-thiones (review)

Data on methods for the production of 5,6-dihydropyridin-2(1H)-ones and 5,6-dihydropyridine-2(H)-thiones and their biological activity are reviewed.Omsk State University, Omsk, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 147–167, February, 1999.     

Electrochemical Investigation of Metal-Free and Nickel-Containing Porphyrazines Carrying Eight Tosylaminoethylthia Groups

Summary.  In this study, the electrochemical properties of metal-free and nickel-containing porphyrazines with eight tosylaminoethylthia groups were investigated using cyclic voltammetry, double potential step chronoamperometry, double potential step chronocoulometry, and controlled potential coulometry. Cyclic voltammetry measurements showed that both compounds exhibit two quasi-reversible and an irreversible reduction waves. The first electron transfer reaction was followed by an irreversible chemical reaction, the second one by a reversible chemical reaction for both species. The electrode processes of metal-free and nickel-containing porphyrazines are diffusion controlled, but the double potential step chronocoulometry measurements indicated that the nickel porphyrazine is adsorbed at the electrode. However, a small adsorption current has no significant effect on the mass transport mechanism of the system. Diffusion coefficients of both compounds were determined by both cyclic voltammetric and chronocoulometric measurements. The diffusion coefficients of the reduced forms of the porphyrazines were found to be smaller than those of the neutral forms. Received October 29, 2001. Accepted (revised) December 17, 2001     

Regioselective Diels-Alder cycloadditions and other reactions of 4,5-, 5,6-, and 6,7-indole arynes

The regioselectivity of Diels-Alder cycloadditions of indole arynes (indolynes) at all three benzenoid positions was examined. Cycloadditions with the 4,5-and 5,6-indolynes, derived via metal-halogen exchange from the corresponding o-dibromo indoles, showed essentially no selectivity with 2-t-butylfuran. In contrast, the 6,7-indolyne displayed virtually complete preference for the more sterically congested cycloadduct. This same cycloadduct undergoes a facile acid-catalyzed rearrangement to afford the annulated enone, or alternatively, undergoes hydrolysis and oxidation in the presence of air to give the indolobenzoquinone. The 5,6-difluoroindoles show anomalous behavior and give either 5-fluoro-6,7-indolynes with n-BuLi in ether, or 5,6-indolynes with n-BuLi in toluene. We have also demonstrated that benzenoid indolynes can be easily and conveniently generated by the fluoride-induced decomposition of o-trimethylsilyl triflates.