Complex Formation of Magnesium(II) with Octaaryltetraazaporphyrins in Pyridine

Complex formation of magnesium with octaphenyltetraazaporphyrin, octakis[p-(chloromethyl)phenyl]tetraazaporphyrin, and octakis[p-(dodecylsulfamoyl)phenyl]tetraazaporphyrin from corresponding ligands and magnesium acetate in pyridine and pyridine-diethylamine was studied. Increase in the basicity of the medium favors a much faster reaction. Some suggestions concerning the mechanism of the reaction were made.     

Synthesis and spectral properties of the Co2+ and Co3+ complexes with octaaryltetraazaporphyrins

Complexes Co²⁺ and Co³⁺ with octaphenyltetraazaporphyrin, octa(4-bromphenyl)tetraazaporphyrin and octa(4-nitrophenyl)tetraazaporphyrin were obtained and identified. The influence of the composition of reaction medium on the oxidation processes of the complexes Co²⁺ → Co³⁺ in DMF was revealed and the optimum conditions of formation of the corresponding compounds were determined.     

Synthesis and Properties of Tetrakis(4-bromophenyl)tetraazaporphyrin

Tetraphenyltetraazaporphyrin was reacted with bromine in trifluoroacetic acid to obtain tetrakis(4-bromophenyl)tetraazaporphyrin. The latter forms with pyridine and dimethyl sulfoxide proton-transfer complexes which differ from each other by the degree of proton transfer from the NH acid to base.     

Synthesis and spectral properties of meso-substituted Ni2+ octaalkylporphyrinates

Nickel(II) 3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporphyrinate and its 5,15-diaza, -diphenyl, and -di(4-bromophenyl) derivatives have been synthesized by the reaction of nickel(II) chloride with corresponding tetrapyrrole ligands in dimethylformamide.     

Complexation of octa(bromophenyl)tetraazaporphyrin with Mn(II) salts in DMF and pyridine

Reactions of octa(bromophenyl)tetraazaporphyrin (H₂OBPTAP) and octaphenyltetraazaporphyrin with Mn(II) acetate and chloride in DMF and pyridine are studied by spectrophotometric method. In the course of formation of octaphenyltetraazaporphyrin complexes, pyridine stabilizes an oxidation state of Mn (+2), and in addition to Mn(II) complex, its radical form is likely to be obtained also in this case. In DMF, the octaphenyltetraazaporphyrinatomanganese(III) complexes are produced. Kinetic studies showed that the complexing capability of Mn acetate in reaction with azaporphyrins drastically differs from that of Mn chloride. H₂OBPTAP does not react with MnCl₂ in pyridine, while its reaction with Mn(OAc)₂ has k_eff²⁹⁸ = (3.1 ± 0.2) × 10^-3 s^-1. Reaction of H₂OBPTAP with Mn(OAc)₂ in DMF occurs instantaneously, whereas in the case of its reaction with MnCl₂, k_eff²⁹⁸ = (1.9 ±0.2) × 10^-3 s^-1.Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 1, 2005, pp. 22–27.Original Russian Text Copyright © 2005 by Klyueva, Repina, Chizhova, Berezin.     

Synthesis and Spectral and Fluorescent Properties of Metal Complexes of Octakis(4-flurophenyl)tetraazaporphyrins

Russian Journal of Organic Chemistry - Zn(II) octakis(4-fluorophenyl)tetraazoporphyrin and Cu(II) octakis(4-fluorophenyl)tetraazorphorphyrin were synthesized by the cyclization of...     

Binuclear iron(III) octakis(perfluorophenyl)tetraazaporphyrin μ-oxodimer: a highly efficient catalyst for biomimetic oxygenation reactions

Binuclear iron(III) octakis(perfluorophenyl)tetraazaporphyrin μ-oxodimer complex was prepared by the reaction of bis(perfluorophenyl)maleonitrile and Fe(CO)₅ and tested in catalytic oxygenation reactions of several hydrocarbons in comparison with the analogous non-fluorinated phthalocyanine complexes. Results of the study demonstrate that this complex is a highly efficient catalyst for the oxygenation of anthracene, 2-tert-butylanthracene, naphthalene, 2-methylnaphthalene, phenanthrene, adamantane, and toluene using iodosylbenzene, oligomeric iodosylbenzene sulfate, or Oxone as stoichiometric oxidants.     

Acid–Base Interactions in Complexation of Magnesium Acetylacetonate with Tetraazaporphyrins in Dimethyl Sulfoxide–Benzene System

Complexation of magnesium acetylacetonate with tetraazaporphine, tetrachlorotetraazaporphine, tetrabromotetraazaporphine, octa(p-bromophenyl)tetraazaporphine, or octa(p-nitrophenyl)tetraazaporphine in DMSO–benzene system was studied. The acid properties of tetrapyrrole were shown to affect the rate and activation parameters of the process. The key role of acid–base interactions in the formation of Mg(II) complex with tetraazaporphyrins was established. The mechanism of the processes under study was suggested.     

芳基噻唑联哌啶酰胺类化合物的合成及生物活性

为了寻找具有生物活性的新型芳香基噻唑联哌啶酰胺类先导化合物,设计并合成了15个未见文献报道的芳基噻唑联哌啶酰胺类化合物,其结构经1HNMR、13CNMR和HRMS确证,生物活性测定结果显示,部分目标化合物表现出高效的抑菌和杀虫活性,如在200μg/mL浓度下,5-(3-溴苯基)-4-甲基-2-(1-((4-硝基苯基)磺酰基)哌啶-4-基)噻唑(6b)对黄瓜霜霉病的抑菌活性为100%,优于嘧菌酯,5-(4-溴苯基)-2-(1-((4-氯苯基)磺酰基)哌啶-4-基)-4-甲基噻唑(6c)对水稻纹枯病的抑菌活性为58.86%,与嘧菌酯相当;在500μg/m L浓度下,(4-(5-(3-溴苯基)-4-甲基噻唑-2-基)哌啶-1-基)(间甲基苯基)酮(6h)对粘虫的杀虫活性为100%.     

1,3-Diaryl-2,2-dihaloaziridines in nitration and bromination reactions

In the nitration of 3-(4-nitrophenyl)-1-phenyl-2,2-dichloroaziridine in acetic acid, 1-(o- and p-nitrophenyl)-derivatives are formed in a 35:65 ratio. 1,3-Di-phenyl-2,2-dichloroaziridine undergoes opening of the three-membered ring under the same conditions, forming a mixture of o- and p-nitroanilides and 2-nitro-4-chloroanilides of 2-acetoxy (or 2-chloro)-2-phenylacetic acids. The bromination of 3-(4-nitrophenyl)-1-phenyl-2,2-dichloroaziridine in aqueous acetic acid leads to 1-(4-bromophenyl)-3-(4-nitrophenyl)-2,2-dichloroaziridine, while in a mixture of acetic acid and acetic anhydride it leads to the anilide of 2-bromo-2-phenyl-acetic acid and 2-bromo-N-(2,4-dibromophenyl)-1-(4-nitrophenyl)-2,2-dichloro-ethylamine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 912–916, July, 1984.     

Synthesis and spectral properties of novel seco-porphyrazines with eight 4-biphenyl groups

Magnesium porphyrazinate substituted with eight 4-biphenyl groups on the periphery positions has been synthesized for the first time from cyclotetramerization of 1,2-bis(4-biphenyl)maleonitrile in the presence of magnesium butanolate. Its demetalation by treatment with trifluoroacetic acid, resulted in a partially oxidized product, namely, octakis(4-biphenyl)-2-seco-porphyrazine-2,3-dione. Further reaction of this product with copper(II) acetate, zinc(II) acetate and cobalt(II) acetate has led to the metallo derivatives, [octakis(4-biphenyl)-2-seco-2,3-dioxoporphyrazinato] M(II) (M = Cu, Zn, Co). These novel compounds have been characterized by elemental analysis, together with FT-IR, ¹H NMR, UV–Vis and mass spectral data.     

Acid-Base Properties of Octaaryltetraazaporphyrins

Stability constants were determined for acid forms of octa(4-chloromethylphenyl)-, octa(4-bromophenyl)-, and octa(4-nitrophenyl)tetraazaporphyrins, formed by acid-base interactions in H₂SO₄-CH₃COOH mixtures. The probability of formation of each form depends not only on the electronic structure of the molecule, but also on the composition and properties of the medium.     

New 6-(4-Bromophenyl)-imidazo[2,1- b ]thiazole Derivatives: Synthesis and Antimicrobial Activity

 New 4-alkyl/aryl-1-((6-(4-bromophenyl)-imidazo[2,1-b]thiazol-3-yl)-acetyl)-3-thiosemicarbazides and 3-alkyl/aryl-2-(((6-(4-bromophenyl)-imidazo[2,1-b]thiazol-3-yl)-acetyl)-hydrazono)-4-thiazolidinones were synthesized from 6-(4-bromophenyl)-imidazo[2,1-b]thiazole-3-acetic acid hydrazide. Their structures were elucidated by elemental analyses and spectroscopic data. All compounds were tested for antibacterial and antifungal activities. The antimicrobial activities of the compounds were assessed by the microbroth dilution technique. The compounds were also evaluated for antituberculosis activity against Mycobacterium tuberculosis H₃₇Rv (ATCC 27294); they exhibited varying degrees of inhibition in the in vitro primary screening at 6.25 μg · cm⁻³. The most active compound was 3-(4-nitrophenyl)-2-(((6-(4-bromophenyl)-imidazo[2,1-b]thiazol-3-yl)-acetyl)-hydrazono)-4-thiazolidinone.     

Metal exchange reaction of magnesium octaphenyltetraazaporphyrin with copper,cobalt, and zinc chlorides in DMSO and DMF

Metal exchange reaction of (octaphenyltetraazaporphyrinato)magnesium(II) with copper, cobalt, and zinc chlorides in dimethyl sulfoxide and dimethylformamide has been studied by spectrophotometry. Kinetic and thermodynamic parameters of the process have been determined, and a probable reaction mechanism has been proposed. Zinc(II), copper(II), cobalt(II), and cobalt(III) complexes of octaphenyltetraazaporphyrin have been isolated and characterized.     

New 6-(4-Bromophenyl)-imidazo[2,1-b]thiazole Derivatives: Synthesis and Antimicrobial Activity

Summary.  New 4-alkyl/aryl-1-((6-(4-bromophenyl)-imidazo[2,1-b]thiazol-3-yl)-acetyl)-3-thiosemicarbazides and 3-alkyl/aryl-2-(((6-(4-bromophenyl)-imidazo[2,1-b]thiazol-3-yl)-acetyl)-hydrazono)-4-thiazolidinones were synthesized from 6-(4-bromophenyl)-imidazo[2,1-b]thiazole-3-acetic acid hydrazide. Their structures were elucidated by elemental analyses and spectroscopic data. All compounds were tested for antibacterial and antifungal activities. The antimicrobial activities of the compounds were assessed by the microbroth dilution technique. The compounds were also evaluated for antituberculosis activity against Mycobacterium tuberculosis H₃₇Rv (ATCC 27294); they exhibited varying degrees of inhibition in the in vitro primary screening at 6.25 μg · cm⁻³. The most active compound was 3-(4-nitrophenyl)-2-(((6-(4-bromophenyl)-imidazo[2,1-b]thiazol-3-yl)-acetyl)-hydrazono)-4-thiazolidinone. Corresponding author. E-mail: nurayulusoy@yahoo.com Received December 10, 2001. Accepted (revised) March 1, 2002     

New Tetraaza Macrobicyclic Ditopic Receptors for Metal Ions: Synthesis,Redox Response and Kinetics of Phosphate Hydrolysis of Unsymmetrical Macrobicyclic Mono- and Binuclear Nickel(II) Complexes

A new series of macrobicyclic ditopic receptors is derived from the precursor compound 3,4:10,11-dibenzo-1,13[N,N′-bis{(3-formyl-2-hydroxy-5-methyl)benzyl}di-aza]-5,9-dioxocyclohexadecane. Using this precursor, mono- and binuclear nickel(II) complexes of type [NiL](ClO₄) and [Ni₂L](ClO₄)₂ have been synthesized to undertake electrochemical and catalytic studies on the basis of macrocyclic ring size. The receptor is a tricompartmental macrocycle consisting of ether oxygen, tertiary nitrogen and imine nitrogen atoms. The redox studies of these systems show that the nickel(II) complexes undergo quasi-reversible one-electron reduction and oxidation. All the nickel(II) complexes have square planar geometry and are EPR silent. Examination of the kinetics of the hydrolysis of 4-nitrophenyl phosphate shows that the catalytic activities of the complexes increase with the macrocyclic ring size of the complexes. As the macrocyclic ring size of the complexes increases, the spectral, electrochemical and catalytic studies of the complexes show considerable variation due to distortion in the geometry around the nickel(II) centre.     

Synthesis and characterization of soluble seco-porphyrazines with bulky substituents

By cyclotetramerization of 3,4-bis(4-tert-butylphenyl)pyrroline-2,5-diimine in the presence of magnesium butanolate, magnesium porphyrazinate with eight (4-tert-butylphenyl) units on the periphery has been synthesized. Its demetalation by the treatment with trifluoroacetic acid resulted in a partially oxidized product, namely, octakis(4-tert-butylphenyl)-2-seco-porphyrazine-2,3-dione. Further reaction of this product with copper(II) acetate, zinc(II) acetate, and cobalt(II) acetate led to the metallo derivatives, [octakis(4-tert-butylphenyl)-2-seco-2, 3-dioxoporphyrazinato]M(II) (M = Cu, Zn, Co). These soluble complexes have been characterized by elemental analysis, FT-IR, ¹H NMR, UV-Vis, and mass spectral data.     

Synthesis and Acid–Base Properties of β-Octabromo-Substituted Unsymmetrical Nitrophenylporphyrins

Russian Journal of Organic Chemistry - The bromination of [5-(4-nitrophenyl)-10,15,20-triphenylporphyrinato]cobalt(II) and [5,10,15-tris-(4-nitrophenyl)-20-phenylporphyrinato]cobalt(II) with...     

Metal exchange of Cd(II) octaphenyltetraazaporphyrin with <Emphasis Type="Italic">d</Emphasis>-metal salts in organic solvents

The metal exchange of Cd(II) octaphenyltetraazaporphyrin with CoCl₂ and MnCl₂ was studied by spectrophotometry in DMF and DMSO. The kinetic parameters of the metal exchange were determined. A possible stoichiometric reaction mechanism was proposed.     

Effect of the nature of the tetrapyrrole macrocycle on the transmetallation of Zn2+ and Cd2+ porphyrins with PdCl2 in dimethylformamide

Transmetallation of zinc (Zn²⁺) and cadmium (Cd²⁺) complexes of 5,10,15,20-tetraphenylporphin, 5,10,15,20-tetra(4-chlorophenyl)porphyrin, 5,10,15,20-tetra(4-methoxyphenyl)porphyrin, tetrabenzoporphyrin, and octaphenyltetraazaporphyrin with PdCl₂ in DMF was studied by spectrophotometry. The influence of the nature of the tetrapyrrole macrocycle on the reactivity of Zn²⁺ porphyrins toward palladium chloride in boiling DMF was established. Palladium(II) complexes of 5,10,15,20-tetraphenylporphyrin, 5,10,15,20-tetra(4-chlorophenyl)porphyrin, 5,10,15,20-tetra(4-methoxyphenylporphyrin), and tetrabenzoporphyrin were prepared and identified.