<Emphasis Type="Italic">N</Emphasis>-arylsulfanyl-<Emphasis Type="Italic">N</Emphasis>-arylsulfonyl(acyl)-<Emphasis Type="Italic">N</Emphasis>′-phenylthiourea sodium salts

Reactions of N-arylsulfonyl(acyl)arenesulfenamide sodium salts with phenyl isothiocyanate afforded N-arylsulfanyl-N-arylsulfonyl(acyl)-N-phenylthioura sodium salts which were found to increase thermal stability of finely dispersed poly(vinyl chloride).Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 10, 2004, pp. 1532–1535.Original Russian Text Copyright © 2004 by Koval, Oleinik.     

Extraction-photometric determination of <Emphasis Type="Italic">N</Emphasis>′,<Emphasis Type="Italic">N</Emphasis>′-dialkylbenzhydrazides as its complexes with copper

A procedure for extraction-photometric determination of N′,N′-dialkylbenzhydrazides has been proposed; the procedure is based on the formation of its colored complex with copper (II) followed by extraction with p-xylene and absorbance measurements at 460 nm (0.1–0.4 mmol of analyte in the sample) or at 330 nm (0.005–0.025 mmol of analyte in the sample).     

Physicochemical properties and complexing ability of <Emphasis Type="Italic">N</Emphasis>-(2-ethylhexanoyl)-<Emphasis Type="Italic">N</Emphasis>′-sulfonylhydrazines

The effect of substituent at the sulfonyl group on the physicochemical properties and complexing ability of the sulfonyl derivatives of 2-ethylhexanoic acid hydrazide of the general formula C₄H₉CH(C₂H₅)C(O)·NHNHSO₂C₆H₅R [R = H, CH₃, NO₂, NHC(O)CH₃, Cl] with respect to Cu(II), Co(II), and Ni(II) ions was studied.     

1,3-Diamino-2-Hydroxypropane-<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>′,<Emphasis Type="Italic">N</Emphasis>′-Tetraacetic Acid: Crystal and Molecular Structures

The synthesis, IR spectroscopic study, and X-ray diffraction analysis (CIF file CCDC no. 1574078) are carried out for 1,3-diamino-2-hydroxypropane-N,N,N′,N′-tetraacetic acid (I). The structural units of a crystal of compound I are (H_4.5HPdta)^0.5– anions, (H_5.5HPdta)^0.5+ cations, and molecules of water of crystallization joined by a branched network of hydrogen bonds: strong intermolecular O–H…O and intramolecular N–H…O bonds.     

Directed Aminomethylation of Pyrrole,Indole, and Carbazole with <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N′</Emphasis>,<Emphasis Type="Italic">N′</Emphasis>-Tetramethylmethanediamine

Catalytic aminomethylation of pyrrole and indole with N,N,N′,N′-tetramethylmethanediamine in the presence of 5 mol % of ZrOCl₂·8H₂O proceeds selectively at the positions 2, 5 of pyrrole and 1, 3 of indole. Carbazole under the same conditions affords 3-formyl-9-aminomethyl derivative. The reaction in the presence of 5 mol % of K₂CO₃ occurs as monoaminomethylation: for pyrrole at the position 2, for indole at the position 3, and for carbazole at the nitrogen atom of the substrate. Water-soluble 1,1′-(1H-pyrrole-2,5-diyl)bis(N,N-dimethylmethanamine) exhibits a fungistatic activity with respect to phytopathogenic fungi Rhizoctonia solani.     

Synthesis of <Emphasis Type="Italic">N</Emphasis>-nitro-<Emphasis Type="Italic">N</Emphasis>′-(trimethylsilyl)carbodiimide

Nitration of N,N′-bis(trimethylsilyl)carbodiimide with N₂O₅ or (NO₂)₂SiF₆ afforded N-nitro-N´-(trimethylsilyl)carbodiimide, the first representative of N-nitro carbodiimides. Its further nitration led to the release of CO₂, which is presumably formed in the course of N,N´-dinitrocarbodiimide decomposition. The reactions of N-nitro-N´-(trimethylsilyl)carbodiimide with nucleophiles take place both at the tri methylsilyl group (for example, with NH₃) to give nitrocyanamide salts and at the carbodiimide C atom (for example, with Et₂NH) to give the corresponding nitroguan idines.     

<Emphasis Type="Italic">N</Emphasis>′-tetrazolylmethoxyl derivatives of <Emphasis Type="Italic">N</Emphasis>-methyldiazene <Emphasis Type="Italic">N</Emphasis>-oxides

A preparation method was developed for previously unknown tetrazole derivatives containing in the 1, 2, and/or 5 positions of the tetrazole ring N-methyldiazene-N-oxide-N′-oxymethyl groups.     

Synthesis and structure of the cobalt(II) coordination compounds with <Emphasis Type="Italic">N,N</Emphasis>-dimethyl-<Emphasis Type="Italic">N</Emphasis>′,<Emphasis Type="Italic">N</Emphasis>′-dimethylthiocarbamoylsulfenamide

The CoLX₂ complexes were obtained by the reaction of N,N-dimethyl-N′,N′-dimethylthio-carbamoylsulfenamide (L) with CoX₂ (X = Cl, Br, I, NCS). The complexes were investigated by elemental and X-ray analysis, IR, ¹H NMR, and electron spectroscopy, conductometry, magnetochemistry, thermogravimetry. It is found that these compounds are high-spin complexes of pseudotetraedral structure with bidentate coordination of L through the thione sulfur atom and sulfenamide nitrogen atom.     

Synthesis and characterization of some <Emphasis Type="Italic">o</Emphasis>,<Emphasis Type="Italic">o</Emphasis>′-dihydroxyazo dyes and their metal complexes

The synthesis and characterization of azo dyes containing o,o′-dihydroxy groups and their azo-metal(II) [Cu, Co, Ni, Zn] chelates by ¹H N.M.R., IR, AAS, UV–VIS, magnetic susceptibility and thin-layer chromatography techniques are reported. The stochiometry of the azo-metal chelates was determined by the spectroscopic titration method to be 1:2 (ML₂). The synthesized azo dyes and azo-metal chelate dyes were applied on wool fabric. Fastness to light and washing were measured.     

RETRACTED ARTICLE: Synthesis and properties of <Emphasis Type="Italic">N′</Emphasis>-hydroxy-2-(hydroxyimino)-<Emphasis Type="Italic">N</Emphasis>-(4-{[(2-hydroxyphenyl)methylene]amino}-1-naphthyl)-ethanimidamide and its metal complexes

A new vicinal dioxime, N′-hydroxy-2-(hydroxyimino)-N-(4-{[(2-hydroxy-phenyl)methylene]amino}-1-naphthyl)ethanimidamide was synthesized. The initial compound for the synthesis of this dioxime was naphthalene. Complexes of this ligand were obtained with nickel, copper, and cobalt. The dioxime and its complexes were characterized by Fourier IR, UV, ¹H NMR spectroscopy, mass spectrometry, elemental analysis, differential thermal analysis, and conductometric measurements.     

Novel mixed-ligand complexes of coumarilate/<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>′-diethylnicotinamide with some transition metals

Coordination complexes of transition metal cations (Co^II, Ni^II, Cu^II and Zn^II) containing coumarilate and N,N′-diethylnicotinamide were synthesized. The structural characterization and thermal behaviour analysis of novel samples synthesized were conducted through elemental analysis, magnetic susceptibility, solid-state UV–Vis, direct and injection probe mass spectra, FTIR spectra, thermoanalytic TG-DTG/DTA and single crystal X-ray diffraction methods. The structural details of single crystals of [Co(dena)₂(H₂O)₄](coum)₂ (I) and [Cu(coum)₂(dena)₂(H₂O)₂] (III) complexes were resolved completely. Moreover, the results of analysis obtained for [Ni(coum)₂(dena)₂(H₂O)₂] (II) and [Zn(dena)₂(H₂O)₄](coum)₂ (IV) complexes were interpreted considering the samples with crystal structures defined and made assumptions about the structural details. It was determined that the complex of Co^II metal cation has salt-type structure and the coordination number of metal is accomplished to six as the sum of 4 mol of water and also 2 mol of N,N′-diethylnicotinamide ligands in trans position located within the coordination sphere. It was observed that 2 mol of coumarilate anions are located outside the coordination sphere and have stabilized to the charge (2+) of metal. The Cu^II complex has totally molecular structure, and the coordination sphere of metal cation was 6 as the sum of 2 mol of water, 2 mol of N,N′-diethylnicotinamide and 2 mol of monoanionic monodentate coumarilate ligands. All ligands have been located in –trans position. The geometry of both complex structures is distorted octahedral. It is assumed that the Ni^II complex structure is isostructural with Cu^II complex structure and also does Zn^II complex with Co^II structure. It was determined that the decomposition products obtained from thermal analysis are the oxides of related metal cations.     

Synthesis of substituted anilides of the alkaloid cytisine and molecular structure of <Emphasis Type="Italic">N</Emphasis>-(2′,6′-dichloro-4′-nitrophenyl)-2-<Emphasis Type="Italic">N</Emphasis>-cytisinoacetamide

Anilides of cytisinylacetic acid were synthesized by reaction of the alkaloid cytisine with 2-bromo-N-(2,6-dihalo-4-nitrophenyl)acetamides. The compositions and structures of the products were confirmed by IR and PMR spectroscopy, mass spectrometry, and x-ray structure analysis.     

Copper(II) complexation and extraction with 2-ethylhexanoic acid <Emphasis Type="Italic">N</Emphasis>′,<Emphasis Type="Italic">N</Emphasis>′-dialkylhydrazides

2-Ethylhexanoic acid N′,N′-dibutylhydrazide (DBH) and N′,N′-diheptylhydrazide (DHH) were synthesized. The existence regions of copper (II), zinc(II), nickel(II), and cobalt(II) complexes formed upon extraction with DBH in kerosene were studied. The neutral complex ML₂ extracted over a wide pH range (from pH ～ 6 to \(c_{NH_3 } \) ～ 4 mol/L) is formed only by copper(II), while zinc(II), nickel(II), and cobalt(II) react with DBH to yield precipitates that float at pH 7–9, 9–10.5, and 9.5–11, respectively. On the basis of IR spectra, elemental analysis, and properties, a structure was suggested for the CuL₂ complex with DBH. The DBH and DHH complexes with copper(II) are readily stripped with H₂SO₄ and H₂SO₄ + CuSO₄ solutions. The capacity of a 1.5 mol/L DHH in kerosene with respect to copper(II) is 26 g/L.     

Synthesis and crystal and molecular structures of <Emphasis Type="Italic">N,N</Emphasis>′-methylenedipyridinium tetrachlorozincate(II) and <Emphasis Type="Italic">N,N</Emphasis>′-methylenedipyridinium tetrachlorocadmate(II)

Treatment of N,N′-methylenedipyridinium dichloride [C₅H₅N-CH₂-NC₅H₅]Cl₂ with MCl₂ (M = Zn or Cd) in aqueous solution gives the organic-inorganic hybrid ionic compounds [C₅H₅N-CH₂-NC₅H₅] · [MCl₄]. Both complex salts were fully characterised by multinuclear NMR spectroscopy, elemental analysis, and their molecular structures confirmed by powder X-ray diffraction studies. The most striking feature in both solid state structures was the presence of the C…Cl-M short contacts between the organic [C₅H₅N-CH₂-NC₅H₅] dication and inorganic [MCl₄] anion, which led to different crystal packing. For [C₅H₅N-CH₂-NC₅H₅]·[ZnCl₄], the C…Cl-Zn interactions led to the alternating arrangement of [C₅H₅N-CH₂-NC₅H₅]²⁺[ZnCl₄]²⁻ to form 1-D chains in the direction [010], and each individual chain had a two-fold rotational axis along the b axis, while for [C₅H₅N-CH₂-NC₅H₅] · [CdCl₄] the C…Cl-Cd associations gave 2-D network. In both solid state structures, the presence of Cl-ring centroid distances gave a strong indication of some form of Cl-π interactions.     

X-ray and computational structural study of neutral <Emphasis Type="Italic">bis</Emphasis>(<Emphasis Type="Italic">N,N,N</Emphasis>′,<Emphasis Type="Italic">N</Emphasis>′-tetramethylthiophosphoramidoyl)-methylamine

The structure of bis(N,N,N′,N′-tetramethylthiophosphoramidoyl)-methylamine 1 has been determined by single-crystal X-ray diffraction. The compound 1 crystallizes in the monoclinic system, with a space group P2₁/c, a = 11.836(2) Å, b = 11.659(2) Å, c = 12.796(5) Å and β = 95.28(3)°, V = 1758.3(5) Å³ and Z = 4. The X-ray crystallographic data have been assessed by semi-empirical and ab-initio density functional theory and by Hartree–Fock molecular orbital methods. A comparative study of the results of the different methods is given.     

Synthesis and Properties of <Emphasis Type="Italic">N</Emphasis>-[R-Adamantan-1(2)-yl]-<Emphasis Type="Italic">N</Emphasis>′-(2-fluorophenyl)ureas—Target-Oriented Soluble Epoxide Hydrolase Inhibitors

2-Fluorophenyl isocyanate reacted with adamantan-1(2)-amines and their homologs in DMF to give 31–92% of the corresponding N,N′-disubstituted ureas that are target-oriented human soluble epoxide hydrolase (sEH) inhibitors. Introduction of a fluorine atom increases the sEH inhibitory activity by a factor of 4.5.     

Facile synthesis of novel bis-derivatives of 2,5-diamino-thiadiazole/<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>′-thiocarbohydrazide and their biological perspective

A series of new bis derivatives of 2,5-thiadiazole and N,N′-thiocarbohydrazide along with their transition metal complexes were synthesized by green methods (sonochemical and microwave), i.e., energy and time efficient and operationally more simple than existing conventional methods. All the synthesized compounds were fully characterized by routine analytical techniques and subjected to a preliminary biological screening. These novel characterized compounds were screened for antimicrobial activities and showed promising results. A few potent compounds were also tested for antitumor activities against MDA-MB231 (human breast carcinoma cell line) and compound 5 has emerged as a potential antitumor compound followed by compound 2, 10 and 9, with IC₅₀ values of 29.48, 32.25, 32.34 and 34.34 μg/ml, respectively. To understand the binding interactions of these compounds, in silico studies were performed using the AUTODOCK 4.2 suite and found to be supportive of the experimental results.     

Thermophysical properties of <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-dimеthylacetamide mixtures with <Emphasis Type="Italic">n</Emphasis>-butanol

The refraction, dielectric, viscosity, density, data of the binary mixtures of N,N-dimethylacetamide (DMA) with n-butanol at 308.15 and 313.15 K. The measured parameters used to obtain derived properties like Bruggeman factor, molar refraction and excess static dielectric constant, excess inverse relaxation time, excess molar volume and excess viscosity, excess molar refraction. The variation in magnitude with composition and temperature of these quantities has been used to discuss the type, strength and nature of binary interactions. Results confirm that there are strong hydrogen-bond interactions between unlike molecules of DMA+ n-butanol mixtures and that 1: 1 complexes are formed and strength of intermolecular interaction increases with temperature.     

Synthesis and reactivity of 2-(2-furyl)-1,7-dimethyl-1<Emphasis Type="Italic">H</Emphasis>,7<Emphasis Type="Italic">H</Emphasis>-benzo[1,2-<Emphasis Type="Italic">d</Emphasis>: 3,4-<Emphasis Type="Italic">d</Emphasis>′]diimidazole

2-(2-Furyl)-1,7-dimethyl-1H,7H-benzo[1,2-d: 3,4-d′]diimidazole was synthesized by the Weidenhagen reaction followed by N-methylation. Electrophilic substitution reactions of the title compound (nitration, bromination, sulfonation, formylation, and acylation) involved both the furan ring and central benzene fragment.