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.     

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.     

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.     

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).     

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.     

Extraction of copper(II) from weakly acid and ammonia media with <Emphasis Type="Italic">N</Emphasis>′,<Emphasis Type="Italic">N</Emphasis>′-dialkylhydrazides of aliphatic carboxylic acids

Dependence of physicochemical properties of N′,N′-dialkylhydrazides of aliphatic carboxylic acids (solubility in kerosene, acid-base properties) on the length of hydrocarbon radicals in the functional group was studied. The extraction capacity for copper(II) salts in weakly acid and ammonia media was examined in the range from pH 5–11 to a NH₃ content of 2.7 M. The capacity of the organic phase for copper(II) and re-extraction conditions were determined for the example of N′,N′-dibutylhydrazide of octanoic acid.     

<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.     

Complex formation of magnesium and calcium ions with trimethylenediamine-<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>’,<Emphasis Type="Italic">N</Emphasis>’-tetraacetic acid

Stability constants and heat effects of the formation reactions of magnesium and calcium trimethylenediaminetetraacetates at 298.15 K and ionic strength of 0.1, 0.5, and 1.0 (mol/L KNO₃) have been determined by means of potentiometry and calorimetry. Standard thermodynamic parameters (log K⁰, Δ_rG⁰, Δ_rH⁰, and Δ_rS⁰) of the studied equilibriums have been determined.     

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.     

Synthesis,characterization and antibacterial activities of two nickel(II) complexes with xanthate derivatives and <Emphasis Type="Italic">N,N,N</Emphasis>′<Emphasis Type="Italic">,N</Emphasis>′-tetramethylethylenediamine as ligands

Two Ni(II) xanthate complexes of composition [Ni(S₂COR)₂(tmeda)] (R=Me (1), Et (2); tmeda = N,N,N′,N′-tetramethylethylenediamine) have been synthesized and characterized by physicochemical and spectroscopic methods. Both the complexes are hexa-coordinate with an NiN₂S₄ core. Methylxanthate adopts an isobidentate coordination mode in complex 1 while ethylxanthate exhibits an anisobidentate binding mode in complex 2. Inter- and intramolecular hydrogen bonds are observed in the crystal structures of both complexes. The antibiotic properties of the complexes were investigated .     

<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.     

Synthesis,spectroscopic and crystallographic characterization of the cobalt(III) ternary mixed-ligand complexes of N(4)-allyl/methyl thiosemicarbazones, <Emphasis Type="Italic">N,N,N</Emphasis>′<Emphasis Type="Italic">,N</Emphasis>′-tetramethylethylenediamine and azide

Mixed-ligand ternary cobalt(III) complexes consisting of N,N,N′,N′-tetramethylethylenediamine (tmen), R-salicylaldehyde-N(4)-allyl/methyl thiosemicarbazones (R=3-OMe (L^I/L^II) or H (L^III/L^IV) and azide, of general formula [CoL(tmen)(N₃)], were synthesized and characterized by physico-chemical and spectroscopic methods. The crystal structure of [CoL^I(tmen)(N₃)] has a slightly distorted octahedral coordination geometry involving the O, N and S atoms of thiosemicarbazone.     

Cyclization of the substituted <Emphasis Type="Italic">N</Emphasis>-(<Emphasis Type="Italic">Ortho</Emphasis>-cyclopropylphenyl)-<Emphasis Type="Italic">N′</Emphasis>-aryl ureas and thioureas in the gas phase and solution

Electron ionization (EI), chemical ionization (CI), tandem mass spectrometry, high-resolution measurements, and labeling studies as well as quantum chemical calculations were used to understand the behavior of the molecular radical cations (EI) and protonated molecules (CI) of substituted N-(ortho-cyclopropylphenyl)-N'-aryl ureas and N-(ortho-cyclopropylphenyl)-N'-aryl thioureas in a mass spectrometer. Fragmentation schemes and possible mechanisms of primary isomerization were proposed. According to the fragmentation pattern, formation of the corresponding benzoxazines and benzothiazines was considered as the major process of isomerization of the original M(+.) and MH(+), although some portions of these ions definitely transformed into other structures. The treatment of N-(ortho-cyclopropylphenyl)-N'-phenyl urea and N-(ortho-cyclopropylphenyl)-N'-phenylthiourea in solution with strong acids formed predicted 4-ethyl-N-phenyl-4H-3,1-benzoxazin-2-amin and 4-ethyl-N-phenyl-4H-3,1-benzothiazin-2-amine as principal products.     

Vanadium(V) extraction from sulfuric and hydrochloric acid solutions with hydrazides and <Emphasis Type="Italic">N</Emphasis>′,<Emphasis Type="Italic">N</Emphasis>′-dialkylhydrazides of Versatic acids

Conditions of vanadium(V) extraction from sulfuric and hydrochloric acid solutions with kerosene solutions of hydrazides and N’,N’-dimethylhydrazides derived from fractions of Versatic 10 and Versatic 1519 branched higher carboxylic acids were studied. Conditions of vanadium(V) back extraction from organic phase were studied. For diluted acid solutions, ratios were found to be [V(V)]: [reagent] = 1: 1 and 1: 5 for sulfuric acid media and 1: 1 and 1: 8 for hydrochloric acid media.     

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.     

SBR composites reinforced with <Emphasis Type="Italic">N</Emphasis>-isopropyl-<Emphasis Type="Italic">N</Emphasis>′-phenyl-<Emphasis Type="Italic">P</Emphasis>-phenylenediamine-modified clay

SBR compounds including the N-isopropyl-N’-phenyl-p-phenylenediamine-modified clay(organoclay) were prepared.Effects of modified clay and antioxidant(IPPD) contents on mechanical and rheological properties of SBR composites were studied.FTIR results confirmed that the clay was chemically modified by IPPD and changed into an organoclay.X-ray diffraction(XRD) results confirmed the increase in interlayer distance of the clay due to the insertion of IPPD.Rheological and cure characteristics of SBR compounds were determined using RPA(Rubber Process Analyzer) and rheometer.Scorch time and cure time of SBR compounds decreased with introduction of the organoclay.Mechanical properties and heat aging resistance of the SBR composites were improved significantly by incorporation of the organoclay.     

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.     

Preparation and crystal structure of bis(triethylene glycol-<Emphasis Type="Italic">O</Emphasis>,<Emphasis Type="Italic">O</Emphasis>′,<Emphasis Type="Italic">O</Emphasis>′’,<Emphasis Type="Italic">O</Emphasis>‴)manganese(II) dibromide

A new complex, bis(triethylene glycol-O,O′,O′’,O?)manganese(II) dibromide [Mn(TEG)₂]²⁺·2Br^?, was prepared. Its structure was studied by single crystal X-ray diffraction. The complex cation [Mn(TEG)₂]²⁺ is of the host-guest type with two TEG ligands (podands) as hosts. Both TEG ligands are disordered and tetradentate, with all the four oxygen atoms of each ligand participating in the coordination. The Mn²⁺ cation has coordination number 8, and its coordination polyhedron is a distorted bisdisphenoid (trigonal dodecahedron). The geometric parameters (bond lengths, bond and torsion angles) of the complex were determined relatively accurately. In the crystal structure, the ions form infinite thick layers by interionic hydrogen bonds O-H···Br^?.