<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.     

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.     

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.     

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.     

Dirhenium Compounds Supported by <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis><Emphasis Type="BoldItalic">′</Emphasis>-Dimethylbenzamidinate: Formation of Linear Polymers via Axial Ligation

The reaction between Re₂(DMBA)₄Cl₂ and NaN(CN)₂ resulted in Re₂(DMBA)₄(N(CN)₂)₂ (1a), where DMBA is N,N′-dimethylbenzamidinate. Molecular compounds Re₂(DMBA)₄(ReO₄)₂ (1b) and Re₂(DMBA)₄(OP(O)(OH)Ph)₂ (1c) were obtained through the reactions between Re₂(DMBA)₄(NO₃)₂ and the respective monoanion. The dirhenium(III) coordination polymers [Re₂(DMBA)₄(μ-O,O′-WO₄)·2H₂O]_∞ (2a), [Re₂(DMBA)₄(μ-O,O′-MoO₄)·2H₂O]_∞ (2b), and [Re₂(DMBA)₄(μ-O,O′-1,4-(O₂C)₂C₆H₄)·2H₂O]_∞ (2c) were similarly prepared through slow diffusion of Re₂(DMBA)₄(NO₃)₂ in acetonitrile into aqueous solution containing the respective dianion. All new compounds were characterized with single crystal X-ray diffraction, which revealed the retention of the essential structural features of Re₂(DMBA)₄ unit upon the formation of coordination polymers.     

Cu<Superscript>I</Superscript>-catalyzed <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>’-diarylation of diamines of adamantane series

A copper(I) complex-catalyzed N,N’-diarylation of diamines based on 1,3-disubstituted adamantane, using aryl iodides bearing electron-donating and electron-withdrawing substituents, was studied. In the case of 2,2’-(adamantane-1,3-diyl)ethanediamine, the optimal catalyst system is CuI—2-(isobutyryl)cyclohexanone—Cs₂CO₃—DMF. The highest yield of diarylation product was reached in the case of 4-methoxyiodobenzene (79%). In the case of more spatially hindered adamantane-1,3-diyldimethanamine, 1,1’-binaphthalene-2,2’-diol (BINOL) should be used, with the highest yield of the target product (84%) being reached in the reaction with iodobenzene.     

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.     

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.     

Electronic structures and X-ray photoelectron spectra of Te<Superscript>IV</Superscript> halides with <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>′-diphenylguanidine

The electronic structures of Te^IV hexahalides with N,N′-diphenylguanidine were studied by X-ray photoelectron spectroscopy and quantum chemistry. New information was obtained for the electronic structures of the complexes, the chemical bond nature for these compounds was established, and the bands of the X-ray photoelectron spectra in the valence band were identified.     

Converting dipyrrinones to lactim ethers to fluorescent <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>′-difluoroboryl derivatives

A high-yield straightforward conversion of lactams to lactim ethers is shown by the conversion of (10H)-dipyrrin-1-ones to (11H)-dipyrrin-1-ol methyl and ethyl ethers in 90% yield from heating in neat trimethyl or triethyl phosphite at 160°C. Unlike the parent dipyrrinones, which form intermolecularly hydrogen-bonded dimers in CHCl₃, their lactim ethers are shown to be monomeric by vapor pressure osmometry. The latter react with boron trifluoride etherate to N,N′-bridged BF₂ derivatives that exhibit strong fluorescence (φ_F 0.6–0.8) near 535 nm. X-Ray crystal structures were obtained of the lactim ethyl ether of kryptopyrromethenone and the BF₂ derivative of the lactim ethyl ether 2,3-diethyl-7,8-dimethyl-(10H)-dipyrrin-1-one. Correspondence: David A. Lightner, Department of Chemistry, University of Nevada, Reno, Nevada 89557-0020 USA.     

NMR Study of the graphite–<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-dimethylformamide system after ultrasonication

A suspension formed as a result of ultrasonication of a mixture of graphite with N,N-dimethylformamide has been studied by ¹H NMR spectroscopy. The dependence of the width of the ¹H NMR signal on the N,N-dimethylformamide content of the suspension has been determined.     

<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.     

Pseudo-Polymorphs of <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>′-Bis(4-nitrophenyl)-2,6-Pyridinedicarboxamide

Three pseudo-polymorphs of N, N′-bis(4-nitrophenyl)-2,6-pyridinedicarboxamide 1 were characterized by X-ray crystallography. The C–H ⋅s O hydrogen bond was found to contribute significantly to the assembly of this host. With the variation of the guest, the host changed the molecular conformation and the supramolecular synthons. In all three cases concerned, the solvent guests were bonded through direct host-guest interaction and accommodated in the voids formed by the assembly of the host.     

Synthesis and properties of new <Emphasis Type="Italic">N,N</Emphasis><Superscript>′</Superscript>-phenyltetrazole podand

The synthesis of a new chromogenic N,N^′-phenyltetrazole receptor is reported here. The cationbinding properties of this receptor in solution were investigated by naked-eye colour change, electrochemical methods and UV-Vis spectroscopy in various solvents (CH3CN, dimethylsulphoxide (DMSO), DMSO/H₂O, CH₃CN/H₂O and CH₃CN/MeOH). In addition, the receptor was used as a sensing material in ion-selective membrane electrodes. The selectivity and sensitivity of these electrodes towards alkali, alkali-earth, transition and heavy metal cations in aqueous solution were tested. The relation between the carrier structure and membrane plasticisers was investigated.     

Chain mechanism of the reactions of <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>′-diphenyl-1,4-benzoquinone diimine with thiophenol and 1-decanethiol

The kinetics of the reactions of N,N′-diphenyl-1,4-benzoquinone diimine with thiophenol and 1-decanethiol in chlorobenzene at 343 K has been investigated spectrophotometrically in an argon atmosphere with monitoring of the disappearance of quinone diimine as its absorbance in the visible range. The acceleration of the reactions in the presence of initiators—tetraphenylhydrazine and azobisisobutyronitrile—indicates that the reactions proceed via a chain mechanism under the chosen experimental conditions. The chain length of the reactions in the absence of an initiator is estimated: ν ≈ 10 units in the reaction of quinone diimine with thiophenol and ν ≈ 100 units in the reaction with 1-decanethiol at a quinone diimine concentration of about 10⁻⁴ mol/L and thiol concentrations of about 10⁻³ mol/L. The dependence of the kinetic parameters of the initiated reaction on the thiophenol concentration suggests that the reaction of the thiyl radical with quinone diimine is the rate-determining step of chain propagation. The rate constant of this reaction is estimated at k _pr = 3.2 × 10⁵ L mol⁻¹ s⁻¹. The rates of chain initiation due to the direct interaction of the initial reactants are estimated. In these reactions, the homolytic cleavage of the S-H bond occurs in the thiol, due to which, other conditions being equal, the radical formation rate in the quinone diiminethiophenol system is at least two orders of magnitude higher than that in the quinone diimine-1-decanethiol, in which the strength of S-H bond is higher. A radical chain mechanism is proposed for the reaction of quinone diimine with the thiols on the basis of the data obtained.     

Baeyer–Villiger oxidation of <Emphasis Type="Italic">N</Emphasis> <Superscript>1</Superscript>,<Emphasis Type="Italic">N</Emphasis> <Superscript>3</Superscript>,2-triaryl-6-hydroxy-6-methyl-4-oxocyclohexane-1,3-dicarboxamides

Baeyer–Villiger oxidation of N¹,N³,2-triaryl-6-hydroxy-6-methyl-4-oxocyclohexane-1,3-dicarboxamides with 30% hydrogen peroxide in acetic acid afforded 2-(4-aryl-3-carbamoyl-2-methyl-5-oxooxolan-2-yl)acetic acids.     

Adsorption of <Emphasis Type="Italic">N</Emphasis>-hydrocinnamoyl-<Emphasis Type="Italic">N</Emphasis>-phenylhydroxylamine on pure minerals

Equilibrium adsorption studies of N-hydrocinnamoyl-N-phenylhydroxylamine (HCNPHA) on galena, sphalerite, pyrite, chalcopyrite and quartz at pH 9 and 10 are reported. All adsorption isotherms followed Langmuir model, however, Freundlich type was observed for quartz. As HCNPHA is a strong chelating agent, formation of monolayers by chemisorption appeared to be the most probable mechanism of adsorption on the base-metal sulphide minerals. Specific adsorption of HCNPHA on iron containing minerals, namely, chalcopyrite and pyrite, was about three times that on galena and sphalerite, and specific adsorption on quartz was the lowest amongst the minerals studied. Specific adsorptions (in μmol/g) of HCNPHA on the minerals at pH 9 are: sphalerite: 30.5; galena: 26.9; chalcopyrite: 112.3; pyrite: 145.4; quartz: 2.9. Compared to pH 9, specific adsorption of HCNPHA on the minerals decreased at pH 10, indicating hydroxylation of mineral sites due to higher hydroxide ion concentration at pH 10. A spectral-colorimetric procedure was developed for the quantitative estimation of HCNPHA. Due to deprotonation of hydroxamic acids direct estimation using UV absorption was not possible. Hence, complexation of HCNPHA with Fe³⁺ was used to develop a purple coloured complex that absorbs in the visible region with λ _max=500 nm. Change in concentration of HCNPHA was measured from absorbance of the HCNPHA- Fe³⁺ complex at 500 nm.     

Volumetric Properties of Sodium Nitrobenzoate in <Emphasis Type="Italic">N</Emphasis>, <Emphasis Type="Italic">N</Emphasis>-Dimethylformamide–Water Mixtures at 298.15 K

Densities of sodium nitrobenzoate (o-, m-, p-) have been measured in dimethylformamide (DMF)–water mixtures at 298.15 K with an oscillating-tube densimeter. From these densities, apparent molar volumes of sodium nitrobenzoate in DMF–H₂O-mixtures have been calculated and partial molar volumes at infinite dilution have been evaluated. Substituent and solvent effects on the transfer volumes of each isomer from water to DMF–H₂O-mixed solvents have also been obtained. The results are explained in terms of solvent–solvent and solute–solvent interactions.     

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.