<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.     

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.     

<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 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.     

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.     

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.     

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.     

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 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.     

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.     

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.     

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 characteristics of <Emphasis Type="Italic">N</Emphasis>-(glyoxyldioxime)-<Emphasis Type="Italic">N</Emphasis>′-(2-hydroxybenzylidene)-1,4-diaminonaphthalene and its metal complexes

A new vic-dioxime, N-(glyoxyldioxime)-N′-(2-hydroxybenzylidene)-1,4-diaminonaphthalene, was synthesized proceeding from naphthalene. Its complexes of nickel, copper and cobalt were prepared. The vicdioxime and its complexes were charecterized by FT-IR, UV, ¹H NMR, mass spectrometry, elemental analysis, DTA/TG analysis techniques and conductometric measurements. Published in Russian in Zhurnal Obshchei Khimii, 2008, Vol. 78, No. 5, pp. 797–802. The text was submitted by authors in English.     

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.     

Structural characterization of <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>′-bis(2-methoxyethyl) -4,5-bis(2,4,6-trimethylphenyl)imidazolinium hexafluorophosphate

The crystal and molecular structure of the N,N′-bis(2-methoxyethyl)-4,5-bis(2,4,6-trimethylphenyl)- imidazolinium hexafluorophosphate, which is the first example of 1,3- and 4,5-disubstituted imidazolinium salts, have been determined and characterized by X-ray single crystal diffraction technique,¹H, ¹³C, ³¹P and ¹⁹F NMR spectroscopy. The compound, C₂₇H₃₉N₂O₂ ⁺·PF₆ ^?, crystallizes in the orthorhombic space group Pba2 with a = 15.8139(4) Å, b = 22.9346(7) Å, c = 8.069(3) Å. Two charge-assisted C–H\(\cdots\)F type crystal packing interactions between the imidazolinium C–H bonds and the F atoms of hexafluorophosphate counteranions build up zigzag chains along a-axis of the unit cell and indicate that the C–H bonds of the imidazolinium ring are also polarized. In addition, the title salt was modeled by DFT calculations in order to verify charge transfer mechanism observed in its imidazolinium ring.     

Nature of intramolecular O→Si bond in <Emphasis Type="Italic">N</Emphasis>-(trifluorosilylmethy)succinimide and <Emphasis Type="Italic">N</Emphasis>-(trifluorosilylmethy)phthalimide

By AIM analysis with application of PBE/TZ2P(SBK-JC) method the O→Si bond in isolated molecules of N-(trifluorosilylmethyl)succinimide (I) and N-(trifluorosilylmethyl)phthalimide (II) is shown to be of donor-acceptor type. In crystalline state of compound I it also is a weak donor-acceptor bond, while in II the interaction between the oxygen and silicon atoms is of electrostatic nature.     

Novel olefin metathetis catalysts with fluorinated <Emphasis Type="Italic">N</Emphasis>-alkyl-<Emphasis Type="Italic">N</Emphasis>´-arylimidazolin-2-ylidene ligands

Novel ruthenium carbene complexes bearing unsymmetrical NHC-ligands based on N-alkyl-N´-arylimidazoline with hexafluoroisopropylmethoxy group in para-position of N-aryl moiety have been synthesized. Catalytic activity of complexes obtained was investigated on model reactions of intra- and intermolecular olefin metathesis.     

Zinc <Emphasis Type="Italic">N</Emphasis>-(4′-benzo-15-crown-5)-2-(amino-<Emphasis Type="Italic">N</Emphasis>-tosyl)phenylaldiminate: Complexation and ion-selective properties

The lithium, sodium, and potassium complexes with zinc N-(4′-benzo-15-crown-5)-2-(amino-N-tosyl)phenylaldiminate (ZnL₂) have been synthesized. Their IR spectra have been studied, and selected vibrational frequencies of the ligand and complexes have been assigned. Based on spectroscopy and elemental analysis data, the structure of the complexes has been suggested. The ion-selective properties of ZnL₂ have been studied by potentiometry.     

Copper <Emphasis Type="Italic">N</Emphasis>-(4′-benzo-15-crown-5)-2-(amino-<Emphasis Type="Italic">N</Emphasis>-tosyl)phenylaldiminate: Complexing and ion-selective properties

Copper(II) chelate with N-(4′-benzo-15-crown-5)-2-(amino-N-tosyl)phenylaldiminate CuL₂ and its coordination compounds with Li, Na, and K salts have been synthesized. Their IR spectra have been studied and assignment of the key vibration frequencies of CuL₂ and complexes based on it. On the basis of spectral, thermogravimetric, and elemental analysis datasassumptions concerning the compound structure are made. The ion-selective properties of CuL₂ are studied by potentiometry.     

Reactions of <Emphasis Type="Italic">N</Emphasis>-(2,2-dichloro-1-cyanoethenyl)-<Emphasis Type="Italic">N</Emphasis>′-methyl(phenyl)ureas with aliphatic amines

Novel derivatives of 3,3-dichloroprop-2-enenitrile containing methylurea or phenylurea fragments have been synthesized. The obtained N-(2,2-dichloro-1-cyanoethenyl)-N′-methyl(phenyl)ureas undergo intramolecular cyclization in the presence of triethylamine to form 4-(dichloromethylidene)-5-imino-1-methyl (phenyl)imidazolidin-2-ones. Reactions of N-(2,2-dichloro-1-cyanoethenyl)-N′-methylurea with aliphatic amines have afforded 4-(alkylamino)-4-(dichloromethyl)-5-imino-1-methylimidazolidin-2-ones.