<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.     

<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 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.     

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.     

TiO<Subscript>2</Subscript>/TiO<Subscript>2−<Emphasis Type="Italic">x</Emphasis></Subscript>N<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> nanocomposite and its acetaldehyde photodecomposition ability

Nitrogen-doped titania was coupled with the commercial titania nanoparticles by mechanical milling in liquid medium. The as-prepared nanocomposites (TiO₂/TiO_2−x N _y ) were characterized by X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) specific surface area, UV–Vis spectroscopy, chemiluminescence, and acetaldehyde decomposition activity techniques. When a small amount of nitrogen-doped titania was added into the commercial titania, higher intensity and longer lifetime of ¹O₂ was observed, and the photocatalytic activity was efficiently improved. The TiO_2−x N _y acts as the acceptor of photoinduced holes. The recombination of the electron-hole was effectively depressed by the heterogeneous electron transfer. This could be an effective way to obtain highly active photocatalysts.     

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.     

Anion coordination complex [Cl⊂Pt(bpt)<Subscript>4</Subscript>]Cl (bpt=<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>′-bis(3-pyridylmethyl)-2-thiourea)

The anion coordination complex, [Cl?Pt(bpt)₄]Cl (bpt=N,N′-bis(3-pyridylmethyl)-2-thiourea), was synthesized and studied by X-ray crystal structure analysis, NMR and FAB mass spectra. In the solid state, the Pt(bpt)₄ anion receptor adopts a cone conformation to bind the chloride anion through hydrogen bonds and electrostatic interaction in which the four branches of the thiourea ligands bind the chloride anion to form N-H?Cl^? hydrogen bonds (3.49–3.81 Å). The entraped chloride anion is situated above the Pt(II) center at 3.52 Å. Further second-sphere coordination assemby from the Pt(bpt)₄ core with 8 zinc(II) tetraphenylporphyrins (ZnPr) is discussed.     

Planar Four-Coordinate Carbon in Star-Like Perlithioannulenes C<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>Li<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript> (<Emphasis Type="Italic">n</Emphasis> = 3–6)

The structure and stability of perlithioannulenes C _n Li _n (n = 3–6) were examined ab initio [MP2(full)/6-311+G**] and in terms of the density functional theory (B3LYP/6-311+G**). The systems with n = 3, 5, and 6 may be stabilized as planar star-like structures with bridging lithium atoms and hypercoordinate carbon atoms. Star-like structures are the most stable isomers of odd-numbered annulenes (n = 3, 5), while the most stable isomers of even-numbered annulenes (n = 4, 6) have less symmetric nonplanar structures.     

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.     

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.     

<Emphasis Type="Italic">N</Emphasis>-alkylation of ethylenediamine with alcohols catalyzed by CuO-NiO/<Emphasis Type="Italic">γ</Emphasis>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

A simple method for N-alkylation of 1,2-diaminoethane with different alcohols in a fixed-bed reactor using cheap CuO-NiO/γ-Al₂O₃ as the catalyst has been developed. The present catalytic system was applicable in the N-alkylation of 1,2-diaminoethane with both primary and secondary alcohols. Mono-N-alkylation of 1,2-diaminoethane with low-carbon alcohols resulted in high yields; the yields of tetra-N-alkylation of 1,2-diaminoethane with low-carbon alcohols declined markedly with the increase of the molecular volume of alcohols.     

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.     

Synthesis of (Ni<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Co<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>)<Subscript>2</Subscript>P (0 ≤ <Emphasis Type="Italic">x</Emphasis> ≤ 0.65) substitution solid solution

The phosphides (Ni_{1 ? x} Co _x )₂P (0 ≤ x ≤ 0.65) crystallizing in the hexagonal system, space group P \(\bar 6\)2m, were synthesized in two steps starting from the continuous solid solution (Ni_{1 ? x} Co _x )₃(PO₄)₂ · 8H₂O. The initial phosphates were first completely dehydrated at 800°C and then reduced with hydrogen at 900–1000°C for 1–2 h.     

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 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.     

Magnetic properties of CuCr<Subscript>2–<Emphasis Type="Italic">х</Emphasis></Subscript>Sb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Se<Subscript>4</Subscript> (<Emphasis Type="Italic">х</Emphasis> = 0–0.5) solid solutions

Magnetic properties of spinel solid solutions CuCr_2–х Sb _x Se₄ (х = 0–0.5) were measured in the temperature range 5–300 K in a constant (50 Oe and 10 kOe) magnetic field. The results are interpreted in terms of the ionic model suggested earlier for CuCr₂Х₄ compounds.     

Phenyl(trimethylsiloxy)fluorosiloxanes PhSi(OSiMe<Subscript>3</Subscript>)<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>F<Subscript>3−<Emphasis Type="Italic">n</Emphasis></Subscript>

The siloxane bond splitting reaction in hexamethyldisiloxanes PhSiCl _n F_3?n was studied.     

Fast evaluation of molecular auxiliary functions <Emphasis Type="Italic">A</Emphasis><Subscript>α</Subscript> and <Emphasis Type="Italic">B</Emphasis><Subscript><Emphasis Type="Italic">n</Emphasis></Subscript> by analytical relations

Analytical relations through the initial values are derived for the molecular auxiliary functions A _α (x) and B _n (x), where α =n+ɛ, 0⩽ ɛ < 1 and n=0,1,2,.... These relations are useful in the fast calculation of multicenter molecular integrals over integer and noninteger n Slater type orbitals. It is shown that the formulas obtained are numerically stable for all values of n,ɛ and x.PACS No: 31.15.+q, 31.20.EjAMS subject classification: 81-V55, 81-V45