Adsorption of N-Nitrosodiethylamine and N-Nitrosodimethylamine on Activated Carbon: A Pre-Concentration Procedure for Gas Chromatographic Analysis

In this study, a rapid pre-concentration procedure, which employs powdered activated carbon as a clean-up and pre-concentration material, is described for the gas chromatographic analysis of N-nitrosodiethylamine (NDEA) and N-nitrosodimethylamine (NDMA) in aqueous solutions. It was found that powdered activated carbon is suitable for the adsorption of volatile N-nitrosamine compounds from aqueous solutions. Adsorption efficiency with spiked beer samples (alcohol content 5% v/v) was found to be 80.5% (NDMA) and 89.4% (NDEA) and recovery of extraction from activated carbon was calculated as 82.1% (NDMA) and 89.7% (NDEA), respectively. The effect of 100µgmL^–1 of tannic acid on the adsorption was also studied, and no significant effect on the adsorption and extraction of volatile N-nitrosamine compounds was found.     

Metallophthalocyanines with rod-shaped substituents

4-(4′-Dioctylaminocarbonylbiphenyloxy) phthalonitrile was synthesized from 4-(4′-carboxybiphenyloxy)phthalonitrile and dioctylamine in the presence of Et₃N. Metallophthalocyanines (Zn, Co and Cu) substituted with four dioctylaminocarbonyl biphenyloxy groups on the peripheral positions were prepared from 4-(4′-dioctylaminocarbonylbiphenyloxy)phthalonitrile and the corresponding divalent metal salts (Zn(CH₃COO)₂, CoCl₂ and CuCl₂). The new phthalocyanines are soluble in common organic solvents. These compounds were characterised by ¹H-NMR, ¹³C-NMR, FT-IR, UV-Vis and mass spectroscopies.     

Der Abbau des Insektizides GS 13005 in der Ratte. Strukturaufklärung der wichtigsten Metabolite [1]

The structures of the essential metabolites which are excreted by the rat after oral application of GS 13005 (O,O-dimethyl-S-[(2-methoxy-1,3,4-thiadiazole-5(4H)-one-4-yl)-methyl] dithiophosphate) have been elucidated. The product of final oxidation, CO₂, was found to be the main metabolite (up to 36% of the dose applied). Among the degradation products excreted in the urine (up to 45% of the dose applied) the two most important were isolated. They are 4-methylsulfinylmethyl and 4-methylsulfonylmethyl derivatives respectively of the intact 2-methoxy-1,3,4-thiadiazole-5-one heterocycle (metabolites III and II, in amounts of 20–25% and 5–7% of the dose applied, respectively). These metabolites originate by methylation and subsequent oxidation from the mercaptomethyl derivative liberated after hydrolysis of the P S bond of the dithiophosphoric acid ester.     

The synthesis and characterization of a new (<Emphasis Type="Italic">E,E</Emphasis>)-dioxime containing 13-membered dithiadiazamacrocyclic moieties and its mononuclear complexes

A new (E,E)-dioxime, (6Z,7Z)-15,16-dihydro-14H-dibenzo[b,h][1,10,4, 7]dithiadiazacyclotride-cine-6,7(5H,8H)-dionedioxime (H ₂ L) has been synthesized by reacting cyanogen-di-N-oxide (2) with 2,2′-[propane-1,3-diylbis(thio)]dianiline (1). Mononuclear complexes (4) and (5) of this ligand have been synthesized by reacting the vic-dioxime (H₂L) with NiCl₂ · 6H₂O and CoCl₂ · 6H₂O, respectively. The BF ₂ ⁺ capped Ni(II) and Co(III) complexes (6) and (7) of the dioxime have been synthesized from (4) and (5). The new compounds were characterized by a combination of elemental analysis, ¹H- and ¹³C-n.m.r, i.r. and m.s. spectral data.     

Metallocene complexes as homogeneous catalysts in olefin polymerization

Ansa metallocene dichloride complexes of titanium, zirconium, and hafnium can be activated by methyl aluminoxane (MAO) to give excellent catalysts for the homogeneous polymerization of ethylene and propylene. The symmetry of the corresponding metaliocene dichloride complexes is essential for the stereospecific polymerization of propylene (isotactic, syndiotactic or atactic). The application of fluorenyl groups instead of cyclopentadienyl groups greatly increases the activity of the catalysts. The first ansa bis(fluorenyl) complexes of zirconium and hafnium, (C₁₃H₈-C₂H₄-C₁₃Hs)MCl₂ (M = Zr, Hf), have been prepared. It was found that after the activation by MAO the zirconium derivative demonstrates a very high activity. Several model complexes are presented in order to discuss the mechanism of the polymerization.This paper was presented at the INEOS-94 Workshop The Modern Problems of Organometallic Chemistry (Moscow, May 21–27, 1994).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 7–14, January, 1995.     

Synthesis and structural studies of (2E,3E)-3-[(6-{[(1E,2E)-2-(hydroxyimino)-1-methylpropylidene]amino}pyridin-2-yl)imino]butan-2-one oxime, ligand and its mono-, di- and trinuclear copper(II) complexes

A new dioxime ligand, (2E,3E)-3-[(6-{[(1E,2E)-2-(hydroxyimino)-1-methylpropylidene]amino}-pyridin-2-yl)imino]butan-2-one oxime, (H₂Pymdo) (3) has been synthesized in H₂O by reacting 2,3-butenedione monoxime (2) with 2,6-diaminopyridine. Mono-, di- and tri-nuclear copper(II) complexes of the dioxime ligand (H₂Pymdo) and/or 1,10-phenanthroline have been prepared. The dioxime ligand (H₂Pymdo) and its copper(II) complexes were characterized by ¹H-n.m.r., ¹³C-n.m.r. and elemental analyses, magnetic moments, i.r. and mass spectral studies. The mononuclear copper(II) complex of H₂Pymdo was found to have a 1:1 metal:ligand ratio. Elemental analyses, stoichiometric and spectroscopic data of the metal complexes indicated that the metal ions are coordinated to the oxime and imine nitrogen atoms (C=N). In the dinuclear complexes, in which the first Cu(II) ion was complexed with nitrogen atoms of the oxime and imine groups, the second Cu(II) ion is ligated with dianionic oxygen atoms of the oxime groups and are linked to the 1,10-phenanthroline nitrogen atoms. The trinuclear copper(II) complex (6) was formed by coordination of the third Cu(II) ion with dianionic oxygen atoms of each of two molecules of the mononuclear copper(II) complexes. The data support the proposed structure of H₂Pymdo and its Cu(II) complexes.     

Synthesis of N-(4′-Benzo[15-crown-5])biphenylaminoglyoxime and Its Complexes with Some Transition Metals

N-(4-Benzo[15-crown-5])biphenylaminoglyoxime (H₂L) and sodium chloride salt of N-(4-benzo[15-crown-5])biphenylaminoglyoxime (H₂L · NaCl) have been prepared from 4-biphenylchloroglyoxime, 4-aminobenzo[15-crown-5], and sodium bicarbonate and sodium chloride. Nickel(II), cobalt(II), and copper(II) complexes with H₂L and H₂L · NaCl have a metal–ligand ratio of 1 : 2 and the ligand coordinates through the two N atoms, as do most of the vic-dioximes. Their IR spectra and elemental analyses are given, together with ¹H NMR spectra of the ligands.     

Metal-Containing Phthalocyanines Substituted with One Branched Bulky Moiety and Six Alkylthio Groups

Summary.  Unsymmetrically substituted metal-phthalocyanines composed of three hexylthio groups and one 1-chloro-3,4-dicyano-6-[2-(2-pyridylmethylamino)phenylthio]benzene moiety was prepared by cyclization of the reactants in the presence of the anhydrous metal salts Zn(CH₃COO)₂, NiCl₂, and CoCl₂. The new unsymmetric phthalocyanines are very soluble in common organic solvents. The compounds were characterised by their elemental analyses, IR, ¹H NMR, MS and UV/Vis spectra. Corresponding author. E-mail: bayir@itu.edu.tr Received November 27, 2002; accepted (revised) December 2, 2002 Published online May 2, 2003     

A novel (E,E)-dioxime and its mono-, di- and trinuclear complexes bearing tetradentate octyl sulfanyl phenylamino substituents. Synthesis,characterization and electrochemical properties of its transition metal complexes

A new vic-dioxime, 13,14-bis-(hydroxyimino)-9,12,15,18-diazadithiaoctacosane, has been synthesized from 2-octylsulfanylaminobenzene and (E,E)-dichloroglyoxime. Mononuclear transition metal complexes of Ni^II, Cu^II, Co^II and Fe^II have been prepared and were found to have a metal–ligand ratio of 1:2. The synthesis of di- and trinuclear complexes was achieved with U^IVO₂ and Cu^II depending on the stoichiometry of the reactants. The complexes were characterized by elemental analysis, ¹H-n.m.r., u.v.–vis, i.r., f.a.b.-m.s. and by cyclic voltammetry.     

Preparation and characterization of Co(II), Ni(II) and Cu(II) complexes of a ligand containing 1,3,4-thiadiazole groups

(1R,2R)-1,2-bis-(5-amino-1,3,4-thiadiazole-2-yl)ethane-1,2-diol (L) has been prepared by the reaction of thiosemicarbazide with (2R,3R)-(+)-tartaric acid (I) and phosphorous oxychloride, and its complexes with Co(II), Ni(II) and Cu(II) have been obtained. The structures of the ligand and its complexes have been established by i. r., ¹H- and ¹³C-n.m.r. spectra, u.v.–vis–nir spectroscopy, elemental analyses, T.g.-D.t.a. and magnetic susceptibility measurements.