Conducting Polymer Layers Obtained by Direct-Current Discharge Polymerization of 1-Amino-9,10-anthraquinone

The polymerization of 1-amino-9,10-anthraquinone in a direct-current discharge was studied. It was found that polymer films with a conductivity of 10^–5–10^{–4 –1} cm^–1 were formed at the cathode. It was assumed that the semiconductor properties are due to the presence of a conjugated cyclic moiety in the films. The layers deposited at the anode turned out to be typical dielectrics with a conductivity of 10^{–16 –1} cm^–1.     

Spectrophotometric determination of iron after separation of its 9,10-phenanthrenequinone monoximate on microcrystalline naphthalene

A sensitive and selective spectrophotometric method has been developed for the determination of iron as Fe(II) or Fe(III) using 9,10-phenanthrenequinone monoxime (PQM) as the complexing agent. Fe(II) and Fe(III) react with PQM to form coloured water insoluble complexes which can be adsorbed on microcrystalline naphthalene in the pH ranges 3.7–6.2 and 2.0–8.4, respectively. The solid mass consisting of the metal complex and naphthalene is dissolved in DMF and the metal determined spectrophotometrically by measuring the absorbances Fe(II) at 745 nm and Fe(III) at 425 nm. Beer's law is obeyed over the concentration range 0.5–20.0 g of iron(II) and 20–170.0 g of Fe(III) in 10 ml of DMF solution. The molar absorptivities are 1.333 × 10⁴ 1 · mole^–1 · cm^–1 for Fe(II) and 2.428 × 10³1· mole^–1 · cm^–1 for Fe(III). The precision of determination is better than 1%. The interference of various ions has been studied and the method has been employed for the determination of iron in various standard reference alloys, bears, wines, ferrous gluconate, human hair and environmental samples.     

Diastereoselective methylation of ls-α-phenylethyl-Δ9,10-octahydroquinol-4-one

The methylation of the lithium derivative of ls--phenylethyl-^9,10-octahydroquinol-4-one under kinetic-control conditions at –70 °C in hexane is highly diastereoselective and leads to (+)-ls--phenylethyl-3-methyl-^9,10-octahydroquinol-4-one in 90% optical yield.Communication 2 in the series Metallation of cis-enamino ketones. See [1] for Communication 1.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 389–392, March, 1984.     

Dehydration of 10,10-dimethyl-9-allyl-9,10-dihydro-10-sila-2-azaanthrol-9

Dehydration under various conditions of the tertiary alcohol 10,10-dimethyl-9-allyl-9,10-dihydro-10-sila-2-azaanthrol-9 yielded the following compounds: Z- and E-isomers of 10,10-dimethyl-9-propenyldiene-9,10-dihydro-10-sila-2-azaanthracene; 10,10-dimethyl-9-allyl-9-ethoxy-9,10-dihydro-10-sila-2-azaanthracene; 1,1,3,3-tetramethyl-1,3-di(3-propenylidenebenzylpyridyl-4)-disiloxane; 1-methyl-3-(4-dimethyloxysilylpyridyl-3)indene.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1566–1569, November, 1988.     

Additivity of theHammett reaction constants ion pairs effect in the polarographic reduction of nitrobenzene and 9,10-anthraquinone derivatives

An attempt has been made to estimate the effect of the subsequent ion pairs formation on the value of theHammett reaction constant measured polarographically. To this purpose, the reduction ofpara-substituted nitrobenzenes and 2-substituted 9,10-anthraquinones was studied at a dropping mercury electrode in N,N-dimethylformamide. The ion pairs reaction constant of substituted nitrobenzene radical anions with tetraethylammonium cations is equal to –1.49 V/ unit. The corresponding reaction constant for the semiquinone—Li⁺ series was estimated to be –0.90 V/ unit. The method of calculation was based on the additivity rule withinHammett's treatment.

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Zur Additivität derHammet'schen Reaktionskonstanten. Paar-Effekte bei der polarographischen Reduktion von Nitrobenzol und 9,10-Anthrachinonderivaten

Zusammenfassung Es wurde eine Abschätzung des Effekts der nachfolgenden Ionenpaarbildung auf den polarographisch bestimmten Wert derHammet'schen Reaktionskonstanten versucht. Dazu wurde die Reduktion vonpara-substituierten Nitrobenzolen und 2-substituierten 9,10-Anthrachinonen an der tropfenden Quecksilberelektrode in N,N-Dimethylformamid untersucht. Die Ionenpaar-Reaktionskonstanten von substituierten Nitrobenzol-Radikalanionen mit Tetraethylammoniumkationen ist gleich –1.49 V/-Einheiten. Die ents prechende Reaktionskonstante für die Semichinon-Li⁺ Serie wurde mit –0.9 V/-Einheiten abgeschätzt. Die Berechnungsmethode basiert auf der Additivitätsregel derHammet'schen Reaktionskonstanten.

     

Preparation of substituted 9,10-dihydro-9-sila-3-azaanthracenes and their derivatives

3-Methyl-4-dimethylphenylsilylpyridine and 3-methyl-4-methyldiphenylsilylpyridine, which were obtained from -picoline and dimethylphenylchlorosilane and methyldiphenylchlorosilane, respectively, were converted by catalytic dehydrocyclization to 9,9-dimethyl-9,10-dihydro-9-sila-3-azaanthracene and 9-methyl-9-phenyl-9,10-dihydro-9-sila-3-azaanthracene. The corresponding silaazaanthrones were obtained from them and were converted to tertiary silaazaanthrols with a methyl or phenyl group attached to the C₁₀ atom. On the basis of an analysis of data from the PMR spectra of the silaazaanthracenes it was assumed that they exist in the form of an equilibrium mixture of boat conformations. 9-Methyl-9-phenyl-10-methylene-9,10-dihydro-9-sila-3-azaanthracene was obtained in the form of a stable crystalline substance by dehydration of the corresponding silaazaanthrol. Potassium tert-butoxide cleaves the Si-C bond in the silaazaanthrone system; this was confirmed by isolation of 1,2-dimethyl-1,2-diphenyl-1,2-bis (2-nicotinoylphenyl)disiloxane.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 240–244, February, 1981.     

Continuous-flow separation and pre-concentration coupled on-line to solid-surface fluorescence spectroscopy for the simultaneous determination of<Emphasis Type="Italic"> o</Emphasis>-phenylphenol and thiabendazole

A novel and single flow-injection system combined with solid-surface fluorescence detection is proposed in this work for the resolution of a mixture of two widely used pesticides (o-phenylphenol and thiabendazole). The continuous-flow methodology is based on the implementation of on-line pre-concentration and separation of both analytes on the surface of C₁₈ silica gel beads placed just inside the flow cell, implemented with gel-phase fluorimetric multi-wavelength detection (using 305/358 and 250/345 nm as excitation/emission wavelengths for thiabendazole and o-phenylphenol, respectively). The separation of the pesticides was possible owing to the different retention/desorption kinetics of their interactions with the solid support in the zone where the stream impinges on the solid material. No previous separation of the analytes before they reach the flow cell is needed thereby simplifying substantially both the procedure and the manifold. By using a sample volume of 2,600 L, the system was calibrated in the range 0.5–16 and 5–120 ng mL^–1 with detection limits of 0.09 and 0.60 ng mL^–1 for thiabendazole and o-phenylphenol, respectively. The RSD values (n=10) were about 1% for both analytes. The proposed methodology was applied to environmental water samples and also to various commercial pesticide formulations containing both analytes. Recovery percentages were 97–103% and 98–102% for thiabendazole and o-phenylphenol, respectively.     

Amino derivatives of 9,9-diorgano-9,10-dihydro-9-sila-3-azaanthracene

Derivatives of 9,9-disubstituted 9,10-dihydro-9-sila-3-azaanthracene (compounds with possible biological activity) were synthesized by means of two methods. 10--Cyanoethyl derivatives were obtained by condensation of dihydrosilaazaanthracenes with acrylonitrole in the presence of Triton B. One of these products was reduced with lithium aluminum hydride to 9,9-dimethyl-10-(-aminopropyl)-9,10-dihydro-9-sila-3-azaanthracene. The second method involves conversion of dihydrosilaazaanthrones (obtained by oxidation of dihydrosilaazaanthracenes) to oximes followed by reduction of the latter with hydrazine hydrate in the presence of Raney nickel to give 10-amino derivatives. The latter were subjected to acylation.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1516–1520, November, 1982.     

Chain termination catalyzed by 1,4-benzoquinones in the oxidation of 9,10-dihydrophenanthrene

Chain termination has been found to be catalyzed by 2,6-R-1,4-benzoquinones (R= H, CH₃, C(CH₃)₃, Cl) in the oxidation of 9,10-dihydrophenanthrene. The mechanism of this effect was elaborated. The oxidation chain termination stoichiometric coefficients at 50°C were found: f = 16 (H), 24 (CH₃). 31 (C(CH₃)₃),9 (Cl).Institute of Bioorganic Chemistry and Petroleum Chemistry, National Academy of Sciences of Ukraine, 1 Murmanskaya St. 252660 Kiev-96, Ukraine. Translated from Teoreticheskaya i Éksperimental'naya Khimiya Vol, 32. No. 1, pp. 32–35. January–February, 1996. Original article submitted April 17, 1995.     

Structure of the products of the reaction of 9,10-dimethylacridinium salts with aromatic o-hydroxy aldehydes

The reaction of 9,10-dimethylacridinium methosulfate with aromatic o-hydroxy aldehydes in alcohol in the presence of piperidine gives 10-methyl-4-(10-methyl-9-acridanylidenemethyl)-spiro[acridan-9,2-chromans]. The structure of the compounds obtained was established by means of the PMR, UV, and IR spectra.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 539–544, April, 1973.     

Photochemical transformations of 1-arylcyanomethyl-9,10-anthraquinones

Photochemical transformations of 1-arylcyanomethyl-9,10-anthraquinones were studied. It was established that under irradiation, the hydrogen atom of the substituted methyl group is transferred to aperi-quinoid oxygen atom to form the corresponding 9-hydroxy1, 10-anthraquinone-1-arylcyanomethides. Dark transformations of photoinduced quinonemethides result from three competing parallel processes: intramolecular transfer of the hydrogen atom, a reaction with a solvent (alcohol), and oxidation by dissolved oxygen. The kinetics of these reactions were studied.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1988–1994, October, 1995.This study was financially supported by the Russian Foundation for Basic Research (Grant No. 95-03-08920) and the Commitee for Higher Education of Russian Federation within the framework of the Chemistry program, Photochemistry course.     

4′-Bromo(and azido)-10,10-dimethylspiro[9,10-dihydro-10-sila-2-azaanthracene-9,2′-tetrahydrofuran]

Dehydrobromination of 10,10-dimethyl-9-(2,3-dibromoprop-1-y1)-9,10-dihydro-10-sila-2-aza-9-anthrol with butyllithium follows two routes to give the Z- and E-isomers of furan ring-brominated spiro(dihydrosilaazaanthracene-9,2-tetrahydrofuran), and the cis- and trans-isomers of 10,10-dimethyl-9-(3-bromoallyl)-9,10-dihydro-10-sila-2-aza-9-anthrol. Analogous compounds have been obtained bearing an azidogroup in the tetrahydrofuran ring, and a spiran with a dihydrofuran fragment. The pure isomers have been isolated, and their structures established.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 696–700, May, 1989.     

Exploring Clathrate Formation with an Optically Resolved Host. X-Ray Crystal Structure of the Inclusion Compound between (11S,12S)-(-)-9,10-Dihydro-9,10-ethanoanthracene-11,12-dicarboxylic Acid and n-Hexane (2 : 1)

The crystal structure of the inclusion compound formed between (11S,12S)-(-)-9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboxylic acid, (1), and n-hexane (2:1) has been studied by X-ray diffraction. It crystallizes in the tetragonal space group P41 and represents a less common type of inclusion compound, which has helical and chiral structural elements. Helical chains, formed by hydrogen-bonded host molecules, wind around the 21 screw axes and encircle the guest molecules. Crystal data: a=b=17.478(1); c=12.021(1)Å, Z=4 host–guest 2:1 units, R=0.043, Rw=0.061 for 2225 observations with I > 3 (I). The general shape and conformational flexibility of 1 with respect to the requirements of inclusion formation and crystal packing are discussed.     

Crystal and molecular structure of the benzene solvate of 2,4,7-trinitro-9,10-phenanthrenequinone

Conclusions An x-ray diffraction structural analysis established the molecular and crystal structure of the benzene solvate of 2,4,7-trinitro-9,10-phenanthrenequinone. The bond length distribution in this trinitrophenanthrenequinone indicates -electron localization at the periphery of the phenanthrenequinone system, whose significant distortion is due to steric and electronic factors.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1284–1290, June, 1986.     

Preparation and evaluation of a new synthetic polymeric chiral stationary phase for HPLC based on the trans-9,10-dihydro-9,10-ethanoanthracene-(11S,12S)-11,12-dicarboxylic acid bis-4-vinylphenylamide monomer

A new synthetic polymeric chiral stationary phase for liquid chromatography was prepared via free-radical-initiated polymerization of trans-9,10-dihydro-9,10-ethanoanthracene-(11S,12S)-11,12-dicarboxylic acid bis-4-vinylphenylamide. The new polymeric chiral stationary phase (CSP) showed enantioselectivity for many chiral compounds in multiple mobile phases. High stability and sample capacities were observed on this polymeric chiral stationary phase. Mobile phase components and additives affected chiral separation greatly. This new synthetic chiral stationary phase is complementary to two other related commercially available CSPs: the P-CAP and P-CAP-DP columns. Interactions between the chiral stationary phase and analytes that lead to retention and chiral recognition include hydrogen bonding, dipolar, and π–π interactions. Repulsive (steric) interactions also contribute to chiral recognition. Figure LC chromatograms showing the analytical (blue) and preparative (red) separations of N-(3,5-dinitrobenzoylleucine) enantiomers on a new synthetic polymeric chiral stationary phase     

Synthesis and transformations of 2-(2-furyl)- and 2-[β-(2-furyl)vinyl] phenanthr [9,10]imidazoles

The corresponding 2-(2-furyl)- and 2-[-(2-furyl)vinyl] phenanthr[9,10]imidazoles were obtained by the condensation of 9,10 phenanthrenequinone with furfural, -(2-furyl)acrolein, and their 5-bromo and 5-nitro derivatives in the presence of ammonium acetate in glacial acetic acid. Their metallation, acetylation, nitration, and replacement of halogen by a nitro group were studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1014–1016, August, 1971.     

Determination of Carotenoids in the Chinese Medical Herb Jiao-Gu-Lan (Gynostemma Pentaphyllum MAKINO) by Liquid Chromatography

A QSTAR Pulsar quadrupole time-of-flight mass spectrometer was used for the determination of chlorophenols in surface water samples. The investigated compounds were: 2-chlorophenol; 4-chloro-3-methylphenol; 2,4-dichlorophenol, 2,4,6-trichlorophenol and pentachlorophenol. Each analyte is listed by the US-EPA as a priority pollutant. Sample enrichment of water samples was achieved by a solid-phase extraction procedure, using a Waters Oasis HLB cartridges followed by LC-Tandem-MS. A narrow-bore 2.1-mm-i.d. reversed phase LC C-18 column operating with a mobile phase flow rate of 0.2 mL min^–1. was used to separate the analytes. The whole column effluent was diverted to the ion spray interface source. For the determination of the analytes the hybrid quadrupole time-of-flight spectrometer operated in product ion scan acquisition mode. Average recoveries from 2 L samples varied from 91 to 110% and relative standard deviations (RSD) were less than 10% for all samples. The limit of detection (signal-to-noise ratio=3) of the method for the phenols in drinking water samples is less than 10 ng L^–1. In real environmental samples, levels of the selected analytes varied from non-detected up to 0.5 g L^–1 for pentachlorophenol.     

9-(2-Oxo-1-azetidinyl)-10,10-dimethyl-9,10-dihydro-10-sila-2-azaanthracenes

9-(3-Methyl-3-bromo-2-oxo-1-azetidinyl)-10,10-dimethyl-9,10-dihydro-10-sila-2-azaanthracene was obtained in the form of a mixture of two diastereomers by intramolecular cyclization of the corresponding 9-(,-dibromoisobutyrylamino)dihydrosilaazaanthracene in the presence of sodium hydride, as well as Triton B. It was established by two-dimensional nuclear Overhauser effect (NOE) spectroscopy that the azetidinyl substituent in the 9 position has a pseudoaxial orientation vis-à-vis a boat conformation of the central silicon-containing ring.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 559–562, April, 1991.     

Determination of Cd, Co, Cr, Cu, Fe, Mn, Ni and Pb in natural waters, alkali and alkaline earth salts by electrothermal atomic absorption spectrometry after preconcentration by column solid phase extraction

Methods are described for the determination of trace and ultra trace amounts of Cd, Co, Cr, Cu, Fe, Mn, Ni and Pb in natural waters, alkali and alkaline earth salts. Separation and preconcentration of trace metals is achieved by a column solid phase extraction procedure using silica gel modified with derivatives of dithiocarbamates — Na-DDTC (sodium diethyldithio-carbamate and HMDTC (ammonium hexamethylene-dithiocarbamate) as column packing material. The influence of the sorbent preparation procedure on the degree of sorption of the trace analytes is examined for different pH values of the sample solution. Isobutylmethyl ketone (IBMK) is proposed as an effective eluent for quantitative elution of retained metal ions. Optimal instrumental parameters for ETAAS determination of preconcentrated elements in organic eluate are presented. Practical application of sorbents in analysis of natural waters and alkali and alkaline earth salts is demonstrated. Proposed preconcentration procedure combined with ETAAS determination of trace analytes allows the determination of 0.04 g l^–1 Cd, 0.1 g l^–1 Cr, Cu, and Mn and 0.3 g l^–1 Co, Fe, Ni and Pb in natural waters and 1.10^–7% Cd, 3.10^–7% Cr and Mn, 7.10^–7% Co, Ni and Pb and 2.10^–6% Cu and Fe in alkali and alkaline earth salts.     

Facile synthesis of an ambient stable pyreno[4,5-b]pyrrole monoanion and pyreno[4,5-b:9,10-b′]dipyrrole dianion: from serendipity to design

The stability of singly or multiply negatively charged π-conjugated organic compounds is greatly influenced by their electronic delocalization. Herein, we report a strategic methodology for isolation of a mysterious compound. The isolated compounds, a pyreno[4,5-b]pyrrole monoanion and pyreno[4,5-b:9,10-b′]dipyrrole dianion, were highly stable under ambient conditions due to high delocalization of the negative charge over multiple electron deficient C N groups and pyrene π-scaffolds and allowed purification by column chromatography. To our knowledge, this is the first report on TCNE type reductive condensation of malononitrile involving pyrene di- and tetraone and formation of pyrenopyrrole. All compounds were characterized by spectroscopic methods and X-ray crystallography. A UV-vis spectroscopic study shows an intense low energy absorption band with a large absorption coefficient (ε).

An ambient stable pyreno[4,5-b]pyrrole monoanion and pyreno[4,5-b:9,10-b′]dipyrrole dianion have been isolated and characterized, showing a low energy intense absorption band with the absorption coefficient reaching 7.1 × 10⁴ dm³ mol⁻¹ cm⁻¹.