Oxidative Addition of <Emphasis Type="Italic">N</Emphasis>-Aminophthalimide to Conjugated and Nonconjugated Alkylazoalkanes

A series of γ,δ-unsaturated azo compounds was prepared by thermal isomerization of allylalkylhydrazones obtained from the simplest carbonyl compounds. The oxidation of N-aminophthalimide with lead tetraacetate in the presence of these unsaturated compounds gave rise to mixtures of adducts at the azo group, regioisomers of phthalimidoazimines. The oxidative addition of N-aminophthalimide to 1-isopropylazocycloalkenes afforded bicyclic C-isopropylazo-N-phthalimidoaziridines, but the same reaction with 2-alkylazopropenes did not result in any adducts with these conjugated azocompounds.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 2, 2005, pp. 214–223.Original Russian Text Copyright © 2005 by Kuznetsov, Belov, Buchaka.     

Synthesis and Study of Thiocyanato(N)iodocuprates(I) and -Argentates(I) of Quaternary Arsonium Cations

The reactions of triarylalkylarsonium acetates with CuI and AgI in the presence of excess potassium thiocyanate yield the corresponding triarylalkylarsonium thiocyanato(N)iodocuprates(I) and -argentates(I). The composition, structure, and thermal behavior (in the range 20–1000°C) of these compounds were studied by chemical analysis, IR spectroscopy, conductometry, and differential thermal analysis.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 5, 2005, pp. 738–741.Original Russian Text Copyright © 2005 by Gigauri, Kikalishvili, Kipiani, Khidesheli, Kutsiya.     

Interaction of Sulfur Dioxide with Aqueous Solutions of Amides

The interactions in the systems H₂O-Am-SO₂ (Am is formamide, dimethylformamide, acetamide, urea, tetramethylurea, tert-butylurea) at 278 and 293 K were studied pH-metrically. The results suggest formation of intermolecular and ion-molecule associates. The composition and stability of the compounds formed strongly depend on the structure and concentration of the solution components and on temperature.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 5, 2005, pp. 771–777.Original Russian Text Copyright © 2005 by Khoma, Gavrilenko, Nikitin.     

Electrotransport Properties of Ceramics Based on Bi<Subscript>4</Subscript>V<Subscript>2 − <Emphasis Type="Italic">x</Emphasis></Subscript>Fe<Subscript>x</Subscript>O<Subscript>11 − <Emphasis Type="Italic">x</Emphasis></Subscript>

Conditions for the formation of single-phase compounds in the synthesis of solid solutions Bi₄V_{2 − x} Fe_xO_{11 − x} are studied. The sequence of phase transitions is determined. Parameters of unit cells of solid solutions are determined. The net conductance as a function of temperature and composition is studied.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 607–609.Original Russian Text Copyright © 2005 by Emel’yanova, Buyanova, Zhukovskii.     

Lower Rim Substituted tert-Butyl calix[4]arene (part VII): Ionophoric Properties of Calix[4]arene-crown-6 Derivatives in Plasticized PVC-Membrane Electrodes and in Solution

The synthesis and characterization of p-tert-butylcalix[4]arene-crown-6 derivatives (compounds 2–9) are presented. Their ability to complex alkali, alkaline earth and some “softer” cations was investigated by using these compounds as ionophores in ion-selective membrane electrodes and determining the potentiometric selectivity coefficients and the complex stability constants in the membrane. The selectivities of these compounds depend on the size and nature of the substituents on the distal phenolic oxygens. The complexing properties of the two cone and partial cone conformers of compound 2 in the PVC membrane were compared with those in acetonitrile solution studied by UV absorption spectrophotometry and with alkali metal picrate liquid–liquid extraction.This revised version was published online in July 2005 with a corrected issue number.     

Analysis of Phytochelatins and Other Thiol-Containing Compounds by RP-HPLC with Monobromobimane Precolumn Derivatization

In this article, a method for quantitative determination of phytochelatins (PC _n being the classic example) and other thiol-containing compounds in mixed standard solution and plant tissues is presented. Thiols were converted to fluorescent derivatives by precolumn derivatization with monobromobimane. The results showed that PC _n and other thiol-containing compounds in standard mixed solutions were rapidly separated within 15 min by using a ACN 0.1% trifluoroacetic acid binary gradient elution. Glutathione was representatively selected to test the precision of this method. The calibration curve was linear in the range of 1.25–160 ng μl⁻¹ (regression coefficient r ²=0.9999). It was confirmed that this method was rapid, simple, highly sensitive, stable, and had the property of simultaneous determination of PC _n and other thiol-containing compounds. This method was applied to determine PC _n and other thiol-containing compounds in a Cd hyperaccumulator Sedum alfredii in response to Cd. It was found that no PC _n was detected in any tissue at any Cd treatment, suggesting that Cd hyperaccumulation and detoxification in this plant is not based on PC synthesis. Translated from Journal of Nanjing University (Natural Science Edition), 2005, 41(3) (in Chinese)     

Effects of gamma irradiation on the yields of volatile extracts of Angelica gigas Nakai

The study was carried out to determine the effects of gamma irradiation on the volatile flavor components including essential oils, of Angelica gigas Nakai. The volatile organic compounds from non- and irradiated A. gigas Nakai at doses of 1, 3, 5, 10 and 20 kGy were extracted by a simultaneous steam distillation and extraction (SDE) method and identified by GC/MS analysis. A total of 116 compounds were identified and quantified from non- and irradiated A. gigas Nakai. The major volatile compounds were identified 2,4,6-trimethyl heptane, α-pinene, camphene, α-limonene, β-eudesmol, α-murrolene and sphatulenol. Among these compounds, the amount of essential oils in non-irradiated sample were 77.13%, and the irradiated samples at doses of 1, 3, 5, 10 and 20 kGy were 84.98%, 83.70%, 83.94%, 82.84% and 82.58%, respectively. Oxygenated terpenes such as β-eudesmol, α-eudesmol, and verbenone were increased after irradiation but did not correlate with the irradiation dose. The yields of active substances such as essential oil were increased after irradiation; however, the yields of essential oils and the irradiation dose were not correlated. Thus, the profile of composition volatiles of A. gigas Nakai did not change with irradiation.     

New organosiloxanes based on 1-vinyl-2-perfluoroalkoxy-2,3,3-trifluorocyclobutanes

A new method for the synthesis of polyfluorinated compounds, viz., chlorosilanes with 2-perfluoroalkoxy-2,3,3-trifluorocyclobutane substituents containing different numbers of tetrafluoro(ethylene oxide) (CF₂CF₂O) _n units (n = 3–6), was developed. The structures of siloxanes formed by the hydrolysis of these chlorosilanes were studied: the hydrolysis of monochlorosilanes affords disiloxanes and that of dichlorosilanes produces cyclotrisiloxanes, cyclotetrasiloxanes, and cyclic (the number of siloxane units >4) and linear polysiloxanes. Dedicated to Academician N. K. Kochetkov on the occasion of his 90th birthday. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1215–1217, May, 2005.     

Arabinogalactan Poly- and Oligosaccharides Modified with 5-Aminosalicylic Acid

Arabinogalactan poly- and oligosaccharides from Siberian larch (Larix sibirica L.) were modified with 5-aminosalicylic acid. The chemical composition and certain physicochemical properties were studied. The optimal conditions for preparing the modified compounds were found. These compounds were demonstrated to possess anti-ulcer and anti-inflammatory activity in tests on experimental animals.__________Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 219–222, May–June, 2005.     

Synthesis and thermal characterization of copper and calcium mixed phosphates

A series of compounds with composition of Ca_1–xCu_xHPO₄, where x varied from 0.05 to 0.5 were synthesized by precipitation method. The compounds were characterized by elemental analysis, X-ray diffraction, infrared spectroscopy, scanning electron microscopy, and thermogravimetry. The chemical stabilities of solids were investigated at several pH. Elemental analysis of copper, calcium and phosphorus are in agreement with the proposed composition. The formation of lamellar phosphates was evidenced. The stability of the set of compounds was better for samples with high copper content.     

Retention Indices As the Best Reproducible Chromatographic Parameters for the Characterization of Phenolic Compounds in Reversed-Phase High-Performance Liquid Chromatography

A comparison of various methods for presenting the retention parameters of analyzed compounds in reversed-phase HPLC under the conditions of stepwise gradient elution demonstrated that retention indices (RIs) based on a standard scale of n-alkyl phenyl ketones exhibited the best reproducibility. However, a new procedure for calculating extrapolated RI values under these conditions should be developed for determining the RIs of the most hydrophilic compounds, which are eluted from a column before a reference component (acetophenone). With this procedure, the RIs of more than 40 phenolic and polyphenolic compounds were determined. The addition of spectroscopic characteristics to these RIs was responsible for the reliable identification of the above compounds in complex mixtures of extractive substances of plant origin.__________Translated from Zhurnal Analiticheskoi Khimii, Vol. 60, No. 7, 2005, pp. 734–746.Original Russian Text Copyright © 2005 by Zenkevich, Kochetova, Larionov, Revina.     

New Tricyclic Amides. Synthesis,Structure, and Oxidation with Peroxyphthalic Acid

4-Azatricyclo[5.2.1.0^2,6]dec-8-ene was synthesized and brought into reactions with benzoyl, o-chlorobenzoyl, p-bromobenzoyl, p-, m-, and o-nitrobenzoyl, and bicyclo[2.2.1]hept-2-ene-endo-5,endo-6-dicarboximidoacetyl chlorides in chloroform in the presence of pyridine. The tricyclic amides thus obtained were epoxidated with peroxyphthalic acid prepared in situ by reaction of phthalic anhydride with a 35% aqueous solution of hydrogen peroxide. The structure of newly synthesized compounds was confirmed by IR and ¹H and ¹³C NMR spectroscopy and mass spectrometry. Their NMR spectra were compared with those of previously synthesized N-arylsulfonyl-4-azatricyclo[5.2.1.0^2,6]dec-8-enes on the basis of conformational composition of the corresponding p-nitrophenyl-substituted derivatives, which was determined by PM3 semi-empirical quantum-chemical calculations.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 6, 2005, pp. 837–845.Original Russian Text Copyright © 2005 by L. Kas’yan, Okovityi, Tarabara, A. Kas’yan, Bondarenko.     

Inhibition of the nicotinamide adenine dinucleotide-oxidoreductase reaction by herbicides and fungicides of various structures

The effect of herbicides (basagran, zenkor, kusagard, roundup, setoxidim, and lontrel and lontrel complexes with some doubly charged metal ions) and fungicides (tachigaren and tilt) on the activity of nicotinamide adenine dinucleotide (NADH)-oxidoreductase from the methylotroph Methylococcus capsulatus (strain M) was studied. All the herbicides and fungicides inhibit the enzyme, differing in the degree and type of inhibition. The inhibition constants K _i for these compounds and for lontrel complexes were determined. A correlation between the K _i values and the complexation constants of these pesticides with NADH was established. The studied compounds are toxic. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1284–1289, May, 2005.     

<Emphasis Type="Italic">meso</Emphasis>-Quinolyl-substituted Tetrabenzoporphins. Synthesis and Properties

Prolonged heating of phthalimide with 2-methylquinoline in the presence of zinc oxide afforded zink complexes of meso-tri-, di- and monoquinolyltetrabenzoporphins. Alternative preparation methods were developed for some among these compounds. The corresponding porphins were prepared by treating complexes with hydrochloric acid. The spectral characteristics of compounds synthesized were investigated.__________Translated from Zhumal Organicheskoi Khimii, Vol. 41, No. 2, 2005, pp. 306–311.Original Russian Text Copyright © 2005 by Galanin, Kudrik, Lebedev, Aleksandriiskii, Shaposhnikov.     

Preconcentration of gold on chelating polymer adsorbents and its determination in rocks and ores

A new class of chelating polymer adsorbents was synthesized on the basis of aminopolystyrene azo compounds and various para-substituted anilines. Physicochemical and analytical properties of adsorbents and their ionic associates with the [AuCl₄]^– anion were studied. Correlations between the ionization constants of amino group (pK _{NH 2}) and the Hammett electronic constant (_n) were found. A linear correlation between the charge on the amino group nitrogen atom and the (_n) value was revealed on the basis of the results of quantum-chemical calculations. A sorption-spectroscopic method was developed for determining gold in ores and rocks. The method was verified by analyzing certified reference samples of ores and rocks in the gold concentration range between n × 10^–3 and n × 10^–6% RSD = 5%.Translated from Zhurnal Analiticheskoi Khimii, Vol. 60, No. 3, 2005, pp. 264–270.Original Russian Text Copyright © 2005 by Basargin, Zueva, Rozovskii, Pashchenko.     

Synthesis and structures of azine-based crown-containing hetarylphenylethenes

Condensation of methyl-substituted six-membered heteroaromatics containing one or two nitrogen atoms with aldehyde derived from benzo-15-crown-5 ether in DMF in the presence of Bu^tOK afforded 15-crown-5-containing hetarylphenylethenes. According to the results of NMR spectroscopy, these compounds exist as mixtures of syn and anti conformers in solution (MeCN-d₃). The structures of two compounds were established by X-ray diffraction analysis. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1650–1659, July, 2005.     

Nonaqueous CE ESI‐IT‐MS analysis of Amaryllidaceae alkaloids

The Amaryllidaceae are widely distributed medical plants. Lycorine, lycoramine, lycoremine, and lycobetaine are the major active alkaloids in Amaryllidaceae plants. A nonaqueous CE ESI‐IT‐MS method for separation, identification, and quantification of the Amaryllidaceae alkaloids has been developed. The MS^1–3 behavior has been studied and the fragmentation pathways of main fragment ions have been proposed. The effects of several factors such as composition and concentration of buffer, applied voltage, composition, and flow rate of the sheath liquid, nebulizing gas pressure, flow rate, and temperature of drying gas were investigated. Under the optimal conditions, the linear concentration range of these compounds was wide with the correlation coefficient (R²) >0.99. RSDs of migration time and peak areas were <10%. The LODs were <240 ng/mL. The proposed method can be successfully applied to the determination of the related alkaloids in the Lycoris radiata roots.     

Chemical Composition of the Essential Oil of <Emphasis Type="Italic">Salvia macilenta</Emphasis> from Iran

The hydrodistilled essential oil composition from the aerial parts of Salvia macilenta (Lamiaceae) from Iran was analyzed by GC and GC-MS. The oil analysis confirmed the characterization of thirty-one compounds, accounting for 99.4% of the total oil. Analysis of the oil showed that the oil of S. macilenta was rich in monoterpene hydrocarbons with a-pinene (60%) as the main component followed by γ-elemene (6.1%), thymol (5.2%), elemol (4.7%), and β-caryophyllene (4.1%).__________Published in Khimiya Prirodnykh Soedinenii, No. 2, pp. 136–137, March–April, 2005.     

Alternating iterative regression method for dead time estimation from experimental designs

An indirect method for dead time (t ₀) estimation in reversed-phase liquid chromatography, based on a relationship between retention time and organic solvent content, is proposed. The method processes the retention data obtained in experimental designs. In order to get more general validity and enhance the accuracy, the information from several compounds is used altogether in an alternating regression fashion. The method was applied to nitrosamines, alkylbenzenes, phenols, benzene derivatives, polycyclic aromatic hydrocarbons and β-blockers, among other compounds, chromatographed in a cyano and several C18 columns. A comprehensive validation was carried out by comparing the results with those provided by the injection of markers, the observation of the solvent front and the homologous series method. It was also found that different groups of compounds yielded the same t ₀ value with the same column, which was verified in different solvent composition windows. The method allows improved models useful for optimisation or for other purposes, since t ₀ can be estimated with the retention data of the target solutes.