Synthesis and characterization of novel phthalocyanines bearing quaternizable coumarin

The synthesis of novel metal-free and zinc phthalocyanines with four 3-[(2-diethylamino)ethyl]-7-oxo-4-methylcoumarin dye groups on the periphery were prepared by cyclotetramerization of a novel 3-[(2-diethylamino)ethyl]-7-[(3,4-dicyanophenoxy)]-4-methylcoumarin. The novel chromogenic compounds were characterized by elemental analysis, ¹H NMR, ¹³C NMR, MALDI-TOF, IR and UV–Vis spectral data. The electronic spectra exhibit bands of coumarin identity along with characteristic Q and B bands of the phthalocyanine (Pc) core. The IR spectra of all the Pcs showed three characteristic intense bands, at 1704 cm⁻¹ for the lactone carbonyl and two bands at 1489–1604 cm⁻¹ for the conjugated olefinic system.     

Metabolites of the pathogenic fungus Verticillium dahliae II. Components of the fraction of neutral lipids from the culture liquid

Summary Di-2-ethylhexyl phthalate has been isolated from the neutral lipids fraction of the culture liquid of the fungusVerticillium dahliae Kleb. Its¹H and¹³C magnetic resonance spectra have been obtained, and an assignment of the signals has been made.On the basis of their UV, IR, and ESR spectra, the chromogenic components of the neutral lipid fractions have been assigned to the melanins.V. I. Lenin Tashkent State University. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 689–693, November–December, 1975.     

Synthesis and characterization of novel α- or β-tetra[6,7-dihexyloxy-3-(4-oxyphenyl)coumarin]-substituted metal-free and metallo phthalocyanines

The synthesis of novel phthalonitriles substituted at 3- or 4-position with 6,7-dihexyloxy-3-(4-oxyphenyl)coumarin were performed. The metal-free and metallo phthalocyanines (MPcs) (M = Zn, Co, Cu) were prepared by cyclotetramerization of 6,7-dihexyloxy-3-[p-(2′,3′-dicyanophenoxy)phenyl]coumarin or 6,7-dihexyloxy-3-[p-(3′,4′-dicyanophenoxy)phenyl]coumarin. The newly prepared compounds, phthalonitriles and Pcs, have been characterized by elemental analysis, ¹H NMR, ¹³C NMR, MALDI-TOF, IR, UV–Vis and fluorescence spectral data. The electronic spectra exhibit bands of coumarin identity along with characteristic Q and B bands of the Pc core. The IR-spectra of all Pcs showed three characteristic intense bands at 1709–1700 cm⁻¹ for lactone carbonyl, two bands at 1489–1604 cm⁻¹ for conjugated olefinic system.     

Vibrational spectra of certain triphenylmethane dyes and their structure in solution

A combined analysis of two types of vibrational spectra (Raman and infrared) has proven the lactone structure of colorless solid preparations of phenolphthalein and thymolphthalein. It has been shown that phenolsulfophthalein, its alkyl derivatives, and bromcresol purple exist in the solid state primarily in the form of an intensely colored zwitterion; bromphenol blue and bromthymol blue exist primarily in the form of a colorless sultone. For the ionized forms of triphenylmethane dyes (cationic and anionic chromophore systems) vibrations with a frequency near 1360 cm^–1 are characteristic in the IR spectra and also in the Raman spectra.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 26, No. 6, pp. 688–698, November–December, 1990.     

Synthesis of 2-methyl-3-carbethoxypyrylium salts by the condensation of ethoxymethyleneacetoacetic ester with ketones

A method is proposed for the synthesis of 2-methyl-3-carbethoxypyrylium salts by the acid condensation of ethoxymethyleneacetoacetic ester with alkyl aryl, heterocyclic, and cyclic ketones or resorcinol. 2-Methyl-3-carbethoxy-6-phenylpyrylium perchlorate was condensed with benzaldehyde, and the product was subjected to acid hydrolysis and decarboxylation to 2-methyl-6-phenylpyrylium perchlorate to confirm the structure of the synthesized salts.The IR spectra of mineral oil pastes of the synthesized samples were obtained with an IKS-14 spectrophotometer at 600–1800 cm^–1 (NaCl prism).Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 435–437, April, 1971.     

Polysaccharides ofCardaria repens and a study of their IR spectra

Five fractions have been obtained by the fractional precipitation of the water-soluble polysaccharide with alcohol: water-insoluble (fractions 1 and 2) and water-soluble (fractions 3-5). Their Fourier IR spectra have been studied and, on the basis of the results obtained, it is suggested that the water solubility of the fractions examined is connected with strong hydrogen bonds.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan, Tashkent, fax (3712) 89 14 75. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 202–205, March–April, 1995. Original article submitted November 14, 1994.     

Solvation of complexes with strong symmetric H bonds in the methanesulfonic acid—2-pyrrolidone system

Multiple Attenuated Total Reflectance (MATR) IR spectra of solutions of methanesulfonic acid (MSA) in 2-pyrrolidone (Pyr) (0—100 % MSA) were examined at 30 °C. Depending on the ratio of components, two types of species with strong symmetric H bonds are formed: uncharged quasi-ion pairs of 1 : 1 composition and anions (AHA)^–. The solvation of quasi-ion pairs by base molecules and of the (AHA)^– anions by acid molecules was detected. The data on the influence of the hydrogen bond donor and acceptor on the IR spectra of the quasi-ion pairs and (AHA)^– anions are presented.     

Extraction of chlororuthenium(III) complexes from hydrochloric acid solutions by petroleum sulfoxides

The extraction of ruthenium(II) by petroleum sulfoxides (PSOs) from hydrochloric acid solutions has been studied. The extraction of ruthenium(III) by PSOs is implemented by the coordination mechanism with the incorporation of the sulfoxide oxygen atom of the extractant into the inner coordination sphere of the ruthenium(III) ion. The composition of the extraction compound is suggested using electronic, ¹H NMR, and IR spectroscopy, the slope method, and elemental analysis.     

Comparison of mild extraction procedures for determination of plant-available arsenic compounds in soil

In this work three mild extraction agents for determination of plant-available fractions of elements in soil were evaluated for arsenic speciation in soil samples. Pepper (Capsicum annum, L.) var. California Wonder was cultivated in pots, and aqueous solutions of arsenite, arsenate, methylarsonic acid, and dimethylarsinic acid, at a concentration of 15 mg As kg^–1 soil, were added at the beginning of the experiment. Control pots (untreated) were also included. Deionized water, 0.01 mol L^–1 CaCl₂, and 0.05 mol L^–1 (NH₄)₂SO₄ were used to extract the plant-available fraction of the arsenic compounds in soil samples collected during the vegetation period of the plants. Whereas in control samples the extractable arsenic fraction did not exceed 1% of total arsenic content, soil amendment by arsenic compounds resulted in extraction of larger amounts, which varied between 1.4 and 8.1% of total arsenic content, depending on soil treatment and on the extracting agent applied. Among arsenic compounds determined by HPLC–ICPMS arsenate was predominant, followed by small amounts of arsenite, methylarsonic acid, and dimethylarsinic acid, depending on the individual soil treatment. In all the experiments in which methylarsonic acid was added to the soil methylarsonous acid was detected in the extracts, suggesting that the soil bacteria are capable of reducing methylarsonic acid before a further methylation occurs. No significant differences were observed between analytical data obtained by using different extraction procedures.     

Physicochemical Speciation of Americium in Soils from Rocky Flats, Colorado, USA

The objective of the research was to characterize the ²⁴¹Am distribution in six operationally defined chemical and mineralogical phases of soil samples taken from the Rocky Flats Environmental Technology Site (RFETS). Soil samples were subjected to selective sequential fractionation procedures to determine ²⁴¹Am association with the soluble, exchangeable, carbonate, organic, sesquioxide and silicate fractions. The highest percentage of ²⁴¹Am was found to be associated with the sesquioxide (hydrous oxide) fraction (39–47%), with lesser amounts in the soluble (14–17%), exchangeable (4–9%), carbonates (4–17%), organic (3–13%), and silicate (10–21%) soil fractions. Differences between americium and plutonium association with various soil fractions were observed.     

Speciation of nickel,copper, zinc,and manganese in different edible nuts: a comparative study of molecular size distribution by SEC–UV–ICP–MS

Molecular size distribution patterns of Cu, Mn, Ni, and Zn were determined in several nut species by size-exclusion liquid chromatography (SEC) coupled on-line to UV and inductively coupled plasma mass spectrometry (ICP–MS) for detection. The molecular weight (MW) fractionation of the different metals was performed with a Superdex Peptide column, injecting 100 L of the extracted solutions. The association of the elements with different MW fractions was observed with sequential detection by UV and ICP–MS. Various separation conditions were evaluated to obtain proper resolution and reproducible results with the size-exclusion column. Complete MW information of the elemental fractions in the nut samples was obtained within a retention time of 30 min. Fractionation of the above mentioned elements was done in nine different nut species commonly found in commercial markets. Variability of the fractionation patterns for two different extraction media, 0.05 mol L^–1 NaOH and 0.05 mol L^–1 HCl, was evaluated for every nut sample. Differences in the elemental fractionation patterns were found depending on the extraction procedure, nut species, and the type of element studied. It was also observed that the elements studied showed predominant association with high MW fractions when extracted with basic solution whereas with acidic extraction media only low MW fractions were obtained.     

Study of the fractional composition of the dioxane lignin from the cotton plant

Summary 1. The dioxane lignin of ripe cotton-plant stems has been separated into six fractions of different molecular weights which were fairly homogeneous and differed considerably in their molecular weights.2. It follows from the semiempirical formulas that in all the fractions guaiacyl structural units predominated. The chemical nonidentity of the fractions is shown by the different amounts of functional groups in the phenylpropane structural units and by the relative optical densities of the main bands in the IR spectra of the fractions.3. The low-molecular-weight fraction differed markedly from the others by a higher content of carbohydrates bound to the lignin and by a greater degree of oxidation.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 69–74, January–February, 1979.     

Structure and properties of furan-2-carboxylic acid esters. 1. Dipole moments and IR spectra

Dipole moment studies have revealed that furan-2-carboxylic acid esters exist in nonpolar solvents predominantly in O,O-cis-conformations. The dipole moment value of a 2-furoate ester depends on the electronic and steric effects of the substituents in the alcohol portion of the ester. The complex nature of the v _C=O band region in the IR spectra of 2-furoates is due primarily to the appearance of resonance absorption bands.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1605–1610, December, 1987.     

Structures of two new flavanones fromVexibia alopecuroides

Two new flavanones — vexibinol and vexibidin — have been isolated from the chloroform fraction of an ethanolic extract of the roots ofVexibia alopecuroides by column chromatography on silica gel. Their structures have been established on the basis of chemical and spectral characteristics. Their IR, UV,¹H, and¹³C NMR, and mass spectra are given.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. I. P. Pavlov Samarkand State Medical Institute. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 35–41, January–February, 1985.     

Vibrational spectra of 2-biphenylmethanol. Spectrum simulation and molecular structure

The vibrational spectra of a solid crystalline sample of 2-biphenylmethanol have been measured at room temperature. The IR absorption spectra were recorded in the range 400 cm^–1–3600 cm^–1; Raman spectra were measured in the range 10 cm^–1–1640 cm^–1. The direct mechanical and optoelectronic problems were solved using the fragment method realized as Lev-100 software; the intensity distribution in the IR spectrum of 2-biphenylmethanol was obtained by the same method. The experimental Raman and IR absorption spectra were interpreted by analyzing the calculated data on the frequencies and forms of normal vibrations and their intensities in the IR spectra. IR absorption spectra were simulated for several models of 2-biphenylmethanol conformers that differ in the mutual orientation of fragments. Based on the results of simulation and comparison of the calculated and experimental spectra of conformers we suggested a model for the conformer realized in the solid phase under normal conditions.Original Russian Text Copyright © 2004 by L. M. Babkov, J. Baran, N. A. Davydova, J. I. Kukielskii, and S. V. TrukhachevTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 4, pp. 624–631, July–August, 2004.This revised version was published online in April 2005 with a corrected cover date.     

孤岛油田含聚污水中酸性组分的分离与组成结构研究

采用石油醚和三氯甲烷分级萃取孤岛油田含聚污水中的油分,得到两个不同极性的组分F1和F2;用碱抽提法从酸值较高的F2组分中分离酸性物质并将其甲酯化,通过柱层析法将甲酯化物分成Ⅰ、Ⅱ和Ⅲ三个甲酯组分。用元素分析、红外光谱分析等对上述各组分的组成及结构进行鉴定,对甲酯组分Ⅰ进行GC MS 结构鉴定。结果表明,含聚污水中酸性乳化活性物质主要富集在F2组分中,降解HPAM是酸性物质的主要的组成部分;甲酯组分Ⅰ主要为石油酸甲酯,甲酯组分Ⅱ主要为含酰胺基的脂肪酸甲酯,甲酯组分Ⅲ除含有较多酰胺基脂肪酸甲酯外,还含有一定量的强极性含硫化合物;孤岛油田含聚污水中的轻质石油酸以单环环烷酸、四环环烷酸和脂肪酸为主,其中环烷酸的含量明显大于脂肪酸的含量。脂肪酸以C16和C18为主,单环环烷酸以C14~18为主,四环环烷酸以C18~21为主。     

Infrared spectra of cyclic ethers and their derivatives

The IR spectra of six monosubstituted and of four 2,6-disubstituted 1,4-dioxanes have been studied in the 650–1800cm^–1 region. The assignment of the bands due to the vibrations of the 1,4-dioxane ring and to the deformation vibrations of the methylene groups of the ring is given. The appearance of a whole series of new absorption bands on passing from unsubstituted 1,4-dioxane to its derivatives is explained by the change in the symmetry of the molecule and the removal of the prohibition from the vibrations previously inactive in the IR spectra connected with this reduction in symmetry. It is proposed to use, in order to confirm the presence of a 1,4-dioxane ring in a molecule from the results of IR spectroscopy, not only the 1126-cm^–1 band but the whole group of bands lying in the frequency ranges 800–950, 1000–1150, and 1200–1300 cm^–1.For part I, see [3].     

Ions with a strong symmetric H-bond in solutions of sodium acetate in acetic acid

The multiple attenuated total reflection IR spectra of solutions of sodium acetate in acetic acid have been recorded in the range from 9000 to 4000 cm^–1. The CH₃COO^– anion and an acid molecule form be complex (CH₃COO...H...OOCCH₃) with a strong symmetric H-bond.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp, 1854–1857, July, 1996.     

Fractionation of metals and metalloids by chemical bonding from particles accumulated by electrostatic precipitation in an Argentine thermal power plant

A study was undertaken to evaluate the distribution of Al, As, Cr, Cu, Fe, Mn, Ni, Pb, Ti, V and Zn in fly ashes collected in the electrostatic precipitator of a thermal power plant in San Nicolás (Argentina). Five samples were collected during one week of operation. For the fractionation, the scheme applied consisted in extracting the elements in four fractions namely (i) soluble and exchangeable elements; (ii) carbonates, oxides and reducible elements; (iii) bound to sulfidic metals; and (iv) residual elements. Metals and metalloids at μg g^− 1 level were determined in each fraction by inductively coupled plasma optical emission spectrometry (ICP OES). For validation, a standard reference material (SRM 1633 coal fly ash) from NIST was subjected to the same chemical sequential extraction procedure that the samples. X-ray diffraction powder (XRD) analysis and scanning electron microscopy (SEM) were used to characterize the major minerals present in the matrix. Total analyte concentration (in μg g^− 1) varied from 10.6 for Pb to 17,622 for Al. Minimum and maximum concentrations (in μg g^− 1) found in individual samples in the four fractions were: Al, 92.7–9668; As, < 0.3–143; Cr, 2.0–10.4; Cu, < 0.2–35.6; Fe, < 0.3–4992; Mn, < 0.1–128; Ni, < 0.3–139; Pb, < 0.5–9.1; Ti, < 0.3–2243; V, 17.0–112.9; and Zn, < 0.1–68.2. The leachability of the 11 elements under study proved to be different. Low percentages of Al (1%), V (7%) and Cr (8%) were detected in the most bioavailable fraction. Arsenic was found to be most abundant in the non-silicate phase, represented by the second and third fractions, while Cr, Fe, Ni, Pb and Zn were mostly associated to the residual fraction.     

A sesquiterpene lactone-semopodin-from the seeds ofFerula oopoda

Conclusions From the seeds ofFerula oopoda (Boiss et Buhse) Boiss. a new sesquiterpene lactone with mp 177–178° C has been isolated which has been given the name semopodin. On the basis of the NMR, UV, and IR spectra semopodin has been ascribed the probable structure I or II.Khimiya Prirodnykh Soedinenii, Vol. 5, No. 4, pp. 241–244, 1969