First Representatives of Nitrophospholipids

General regularities of the phosphorylation of trimethylolnitromethane and its derivatives with amides and amidoesters of phosphorous acids were investigated. These procedures were found to hold promise for the design of amphiphilic phospholipids of a new type.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 7, 2005, pp. 1100–1105.Original Russian Text Copyright © 2005 by Predvoditelev, Malenkovskaya, Sipin, Nifant’ev.     

Sulfonamides as ionophores for ion-selective electrodes. IV. New secondary sulfonamide podands and cryptands

New compounds — podands and cryptands with two secondary sulfonamide groups —have been synthesized and are described. They were tested as ionophores for guanidinium ions in PVC-membrane electrodes with bis (2-ethylhexyl)sebacate (DOS) as plasticizer.     

α-Hydroxy-α-aminophosphinic Acids: I. Synthesis of a New Analog of Phenylglycine and Its Enantiomers

Methods for synthesis of a new phosphinic analog of phenylglycine, (-α-aminobenzyl)(hydroxy-methyl) phosphinic acid and its enantiomers are developed.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 4, 2005, pp. 571–574.Original Russian Text Copyright © 2005 by Rozhko, Ragulun.     

Phosphorus-containing Aminocarboxylic Acids: XIV. Synthesis of Analogs of α-Substituted Glutamic Acid

Addition of Schiff bases derived from amino acid esters to appropriate vinylphosphoryl compounds, followed by hydrolysis of the adducts formed gives a series of new α-alkylated phosphorus-containing α-aminocarboxylic acids, viz. phosphonic and phosphinic analogs of glutamic acid.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 7, 2005, pp. 1140–1147.Original Russian Text Copyright © 2005 by Saratovskikh, Ragulin.     

Nucleophilic Addition to Acetylenes in Superbasic Catalytic Systems: XIV. Vinilation of Diols in a System CsF-NaOH

A new catalytic system CsF-NaOH was developed for the synthesis of mono- and divinyl ethers of alkanediols exceeding in efficiency KOH. The nucleophilic addition of diols to acetylene in the presence of this system occurs both at enhance pressure (without solvent, 140–160°C) and atmospheric pressure (in DMSO medium, 100°C) of acetylene. Conditions were established of a selective preparation in a high yield of divinyl ethers from diols.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 5, 2005, pp. 677–683.Original Russian Text Copyright © 2005 by Oparina, Khil’ko, Chernyshova, Shaikhudinova, Parshina, Preiss, Henkelmann, Trofimov.     

New Method of Analysis of Intermolecular Contacts in the Crystal Structure: π-Complexes

A new method for analysis of intermolecular contacts in the crystal structure based on characteristics of the Voronoi-Dirichlet polyhedra (VDP) is considered using metal π-complexes as examples. The crystal data of the compounds were used to determine the surface area of the VDP faces corresponding to all intermolecular contacts in one π-complex, the total volume of the pyramids with VDP faces as bases and the nuclei of atoms involved in the intermolecular contacts at the vertices, and the total solid angle at which the “intermolecular” VDP faces are seen from the corresponding nuclei of the molecule. A common linear correlation between the enthalpy of sublimation of π-complexes and saturated or unsaturated hydrocarbons and the molecular VDP characteristics was elucidated. On the basis of the results, the enthalpies of sublimation were calculated for some iron π-complexes (for which data on the crystal structure were available) and C₆₀ and C₇₀ fullerenes.__________Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 7, 2005, pp. 495–505.Original Russian Text Copyright © 2005 by Serezhkin, Shevchenko, Serezhkina.     

Flavonoids of <Emphasis Type="Italic">Scutellaria immaculata</Emphasis> Roots

(±)-5,2′-Dihydroxy-6,7,6′-trimethoxyflavanone, (-)-5,2′-dihydroxy-6,7,8,6′-tetramethoxyflavanone, chrysin, wogonin, apigenin, isoscutellarein, scutellarein, cosmosiin, and the new flavonoid wogonin-7-O-β-D-glucopyranoside, the structure of which was established using chemical transformations and spectral data, were isolated from Scutellaria immaculata roots.__________Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 26–28, January–February, 2005.     

Optimization of the curing conditions of PVC plastisols based on the use of an epoxidized fatty acid ester plasticizer

The use of an epoxidized fatty acid ester (EFAE) as a natural-based plasticizer for plasticized PVC (P-PVC) has been evaluated in this work. The effect of the curing conditions has been studied by following several test techniques such as mechanical properties, thermal behavior, color changes, solvent migration and microstructure. Different curing processes at isothermal conditions (ranging from 160 °C to 220 °C) have been carried at curing times in the 6–16 min range. The optimum mechanical response (tensile strength values in the 9–10 MPa range and elongation at break close to 250%) is obtained for plastisols cured at 200 and 220 °C for 12 and 8 min curing times, respectively. These curing conditions also offer the lowest migration in n-hexane (lower than 11%) which is indicative of plasticizer total absorption. Furthermore, the use of these curing conditions does not lead to thermal degradation as confirmed by color measurements.     

Long-term performance of poly(vinyl chloride) cables, Part 2: Migration of plasticizer

Cable samples with plasticized poly(vinyl chloride) insulations were aged in air at temperatures between 80 and 155 °C. The concentrations of the plasticizer (di-(2-ethylhexyl) phthalate, DEHP) in the insulations of the aged cables were determined by extraction of samples in tetrahydrofuran followed by analysis of the extract by liquid chromatography. The plasticizer concentration data for different ageing times were analysed by numerical methods, fitting Fick's second law with a concentration-dependent diffusivity. The analysis showed that the transport of the plasticizer to the surrounding air phase was controlled by diffusion at 120 and 155 °C with an activation energy of 89 kJ mol⁻¹. The evaporation of the plasticizer from the outer boundary was rate controlling at lower temperatures (≤100 °C). The rate of evaporation was initially constant and independent of the plasticizer concentration at both 80 and 100 °C. The activation energy for the initial DEHP loss rate from PVC at these temperatures was the same as that obtained for evaporation of pure DEHP on a glass plate at 60-100 °C measured by thermogravimetry, 98 ± 2 kJ mol⁻¹. Furthermore, the evaporation rate of pure DEHP on a glass plate was also of the same order of magnitude as the rate of plasticizer loss from the cable insulation. Extrapolation of the plasticizer loss rate data (from the cable at 80 °C and from pure liquid DEHP at temperatures between 60 and 100 °C) to 25 °C predicted a maximum loss of plasticizer of 1% over 25 years. This is in accordance with earlier presented data and with the data presented in this report.     

Reaction of Sulfur Chlorides with Metal β-Diketonates

Metal β-diketonates react with sulfur dichloride to form sulfenyl chlorides irrespective of β-substituent. Bulky phenyl and tert-butyl groups do not prevent formation of fully substituted complexes. The possibility of preparing sulfenyl chloride derivatives of rhodium, ruthenium, and vanadium β-diketonates was demonstrated. A new procedure was suggested for preparing chlorosulfenyl-substituted β-diketonates. Disulfur dichloride reacts with metal chelates with the substitution of both chlorine atoms and formation of polynuclear complexes in which the diketonate groups are linked by disulfide bridges.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 3, 2005, pp. 367–374.Original Russian Text Copyright © 2005 by Svistunova, Shapkin, Nikolaeva.     

Synthesis of Mesityl Oxide π-Complexes with Metals of Chromium Subgroup and with Iron. Theoretical and Experimental Investigation of the Ligand Dissociation Energy

At the use of photochemical and thermochemical activation new π-complexes of chromium, molybdenum, and tungsten were prepared containing in the coordination sphere η²- and η⁴-molecules of 4-methyl-3-penten-2-one. Nonempirical methods were applied to calculation of the energy parameters of the coordinated molecules, and the factors governing the η²- and η⁴-coordination of the oxodiene system were established. A thermochemical study was performed on the 4-methyl-3-penten-2-one η⁴-coordination product with carbonyl metal core. A scheme of the thermal decomposition was suggested for the iron (0) η ⁴-(4-methyl-3-penten-2-one)tricarbonyl.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 5, 2005, pp. 665–671.Original Russian Text Copyright © 2005 by Kuramshin, Kuramshina, Cherkasov.     

Ketoimines of Cardenolides

3-Keto-derivatives of the cardenolides digitoxigenin and cardiogenin were prepared with subsequent conversion to new ketoimines (1–19, 24–44), the oxime (23), and for the first time to pure cardiogenin (14,16-dianhydrogitoxigenin, 20), its acetate (21), and cardiogenone (22). Their physicochemical properties were described.__________Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 42–45, January–February, 2005.     

New Heterocyclic Derivatives of α-Spirodilactones

8-Alkoxymethyl-3-bromoacetyl-3-methyl-2,7-dioxaspiro[4.4]nonane-1,6-diones react with thiourea, substituted thioureas, and 5-aryl-1,2,4-triazole-3-thiols to give new heterocyclic compounds containing an α-spirobutanolide fragment.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 6, 2005, pp. 913–916.Original Russian Text Copyright © 2005 by Kochikyan, Samvelyan, Arutyunyan, Avetisyan.     

Nonadditive effect of components of a binary plasticizer on the properties of polyether-urethane-ureas

The effect of a mixture of di(2-ethylhexyl) phthalate and tributyl phosphate on the properties of segmented polyether-urethane-ureas was examined. The data obtained for the elastomers with individual and mixed plasticizers were compared. The efficiency of using the binary plasticizer for controlling the properties of polyether-urethane-ureas was assessed.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 9, 2004, pp. 1551–1554.Original Russian Text Copyright © 2004 by Tereshatov, Fedchenko, Tereshatova, Makarova.     

1,2,4-Thiadiazole derivatives of cytisine

Several new derivatives were prepared by reaction of 3-alkylthio-5-chloroacetamido-1,2,4-thiadiazoles with cytisine.Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 479–480, November–December, 2004.This revised version was published online in April 2005 with a corrected cover date.     

Aldimines of Cardenolides and Cardenolide-Glycosides

New aldimines were synthesized from the cardenolide strophantidin and cardenolide-glycosides erysimin and cymarin and included morpholine, nitrile, pyridine, furan, hydroxy- and methoxyphenyl, piperidine, and other derivatives. An effective modified method for synthesizing aldimines was proposed. 52 new compounds were synthesized. Their structures were confirmed by IR and PMR spectra and elemental analysis.__________Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 268–271, May–June, 2005.     

Modification of Natural Shungites To Obtain a Mixed Nanocarbon Material (MNS)

An original technology for processing of a natural material, shungite-3 from the Zazhogino deposit (Karelia), was developed in order to obtain a new product, mixed nanocarbon material (MNS).__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 6, 2005, pp. 887–890.Original Russian Text Copyright © 2005 by Charykov, Alekseev, Arapov, Alekhin, Gerasimov, Nekrasov, Polekhovskii, Semenov.     

Transport numbers of ionic electrolyte components: A new measuring method based on bidirectional capillary isotachophoresis

A concept of a new isotachophoretic method for measuring transport numbers of ionic components and electromigration transport of solvent in electrolytes, which is free of many drawbacks of other methods evident at high concentrations, is proposed and substantiated.Translated from Elektrokhimiya, Vol. 41, No. 3, 2005, pp. 375–379.Original Russian Text Copyright © 2005 by Gorshkov.     

Macroheterocyclic Compounds with p-Diamines of the Diaryl Series

The reactions of indane-1,3-dione with 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide, and 4,4′-diaminodiphenyl ether were used to synthesize symmetrical macroheterocyclic compounds.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 6, 2005, pp. 1017–1021.Original Russian Text Copyright © 2005 by Berezina, Vorob’ev, Vorob’eva, Sadova.     

New Derivatives of 3,4-Polymethylene-1,2,4-benzothiadiazine S,S-Dioxides

A new method is proposed for obtaining 3,4-polymethylene-1,2,4-benzothiadiazine 1,1-dioxides by reacting o-halobenzenesulfonamides with lactim ethers. Attempts were undertaken to synthesize quaternary salts of the heterocycles obtained.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 225–229, February, 2005.