Übergangsmetall-methylen-komplexe: LVI. Organoruthenium-komplexe mit offenkettigen und carbocyclischen alkyliden-brücken: Synthese,konstitution, isomerie,protonierung und thermolytischer abbau

The eighteen new μ-alkylidene ruthenium complexes 5a–r and 5t are very easily and cleanly obtained along the diazoalkane or the hydrazone routes that involve treatment of the dinuclear, metal-metal doubly bonded precursor compound [(η⁵-C₅H₅)Ru(μ-NO)]₂ (3) either with the diazoalkanes oxidizing agent (e.g., MnO₂), with the respective hydrazones. Similarly, sulfur dioxide adds cleanly to the RuRu double bond of 3, thus giving the complex (μ-SO₂)[(η⁵-C₅H₅)Ru(NO)]₂ (5s). Regardless of the nature of the carbene bridge ligands, the dimetallacyclopropanes exhibit, in contrast to their iron analogues, exclusively terminal nitrosyl ligands. cis/trans-Isomerism with predominating amounts of the trans-isomers is observed for the derivatives that display unsymmetrically substituted carbene bridges.Treatment of the μ-methylene- and μ-ethylidene complexes (μ-CH₂)[(η⁵-C₅H₅)Ru(NO)]₂ (5a) and (μ-CHCH₃)[(η⁵-C tetrafluoroboric acid or trifluoromethanesulfonic acid in diethyl ether yields, at ambient temperature, quantitatively the ionic complexes 6a,b and 7a,b, respectively, which were shown by ¹H NMR spectroscopy to contain metal-metal bridging hydrogen functionalities. The reaction of hydrogen bromide with 5a under the same conditions gives the neutral bromo(methyl) complex 6d. This latter compound results from the isolable ionic intermediate of composition [(μ-CH₂)(μ-H){(η⁵C₅H₅)Ru(NO)}₂]⁺Br^? (6c), which reaction stems from the nucleophilicity of the halide ion present in 6c.     

Structural chemistry of amino acid complexes

Summary Complex formation between Co^II, Ni^II and Cu^II and the amino acids (cysteine, cystine and methionine) in the solid state were investigated by elemental analyses, i.r. and electronic spectra, and magnetic susceptibilities     

Aqueous polymerization of methyl methacrylate catalyzed by copper metal and some of its compounds

The aqueous polymerization of methyl methacrylate (MMA) with sodium bisulfite as initiator was carried out in a nitrogen atmosphere with and without inorganic substances like copper metal, cupric and cuprous oxides, and cupric sulfide. It was also done in the presence of organocopper compounds like copper phthalocyanine and copper biphthalocyanine. The catalytic effect of these compounds was studied. Mildly heated cupric sulfide proved to have a small catalytic effect on the polymerization process that may be attributed to the retarding effect of the released elementary sulfur. The catalytic effect of the different copper compounds and the copper metal equivalent contained in them was studied. The polymerization process revealed that cuprous and cupric oxides possess the highest catalytic influence. An attempt was made to investigate the role of the different anions on the polymerization process. It was found that an increase on the concentration of the copper compounds leads to a corresponding increase in the catalytic effect. It was also observed that the behavior of insoluble copper catalysts is different from that of the soluble. The effect of these catalysts on the average molecular weight of the poly(methyl methacrylate) (PMMA) produced was also examined.     

The use of Omega Chrome Fast Blue 2G in the microdetermination of some metals

Summary Omega Chrome Fast Blue 2G has been found to be a suitable indicator for the detection of the equivalence point of calcium, magnesium and manganese in the presence of cadmium, nickel, and aluminium, when they are masked by the addition of cyanide or triethanolamine. It is also a suitable indicator for the back titration of aluminium using calcium or magnesium as a back titrant.This dye has also been found to be a suitable reagent for the colorimetric determination of calcium, magnesium, manganese and thorium.     

Selection of a Representative Matrix for Calibration in Multianalyte Determination of Pesticides in Vegetables by Liquid Chromatography-Electrospray Tandem Mass Spectrometry

An analytical method for determining residues of twenty pesticides by liquid chromatography (LC) coupled to electrospray ionisation (ESI) tandem mass spectrometry (MS-MS) in eight commodities, cucumber, tomato, pepper, green bean, eggplant, zucchini, melon and watermelon, has been developed and validated. On one hand, calibration curves prepared in solvent were compared with calibration curves prepared in a blank matrix extract of each target matrix. On the other hand, calibration curves and recoveries for each commodity were compared. Cucumber was selected as potential reference matrix for the target vegetables.     

Transport properties of LaCu2Si2 and CeCu2Si2 between 1.5K and 300K

We report measurements of the electrical resistivity, the thermal conductivityk and the thermoelectric powerS between 1.5K and 300K on the anomalous CeCu₂Si₂ compound and on LaCu₂Si₂ as reference compound. For LaCu₂Si₂ the temperature dependences of andS are in accord with those found in otherd band metals. For CeCu₂Si₂ the observed resistivity (220 µ cm at 200K) leads to a very short electronic mean free path which is of the order of the Ce-Ce spacing. Correspondingly,k is almost identical with the phonon contributionk _p . Below 20K, resistivity and thermoelectric power strongly suggest Fermi liquid behavior with a degeneracy temperature between 20K and 40K. Above 200K, both andS decrease proportionally to –ln(T/1 K).Work performed within the research program of the Sonderforschungsbereich 125 Aachen/Jülich/KölnPart of this work will be presented at the Int. Conf. on Rare Earths in the Metallic State, St. Pierre de Chartreuse, Sept. 1978     

Radiation-induced graft polymerization of acrylic acid onto fluorinated polymers. I. Kinetic study on the grafting onto poly(tetrafluoroethylene-ethylene) copolymer

Direct radiation-induced grafting of aqueous acrylic acid (AAc) onto poly(tetrafluoroethylene-ethylene) (ET) film has been studied. The effect of grafting conditions such as monomer concentration, exposure dose, dose rate, and film thickness on the grafting yield was investigated. The dependence of the grafting rate on monomer concentration was found to be 1.2 order. The dependence of the grafting rate on dose rate was found to be 0.6 order regardless of the film thickness. The relationship between the grafting rate and film thickness gave a negative first-order dependence. The results suggest that the grafting process is mainly controlled by monomer diffusion, and it was concluded that this grafting system proceeded by the front mechanism. The swelling behavior increases linearly with degree of grafting. The electrical conductivity and mechanical properties for the trunk and grafted polymer were investigated at different irradiation doses in air and under vacuum irradiations. © 1992 John Wiley & Sons, Inc.     

Phosphomolybdic acid supported on silica gel and promoted with alkali metal ions as catalysts for the esterification of acetic acid by ethanol

Different ratios of phosphomolybdic acid PMA supported on silica gel (1–30 wt%) and promoted with alkali metal hydroxide have been prepared by an impregnation method and calcinated at 350 °C for 4 h. The catalysts were characterized by thermogravimetry (TG), differential thermal analysis (DTA), X-ray diffraction, FT-IR spectroscopy and N₂ adsorption measurements. The surface acidity and basicity of the catalysts were determined by adsorption of pyridine and the dehydration–dehydrogenation of 2-propanol. The gas-phase esterification of acetic acid by ethanol was carried out in a conventional flow bed reactor. The results clearly revealed that among the PMA loading, the use of 10 wt% catalyst showed maximum yield of ethyl acetate. This catalyst also improved on addition of Na or K-hydroxide. These results were correlated with the structure and the acid–base properties of the prepared catalysts.     

Fused quinoline heterocycles VI: Synthesis of 5H‐1‐thia‐3,5,6‐triazaaceanthrylenes and 5H‐1‐thia‐3,4,5,6‐tetraazaaceanthrylenes

Ethyl 3‐amino‐4‐chlorothieno[3,2‐c]quinoline‐2‐carboxylate ( 4 ) is a versatile synthon, prepared by reacting an equimolar amount of 2,4‐dichloroquinoline‐3‐carbonitrile ( 1 ) with ethyl mercaptoacetate ( 2 ). Ethyl 5‐alkyl‐5H‐1‐thia‐3,5,6‐triazaaceanfhrylene‐2‐carboxylates 9a‐c , novel perianellated tetracyclic heteroaro‐matics, were prepared by refluxing 4 with excess of primary amines 7a‐c to yield the corresponding amino‐thieno[3,2‐c]quinolines 8a‐c . Subsequent reaction with an excess of triethyl orthoformate (TEO) furnished 9a‐c . Reaction of 4 with TEO in Ac₂O at reflux, gave the simple acetylated compounds, thieno[3,2‐c]‐quinolines 12 and 13 . Refluxing 4 with benzylamine ( 7d ) gave 10 , and subsequent treatment with TEO gave the tetracyclic compound 11 . Refluxing 13 with an excess of alkylamines 7a‐d gave the fhieno[3,2‐c]quino‐lines 15 . Refluxing the aminothienoquinolines 8b with an excess of triethyl orthoacetate gave thieno[3,2‐c]quinoline 17 , while heating with Ac₂O gave 18 and 19 , with small amounts of 16 . Reaction of 8a,b with ethyl chloroformate and phenylisothiocyanate generated the new 1‐thia‐3,5,6‐triazaaceanthrylenes 20a,b and 21a,b , respectively. Diazotization of 8a‐c afforded the novel tetracyclic ethyl 5‐alkyl‐5H‐1‐fhia‐3,4,5,6‐tetraazaaceanthrylene‐2‐carboxylates 22a‐c in good yields.     

LC-ESI-MS/MS profiling of alkaloids and antiproliferative activity of Pachypoduim lamerei drake leaves

Abstract

In the present study, evaluation of the antiproliferative activity of Pachypodium lamerei Drake leaves (family Apocyaceae) against human breast cancer cell lines MDA-MB-231 was done for the total methanolic extract, crude alkaloidal mixture and ursolic acid using the MTT colorimetric assay. The methanolic extract showed the strongest antiproliferative activity followed by ursolic acid and crude alkaloidal fraction with an IC₅₀ equal to 6.2, 14.55 and 56.3?µg/ml respectively compared to oleocanthal. It is the first record for the LC/ESI-MS/MS alkaloidal profiling of the leaves of P. lamerei. Seven alkaloids were tentatively identified according to their fragmentation patterns. Four alkaloids were related to the parent indole class and two alkaloids belong to the quinoline class in addition to one steroidal alkaloid with a pregnan nucleus. Phytochemical investigation of the methanolic extract led to the isolation of three triterpenoidal compounds including ursolic acid, 11,12-didehydroursolic acid lactone and ursolic acid lactone.