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81.
Philip M. Carabateas R. Pauline Brundage Karl O. Gelotte Monte D. Gruett Roman R. Lorenz Chester J. Opalka Jr. Baldev Singh William H. Thielking Gordon L. Williams George Y. Lesher 《Journal of heterocyclic chemistry》1984,21(6):1849-1856
A series of substituted 3- and 4-(3-aminophenyl)pyridines has been prepared as intermediates for the synthesis of some 1-alkyl-1,4-dihydro-4-oxo-7-pyridinyl-3-quinolinecarboxylic acids. The Hantzsch, Hauser and other pyridine syntheses were used. 4-(3-Aminophenyl)pyridine was prepared via 3-(4-pyridinyl)-2-cyclohexen-1-one using the Semmler-Wolff reaction. 相似文献
82.
Kaupp M Patrakov A Reviakine R Malkina OL 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(9):2773-2782
The characteristic dependence of J(31P,31P) spin-spin coupling constants of alkali metal tetraphosphane-1,4-diides on structure and composition has been analyzed by density functional methods. The computations confirm that the structure of the contact ion pairs is conserved in solution. Calculations on model systems M2P4H4, on naked P4H4(2-) anions, and on models including point charges, show that the role of the cations is mainly structural and to a smaller extent electrostatic. Three of the four J(P,P) coupling constants depend characteristically on the conformation of the anion, which in turn is determined by the substituents R and by cation-anion interactions. Several couplings exhibit a large through-space component and are thus strongly dependent on the relative orientation of nonbonding electron pairs on the phosphorus atoms involved. This is shown by visualization of coupling pathways using the recently introduced coupling energy density (CED), in combination with the electron localization function (ELF). 相似文献
83.
Shchepin V. V. Kirillov N. F. Nedugov A. N. 《Russian Journal of General Chemistry》2003,73(8):1264-1266
Methyl esters of 1-(-bromoisobutyryl)cyclohexanecarboxylic or 3-(1-bromocyclohexyl)-2,2-dimethyl-3-oxopropanoic acids react with zinc and arylglyoxals to form 3-aroyl-4,4-dimethyl-2-oxaspiro[5.5]undecane-1,5-diones or 1-aroyl-4,4-dimethyl-2-oxaspiro[5.5]undecane-3,5-diones, respectively. The former products react with phenylhydrazine, yielding 3-[aryl(2-phenylhydrazono)methyl]-4,4-dimethyl-2-oxaspiro[5.5]undecane-1,5-diones. 相似文献
84.
Kolárová L Holcapek M Jambor R Dostál L Nádvorník M Růzicka A 《Journal of mass spectrometry : JMS》2004,39(6):621-629
Electrospray ionization (ESI) mass spectrometry was applied to the structural analysis of 23 2,6-[bis(alkyloxy)methyl]phenyltin(IV) derivatives. The mass spectra were measured in both polarity modes and multistage tandem mass spectrometric (MS(n)) measurements were performed on the ion trap analyser for positively charged tin-containing ions. The sum of complementary ions observed in the positive-ion mode (i.e. [M-R(3)](+) ion) and in the negative-ion mode (i.e. [R(3)](-) ion) permits molecular mass determination in spite of the fact that the molecular adducts were often missing even in the first-order mass spectra. The subsequent fragmentation of [M-R(3)](+) ions studied by MS(n) and the correlation of observed fragment ions with the expected structures of synthesized organotin(IV) compounds allowed us to understand the fragmentation behaviour and the mechanism of the ion formation for studied compounds. The typical neutral losses are alkenes, alcohols and aldehydes. The fragmentation pattern of one selected compound was supported by MS(n) measurements of an isotopically labelled analogue to confirm unusual ion-molecule reactions of some fragment ions with water in the ion trap. 相似文献
85.
Tat'yana T Kucherenko Roman Gutsul Vladimir M Kisel Vladimir A Kovtunenko 《Tetrahedron》2004,60(1):211-217
Previously unknown 3-arylamino-1,2-dihydro-1-isoquinolones were obtained by condensation of 2-cyanomethylbenzoic acid with arylamines. Isonicotinoylation of the compounds was shown to proceed at the carbon atom in the 4-position to give 3-arylamino-4-isonicotinoyl-1,2-dihydro-1-isoquinolones which were quaternized with alkylating agents and formed the corresponding pyridinium salts. Deprotonation of the latter induced intramolecular conjugated addition with the pyrrole ring closure and formation of spiro compounds. The structure of the products was confirmed by NMR, IR and UV spectroscopy and by synthesis of the model compound, 3-(4-tolyl)-2,3,4,5-tetrahydro-1H-pyrrolo[2,3-c]isoquinoline-1,5-dione. 相似文献
86.
Kuśtrowski P Chmielarz L Dziembaj R Cool P Vansant EF 《The journal of physical chemistry. A》2005,109(2):330-336
The novel mesoporous templated silicas (MCM-48, SBA-15, MCF, and MSU) were used as supports for transition metal (Cu, Cr, or Fe) oxides. The catalysts were synthesized using the incipient wetness impregnation, and characterized by low-temperature N2 sorption, DRIFT, photoacoustic IR spectroscopy, UV-vis diffuse reflectance spectroscopy, and temperature-programmed desorption of ammonia. It was shown that the preparation method used results in different distributions and dimensions of the transition metal oxide clusters on the inert support surface. The prepared catalysts were tested in the reaction of oxidative dehydrogenation of ethylbenzene in the presence of nitrous oxide. The iron-containing catalysts showed the highest catalytic activity. The presence of isolated Fe3+ was found to be the most important factor influencing the ethylbenzene conversion. The undesirable effect of the increase in selectivity toward CO2 was observed for the samples with the highest concentrations of acidic surface sites. 相似文献
87.
Boulatov R Collman JP Shiryaeva IM Sunderland CJ 《Journal of the American Chemical Society》2002,124(40):11923-11935
Catalytic reduction of O(2) and H(2)O(2) by new synthetic analogues of the heme/Cu site in cytochrome c and ubiquinol oxidases has been studied in aqueous buffers. Among the synthetic porphyrins yet reported, those employed in this study most faithfully mimic the immediate coordination environment of the Fe/Cu core. Under physiologically relevant conditions, these biomimetic catalysts reproduce key aspects of the O(2) and H(2)O(2) chemistry of the enzyme. When deposited on an electrode surface, they catalyze the selective reduction of O(2) to H(2)O at potentials comparable to the midpoint potential of cytochrome c. The pH dependence of the half-wave potentials and other data are consistent with O-O bond activation at these centers proceeding via a slow generation of a formally ferric-hydroperoxo intermediate, followed by its rapid reduction to the level of water. This kinetics is analogous to that proposed for the O-O reduction step at the heme/Cu site. It minimizes the steady-state concentration of the catalytic intermediate whose decomposition would release free H(2)O(2). The maximum catalytic rate constants of O(2) reduction by the ferrous catalyst and of H(2)O(2) reduction by both ferric and ferrous catalysts are comparable to those reported for cytochrome oxidase. The oxidized catalyst also displays catalase activity. Comparison of the catalytic properties of the biomimetic complexes in the FeCu and Cu-free forms indicates that, in the regime of rapid electron flux, Cu does not significantly affect the turnover frequency or the stability of the catalysts, but it suppresses superoxide-releasing autoxidation of an O(2)-catalyst adduct. The distal Cu also accelerates O(2) binding and minimizes O-O bond homolysis in the reduction of H(2)O(2). 相似文献
88.
In this work, a simple, fast and reproducible method is presented for the determination of fibre/liquid-phase and fibre/gas-phase
partition coefficients of five chlorinated ethenes on a poly-(dimethylsiloxane), PDMS-coated, solid-phase microextraction
fibre, by employing a headspace HS-SPME coupled with gas chromatography. The partition coefficients were estimated by a numerical
method using a Level-I fugacity method coupled with parameter-estimation software. Dimensionless partition coefficients between
SPME fibre and liquid as well as gas phases were obtained at temperatures of 10 °C, 25 °C and 30 °C. The partition coefficients
of the fibre and the gas phase, K
fg, increase with decreasing temperature by a factor of ≈2 to 6, and they are directly proportional to the linear slope of the
regression line. The same tendency is observed for the partition coefficient of the fibre and liquid phase, K
fw, in a factor ≈1.2 to 2.0. The sorption enthalpy is higher in the gas phase; therefore, the sorption onto the fibre is favoured
at lower temperatures. The correlation of the log K
ow versus log K
fw and log K
oa versus log K
fg shows a linear relationship with the number of chlorine atoms in the C = C molecule. Long-term experiments resulted in sorption
to Teflon surfaces and possible losses in 43 mL vials, not observed in 250 mL Boston bottles. 相似文献
89.
Vladimír Kočí Tomáš Ocelka Martin Mlejnek Roman Grabic 《Central European Journal of Chemistry》2004,2(1):91-112
The efficiency of treatment processes forboth municipal and industrial wastewater (treatment plant-Ostrava, Czech Republic)
focused on persistent organic pollutants (POPs) was assessed. Semipermeable membrane devices (SPMDs) as a sampling system
were applied. Exposed SPMDs were analyzed both for chemical contaminants of POPs and toxicity response. The chemical analyses
of PAHs were made by HPLC-FLD, PCDD/Fs and PCBs were analysed by GC/MS/MS on GCQ or PolarisQ (Thermoquest). Ecotoxicity data
on chlorococcal alga Desmodesmus subspicatus (Scenedesmus subspicatus) and luminescent bacteria Vibrio fischeri are presented here. All toxicity data as effective volume Vtox are expressed. The results show good treatment ability of
the treatment plant and proved used system as an appropriate tool for efficiency assessment of treatment and/or decontamination
processes. 相似文献
90.
Acylation of substituted 4-(furyl-2)-4-arylaminobut-1-enes with maleic anhydride provided 2-allyl-6-carboxy-4-oxo-3-aza-10-oxatricyclo[5.2.1.01,5]dec-8-enes in high yield under mild reaction conditions. The Diels-Alder adducts are formed via an initial amide formation followed by a stereoselective intramolecular [4+2] exo-cycloaddition reaction. Treatment of the tricyclic compounds with phosphoric acid at high temperatures (70-120 °C) promoted cyclic ether opening, intramolecular cyclization and aromatization to give the corresponding tetracyclic compounds, 5,6,6a,11-tetrahydro-10-carboxyisoindolo[2,1-a]quinolines, in moderate yields. The influence of the acid and the reaction temperature on the cyclization reactions are also discussed. 相似文献