2-Amino-1-cyan-glutaconsäureamid-1-methylester,ein Dimeres des Cyanessigesters und Cyanacetamid

Synthesis of methyl 3-amino-4-carbomyl-2-cyano-2-butenoate is described and2 a classified as a dimer of methyl cyanoacetate and cyanoacetamide. By ammonolysis of the dimer of methyl cyanoacetate with dimethylamine and anilines, resp. the dimethylamide and anilides, resp. (2 b and3 a–j) are obtained. Condensation with salicylaldehyde to the pyrone derivative4 proves the structure of2 a, ring closure reactions in basic or acidic medium yield the pyridones6 a and7 a,b, coupling with diazonium salts the pyridazines8 a–d. The amides2 and the anilides3 show hindered rotation of the enamino- and the amide-group by hydrogen bonds between the nitrogen functions and the ester carbonyl (Z-form). The G values are reported.

     

Kinetics of anation of chromium(III) by L-phenylalanine

Summary The kinetics of anation of chromium(III) species, [Cr(H₂O)₆]⁴⁺ and [Cr(H₂O)₅OH]²⁺, by L-phenylalanine in aqueous acid has been studied spectrophotometrically. Effects of varying [substrate], [ligand], [H⁺], , % ethanol and temperature were investigated. The kinetic data suggest a mechanism where outersphere-associations [between chromium(III) species and phenylalanine in the zwitterionic form] precede anation. Comparison of the results with published data suggest an I_a path for the [Cr(H₂O)₆]³⁺ reaction and I_d path for the [Cr(H₂O)₅OH]²⁺ reaction.     

Slurry sampling techniques for the determination of lead in Bangladeshi fish samples by electrothermal atomic absorption spectrometry with a metal tube atomizer

Ultrasonic slurry sampling electrothermal atomic absorption spectrometry with a metal tube atomizer has been applied to the determination of lead in Bangladeshi fish samples. The slurry sampling conditions, such as slurry stabilizing agent, slurry concentration, pyrolysis temperature for the slurried fish samples, particle size and ultrasonic agitation time, were optimized for electrothermal atomic absorption spectrometry with the Mo tube atomizer. Thiourea was used as the chemical modifier for the interference of matrix elements. The detection limit was 53 fg (3S/N). The determined amount of lead in Bangladeshi fish samples was consistent with those measured in the dissolved acid-digested samples. The advantages of the proposed methods are easy calibration, simplicity, low cost and rapid analysis.     

Spectrofluorimetric study of host-guest complexation of ibuprofen with beta-cyclodextrin and its analytical application

The characteristics of host-guest complexation between beta-cyclodextrin (beta-CD) and two forms of ibuprofen (protonated and deprotonated) were investigated by fluorescence spectrometry. 1:1 stoichiometries for both complexes were established and their association constants at different temperatures were calculated by applying a non-linear regression method to the change in the fluorescence of ibuprofen that brought about by the presence of beta-CD. The thermodynamic parameters (deltaH, deltaS and deltaG) associated with the inclusion process were also determined. Based on the obtained results, a sensitive spectrofluorimetric method for the determination of ibuprofen was developed with a linear range of 0.1-2 microg ml(-1) and a detection limit of 0.03 microg ml(-1). The method was applied satisfactorily to the determination of ibuprofen in pharmaceutical preparations.     

A theoretical prediction for exclusive decaysB→K(K*)η c

The decay rates for the exclusiveB decaysBK _c andBK* _c are calculated in the context of the heavy quark effective theory. We obtain(BK _c )/ (BK)=1.6±0.2 and(BK* _c )/ (K*)=0.39±0.04. These results lead to estimates BR(BK _c )=(0.11±0.02)% and BR(BK* _c )=(0.05±0.01)% if we use the central current experimental values forB(K, K ^*) branching ratios.     

Preconcentration of trace cobalt with the ion pair of 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol and tetraphenylborate onto microcrystalline naphthalene or column method and its determination by derivative spectrophotometry

Cobalt-2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP)-tetraphenylborate ion associated complex is quantitatively adsorbed on microcrystalline naphthalene in the pH range 3.5-9.5 from a fairly large volume of the aqueous samples (preconcentration factor ~30). After filtration, the solid mass consisting of the cobalt complex and naphthalene was dissolved with 5 ml of dimethylformamide (DMF) and the metal determined by first-derivative spectrophotometry. The cobalt-5-Br-PADAP complex can alternatively be quantitatively retained on ammonium tetraphenylborate-naphthalene adsorbent filled in a column (preconcentration factor 120) in the same pH range and determined similarly. The detection limit is 30 ppb (signal-to-noise ratio=2) and the calibration curve is linear over 0.3-8.0 mug of cobalt in 5 ml of the final DMF solution. Eight replicate determinations of 1.0 mug of cobalt gave a mean peak height of 0.208 (at 611.5 nm) with a relative standard deviation of 1.2%. The sensitivity of the method is 1.04 (dA/dnm) ml mug(-1) found from the slope of the calibration curve. The interference of a large number of anions and cations on the determination of cobalt has been studied and the optimized conditions developed were utilized for its trace determination in various standard alloys and biological samples.     

Highly Efficient and Practical Syntheses of Lavendamycin Methyl Ester and Related Novel Quinolindiones

The novel 7-(N-formyl-, 7-(N-acetyl-, and 7-(N-isobutyrylamino)-2-methylquinoline-5,8-diones were synthesized in excellent overall yields in three steps via the nitration of the commercially available 8-hydroxy-2-methylquinoline followed by a reduction-acylation step and then oxidation. Acid hydrolysis of 7-(N-acetylamino)-2-methylquinoline-5,8-dione (14a) afforded the novel 7-aminoquinoline-5,8-dione 7 in excellent yields. Due to our efficient preparation of dione 14a, we now report a short and practical method for the total synthesis of the potent antitumor agent lavendamycin methyl ester (1b) with an excellent overall yield.     

Wet carbon-based solid acid/NaNO_3 as a mild and efficient reagent for nitration of aromatic compound under solvent free conditions

Nitro aromatic compound can be obtained in high yields via nitration of aromatic compound with wet carbon-based solid acid and NaNO_3 under solvent free oxidation at room temperature.     

A convenient synthesis of chiral succinic acid-d2 by catalytic asymmetric reduction using a ruthenium BINAP catalyst

The synthesis of (2R,3R) and (2S,3S) dideuteriosuccinic acid in 63 ± 10% enantiomeric excess by reduction of the half acid ester of ethyl fumarate from (R) and (S) BINAP ruthenium (II) diacetate complex, respectively, is reported. (2R,3R) and (2S,3S)-Dideuteriosuccinic acid has also been prepared from (R)-BINAP ruthenium (II) dicarboxylate complex directly in similar optical purity by reversing the sequence of introduction of the isotopic label.     

Time-Resolved Fluorescence and Transient Spectroscopy in Determining Photochemical and Photophysical Channels in Reacting Systems in Solutions and Microheterogeneous Media

Abstract— Characterization of short-lived intermediates in homogeneous and microheterogeneous systems has been carried out using time-resolved spectroscopic techniques. The data obtained from these techniques have been analyzed in a relatively unconventional manner to elucidate complex transient behavior for two reactive systems. The highly nonexponential fluorescence decay for a series of fraws-stilbene-derivatized amphiphiles that readily form bilayer systems in aqueous media has been analyzed using a distribution of lifetimes analysis (DLA). The utility of DLA for quantitative studies was first determined by simulation of artificial decay data. Despite some limitations in DLA, qualitative conclusions as to the nature of the fluorescing species may be drawn when supplementary information such as steady-state spectroscopic data are also considered. The results indicate that the observed fluorescence originates from different types of excited-state species that consist of two or more trans-stilbene units; one of the emissions is attributed to the excited state of a ground-state aggregate while the other is assigned to an excimer that may arise from a 'defect'in the bilayer. The nonexponential nature of the decays is attributed to distributions of environments experienced by the fluorescing species. Electron transfer (ET) reactions between several excited pinacols and carbon tetrachloride in solution have been found to yield products with quantum yields that are higher than unity in the presence of oxygen, suggesting a chain mechanism for product formation. In these systems both the donor and the acceptor undergo bond fragmentation following the initial ET step. The individual steps involved in the proposed mechanism for these systems have been investigated in part using different steady-state and time-resolved laser spectroscopic techniques. However, it was also necessary to utilize pulse radiolysis in order to confirm the involvement of certain radical intermediates that were not observable by the usual flash photolysis techniques.