Synthesis of Highly Functionalized Isoxazolinediones from One-pot Reaction of Alkylidene Meldrum ’s Acid with Alkyl Isocyanides in the Presence of Arylhydroxylamines

Alkyl isocyanides undergo a smooth reaction with alkylidene Meldrum’s acids in the presence of arylhydroxylamines to produce N ¹-alkyl-2-(3,5-dioxo-2-aryltetrahydro-4-isoxazolyl)alkanamides in high yields.     

Normal forms for nonlinear control systems with scalar output

We propose a normal form for nonlinear control systems with scalar output. We follow an approach proposed by Poincaré and adapted for control systems by Kang and Krener which consists of analyzing, step-by-step, the action of the change of coordinates on the system. To cite this article: I.A. Tall, M. Balde, C. R. Acad. Sci. Paris, Ser. I 341 (2005).     

Spectrophotometry Determination of Copper and Palladium Using Some 1,3,5-Triphenylformazans

A new rapid and accurate method for the spectrophotometric microdetermination of Cu(II) and Pd(II) using some 1,3,5-triphenylformazans (I) is given. The optimum conditions for the formation of the complexes are extensively investigated. The ligands form 1:1 and 1:2 (M:L) complexes with Cu and Pd ions, Beer's law is obeyed up to 3.8 and 6.5 ppm Cu and Pd respectively. The influence of foreign ions is investigated. The ligands were used successfully as indicators in spectrophotometric titration of Cu and Pd ions with EDTA and CDTA.     

Oxidation with permanganate in presence of fluoride potentiometric determination of manganese(II)

The effects of acidity, fluoride concentration, temperature and concentration of manganese in the reaction between KMnO(4) and Mn(II) were studied potentiometrically. The rate of reaction is increased by increasing the fluoride concentration and/or decreasing the acidity of the solution. The formal redox potentials of the MnO(-)(4)/Mn(III) and the Mn(III)/Mn(II) systems were determined at different pH values. The E degrees values obtained by extrapolation to pH = 0 were 1.58 and 1.52 V respectively. The amount of Mn(II) determined was varied from 5 to 56 mg. The net reaction can be represented as MnO(-)(4) + 10HF(-)(2) + 4Mn(2+) right harpoon over left harpoon 5MnF(-)(4) + 2H(+) + 4H(2)O.     

One-step synthesis of N-alkyl-2-aryl-2-oxoacetamides and N,N-dialkyl-2-aryl-4H-1,3-benzodioxine-2,4-dicarboxamides

Alkyl isocyanides react with 2-hydroxybenzaldehyde or 2-hydroxy-5-nitrobenzaldehyde to afford N-alkyl-2-aryl-2-oxoacetamides and N²,N⁴-dialkyl-2-aryl-4H-1,3-benzodioxine-2,4-dicarboxamides in nearly 1:1 ratios. Treatment of 2,6-dimethylphenyl isocyanide with 2-hydroxy-5-nitrobenzaldehyde affords only the 2-oxoacetamide derivative.     

Spectrophotometric assay of cephalosporins in pharmaceutical products,using chromotrope 2B and chromotrope 2R

A simple, rapid and sensitive Spectrophotometric method is proposed for the determination of cephadroxil (I), cephalexin (II) and cephradine (III). The method is based on ion-pair complex formation between these derivatives and Chromotrope 2B (C2B) or Chromotrope 2R (C2R), to give a highly coloured radical anion. The coloured products are quantified spectrophotometrically at 542 and 564 nm for C2B and C2R, respectively. The optimization of the experimental conditions is described. The method has been used for the determination of 0.4–15, 0.4–14 and 0.4–18 g/ml of drugs I, II and III, respectively. The accuracy of the method is indicated by the excellent recovery (100.0±1.7%) and the precision is supported by the low relative standard deviations 1.5%. The sensitivity of the method is discussed and the results are compared with the official method. The interference from common degradation products and excipients was also studied. The proposed method was applied successfully to the determination of the different cephalosporins in dosage forms, with good precision and accuracy. The results were compared with those given by the official B.P. 1993 method.     

Synthesis and Dynamic NMR Study of Functionalized 1-(3-Furyl)-1H-indole-2,3-diones

Protonation of the highly reactive 1:1 intermediates produced in the reaction between alkyl(aryl) isocyanides and dibenzoylacetylene by isatin, leads to vinylnitrilium cations, which undergo carbon-centered Michael-type addition with the conjugate base of the NH-acid to produce highly functionalized 1-(3-furyl)-1H-indole-2,3-diones. A dynamic NMR effect is observed in the ¹H NMR spectra of these compounds as a result of restricted rotation around the single bond linking the indole moiety and the furan system. The free-energy of activation (ΔG ^#) for this process is 69–71 ± 2 kJ mol⁻¹.     

Application of Alizarine Derivatives as Chromogenic Reagents for the Spectrophotometric Determination of Some Sulfa Drugs

A spectrophotometric procedure for the determination of six pharmaceutical sulfonamides containing a primary aromatic amino group using alizarine (I), alizarine blue (II), alizarine red (III), and quinalizarine (IV), that offers advantages of simplicity, rapidity, sensitivity, precision, and stability, has been developed. The proposed method is based on the formation of colored products with the chromogenic reagents (I-IV). A linear correlation was found between absorbance at λ_max and the concentration. For more accurate results, Ringbom optimum concentration ranges are evaluated. The molar absorptivities (ε), absorptivities (a), and Sandell sensitivities for all sulfonamides derivatives with the chromogenic reagents tested were calculated. The procedures developed are applied for bulk sulfa drugs and some of their dosage forms.     

Oxidations with alkaline permanganate using monovalent thallium for the back-titration: Determination of iodate,iodide and ferrocyanide

Iodate, iodide, iodine and ferrocyanide can be estimated by oxidation with KmnO₄ in alkaline media; the excess is back-titrated with TI⁷. I^- and I₂ are oxidized to IO₄^- in the presence of Ba⁺² ions but only to IO₃^- in absence of such ions. The direct titration of IO₃^-, I^- with KmnO₄ proved valueless.Ferrocyanide is oxidized by KmnO₄ in alkaline solutions and MnO₂ is formed. In the presence of telluric acid and 0.025–0.1 N NaOH satisfactory results are obtained. Reduction of MnO₄^- with ferrocyanide gives MnO₄^-2 and the results are variable, depending on the rate of adding the ferrocyanide.