Synthesis and NMR Study of α‐Keto Stabilized Ylides of the Type RCOCH=PAr3, (R=MeO‐C6H4, Cl‐C6H4, NO2‐C6H4, α‐Thiophenyl and Naphthyl; Ar = p‐Tolyl or Phenyl)

Synthesis and characterization of five new phosphonium salts and related phosphorus ylides of the type R‐COCH=PAr₃ are reported. The reaction of bromo 4′‐methoxo/chloro/nitro acetophenone, α‐thiophenyl and naphthoyl acetophenone with triphenylphosphine or triparatolylphosphine in acetone gives phosphonium salts. Dehydrogenation of these salts in aqueous sodium hydroxide solution form ylides. Characterization of obtained compounds was performed by IR, ¹H, ¹³C, ³¹PNMR and elemental analysis.     

A convergent paired electrochemical synthesis of new heterocyclic compounds. Reaction of benzoquinones with 3-Amino-4-hydroxycoumarin

Electrochemical oxidation of catechols (1) has been studied in the presence of cathodically generated 3-amino-4-hydroxycoumarin (3a) as a nucleophile in aqueous solutions, using cyclic voltammetry and controlled-potential coulometry. The results indicate that the o-benzoquinones derived from catechols (1) participate in Michael addition reaction with 3-amino-4-hydroxycoumarin (3a) to form the corresponding new heterocyclic compounds (7) (oxidized form of coumestan derivatives). The electrochemical process consists of a multi-step including (a) cathodic reduction of 4-hydroxy-3-nitrocoumarin (3) to 3-amino-4-hydroxycoumarin (3a), (b) anodic oxidation of catechols (1) to related o-benzoquinone (2), (c) the Michael addition reaction of 3-amino-4-hydroxycoumarin (3a) to o-benzoquinone (2), and (d) anodic oxidation of formed adduct. The paired electrochemical synthesis of compounds 7a and 7b has been successfully performed in a one-pot process at carbon rods as working and counter electrodes in an undivided cell.     

Synergistic adsorption of Triton X-100 and CTAB surfactants at the toluene + water interface

Equilibrium interfacial tension measurements at 25.0 °C of the toluene + water system with two widely used surfactants, octylphenol decaethylene glycol ether (Triton X-100) and cetyl trimethyl ammonium bromide (CTAB) having concentrations much lower than their CMC were performed. According to the obtained parameters from the Szyszkowski equation, Triton has higher adsorption tendency than of CTAB. The results obtained for surfactants mixtures are analyzed by the theory of non-ideal interactions in binary mixtures (NIBMs) and the interfacial composition and the interaction parameter in the mixed adsorbed monolayer are determined. The attractive interaction shows a maximum value at nearly equal surfactants bulk mole fraction. The synergism is achieved for Triton bulk mole fractions of 0.30 and higher, and the highest degree of synergism (40.6%) is found for the bulk mole fraction of 0.52 with the lowest investigated constant interfacial tension of 28.0 mN m⁻¹. A correlation was developed for variation of the interaction parameter with bulk mole fraction.     

Automated prediction of three-way junction topological families in RNA secondary structures

We present an algorithm for automatically predicting the topological family of any RNA three-way junction, given only the information from the secondary structure: the sequence and the Watson–Crick pairings. The parameters of the algorithm have been determined on a data set of 33 three-way junctions whose 3D conformation is known. We applied the algorithm on 53 other junctions and compared the predictions to the real shape of those junctions. We show that the correct answer is selected out of nine possible configurations 64% of the time. Additionally, these results are noticeably improved if homology information is used. The resulting software, Cartaj, is available online and downloadable (with source) at: http://cartaj.lri.fr.     

Synthesis, characterization and X-ray structural determination of a stable dication derived from symmetrical ortho-aminophenyl diamine and 2-pyridinecarboxaldehyde

N,N′-Bis(2-aminophenyl)-1,2-ethanediamine is synthesized from 1,2-diaminoethane and 1-chloro-2-nitrobenzene in the presence of sodium carbonate and the product reduced by zinc dust and ammonium chloride. A novel stable dication is synthesized by reaction of N,N′-bis(2-aminophenyl)-1,2-ethanediamine and 2-pyridinecarboxaldehyde in the presence of manganese chloride in methanol. The X-ray structural analysis shows formation of the dication.     

Mössbauer study and magnetic properties of Fe–Si–B–Cu amorphous systems with minor substitution of carbon

Journal of Radioanalytical and Nuclear Chemistry - The effect of minor substitution of carbon on the structure and magnetic properties of Fe–Si–B–Cu-type metallic glasses was...     

An alkylzinc bromide and a lithium alkyldibromozincate containing tris(organosilyl)methyl groups

The lithium reagent (3) reacts with a molar equivalent of anhydrous zinc bromide to give the dimeric compound (2a), in which zinc is four-coordinate. The product from a similar reaction with Li{C(SiMe₃)₂(SiMe₂NPhMe)} is the lithium zincate [Li(THF)₂(μ-Br)₂Zn{C(SiMe₃)₂(SiMe₂NPhMe)}] (4), in which the zinc is only three-coordinate. The crystal structures of 2a and 4 have been determined.     

Evaluation of feed-forward back propagation and radial basis function neural networks in simultaneous kinetic spectrophotometric determination of nitroaniline isomers

Mixtures of 2-, 3-, and 4-nitoroanilines, are simultaneously analyzed with spectrophotometry, based on their different kinetic properties. These nitroanilines react differentially with 1,2-naphtoquinone-4-sulphonate (NQS) at pH 7 in micellar medium to produce colored product. The differential kinetic spectra were monitored and recorded at 500 nm, and the data obtained from the experiments were processed by chemometric approaches, such as back-propagation neural networks (BPNNs), radial basis function neural networks (RBFNNs), and partial least squares (PLS). Experimental conditions were optimized and training the network was performed using principal components (PCs) of the original data. A set of synthetic mixtures of nitroanilines was evaluated and the results obtained by the application of these chemometric approaches were discussed and compared. The analytical performance of the models was characterized by relative standard errors. It was found that the artificial neural networks model affords relatively better results than PLS. The proposed method was applied to the determination of considered nitroanilines in water samples.