Solvent Incorporation in Bromination of Alkynes With Tetrabutylammonium Tribromide in Methanol

ABSTRACT: The reaction of tetrabutylammonium tribromide (TBABr₃) with mono and disubstituted alkynes in methanol at 20°C leads to the formation of mainly the corresponding α,α-dibromo, β,β-dimethoxyalkane and the E-(α,β)-dibromoalkene. The additions are faster using sonication.     

Schistosomiasis Chemotherapy

After malaria, schistosomiasis (or bilharzia) is the second most prevalent disease in Africa, and is occurring in over 70 countries in tropical and subtropical regions. It is estimated that 600 million people are at risk of infection, 200 million people are infected, and at least 200 000 deaths per year are associated with the disease. All schistosome species are transmitted through contact with fresh water that is infested with free‐swimming forms of the parasite, which is known as cercariae and produced by snails. When located in the blood vessels of the host, larval and adult schistosomes digest red cells to acquire amino acids for growth and development. Vaccine candidates have been unsuccessful up to now. Against such devastating parasitic disease, the antischistosomal arsenal is currently limited to a single drug, praziquantel, which has been used for more than 35 years. Because the question of the reduction of the activity of praziquantel was raised recently, it is thus urgent to create new and safe antischistosomal drugs that should be combined with praziquantel to develop efficient bitherapies.     

A Convenient,Large-Scale Preparation of 2,4-Dichlorophenyl-4-bromomethyl-phenoxyacetate Suitable for Resin Anchorage of the First Fmoc Amino Acid

2,4-dichlorophenyl-4-bromomethyl-phenoxyacetate 3 was prepared by NBS treatement of 2,4-dichlorophenyl-4-methylphenoxyacetate 2. This ester is a key intermediate in the preparation of 2,4-dichlorophenyl-N^α-Fmoc-aminoacyl-4-oxymethylphenoxy-acetates suitable for anchorage of the first amino acid on amine-functionalized polymers.     

Early transition metal dopants in cuprous oxide: To spin or not to spin

We present a trend study of a large variety of dopants at the cation site in Cu₂O (i.e. substituting Cu), focussing largely on the early 3d-, 4d-, and 5d-transition metals (TMs) in which many of them are known to be non-magnetic. We also include s-, sp- and d¹⁰-metals for comparison. We find that doping with sp-elements results in zero spin moment while dopants with a partially filled d-band show a stronger tendency to magnetize and 3d-TM dopants exhibit a larger magnetic moment than most of the 4d- and 5d-TM dopants. From this trend study, we also find a correlation between their substitution enthalpy and associated interatomic relaxations. In particular, Ti-doped Cu₂O appears to be an interesting system, given its “peculiar” ability to exhibit a spin moment when doped with a non-magnetic substituent like Ti. We also find that the interaction between two doped Ti atoms in Ti₂:Cu₂O is predominantly antiferromagnetic, and interestingly (and unexpectedly), this interaction rapidly declines as a function of inter-dopant distance, as in the case for the magnetic late-TM dopants like Co₂:Cu₂O.     

A New Approach to the Intensity of the Secondary Transition of the Benzene Chromophore with-CH3,-OH,-OCH3, Substituents

Since the beginning of the UV absorption spectroscopy, the intensity of the secondary transition of the benzene chromophore in organic derivatives has been a puzzling challenge. The well known vector model has led to some qualitative evaluation of intensity, but accuracy is very low, and sometimes leads to no less than 50% or 100% error. ^1–8 It is designed for very weak perturbations only, as in methylbenzenes. But, even in that latter case, it is not completely satisfactory. Nevertheless, that model is very easy to use; it allows to determine the sensitive positions around the benzene nucleus: those which could enhance or quench intensity for a given pattern of substitution. On that ground it has been of much help for qualitative evaluations. With SCF methods and CI calculations, evaluation of transition moments for several benzene derivatives has been possible on a firmer ground. In fact, such an approach is useful mainly from a theoretical point of view, when accuracy is not the first aim, for some choosen molecules at the same time, since the involvement of computation is far from being negligible, and since the method is not part of the ones that are of common use in organic chemistry ^9,10 (for a recent example on oscillator strength calculations of π systems see:¹¹). In other words, it is not perfectly valuable on a large scale and routine approach and, from that point of view, UV spectroscopy of benzene derivatives appeared sometimes, from 1965 till now, as being in a cul-de-sac, although it was under thorough examination (for example: 12–30). Until recently ab initio calculations have failed to reach a fit with experiment better than 1 eV for the spectrum of the benzene molecule^31–32)     

X-ray study of the reentrant modulated phase of Bis-Propylammonium Tetrachlorocuprate(II) at high temperature

The modulated phase of (C₃H₇NH₃)CuCl₄ stable between 386 and 412 K has been analyzed by single-crystal X-ray diffraction. The structure was solved in the frame of the superspace group approach. The modulation is characterized by a wavelike displacement of the CuCl₄ layer.     

A Convenient One-Step Synthesis of 5-(α-alkanonyl) and 5-(α-Cyclanonyl)-4-Pentanolides

The thermolysis of t-butyl perpent-4-enoate in ketones leads to the formation of 5-(α-alkanonyl) and 5-(α-cyclanonyl)-4-pentanolides with fairly good yields.     

Access to nonisocyanate poly(thio)urethanes: A comparative study

This article describes the synthesis of new cyclic compounds able to react with amines to get nonisocyanate polyurethanes (NIPUs). The contribution of the most studied five‐membered cyclic carbonate was compared to five‐membered cyclic dithiocarbonate analogous and to a six‐membered cyclic carbonate. Difunctional reactive species were obtained by a simple substitution reaction or an efficient thiol–ene coupling reaction. The products, obtained with high yields, were characterized by 1H NMR, 13C NMR, and Fourier tansform infrared spectroscopy analysis. The dicyclocarbonates were then used to synthesize NIPUs by step growth polymerization with several diamines. These materials exhibited glass transition temperatures from 19 to ?29 °C, molar mass from 1800 to 20,400 g mol^?1, and a 20% mass loss temperature (T_d = 20%) between 249 and 296 °C. Such materials are interesting candidates for coating applications. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3284–3296     

Impedance Response of a Thin Film on an Electrode: Deciphering the Influence of the Double Layer Capacitance

The different contributions of the interfacial capacitance are identified in the case of passive materials or thin protective coatings deposited on the electrode surface. The method is based on a graphical analysis of the EIS results to determine both the passive-film capacitance in the high-frequency domain and the double-layer capacitance in the low-frequency domain. The proposed analysis is shown to be independent of the physicochemical origins of the frequency dispersion of the interfacial capacitances which results, from an analysis point of view of the experimental results, in the use of a constant-phase element However, for a correct evaluation of the thin-film properties such as its thickness, the high-frequency data must be corrected for the double-layer contribution. In particular, it is shown that if the double-layer capacitance gives a frequency-dispersed response, it is necessary to correct the high-frequency part for the double-layer constant-phase elements. This is first demonstrated on synthetic data and then used for the determination of the thickness of thin oxide film formed on Al in neutral pH solution.