Matrix Isolation ir Spectra of Methyl Acetate II.Stoechiometry of Methyl Acetate…H2O Complexes in AR Matrices. Comparison with Methyl Benzoate…H20

The earlier reported matrix system methylacetate/ H₂O/Ar has been reinvestigated by IR spectroscopy. The complex band pattern of the ester ν _c=0 and the water ν₃, ν₁ and ν₂ modes can be explained by the coexistence of 1:1, linear 1:2 and linear 2:1 H-bonded complexes. The study of methyl benzoate/H₂O/Ar supports the proposed interpretation.     

Shear thickening, temporal shear oscillations, and degradation of dilute equimolar CTAB/NaSal wormlike solutions

The rheological characterization of dilute and semi-dilute equimolar cetyltrimethylammonium bromide and sodium salicylate solutions is reported, including their linear and nonlinear responses. Start-up experiments and direct birefringence measurements suggest that even at a concentration of as low as 1.0 mM, temporal shear oscillations occur at low shear rates. At concentrations above 10 mM, those low-stress structures vanish and give way to shear-thickening and shear-banding behaviors as seen for other semi-dilute surfactant solutions. Also, the degradation of these solutions after exposure to rubber pump tubing is covered.     

Inversion of Aromaticity of NH-Tautomers of Free-Base Corroles in the Lowest Triplet T1-State

Journal of Applied Spectroscopy - The aromaticity in the lowest triplet T1-state of NH-tautomers of corrole free bases with different peripheral substitution architecture was investigated using...     

Oxidative Addition of Haloheteroarenes to Palladium(0): Concerted versus SNAr‐Type Mechanism

The kinetics of the oxidative additions of haloheteroarenes HetX (X=I, Br, Cl) to [Pd⁰(PPh₃)₂] (generated from [Pd⁰(PPh₃)₄]) have been investigated in THF and DMF and the rate constants have been determined. In contrast to the generally accepted concerted mechanism, Hammett plots obtained for substituted 2‐halopyridines and solvent effects reveal a reaction mechanism dependent on the halide X of HetX: an unprecedented S_NAr‐type mechanism for X=Br or Cl and a classical concerted mechanism for X=I. These results are supported by DFT studies.     

Matrix Isolation Infrared Spectra of Methylacetate III. UV-Induced Z→E photorotamerisation of Methylacetate in Argon Matrices

Abstract

Broadband UV-irradiation of methylacetate isolated in argon matrices causes rather strong modifications to appear in the IR spectrum. Evidence was obtained for a photochemical interconversion of the stable Z-conformer into the less stable E-conformer followed by photolytic decomposition of the latter into stable products. Most of these products could be identified from their IR absorptions. The reverse E→Z interconversion is a thermal process with an activation energy of about 10 kJmole^?1. A normal coordinate analysis based on a transferable valence force field obtained from the literature allowed to assign approximate IR frequencies of E-methylacetate.     

Development of Novel Isoindolone-Based Compounds against Trypanosoma brucei rhodesiense

This study identified the isoindolone ring as a scaffold for novel agents against Trypanosoma brucei rhodesiense and explored the structure-activity relationships of various aromatic ring substitutions. The compounds were evaluated in an integrated in vitro screen. Eight compounds exhibited selective activity against T. b. rhodesiense (IC₅₀<2.2 μm ) with no detectable side activity against T. cruzi and Leishmania infantum. Compound 20 showed low nanomolar potency against T. b. rhodesiense (IC₅₀=40 nm ) and no toxicity against MRC-5 and PMM cell lines and may be regarded as a new lead template for agents against T. b. rhodesiense. The isoindolone-based compounds have the potential to progress into lead optimization in view of their highly selective in vitro potency, absence of cytotoxicity and acceptable metabolic stability. However, the solubility of the compounds represents a limiting factor that should be addressed to improve the physicochemical properties that are required to proceed further in the development of in vivo-active derivatives.     

Sustainable Three‐Component Synthesis of Isothioureas from Isocyanides,Thiosulfonates, and Amines

Multiple applications of isothioureas as fine chemicals (or their precursors) are known, but a general sustainable method for their synthesis was hitherto unavailable. We report a novel general approach towards S‐alkyl and S‐aryl isothioureas through a copper(I)‐catalyzed three‐component reaction between amines, isocyanides, and thiosulfonates. The formal synthesis of a superpotent sweetener further illustrates the applicability of our method.