Mechanism of the acid-catalyzed hydrolysis of N-acylsulfamates

The kinetics of hydrolysis of a series of N-acylsulfamate esters p-XC₆H₄OSO₂NHCOR as models for more complex, biologically important compounds has been examined. Structure-reactivity, solvent-reactivity, thermodynamic data, etc. support a bimolecular mechanism involving water in the transition state (TS).     

The preparation of 4-oxo-N-aryl-4H-1-benzopyran-2-acetamides by the condensation/cyclization of trilithiated acetoacetanilides with lithiated methyl salicylates

Several acetoacetanilides were trilithiated in excess lithium diisopropylamide, and the resulting polylithiated intermediates were regioselectively condensed with lithiated methyl salicylates followed by acid cyclization to substituted 4-oxo-N-aryl-4H-1-benzopyran-2-acetamides (benzopyranone-2-acetamides).     

Action de O- et N-nucléophiles sur les sels de phényl-3 benzopyrylium-1

3-Phenyl-1-benzopyrylium percholorates 1a, 1i react exculusively at C-2 with ethanol and isopropyl alcohol, affording mixed acetals 2a, 3a, 3i . Aqueous ammonia gives symmetrical secondary amines 4a, 4b or bis(3-phenyl-2H-1-benzopyran-2-yl)amines, while with aqueous aliphatic amines (40%) bis-acetals 5a, 5b or 2,2′-oxy-bis(3-phenyl-2H-1-benzopyrans) are characterized. In some other acidic conditions, 5a and 5b are also obtained.     

Plastic crystals and their potential use in new technologies

The paper gives some comments about the potential use of plastic crystals in energy storage. The main point deals with the possibilities of binary solid solution formation. Three binary phase diagrams in the pentaerythritol series are commented on.     

Action des perfluoroalkylcuivre(I) sur les perfluoroalkylethylenes

A series of new polyfluorinated dienes 3, containing the novel -CFCHCHCF-, pattern has been synthesized (50–70% yields) by reacting perfluoroalkyl iodides with perfluoroalkyl-ethylenes in the presence of copper. The monoalkenes R_fCFCHCH₂CF₂R′_f and the saturated compounds R_fCF₂CH₂CH₂CF₂R′_f were obtained by varying the experimental conditions. The ¹H and ¹⁹F NMR spectra are analysed and the reaction mechanism is discussed.     

The Preparation of Substituted Hydroxyphenyl-pyridyl-ethanols and α-Hydroxyphenyl-α-methylpyridineethanols by the Condensation of 2-, 3-, or 4-Picolyllithium with Select Hydroxy-benzaldehydes and 4-Hydroxyacetophenone

2-, 3-, or 4-Picolyllithium was prepared in excess lithium diiso-propylamide and condensed with several hydroxy-benzaldehydes and 4-hydroxy-acetophenone to afford substituted hydroxyphenyl-pyridyl-ethanols and α-hydroxyphenyl-α-methylpyridineethanols. In two instances. 3-picolyllithium condensed with aldehydes to presumably form the hydroxyphenyl-pyridyl-ethanol, which underwent linear dehydration to the substituted pyridyl-ethylenyl-phenol.     

Hydrosilylation Reactions Catalyzed by Rhenium

Hydrosilylation is an important process, not only in the silicon industry to produce silicon polymers, but also in fine chemistry. In this review, the development of rhenium-based catalysts for the hydrosilylation of unsaturated bonds in carbonyl-, cyano-, nitro-, carboxylic acid derivatives and alkenes is summarized. Mechanisms of rhenium-catalyzed hydrosilylation are discussed.     

An improved palladium(II)-catalyzed method for the synthesis of aryl ketones from aryl carboxylic acids and organonitriles

A palladium(II)-catalyzed decarboxylative protocol for the synthesis of aryl ketones has been developed. The addition of TFA was shown to improve the reaction yield and employing THF as solvent enabled the use of solid nitriles and in only a small excess. Using this method, five different benzoic acids reacted with a wide range of nitriles to produce 29 diverse (hetero)aryl ketone derivatives in up to 94% yield.     

Self-propelled droplets

Self-propelled droplets are a special kind of self-propelled matter that are easily fabricated by standard microfluidic tools and locomote for a certain time without external sources of energy. The typical driving mechanism is a Marangoni flow due to gradients in the interfacial energy on the droplet interface. In this article we review the hydrodynamic prerequisites for self-sustained locomotion and present two examples to realize those conditions for emulsion droplets, i.e. droplets stabilized by a surfactant layer in a surrounding immiscible liquid. One possibility to achieve self-propelled motion relies on chemical reactions affecting the surface active properties of the surfactant molecules. The other relies on micellar solubilization of the droplet phase into the surrounding liquid phase. Remarkable cruising ranges can be achieved in both cases and the relative insensitivity to their own ‘exhausts’ allows to additionally study collective phenomena.