Selective deacylation of enol esters with hydroxylamine

An effective procedure for selectively cleaving enol esters in the presence of normal ester functions has been developed, involving hydroxylaminolysis to the oxime of the parent ketone.     

Milling of Organic Solids in a Jet Mill. Part 2: Checking the Validity of the Predicted Rate of Breakage Function

The particle size distribution of fine chemicals in the solid state, like active pharmaceutical ingredients, is often a critical parameter. To achieve the desired particle size distribution, milling of such materials is usually the method of choice. Since these chemicals are often scarcely available, experimental optimization of milling is not possible. Therefore, a model to predict the milling conditions has been developed. The model estimates the rate of breakage function, and needs mechanical properties like hardness and yield strength as input to calculate the rate of breakage function. This paper attempts to check the validity of the model by a series of experiments. A comparison of the experimental results with the outcomes of the model using five different model compounds has been performed. It appears that the rate of breakage function can be estimated by: The model is able to rank the compounds by degree of fracture as an effect of milling. It was also possible to perform a quantitative prediction of the impact of milling pressure on the milling behavior. Finally, it appeared that the prediction of the large particles in the distribution was significantly better than small ones. Because the oversized material is usually the most critical parameter, the conclusion is that the model has acceptable practical applicability.     

Nanofluidics: viscous dissipation in layered liquid films

We studied the layer-by-layer collapse of molecularly thin films of a model lubricant confined between two atomically smooth substrates. The dynamics of the consecutive expulsion of four molecular layers were found to slow down with decreasing film thickness but showed no evidence for confinement-induced solidification. Using a hydrodynamic model, we show that the sliding friction of liquid layers on top of the solid substrates is approximately 18 times higher than the mutual friction between adjacent liquid layers. The latter was independent of film thickness and in close agreement with the bulk viscosity.     

Interface profiles near three-phase contact lines in electric fields

Long-range electrostatic fields deform the surface profile of a conductive liquid in the vicinity of the contact line. We have investigated the equilibrium profiles by balancing electrostatic and capillary forces locally at the liquid vapor interface. Numerical results show that the contact angle at the contact line approaches Young's angle. Simultaneously, the local curvature displays a weak algebraic divergence. Furthermore, we present an asymptotic analytical model, which confirms these results and elucidates the scaling behavior of the profile close to the contact line.     

Donor-substituted peralkynylated "radiaannulenes": novel all-carbon macrocycles with an intense intramolecular charge-transfer

A novel class of planar, highly conjugated all-carbon macrocycles, which we christened "radiaannulenes", have been prepared based on acetylenic scaffolding using tetraethynylethene (TEE) building blocks; these structures are powerful electron acceptors and, upon peripheral substitution with electron-donating N,N-dialkylanilino groups, display intense intramolecular charge-transfer.     

Ultrasonic Broadband Spectrometry of Liquids A Research Tool in Pure and Applied Chemistry and Chemical Physics

This review is a survey of the many scientific applications of ultrasonic broadbandspectrometry (absorption and velocity measurements with coherent sound waves)in liquids and liquid systems, covering, at present, a frequency range from nearly10 kHz to 10 GHz. Ultrasonic spectrometry has proved to be an almost universalresearch tool in many laboratories, one that is useful for investigation of variouschemical, biochemical, and physicochemical systems. Sound waves traversingliquids induce periodic perturbations in pressure and temperature, which can shiftequilibria, resulting in characteristic sound absorption and velocity dispersionspectra. An analysis of such spectra yields valuable information about thermodynamic and kinetic parameters of the particular system that is often difficult toobtain by other methods. Since such periodic perturbations imposed on the systemare incremental in nearly all cases, the system can be studied under equilibriumconditions. All nonlinear effects (heating, nonconstant fluid compressibility, andothers) are negligible, permitting, for instance, the application of linearized rateequations. In this review, various examples of measured broadband spectra arepresented. Related elementary processes are discussed. Among these are ionicand molecular reactions, including mechanisms of association and complexation,proton transfer, solvation, isomerization, interconversion, side-group rotation,hydrogen-bonding, as well as stacking processes and micelle formation. Specialattention will be given to the extensive research on chemical relaxation.Fundamental early and recent publications are cited and discussed. Many referencesare included with particular emphasis on less well known research and publicationsfrom countries of the former USSR. This review aims at a demonstration of thewidespread applications of modern ultrasonic techniques in many fields ofliquid-state research.     

Expedient Conversion of Lactose into Versatile Derivatives of Lactosamine and β-d-Galactosyl-(1→4)-d-mannosamine

Abstract

A practical, nine-step protocol is described for the preparation of synthetically useful N-acetyllactosamine (LacNAc) derivatives as well as LacNAc itself from lactose using the benzoylated oxime of lactos-2-ulosyl bromide 2 as the key intermediate. All steps are performed with simple reagents, do not require chromatography, are large-scale adaptable and allow overall yields of 30%.