Enantiospecific formal total syntheses of (-)-salicylihalamides A and B from D-glucose and L-rhamnose

[reaction: see text] Two formal chiral pool syntheses of the (-)-salicylihalamides A and B were achieved from commercially available 1,2,5,6-diacetone-d-glucose and l-rhamnose.     

Synthesis and structure of novel 1lambda4,2,6-thiadiazines

S,S-Disubstituted sulfodiimines 9 are known to be versatile building blocks for the synthesis of various sulfur-nitrogen-containing heterocycles. Addition-condensation reactions of 9 with three different activated carbonylsubstrates 14-16 lead to several new 1lambda(6),2,6-thiadiazine-3-ones 17-20. S-Debenzylation via a novel synthetic approach utilizing different electrophiles such as TMSCl, Alk(3)O(+)BF(4)(-), Tos(2)O, and Mes(2)O gives rise to a variety of so far hardly known 1lambda(4),2,6-thiadiazine-3-ones 25 and 26. Structure elucidation reveals NH/CH tautomers in solution as well as a tetrahedral asymmetric sulfur attached to the conjugated planar N/C skeleton. The structural features of the 1lambda(4),2,6-thiadiazines 25 and 26 as well as their reactivity toward certain electrophiles will be discussed in detail. Alkylation with Alk(3)O(+)BF(4)(-) preferably results in formation of the 3-alkoxy-1lambda(4)-2,6-thiadiazines 29. In the presence of acid or base, also the N-2-alkyl isomers 30 are formed. Mesylation of 26 with methanesulfonic acid anhydride followed by aminolysis furnishes a variety of the desired heterocycles 5 in moderate overall yield.     

Formal total syntheses of the (-)-salicylihalamides A and B from D-glucose and L-rhamnose

[reaction: see text] Two formal total syntheses of the (-)-salicylihalamides, based on chiral pool approaches, are reported. D-glucose and L-rhamnose were used to prepare advanced intermediates 23 and 54, which can be converted in three or four steps, respectively, to the target compounds. The synthesis of 23 from a known D-glucose-derivative was accomplished in 12 steps and 17% overall yield, and the synthesis of 54 from a known L-rhamnose-derivative was done in nine steps and 6% overall yield. A key step in the synthesis was a ring-closing metathesis reaction to prepare the macrocyclic ring system. It was demonstrated that the phenolic protecting group was critical for inducing the preferential formation of the desired E isomer. It was further shown that the protecting group at the C13 hydroxyl group had no significant influence on the E:Z ratio during the ring-closing metathesis reaction.     

Untersuchungen zur Umsetzung von Kaliumjodat mit Ammoniumsalzen in wäßriger Lösung

On the interaction of potassium iodate with ammonium salts in aqueous solution A quantitative metathetic conversion of KIO₃ into NH₄IO₃ in aqueous medium, which may be expected from the solubility data, can not be achieved. Instead, mixed crystals K_x(NHJ₄)_1?xIO₃ of the perovskite type structure do crystallize, as has been revealed from X-ray powder diagrams.     

What Kind of Image is Drawn by a MALDI-Experiment of Grafted Nanoparticles? - How to Distinguish between Chemically and Physically Adsorbed Parts

Summary: The modern MALDI-TOF mass spectrometry is a powerful technique for the fast and accurate determination of a number of polymer characteristics like end group analysis. It can also be used to analyze the grafted shell around silane modified nanoparticles. This shell contains physically and chemically adsorbed parts. It is a question of great interest what kind of adsorbent can be visualized by using MALDI-TOF mass spectrometry, while it is not possible to ionize the whole AEROSIL® particle. Therefore we chose the system MPTMS/AEROSIL®200 to address this issue. We grafted AEROSIL®200 with methacryloxy(propyl)-trimethoxysilane (MPTMS) under acid conditions. The grafted nanoparticles were treated via Soxhlet extraction. The resulting fractions (the washed nanoparticles and the Soxhlet extract) were systematically analyzed by using MALDI-TOF MS as well as the grafted nanoparticles themselves. As a crosscheck MPTMS was homopolymerized and analyzed. Our results show that for the system under investigation there is strong evidence that only the physically adsorbed part can be analyzed via MALDI-TOF MS.     

Preparation and characterization of GIAR-films for monochromatization of synchrotron radiation

The use of GIAR-films for nuclear resonant filtering of synchrotron radiation has been proposed. A deposition setup was developed to produce suitable layer systems. Various alloy coatings containing⁵⁷Fe were prepared. The hyperfine splittings have been investigated by CEMS. The layer systems have been analyzed in grazing incidence geometry with respect to thickness, density and boundary roughness using Mo K_α radiation.     

Development and experimental validation of a continuum micromechanics model for the elasticity of wood

This contribution covers the development and validation of a microelastic model for wood, based on a four-step homogenization scheme. At a length scale of several tens of nanometers, hemicellulose, lignin, and water are intimately mixed, and build up a polymer (polycrystal-type) network. At a length scale of around one micron, fiberlike aggregates of crystalline and amorphous cellulose are embedded in an contiguous polymer matrix, constituting the so-called cell wall material. At a length scale of about one hundred microns, the material softwood is defined, comprising cylindrical pores (lumen) in the cell wall material of the preceding homogenization step. Finally, at a length scale of several millimeters, hardwood comprises larger cylindrical pores (vessels) embedded in the softwood-type material homogenized before. Model validation rests on statistically and physically independent experiments: The macroscopic stiffness values (of hardwood or softwood) predicted by the micromechanical model on the basis of tissue-independent (‘universal’) phase stiffness properties of hemicellulose, amorphous cellulose, crystalline cellulose, lignin, and water (experimental set I) for tissue-specific composition data (experimental set IIb) are compared to corresponding experimentally determined tissue-specific stiffness values (experimental set IIa).     

Assessing the RAFT Equilibrium Constant via Model Systems: An EPR Study

Reversible addition‐fragmentation chain transfer (RAFT) equilibrium constants, K_eq, for the model system cyano‐iso‐propyl dithiobenzoate (CPDB) – cyano‐iso‐propyl radical (CIP) have been deduced via electron paramagnetic reso1494nce (EPR) spectroscopy. The CIP species is produced by thermal decomposition of azobis‐iso‐butyronitrile (AIBN). In solution of toluene at 70 °C, K_eq has been determined to be (9 ± 1) L · mol⁻¹. Measurement of K_eq = k_ad/k_β between 60 and 100 °C yields ΔE_a = (–28 ± 4) kJ · mol⁻¹ as the difference in the activation energies of k_ad and k_β. The data measured on the model system are indicative of fast fragmentation of the intermediate radical produced by addition of CIP to CPDB.