Expedient and Diastereodivergent Assembly of Terpenoid Decalin Subunits having Quaternary Stereocenters through Organocatalytic Robinson Annulation of Nazarov Reagent

We report an expedient approach to highly functionalized cis‐ and trans‐decalines that could function as key structural subunits toward the synthesis of various classes of terpenoids. Key to the strategy is an organocatalyzed Robinson annulation reaction of the Nazarov reagent that affords chiral enone building blocks with high enantioselectivities. The quaternary carbon stereogenic center can direct the subsequent reactions and allow the rapid and diastereoconvergent assembly of complex decalines with contiguous stereocenters.     

Chromatography-Free Multicomponent Synthesis of Thioureas Enabled by Aqueous Solution of Elemental Sulfur

The development of a new three-component chromatography-free reaction of isocyanides, amines and elemental sulfur allowed us the straightforward synthesis of thioureas in water. Considering a large pool of organic and inorganic bases, we first optimized the preparation of aqueous polysulfide solution from elemental sulfur. Using polysulfide solution, we were able to omit the otherwise mandatory chromatography, and to isolate the crystalline products directly from the reaction mixture by a simple filtration, retaining the sulfur in the solution phase. A wide range of thioureas synthesized in this way confirmed the reasonable substrate and functional group tolerance of our protocol.     

Comparative study of the thermal behavior of Sr–Cu–O gels obtained by sol–gel and microwave-assisted sol–gel method

Journal of Thermal Analysis and Calorimetry - In the literature data, several papers reported the synthesis by various chemical or physical methods of the SrCu2O2 (SCO) having possible applications...     

Direct analysis in real time mass spectrometry (DART‐MS) of highly non‐polar low molecular weight polyisobutylenes

Low molecular weight polyisobutylenes (PIB) with chlorine, olefin and succinic acid end‐groups were studied using direct analysis in real time mass spectrometry (DART‐MS). To facilitate the adduct ion formation under DART conditions, NH₄Cl as an auxiliary reagent was deposited onto the PIB surface. It was found that chlorinated adduct ions of olefin and chlorine telechelic PIBs, i.e. [M + Cl]^? up to m/z 1100, and the deprotonated polyisobutylene succinic acid [M? H]^? were formed as observed in the negative ion mode. In the positive ion mode formation of [M + NH₄]⁺, adduct ions were detected. In the tandem mass (MS/MS) spectra of [M + Cl]^?, product ions were absent, suggesting a simple dissociation of the precursor [M + Cl]^? into a Cl^? ion and a neutral M without fragmentation of the PIB backbones. However, structurally important product ions were produced from the corresponding [M + NH₄]⁺ ions, allowing us to obtain valuable information on the arm‐length distributions of the PIBs containing aromatic initiator moiety. In addition, a model was developed to interpret the oligomer distributions and the number average molecular weights observed in DART‐MS for PIBs and other polymers of low molecular weight. Copyright © 2015 John Wiley & Sons, Ltd.     

Low volatile monofunctional reactive diluents for radiation curable formulations

In the last decades the importance of UV curable formulations has increased continuously. Their fast curing speed, solvent-free polymerization conditions, and the formation of hard and highly crosslinked photopolymer networks represent major benefits. Commercial UV resins generally consist of multi-functional vinyl oligomers, photoinitiators, additives, and reactive diluents. Mono- and multi-functional reactive diluents serve as thinners to lower the overall resin viscosity and to improve processability. However, many monofunctional reactive diluents like isobornyl (meth)acrylate or benzyl (meth)acrylate exhibit high volatility, often already at room temperature. This causes adverse effects such as unpleasant odor, potential health risks, and changing resin composition during processing. A new group of monomers that show high potential for replacing traditional highly volatile reactive diluents are salicylate (meth)acrylates. In this work, salicylate-based thinners are synthesized, polymerized, and characterized with respect to their viscosity, volatility, thermal stability, photoreactivity, and thermomechanical properties of their homopolymers. Additionally, a first example of their diluting effect in a highly viscous difunctional polyester urethane methacrylate is demonstrated with 30 wt% of a cycloaliphatically and an aromatically substituted salicylate methacrylate. The polymers of the diluted resin exhibit similarly high glass transition temperatures of 110 and 126 °C, which are in the range of the polymers of the undiluted resin.     

Green chemical syntheses and applications within organophosphorus chemistry

Application of the microwave (MW) technique offers many advantages in organophosphorus syntheses. Reluctant reactions may take place on MW irradiation. In most cases, MWs make the reactions more efficient in respect of rate, selectivity and yield. The benefits are shown via representative examples. MW irradiation may replace a catalyst, or simplify catalytic systems. The synthesis of catalysts incorporating heterocyclic P-ligands is also discussed. Where it was relevant, structural chemical details were also provided.     

Generalized Maxwell model for the viscoelastic behavior of a soda-lime-silica glass under low frequency shear loading

The linear viscoelastic behavior of a soda-lime-silica glass under low frequency shear loading is investigated in the glass transition range. Using the time-temperature superposition technique, the master curves of the shear dynamic relaxation moduli are obtained at a reference temperature of 566°C. A method to determine the viscoelastic constants from dynamic relaxation moduli is proposed. However, some viscoelastic constants cannot be directly measured from the experimental curves and others cannot be precisely obtained due to non-linearity effects at very low frequencies. The generalized Maxwell model is investigated from the experimental dynamic moduli without fixing the viscoelastic constants. A set of parameters is shown to be in good agreement with the experimental dynamic relaxation moduli, but does not give the correct values of the viscoelastic constants of the investigated glass. The soda-lime-silica glass exhibits a non-linear viscoelastic behavior at very low stress level which is usually observed for organic glasses. This non-linear behavior is questioned.     

Quasiliving Carbocationic Polymerization. XV. Forced Ideal Copolymerization of Isobutylene-lsoprene

Forced ideal carbocationic copolymerization of isobutylene and isoprene has been achieved by continuous addition of monomer mixtures of different compositions to cumyl chloride/TiCl₄ charges at -50°C. The overall rate of copolymerization could be kept equal to that of addition rate with up to 10 mol% isoprene in the mixed monomer feed. In this monomer concentration range the composition of the copolymer was identical to that of the feeds. At higher diene concentrations in the feed, chain transfer to monomer and other side reactions (intramolecular cyclization, gel formation) could not be completely avoided. The number-average molecular weight of the copolymers increased almost linearly with the amount of consumed monomers at 10 mol% isoprene concentrations in the feed (i.e., in the quasiliving range). According to ¹H-NMR and ¹³C-NMR spectroscopy, the products are random copolymers.     

Synthesis of Ristriose

ABSTRACT

A new reducing trisaccharide 0-α-D-arabinofuranosyl-(1→ 2)-0-α-D-mannopyranosyl-(1→2)-0-D-glucopyranose (11), named ristriose, has been synthesized in twenty one steps, starting from D-glucose, D-mannose and D-arabinose, with an overall yield of 3.5 %.