General and efficient method for the synthesis of alkoxymethylsilanes

Although alkoxymethylsilanes serve as useful building blocks, various efforts to synthesize them by substitution reaction with an alkoxide ion at the carbon adjacent to the silicon failed. To solve this synthetic problem a new route which is very simple to perform was developed. Bromination of (methoxymethyl)trimethylsilane by using N‐bromosuccinimide/2,2′‐azobisisobutyronitrile (NBS/AIBN) was followed by a substitution by alcohols in the presence of triethylamine to give the corresponding [alkoxy‐­(methoxy)methyl]trimethylsilanes. These acetals can be used directly for the next reduction with di‐isobutylaluminium hydride (DIBAL‐H) or Et₃SiH/BF₃·OEt₂ to give alkoxymethylsilanes in good to moderate yields. The success of the substitution reaction with the alcohols suggests that the mechanism is of somewhat S_N1 by nature and formation of the cationic intermediate seems to release the steric hindrance around the carbon, allowing the attack of alcohols. Copyright © 1999 John Wiley & Sons, Ltd.     

Stereoselective Synthesis of the Halaven C14–C26 Fragment from D‐Quinic Acid: Crystallization‐Induced Diastereoselective Transformation of an α‐Methyl Nitrile

Crystallization‐induced diastereoselective transformation (CIDT) of an α‐methyl nitrile completes an entirely non‐chromatographic synthesis of the halichondrin B C14–C26 stereochemical array. The requisite α‐methyl nitrile substrate is derived from D ‐quinic acid through a series of substrate‐controlled stereoselective reactions via a number of crystalline intermediates that benefit from a rigid polycyclic template. Therefore, all four stereogenic centers in the Halaven C14–C26 fragment were derived from the single chiral source D ‐quinic acid.     

Synthesis and thermal properties of cellulose-based polycaprolactones

Cellulose-based polycaprolactone (CAPCL) sheets were prepared from cellulose acetate (CA) and ϵ-caprolactone (CL). Thermal properties of the obtained CAPCL's were studied by differential scanning calorimetry (DSC), thermogravimetry (TG) and TG-Fourier transform infrared spectrometry (TG-FTIR). The glass transition temperatures (T_g 's) of CAPCL decreased with increasing CL/OH ratio, until CL/OH ratio reached 15 and then increased above that ratio. Melting of CAPCL was observed when CL/OH ratio was over 10. The thermal degradation temperatures (T_d 's) of CAPCL increased from ca. 350 °C to 390 °C with increasing CL/OH ratio. The results obtained by TG-FTIR analysis of CAPCL showed that gases with OH, CH, C=O, C-O-C groups evolved by thermal degradation.     

Electronic Structures and Magnetic Properties of Transition Metal Doped CsPbI3 Perovskite Compounds by First-Principles Calculation

Physics of the Solid State - Transition metal doped cesium lead halide (CsPbI3) perovskite compounds were studied for application in photovoltaic solar cells. Electronic structures, chemical shifts...     

Hydrogen bonding and clusters in supercritical methanol–water mixture by neutron diffraction with H/D substitution combined with empirical potential structure refinement modelling

ABSTRACT

Neutron diffraction measurements of H/D isotopic substitution have been performed for seven H/D substituted methanol-water mixtures of 0.3?mol fraction of methanol (x_M) under the supercritical (618?K, 100?MPa) and ambient (298?K, 0.1?MPa) conditions. The seven structure factors obtained were subjected to an empirical potential structure refinement (EPSR) modelling to derive all site-site pair correlation functions, coordination number distributions, spatial density functions, and cluster distributions. Water has a four coordinated structure in the first coordination shell under both ambient and supercritical conditions; however, the spatial density distribution of water molecules in the second coordination shell is delocalised under the supercritical condition. The mean coordination number of all atomic pairs with hydrophilic interactions decreases in the supercritical state. On the other hand, the mean coordination number of interactions between the hydrophobic part of methanol and water molecule is less sensitive to temperature. In the supercritical condition, water clusters with a wide size distribution are generated in a methanol-water mixture as well as in pure water. Since the critical temperature of a methanol-water mixture is lower than that of pure water, it can be concluded that the addition of methanol can generate fragment water clusters at a lower temperature.     

Linear viscoelastic analysis using frequency-domain algorithm on oscillating circular shear flows for bubble suspensions

To achieve a stable evaluation of the linear viscoelasticity of bubble suspensions, which have difficulties for conventional rheometers from spatial distributions of rheological properties with bubble deformations, we proposed a novel rheometry based on spatio-temporal velocity data obtained by ultrasonic velocity profiling (UVP). A frequency-domain algorithm was adopted to overcome a critical influence of measurement noise on the rheological assessment, which is inferred from error propagation characteristics through the equations of motion in discretized form. Applicability and advantage of the present rheometry with the frequency-domain algorithm were verified by two kinds of fluids: high viscous oil as a Newtonian fluid and polyacrylamide aqueous solution as a shear thinning, viscoelastic fluid. The rheometry was finally adopted for bubble suspensions subject to high oscillatory shear, and it could validly extract elasticity-originated momentum transfer as a function of space.