Synthetic Utilization of α-Phosphonovinyl Anions

The α-phosphonovinyl anions, generated in situ from treatment of β-hetero-substituted vinyl-phosphonates 1a-c with LDA (or LTMP), were trapped with various electrophiles such as chlorotriorganosilanes, chlorotrimethylgermane, chlorotriorganotins, dimethyl disulfide, and halogen to afford the corresponding β-hetero-substituted α-functionalized vinylphosphonates 2–14 in good to excellent yields. The Friedel-Crafts reaction of α-(silyl) or α-(germyl)phosphonoketene dithioacetals 2, 9 or 4 with acid chlorides gave α-acylated phosphonoketene dithioacetals 15–19 in 53–91 % yields. The palladium-catalyzed cross-coupling reaction of β-ethoxy-α-(tributylstannyl)vinylphosphonate 13 with a variety of organic halides (R = acyl, allyl, aryl etc.) provided β-ethoxy-α-substituted vinylphosphonates 20–25 in good to moderate yields. The palladium-mediated cross-coupling reaction of α-(iodo)-vinyl-phosphonates 7, 14 with terminal acetylenes afforded α-alkynylated vinylphosphonates 26–29 in 69–83 % yields.     

Preparation and characterization of conducting polyaniline layered magnetic nano composite polymer particles

Considering the application potentials of organic materials possessing both conducting and ferromagnetic functions in various electronic devices, an attempt was made to prepare conducting polyaniline (PANI) layered magnetic nano composite polymer particles. Two routes were used to modify magnetic Fe₃O₄ core particles. In one route, seeded emulsion polymerization of methyl methacrylate (MMA) was carried out in presence of nano‐sized Fe₃O₄ core particles. In another route, cross‐linker ethyleneglycol dimethacrylate (EGDM) was used in addition to MMA. The modified composite particles were named as Fe₃O₄/PMMA and Fe₃O₄/P(MMA‐EGDM), respectively. Finally, seeded chemical oxidative polymerization of aniline was carried out in the presence of Fe₃O₄/PMMA and Fe₃O₄/P(MMA‐EGDM) composite seed particles to obtain Fe₃O₄/PMMA/PANI and Fe₃O₄/P(MMA‐EGDM)/PANI composite polymer particles. The modification of Fe₃O₄ core particles was confirmed by electron micrographs, FTIR, UV–visible spectra, X‐ray photoelectron spectra, X‐ray diffraction pattern and thermogravimetric analyses. A comparative study showed that crosslinking of intermediate shell improved the magnetic susceptibility and electrical conductivity of PANI layered magnetic nano composite particles. Copyright © 2013 John Wiley & Sons, Ltd.     

Ni-catalyzed α-arylation of secondary α-bromo-α-fluoro-β-lactam: cross-coupling of a secondary fluorine-containing electrophile

A highly diastereoselective cross-coupling reaction of an α-bromo-α-fluoro-β-lactam with a wide range of aryl Grignard reagents was catalyzed by Ni/bis(oxazoline) in yields of up to 98%. The product was obtained diastereoselectively as an anti-isomer. This is the first successful α-arylation of an α-fluoro-β-lactam to produce diverse α-aryl-α-fluoro-β-lactams.     

Concentration dependences of dielectric properties at 105 Hz and 106 Hz for aqueous solutions of hydroxypropyl cellulose

The concentration dependences of dielectric properties measured at 10⁵ Hz and 10⁶ Hz are reported for aqueous solutions of hydroxypropyl cellulose. Phase behaviour of the solutions was also observed with a polarizing optical microscope. For solutions with concentrations well above 40 wt %, polydomain textures, including the banded texture, were observed after a prehistory of deformation. No significant discontinuous changes in the dielectric constant, ε_r′, and loss factor, ε_r″, were found at the concentrations around the onset of the isotropic–cholesteric phase transition and in the biphasic region. In contrast, the steeper changes in ε_r′ and ε_r″ were found at the critical concentration for the fully developed cholesteric phase transition with the polydomain textures.     

A new memory effect: smectic liquid crystalline memory having both conductive and optical memory

In order to compensate for light leakage in the oblique viewing directions of the dark state of the horizontal-switching mode such as the in-plane switching and fringe field switching modes. The viewing angle performance of the horizontal-switching mode with an compensation film has been evaluated on a case by case basis according to the retardation values of the films. Consequently, we found that a much better dark state can be achieved by using an optimised compensation film.     

Conductive liquid crystalline compounds having a piperazine structure

New conductive thermotropic liquid crystalline materials having a piperazine ring in the central core: 1-[4-(9-decenyloxy)phenyl]-4-alkylpiperazines (6) were synthesized. The mesomorphic behaviours of these compounds and their conductivity in the liquid crystal phase were measured. The principal features of these compounds are to exhibit a smectic B phase around room temperature (for example 6: Cr 50 SmB 81 I, °C) and to exhibit a large dark current (6d: 430 μA cm^?2, applied voltage 20 V, at 70°C) in the smectic B phase.     

Highly oriented growth of titanate nanotubes (TNTs) in micro and confinement spaces on sol–gel derived amorphous TiO2 thin films under moderate hydrothermal condition

Synthesis of titanate nanotubes (TNTs) from sol–gel derived amorphous TiO₂ thin films under moderate hydrothermal condition has been reported. TNTs from film possess a tubular morphology that is the same crystalline phase as one synthesized from TiO₂ powder so far. TNTs obtained in this study are not entangled one another but oriented and isolated on the substrate. Growth of highly oriented TNTs is observed in micro grooves of amorphous TiO₂ thin film. Their orientation is also maintained with the growth of TNTs.