Cross‐Coupling of Organolithium with Ethers or Aryl Ammonium Salts by C−O or C−N Bond Cleavage

Various aryl‐, alkenyl‐, and/or alkyllithium species reacted smoothly with aryl and/or benzyl ethers with cleavage of the inert C?O bond to afford cross‐coupled products, catalyzed by commercially available [Ni(cod)₂] (cod=1,5‐cyclooctadiene) catalysts with N‐heterocyclic carbene (NHC) ligands. Furthermore, the coupling reaction between the aryllithium compounds and aryl ammonium salts proceeded under mild conditions with C?N bond cleavage in the presence of a [Pd(PPh₃)₂Cl₂] catalyst. These methods enable selective sequential functionalizations of arenes having both C?N and C?O bonds in one pot.     

Redox-Induced Modulation of Exchange Interaction in a High-Spin Ground-State Diradical/Triradical System

A triplet ground-state diradical molecule, bis(nitronyl nitroxide)-substituted diphenyldihydrophenazine ( 1 ^..), that can be converted into a one-electron oxidized species, 1 ^{… +} , in the quartet ground state has been developed. Surprisingly, these species, 1 ^.. and 1 ^{… +} , can be used under ambient conditions because they are reasonably stable under aerobic conditions, even in solution. The temperature-dependent magnetic susceptibilities reveal that 1 ^.. and 1 ^{… +} are in the triplet state, with a weak exchange interaction (J₁/k_B = +3.1 K) and quartet ground state with a strong exchange interaction (J₂/k_B = +160 K), respectively. The interconversion between the neutral and one-electron oxidized species can be realized through electrochemical reactions. Significantly different absorption bands in the near-IR region newly appeared in the electronic spectra acquired during electrochemical oxidation/reduction.     

Comparison between Abel test stability and thermal decomposition behavior of nitrocellulose

Journal of Thermal Analysis and Calorimetry - Nitrocellulose (NC) is prone to spontaneous decomposition with exothermic heat release and thus is generally evaluated for stability during the storage...     

An integrated platform for gas-diffusion separation and electrochemical determination of ethanol on fermentation broths

An integrated platform was developed for point-of-use determination of ethanol in sugar cane fermentation broths. Such analysis is important because ethanol reduces its fuel production efficiency by altering the alcoholic fermentation step when in excess. The custom-designed platform integrates gas diffusion separation with voltammetric detection in a single analysis module. The detector relied on a Ni(OH)₂-modified electrode. It was stabilized by uniformly depositing cobalt and cadmium hydroxides as shown by XPS measurements. Such tests were in accordance with the hypothesis related to stabilization of the Ni(OH)₂ structure by insertion of Co²⁺ and Cd²⁺ ions in this structure. The separation step, in turn, was based on a hydrophobic PTFE membrane, which separates the sample from receptor solution (electrolyte) where the electrodes were placed. Parameters of limit of detection and analytical sensitivity were estimated to be 0.2% v/v and 2.90 μA % (v/v)⁻¹, respectively. Samples of fermentation broth were analyzed by both standard addition method and direct interpolation in saline medium based-analytical curve. In this case, the saline solution exhibited ionic strength similar to those of the samples intended to surpass the tonometry colligative effect of the samples over analyte concentration data by attributing the reduction in quantity of diffused ethanol vapor majorly to the electrolyte. The approach of analytical curve provided rapid, simple and accurate analysis, thus contributing for deployment of point-of-use technologies. All of the results were accurate with respect to those obtained by FTIR method at 95% confidence level.     

Hydrogen bond network-stabilisation of blue phases by addition of a chiral N-(10-hydroxydecyl)succinimide derivative and alkane diols

Blue phases (BPs) obtained by doping a commercially available liquid crystalline compound (4-butyl-N-(4-ethoxybenzylidene)aniline (EBBA)) with (2R,3R)-2,3-bis(4-octyloxyphenylbenzoyloxy)-N-(hydroxydecyl)succinimide (1) were highly stabilised by the addition of a small amount of alkane diols. Especially, addition of only 0.5 mol% of octane-1,8-diol increased the BP–Iso transition temperature by 10 K and widened the BP temperature range up to 35 K. A model stabilisation mechanism based on the construction of a hydrogen bond network in each disclination zone in BPs was proposed.     

Micro‐ and Nano‐Liquid Phases Coexistent with Ice as Separation and Reaction Media.

Ice has a variety of scientifically interesting features, some of which have not been reasonably interpreted despite substantial efforts by researchers. Most chemical studies of ice have focused on the elucidation of its physicochemical nature and its roles in the natural environment. Ice often contains impurities, such as salts, and in such cases, a liquid phase coexists with solid ice over a wide temperature range. This impure ice also acts as a cryoreactor, governing the circulation of chemical species of environmental importance. Reactions and phenomena occurring in this liquid phase show features different from those seen in normal bulk aqueous solutions. In the present account, we discuss the chemical characteristics of the liquid phase that develops in a frozen aqueous phase and show how novel analytical systems can be designed based on he features of the liquid phase which are predictable in some cases but unpredictable in others.     

A new <Emphasis Type="Italic">q</Emphasis>-Selberg integral,Schur functions,and Young books

Recently, Kim and Oh expressed the Selberg integral in terms of the number of Young books which are a generalization of standard Young tableaux of shifted staircase shape. In this paper the generating function for Young books according to major index statistic is considered. It is shown that this generating function can be written as a Jackson integral which gives a new q-Selberg integral. It is also shown that the new q-Selberg integral has an expression in terms of Schur functions.     

Dynamic shearing resistance of molten metal films under high pressures and extremely high shearing rates

In the present study plate-impact pressureshear experiments have been conducted to study the dynamic shearing resistance of molten metal films at shearing rates of approximately 10⁷ s⁻¹. These molten films are generated by pressure-shear impact of relatively low melt-point metals such as 7075-T6 Al alloy with high hardness and high flow-strength tool-steel plates. By employing high impact speeds and relatively smooth impacting surfaces, normal interfacial pressures ranging from 1–3 GPa and slip speeds of over 100 m/s are generated during the pressure-shear loading. The resulting friction stress (∼100 to 400 MPa) combined with the high slip speeds generate conditions conductive to interfacial temperatures approaching the fully melt temperature regime of the lower melt-point metal (7075-T6 aluminum alloy) comprising the tribo-pair. During pressure-shear loading, laser interferometry is employed to measure normal and transverse motion at the rear surface of the target plate. The normal component of the particle velocity provides the interfacial normal traction while the transverse component provides the shearing resistance of the interface as it passes through melt. In order to extract the critical interfacial parameters, such as the interfacial slip-speed and interfacial temperatures, a Lagrangian finiteelement code is developed. The computational procedure accounts for dynamic effects, heat conduction, contact with friction, and full thermo-mechanical coupling. At temperatures below melt the flyer and target materials are described as an isotropic thermally softening elastic-viscoplastic solid. For material elements with temperatures in excess of the melt point, a purely Newtonian fluid constitutive model is employed. The results of this hybrid experimental-computational study provide insights into the dynamic shearing resistance of molten metal films at high pressures and extremely high shearing rates.     

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.     

Facile Synthesis of Novel Pentofuranose Analogs of Phospha Sugar Derivatives

Novel pentofuranose analogs of phospha sugar derivatives were synthesized starting from 1-phenyl-2-phospholene 1-oxide ( 1 ). First, the allylic oxidation of 1-phenyl-2-phospholene 1-oxide ( 1 ) with CrO 3 in Ac 2 O-AcOH or 3-hydroxy-1-phenyl-2-phospholene ( 2 ) with MnO 2 afforded 1-phenyl-4-oxo-2-phospholene 1-oxide ( 3 ). The C-5 alkylation of 3 in the presence of NaH by using benzyl bromide or methyl iodide as electrophiles afforded the target title compounds.