Electrochemical Characteristics of a Triphenylamine Derivative by Microelectrode Voltammetry

With the objective of understanding the kinetic redox properties of triphenylamine derivatives in association with chemical reactions, for their future application in functional organic semiconductor devices, the electrochemical characteristics of 4‐(2,2‐diphenylethenyl)‐N,N‐bis(4‐methylphenyl)‐benzenamine (TPA) were evaluated. Based on cyclic voltammograms of TPA on Pt disk electrodes with diameters of 300 μm and 10 μm at slow and fast scan rates in an acetonitrile solution, the TPA^.+ is stable, while the TPA²⁺ is unstable. Importantly, the unstable TPA²⁺ appears to break down by a subsequent chemical reaction. A Cottrell plot analysis from chronoamperometry of a solution containing TPA reveals that both the first and second oxidations are one‐electron reactions. Concerning the stabilization mechanism of the first oxidation state of TPA, the results of molecular orbital calculations indicate that the electrons of the HOMO level are distributed in the triphenylamine group, which induces a resonance‐stabilized TPA^.+. Based on these results, TPA/TPA^.+ is suggested to have a sufficient stability for further application in organic semiconductor devices.     

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...     

Regio- and Z-Selective Alkyne Hydroamination and Hydrophenoxylation using Tetrafluoro-λ6-Sulfanyl Alkynes under Superbasic,Naked Anion Conditions

Alkyne hydroamination is an effective approach for the production of enamines and enamine-containing N-heterocycles. However, stereoselectivity control is a considerable challenge in this reaction because of the electronic repulsion between an incoming nitrogen lone pair and the alkyne π-system. Herein, we propose a methodology involving β-regio- and Z-selective alkyne hydroamination by using tetrafluoro-λ⁶-sulfanyl (SF₄) alkynes under superbasic, naked anion conditions. The reaction is compatible with a wide variety of N-heterocycles, including indoles, carbazoles, pyrazoles, and imidazoles, and selectively furnishes SF₄-linked Z-vinyl enamines with β-regioselectively. Moreover, the method can be extended to the β- and Z-controlled, base-mediated alkyne hydrophenoxylation with phenols to provide SF₄-linked Z-vinyl ethers in high yields. As the SF₄ unit has attracted attention as a bioisostere for alkynes, p-benzenes, bicyclo[1.1.1]pentyl (BCP) groups, and cubanes in medicinal chemistry, this chemistry represents an effective approach to creating novel drug candidates incorporating SF₄-containing molecules.     

Current State of Microflow Trifluoromethylation Reactions

The trifluoromethyl group is a powerful structural motif in drugs and polymers; thus, developing trifluoromethylation reactions is an important area of research in organic chemistry. Over the past few decades, significant progress has been made in developing new methods for the trifluoromethylation of organic molecules, ranging from nucleophilic and electrophilic approaches to transition-metal catalysis, photocatalysis, and electrolytic reactions. While these reactions were initially developed in batch systems, more recent microflow versions are highly attractive for industrial applications owing to their scalability, safety, and time efficiency. In this review, we discuss the current state of microflow trifluoromethylation. Approaches for microflow trifluoromethylation based on different trifluoromethylation reagents are described, including continuous flow, flow photochemical, microfluidic electrochemical reactions, and large-scale microflow reactions.     

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.     

Production of Alkyl Aryl Sulfides from Aromatic Disulfides and Alkyl Carboxylates via a Disilathiane–Disulfide Interchange Reaction

The results of this study show that disilathiane is an effective mediator in the synthesis of alkyl aryl sulfides with disulfides and alkyl carboxylates. Mechanistic studies suggest that disilathiane promotes cleavage of the sulfur–sulfur bond of disulfides to generate thiosilane as a key intermediate. Diselenides were also applicable to this transformation to produce the corresponding selenides.     

Transition-Metal Free Catalytic Synthesis of Trifluoromethyl Indolines by [4+1] Cycloaddition of Trifluoromethyl Benzoxazinones with Sulfur Ylides

Stereoselective catalytic synthesis of 3-trifluoromethyl indolines through the [4+1] cycloaddition of benzoxazinones and sulfur ylides in a transition-metal-free manner was developed. In the presence of a catalytic amount of sodium hydride, aza-ortho-quinone methide intermediates were formed from trifluoromethyl benzoxazinones through decarboxylation after the first nucleophilic attack of sulfur ylides, which progressed to a second nucleophilic attack of sulfur ylides, resulting in the [4+1] cycloaddition. The key for this catalytic transformation is the dual attack of sulfur ylides on substrates. This unique transition-metal-free protocol is applicable to the synthesis of non-fluorinated vinyl-, ethynyl- or methyl-substituted indolines. The synthesis of 3-trifluoromethyl indoles was also achieved described under stoichiometric conditions.