Intensely Fluorescent Azobenzenes: Synthesis,Crystal Structures,Effects of Substituents,and Application to Fluorescent Vital Stain

2‐[Bis(pentafluorophenyl)boryl]azobenzenes bearing hydrogen, methoxy, dimethylamino, trifluoromethyl, fluoro, n‐butyl, and tert‐butyldimethylsiloxy groups at the 4′‐position or methoxy and bromo groups at the 4‐position have been synthesized. The 4‐bromo group of the 2‐boryl‐4‐bromoazobenzene derivative was converted to phenyl and diphenylamino groups by palladium‐catalyzed reactions. The absorption and fluorescence properties have been investigated using UV/Vis and fluorescence spectroscopy. The 2‐borylazobenzenes emitted an intense green, yellow, and orange fluorescence, in marked contrast to the usual azobenzene fluorescence. The 4′‐siloxy derivative showed the highest fluorescence quantum yield (0.90) among those reported for azobenzenes to date. The correlation between the substituent and the fluorescence properties was elucidated by studying the effect of the substituent on the relaxation process and from DFT and TD‐DFT calculations. An electron‐donating group at the 4′‐position was found to be important for an intense emission. Application of fluorescent azobenzenes as a fluorescent vital stain for the visualization of living tissues was also investigated by microinjection into Xenopus embryos, suggesting these compounds are nontoxic towards embryos.     

Development of direct fluorination technology for application to materials for lithium battery

Direct fluorination of 1,3-dioxolan-2-one with elemental fluorine was successfully carried out to provide 4-fluoro-1,3-dioxolan-2-one, which was expected as an additive for lithium ion secondary battery. 4-Fluoro-1,3-dioxolan-2-one was also further fluorinated with elemental fluorine to give three isomers of difluoro derivatives by the same methodology. Another topic is the preparation of trifluoromethanesulfonyl fluoride, an intermediate of lithium battery electrolyte, by the reaction of methanesulfonyl fluoride with elemental fluorine. The use of perfluoro-2-methylpentane as a solvent gave satisfactory selectivity of trifluoromethanesulfonyl fluoride.     

Synthesis and characterization of manganese and cobalt pyroborates: M2B2O5 (M = Mn,Co)

The magnetic property of Co₂B₂O₅ and the optical property of M₂B₂O₅ (M = Mn, Co) were investigated. Co₂B₂O₅ showed antiferromagnetic behavior below the Néel temperature of T_N ≈ 45 K, and the Weiss temperature was T_W = +7.7 K. The effective magnetic moment of Co was 4.96 μ_B, which indicated that Co was divalent and in a high-spin state. Absorptions attributed to the d–d transitions in Mn²⁺ and Co²⁺ ions were observed at 250–650 nm in the diffuse reflection spectra. The optical absorption edges of Mn₂B₂O₅ and Co₂B₂O₅ were at 243 nm (5.11 eV) and 299 nm (4.15 eV), respectively.     

Y-931, a novel atypical antipsychotic drug,is less sensitive to oxidative phenomena

The oxidation behavior of Y-931, a potent atypical antipsychotic drug, was compared with that of clozapine and olanzapine. In two enzymatic systems (horseradish peroxidase (HRP)/glutathione (GSH) and HRP/H(2)O(2)/GSH) which generate thiyl radicals, clozapine markedly strengthened the electron paramagnetic resonance (EPR) signal for the radical. Olanzapine, Y-931 and the major metabolites (compounds 1-3) had no or minimal effect on the intensity of this signal. In addition, the redox potential values for the three derivatives were in accord with the EPR spin trapping results. In toxicological experiments in human leukocytes, a concentration-dependent toxicity was observed when neutrophils were incubated with clozapine (1-10 micromol/l) and H(2)O(2) (1 mmol/l). However, Y-931 and olanzapine did not show remarkable toxicity under the conditions.     

A practical synthesis of L-ribose

L-Ribose was synthesized by a simple four-step method with overall yield of 76.3% from a protected L-arabinose derivative, which is a compatible intermediate for the synthesis of L-deoxyribose. The key step of this strategy is the Swern oxidation and subsequent stereoselective reduction accompanied by inversion of the 2-hydroxy group of protected L-arabinose.     

Palladium-catalyzed multiple arylation of thiophenes

Secondary 2-thiophenecarboxamides efficiently undergo unique triarylation accompanied by formal decarbamoylation under palladium catalysis. 3-Substituted thiophenes, especially having an electron-withdrawing group, can also be triarylated.     

The hydrophilization of polystyrene substrates by 172-nm vacuum ultraviolet light

This paper describes the photochemical surface modification of polystyrene (PS) substrates using vacuum ultraviolet (VUV) light 172 nm in wavelength. We have particularly focused on the effects of atmospheric pressure during VUV irradiation on the obtained surface's wettability and the stability of the wettability, in addition to its chemical structure, morphology, and photooxidation rate. Samples were photoirradiated with VUV light under pressures of 10, 10(3), or 10(5) Pa. Although, in each case, the originally hydrophobic PS surface became highly hydrophilic, the final water-contact angle and photooxidation rate depended on the atmospheric pressure. The samples treated at 10 Pa were less wettable than those prepared at 10(3) and 10(5) Pa due to the shortage of oxygen molecules in the atmosphere. The minimum water-contact angles of the samples treated at 10, 10(3), and 10(5) Pa were about 8 degrees, 0 degrees, and 0 degrees, respectively. With the samples prepared at 10 and 10(3) Pa, photooxidation reactions proceeded in the topmost region closest to the surface, while at 10(5) Pa photooxidation was found to be greatly enhanced in the deeper regions, as evidenced by angle-resolved X-ray photoelectron spectroscopy. Photoetching rates were determined through atomic force microscope observation of microstructured PS samples prepared by a simple mesh-contact method. As estimated from AFM images of the latticed microstructures obtained, the rates of samples prepared at 10(3) and 10(5) Pa were about 1.5 and 1.3 nm/min, respectively. However, no photoetched features were observable on the sample surface prepared at 10 Pa. Hydrophilic stability also varied greatly depending on atmospheric pressure. The hydrophilicity of samples treated at 10 and 10(3) Pa gradually decreased as they were exposed to air. On the other hand, the sample surface prepared at 10(5) Pa showed excellent hydrophilicity even after being left in air for 30 days.     

Photoinduced face-inversion of conjugated tetraene ligands on a Pd-Pd-Pd moiety

The linear sandwich tripalladium complexes [Pd3{Ar(CH=CH)4Ar}2[BArf]2 (Ar = Ph, p-t-Bu-C6H4, p-styryl-C6H4) undergo photoinduced isomerization involving face-inversion of the tetraene ligands. Irradiation of these complexes with visible light (>510 nm) resulted in rac (staggered sandwich) to meso (eclipsed sandwich) isomerization. The structures of rac and meso isomers are determined by X-ray crystallographic analyses.     

Selective synthesis of dehydroamino acids from threonines

Dehydropeptides containing dehydroamino acid (ΔAA) are frequently found in natural resources with important biological activity. Herein, we report the selective synthesis of Z- and E-ΔAbu from l- and l-allo-threonine as starting materials through selenation and oxidative elimination. The detailed reaction mechanism of phosphine-assisted selenoether formation is also discussed.     

The effect of fluorination: a crystallographic and computational study of mesogenic alkyl 4-[2-(perfluorooctyl)ethoxy]benzoates

The series of alkyl 4-[2-(perfluorooctyl)ethoxy]benzoates (F8-n) shows a systematic change of crystal structures depending on the length of the alkyl chain: separate packing of perfluorooctyl (Rf) and alkyl (Rh) chains from each other for shorter (n=2) and longer (n=11) members, alternate packing of Rf and Rh chains for middle (n=6,7) members, and an intermediate type of packing for n=4. Semiempirical MO calculations show slightly repulsive interactions between the Rf chains, and attractive ones between Rf and Rh chains and between Rh and the core of a molecular pair. It is concluded that fluorination determines the molecular shape of the crystal structures by making the chain rigid. It is confirmed that the interactions between Rf chains are small compared with those between other moieties and that they are forced to aggregate owing to the exclusion from other moieties. Thus, the effect is dependent on the geometries and intermolecular interactions of the other moieties.