NMR and DFT studies on persistent carbocations derived from benzo[kl]xanthene,dibenzo[d,d′]benzo[1,2‐b:4,3‐b′]difuran,and dibenzo[d,d′]benzo[1,2‐b:4,5‐b′]difuran in superacidic media

Persistent carbocations generated by the protonation of hetero‐polycyclic aromatic compounds with oxygen atom(s) were studied by experimental NMR and density function theory calculations. Benzo[kl]xanthene ( 1 ), dibenzo[d,d′]benzo[1,2‐b:4,3‐b′]difuran ( 2 ), and dibenzo[d,d′]benzo[1,2‐b:4,5‐b′]difuran ( 3 ) were synthesized by the annulation of arenediazonium salts. Compound 1 in FSO₃H‐SbF₅ (4:1)/SO₂ClF and 3 in FSO₃H‐SbF₅ (1:1)/SO₂ClF ionized to 1aH⁺ with protonation at C(4) and to 3aH⁺ with protonation at C(6), and these cations were successfully observed by NMR at low temperatures. The density function theory calculations indicated that 1aH⁺ and 3aH⁺ were the most stable protonated carbocations and that 2 should ionize to 2aH⁺ with protonation at C(6). According to the changes in ¹³C chemical shifts (Δδ¹³C), the positive charge was delocalized into the naphthalene unit for 1aH⁺ , into one benzo[b,d]furan unit for 2aH⁺ , and into one benzo[b,d]furan unit for 3aH⁺ . Copyright © 2015 John Wiley & Sons, Ltd.     

Specific reactivity of 2,4,6-tri-tert-butylanilide anions and its application to benzylation reagent

The reaction of methyl iodide with an anilide anion prepared from 2,4,6-tri-tert-butylanilide and NaH in CH₃CN gave N-methyl anilide (N-alkylation product) as a major product, while in the reaction of benzyl bromide with the anilide anion in DMF, O-benzyl imidate (O-alkylation product) was obtained with almost complete selectivity. The treatment of O-benzyl imidate with alcohols and carboxylic acids in the presence of trifluoromethane sulfonic acid gave benzyl ethers and benzyl esters, respectively.     

Discovery of Hexagonal Structured Pd–B Nanocrystals

We report on hexagonal close-packed (hcp) palladium (Pd)–boron (B) nanocrystals (NCs) by heavy B doping into face-centered cubic (fcc) Pd NCs. Scanning transmission electron microscopy–electron energy loss spectroscopy and synchrotron powder X-ray diffraction measurements demonstrated that the B atoms are homogeneously distributed inside the hcp Pd lattice. The large paramagnetic susceptibility of Pd is significantly suppressed in Pd–B NCs in good agreement with the reduction of density of states at Fermi energy suggested by X-ray absorption near-edge structure and theoretical calculations.     

Solvent effect of fluorescence on/off switching of diarylethene linked to excited-state intramolecular proton transfer fluorophore

Efficient fluorescence on/off switching of a dyad consisting of a photochromic diarylethene and a fluorescence dye based on excited state intramolecular proton transfer (ESIPT) was designed and demonstrated. Diarylethenes linked to (2-(2-methoxy-5-methylphenyl)benzothiazol-6-yl)- and (2-(2-hydroxy-5-methylphenyl)benzothiazol-6-yl)-9,9-dioctylfluorene moieties (1a and 2a, respectively) exhibited fluorescence on/off switching upon alternating irradiation with ultraviolet and visible light in various solvents. The fluorescence on/off contrast of 2a was found to be higher than that of 1a in n-hexane because the overlap integral between the absorption spectrum of the diarylethene closed-ring form and the fluorescence spectrum of 2a is larger than that of 1a. Diarylethene 2a exhibited green fluorescence with large Stokes shift in n-hexane, which is ascribed to the ESIPT process from the enol form to the keto form. In contrast, the fluorescence of 2a in N,N-dimethylsulfoxide (DMSO) was mainly observed as blue fluorescence from enol form, while diarylethene 1a exhibited blue fluorescence in n-hexane and DMSO. The fluorescence on/off contrast of 2a in n-hexane was higher than that in DMSO because of the difference in the spectral overlaps in n-hexane and DMSO.     

Development of continuous process enabling nanofibrillation of pulp and melt compounding

Microfibrillated cellulose (MFC), a mechanically fibrillated pulp mostly consisting of nanofibrils, is a very attractive material because of its high elastic modulus and strength. Although much research has been done on composites of MFC and polypropylene (PP), it has been difficult to produce such composites at an industrial level because of the difficulties in using MFC in such composites are not only connected to the polarity (that can be improved with compatibilizers), but also with the challenge to make a homogeneous blend of the components, and also the low temperature stability of cellulose that could cause problems during processing. We developed a new processing method which enables continuous microfibrillation of pulp and its melt compounding with PP. Never-dried kraft pulp and powdered PP were used as raw materials to obtain MFC by kneading via a twin-screw extruder. Scanning electron microscopy showed nano to submicron wide fibers entangled in the powdered PP. MFC did not aggregate during the melt compounding process, during which the water content was evaporated. Maleic anhydride polypropylene (MAPP) was used as a compatibilizer to reinforce interfacial adhesion between the polar hydroxyl groups of MFC and non-polar PP. We investigated the effect of MAPP content on the mechanical properties of the composite, which were drastically improved by MAPP addition. Needle-leaf unbleached kraft pulp (NUKP)-derived MFC composites had better mechanical properties than needle-leaf bleached kraft pulp (NBKP)-derived MFC composites. Injection molded NUKP-derived MFC composites had good mechanical and thermal properties. The tensile modulus of 50 wt% MFC composite was two times, and the tensile strength 1.5 times higher than that of neat PP. The heat distortion temperature of 50 wt% MFC content composite under 1.82 MPa flexural load was increased by 53 °C, from 69 to 122 °C. This newly developed continuous process using powder resin has the potential for application at an industrial level.     

Flavin-catalyzed aerobic oxidation of sulfides in aqueous media

An aerobic, organocatalytic, and aqueous method for the oxidation of sulfides is described. Synthetic flavin, 5-ethyl-3,7,8,10-tetramethylisoalloxazinium perchlorate, acts as an efficient catalyst for the oxidation of sulfides in water under an oxygen atmosphere (1 atm) with the assistance of ascorbic acid as a reductant. This is an inexpensive, convenient, and environmentally benign method for the selective oxidative transformation of sulfides into sulfoxides.