Synthesis of 6-hydroxy-2-naphthoic acid from 2,6-diisopropylnaphthalene using NHPI as a key catalyst

A new strategy to 6-hydroxy-2-naphthoic acid (HNPA) and 4-hydroxybenzoic acid from 2,6-diisopropylnaphthalene and p-cymene, respectively, was developed using the NHPI-catalyzed aerobic oxidation as a principal reaction. 2,6-Diisopropylnaphthalene was oxidized by the oxidation with O₂ (1 atm) by NHPI (10 mol %) combined with Co(OAc)₂ (0.5 mol %) to give 6-acetyl-2-isopropylnaphthalene, which then was converted to 6-isopropyl-2-naphthoic acid under O₂ (1 atm) in the presence of Co(OAc)₂ (0.5 mol %) and Mn(OAc)₂ (0.5 mol %). Esterification of the resulting acid followed by the aerobic oxidation produced methyl 6-hydroxy-2-naphthoate whose hydrolysis led to the desired HNPA. An alternative route involves the oxidation of 6-acetyl-2-isopropylnaphthalene to 6-acetyl-2-naphthol on which subsequent oxidation and deacetylation gave HNPA. This method was successfully extended to the synthesis of 4-hydroxybenzoic acid from p-cymene.     

trans–cis Photoisomerization of Azobenzene‐Conjugated Dithiolato‐Bipyridine Platinum(II) Complexes: Extension of Photoresponse to Longer Wavelengths and Photocontrollable Tristability

Azobenzene derivatives modified with dithiolato‐bipyridine platinum(II) complexes were synthesized, revealing their highly extended photoresponses to the long wavelength region as well as unique photocontrollable tristability. The absorptions of trans‐ 1 and trans‐ 2 with one azobenzene group on the dithiolene and bipyridine ligands, respectively, cover the range from 300 to 700 nm. These absorptions are ascribed, by means of time‐dependent (TD)DFT calculations, to transitions from dithiolene(π) to bipyridine(π*), namely, interligand charge transfer (CT), π–π*, and n–π* transitions of the azobenzene unit, and π–π* transitions of the bipyridine ligand. In addition, only trans‐ 1 shows distinctive electronic bands, assignable to transitions from the dithiolene(π) to azobenzene(π*), defined as intraligand CT. Complex 1 shows photoisomerization behavior opposite to that of azobenzene: trans‐to‐cis and cis‐to‐trans conversions proceed with 405 and 312 nm irradiation, which correspond to excitation with the intraligand CT, and π–π* bands of the azobenzene and bipyridine units, respectively. In contrast, complex 2 shows photoisomerization similar to that of azobenzene: trans‐to‐cis and cis‐to‐trans transformations occur with 365 and 405 nm irradiation, respectively. Irradiation at 578 nm, corresponding to excitation of the interligand CT transitions, results in cis‐to‐trans conversion of both 1 and 2 , which is the longest wavelength ever reported to effect the photoisomerization of the azobenzene group. The absorption and photochromism of 4 , which has azobenzene groups on both the dithiolato and bipyridine ligands, have characteristics quite similar to those of 1 and 2 , which furnishes 4 with photocontrollable tristability in a single molecule using light at 365, 405, and 578 nm. We also clarified that 1 and 2 have high photoisomerization efficiencies, and good thermal stability of the cis forms. Complexes 3 and 5 have almost the identical photoresponse to those of their positional isomers, complexes 2 and 4 .     

Observation of intermolecular N–I interaction during the growth of a 4-cyano-4′-iodobiphenyl molecular crystal on GeS(001)

The electronic and atomic structures of 4-cyano-4′-iodobiphenyl (CIB) during the growth of a molecular crystal on a GeS(001) substrate were studied by ultraviolet photoemission spectroscopy (UPS), atomic force microscopy (AFM), and extended X-ray absorption fine structure (EXAFS) spectroscopy. AFM images suggest that the CIB molecule grows as a microcrystal at a nominal thickness of 80 Å. The microcrystal grows with the crystal plane parallel to the surface and isotropic crystal axis orientation. EXAFS analysis suggests that a CIB crystal forms by strong N···I interaction, called halogen bonding. The formation of the intermolecular N···I bond was demonstrated by EXAFS analyses in which the N–I distance was determined to be 3.29 Å. An upward shift of the highest occupied molecular orbital level was observed by UPS and can be attributed to the aggregation of CIB molecules caused by halogen bonding.     

Comparison of measured and calculated in-air secondary neutrons in passive carbon-ion radiotherapy

Undesired radiation exposure in normal tissues around a treatment volume in proton and carbon-ion radiotherapies is less than that in the conventional radiotherapies due to physical and/or biological properties of charged particles. Such exposure is always considered in a treatment planning, however, undesired exposure in normal tissues far from the treatment volume cannot be considered in the treatment planning, because it is caused by secondary radiation as well as leakage primary particles. Though this exposure is considerably lower than that near the treatment volume, it may be not negligible to estimate the risk of secondary cancer especially for the young patients. In particular, the assessment of the secondary neutrons that inevitably produced within the patient and beam line devices is very important due to the potency of their biological effect. The distributions of the absorbed dose and the biological effectiveness in phantom/patient are required to assess the risk, and Monte Carlo calculation plays a key role due to a difficulty of the measurements. In this study, comparison of measured and calculated in-air neutrons at the patient position in the Heavy Ion Medical Accelerator in Chiba (HIMAC) treatment room are performed to verify the accuracy of the Monte Carlo code, PHITS. Our calculations underestimated epithermal neutrons measured by Bonner sphere system. This discrepancy may be caused by an insufficiency of the calculational geometry modeling, consequently an underestimation of neutrons scattered and moderated by the beam line devices. However, it is unlikely that the underestimation significantly contribute to the dose estimation in phantom. On the other hand, the calculation reproduced the measured ambient dose equivalents well because they were dominated by neutrons above 0.1 MeV. This result showed that the PHITS code has a potential ability to evaluate the neutron exposure of the patient in passive carbon-ion radiotherapy.     

Cross-sectional morphological profiles of ripples on Si, SiC, and HOPG

The cross-sectional profiles of ripple structures on silicon (Si), silicon carbide (SiC), and highly oriented pyrolytic graphite (HOPG) were studied by direct observation. The ripple structures were cut by an ion beam, and their cross sections were observed by scanning electron microscopy. The results showed that the cross sections of coarse ripples on Si and SiC have a convex shape with narrower valleys, whereas those of HOPG have sharp ridges and wide wings with a poorer aspect ratio. This difference may arise from the difference in material phase conversion processes induced by femtosecond laser irradiation. The cross-sectional profiles of fine ripples on SiC and HOPG, which give useful information on the ripple formation process, are also discussed.     

Palladium‐Catalyzed C?H Fluorosilylation of 2‐Phenylpyridines: Synthesis of Silafluorene Equivalents

Treatment of 2‐phenylpyridines with amino(1,3,2‐dioxaborolan‐2‐yl)diphenylsilane produced fluorosilylated 2‐phenylpyridines in good to excellent yields under palladium catalysis. This reaction is the first example of C H fluorosilylation. Single‐crystal X‐ray structure analysis revealed a Lewis acid–base interaction between the silicon and nitrogen atoms, and the obtained fluorosilylated products are silafluorene equivalents. The fluorosilylated products showed stronger fluorescence than the corresponding silafluorene derivative.     

Strain imaging of a Cu2S switching device

Strain imaging of electrochemical behavior of a solid electrolyte Cu₂S in switching devices for nonvolatile memories is presented. The precipitation and dissolution of Cu, and the nonstoichiometry changes cause changes in volume. Strain imaging we have proposed detects the volume changes through the surface displacements using scanning probe microscopy and provides high resolution images. We observed the distributions of the electrochemical reactions in Cu₂S and located the Cu bridges causing switching.     

Hydroxamic Acid‐Piperidine Conjugate is an Activated Catalyst for Lysine Acetylation under Physiological Conditions

Lysine acylation of proteins is an essential chemical reaction for posttranslational modification and as a means of protein modification in various applications. N,N‐Dimethyl‐4‐aminopyridine (DMAP) derivatives are widely‐used catalysts for lysine acylation of proteins; however, the DMAP moiety mostly exists in a protonated, and thus deactivated, form under physiological conditions due to its basicity. An alternative catalytic motif furnishing higher acylation activity would further broaden the possible applications of chemical lysine acylation. We herein report that the hydroxamic acid‐piperidine conjugate Ph‐HXA is a more active catalytic motif for lysine acetylation than DMAP under physiological conditions. In contrast to DMAP, the hydroxamic acid moiety is mostly deprotonated under aqueous neutral pH, resulting in a higher concentration of the activated form. The Ph‐HXA catalyst is also more tolerant of deactivation by a high concentration of glutathione than DMAP. Therefore, Ph‐HXA might be a suitable catalytic motif for target protein‐selective and site‐selective acetylation in cells.     

Rhodium‐Catalyzed Highly Diastereo‐ and Enantioselective Synthesis of a Configurationally Stable S‐Shaped Double Helicene‐Like Molecule

An S‐shaped double helicene‐like molecule (>99 % ee), possessing stable helical chirality, has been synthesized by the rhodium(I)/difluorphos complex‐catalyzed highly diastereo‐ and enantioselective intramolecular double [2+2+2] cycloaddition of a 2‐naphthol‐ and benzene‐linked hexayne. The collision between two terminal naphthalene rings destabilizes the helical chirality of the S‐shaped double helicene‐like molecule, but the introduction of two additional fused benzene rings significantly increases the configurational stability. Thus, no epimerization and racemization were observed even at 100 °C. The enantiopure S‐shaped double helicene‐like molecule forms a trimer through the multiple C?H???π and C?H???O interactions in the solid‐state. The trimers stack to form columnar packing structures, in which neighboring stacks have opposite dipole directions. The accumulation of helical structures in the same direction in the S‐shaped double helicene‐like molecule enhanced the chiroptical properties.