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761.
Synthesis of 6-hydroxy-2-naphthoic acid from 2,6-diisopropylnaphthalene using NHPI as a key catalyst
Ryota Nakamura 《Tetrahedron》2009,65(18):3577-4102
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. 相似文献
762.
Ryota Sakamoto Dr. Shoko Kume Dr. Manabu Sugimoto Prof. Dr. Hiroshi Nishihara Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(6):1429-1439
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 . 相似文献
763.
Natalya Hessenauer‐Ilicheva Alicja Franke Dr. Maria Wolak Dr. Tsunehiko Higuchi Prof. Dr. Rudi van Eldik Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(45):12447-12459
Kinetic and mechanistic studies on the formation of an oxoiron(IV) porphyrin cation radical bearing a thiolate group as proximal ligand are reported. The SR complex, a functional enzyme mimic of P450, was oxidized in peroxo‐shunt reactions under different experimental conditions with variation of solvent, temperature, and identity and excess of oxidant in the presence of different organic substrates. Through the application of a low‐temperature rapid‐scan stopped‐flow technique, the reactive intermediates in the SR catalytic cycle, such as the initially formed SR acylperoxoiron(III) complex and the SR high‐valent iron(IV) porphyrin cation radical complex [( SR .+)FeIV?O], were successfully identified and kinetically characterized. The oxidation of the SR complex under catalytic conditions provided direct spectroscopic information on the reactivity of [( SR .+)FeIV?O] towards the oxidation of selected organic substrates. Because the catalytically active species is a synthetic oxoiron(IV) porphyrin cation radical bearing a thiolate proximal group, the effect of the strong electron donor ligand on the formation and reactivity/stability of the SR high‐valent iron species is addressed and discussed in the light of the reactivity pattern observed in substrate oxygenation reactions catalyzed by native P450 enzyme systems. 相似文献
764.
Takuro Tomita Ryota Kumai Shigeki Matsuo Shuichi Hashimoto Makoto Yamaguchi 《Applied Physics A: Materials Science & Processing》2009,97(2):271-276
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. 相似文献
765.
766.
Ryo Shomura Shuhei Higashibayashi Hidehiro Sakurai Yoshitaka Matsushita Akira Sato Masayoshi Higuchi 《Tetrahedron letters》2012,53(7):783-785
Enantiopure phenylazomethine cages ((S)- and (R)-PAC) were selectively obtained by one-pot dehydration of chiral (S)- and (R)-syn-tris(norborneno)benzene with p-phenylenediamine in moderate yields (56% and 50%), respectively. The structure and chirality of PACs in solution and solid state were confirmed by NMR, CD, X-ray diffraction and DFT calculations. 相似文献
767.
Keiji Takata Ryota Tamura Toshihiro Kasama Masataka Fukuyama Shin Yokoyama Hiroshi Kajiyama 《Current Applied Physics》2011,11(6):1364-1367
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. 相似文献
768.
769.
Suzuka Kinoshita Ryota Yamano Yu Shibata Yusuke Tanaka Kyoichi Hanada Takashi Matsumoto Kazunori Miyamoto Atsuya Muranaka Masanobu Uchiyama Ken Tanaka 《Angewandte Chemie (International ed. in English)》2020,59(27):11020-11027
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. 相似文献
770.
Munehiro Inukai Masanori Tamura Satoshi Horike Masakazu Higuchi Susumu Kitagawa Koichi Nakamura 《Angewandte Chemie (International ed. in English)》2018,57(28):8687-8690
Design to store gas molecules, such as CO2, H2, and CH4, under low pressure is one of the most important challenges in chemistry and materials science. Herein, we describe the storage of CO2 in the cavities of a porous coordination polymer (PCP) using molecular rotor dynamics. Owing to the narrow pore windows of PCP, CO2 was not adsorbed at 195 K. As the temperature increased, the rotors exhibited rotational modes; such rotations dynamically expanded the size of the windows, leading to CO2 adsorption. The rotational frequencies of the rotors (k≈10?6 s) and correlation times of adsorbed CO2 (τ≈10?8 s) were elucidated via solid‐state NMR studies, which suggest that the slow rotation of the rotors sterically restricts CO2 diffusion in the pores. This restriction results in an unusually slow CO2 mobility close to solid state (τ≥10?8 s). Once adsorbed at room temperature, CO2 is robustly stored in the PCP under vacuum at 195–233 K because of the steric hindrance of the rotors. We also demonstrate that this mechanism can be applied to the storage of CH4. 相似文献