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Faculty of Education Science education |
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ARII Hidekazu
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Research Areas 【 display / non-display 】
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Nanotechnology/Materials / Inorganic/coordination chemistry
Papers 【 display / non-display 】
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Dehydrogenative Annulation of Silylated 1H-Indoles with Alkynes via Silyl Migration Reviewed
Arii H., Nakane D., Nakao K., Masuda H., Kawashima T.
Organic Letters 25 ( 29 ) 5416 - 5420 2023.7
Authorship：Lead author Language：English Publishing type：Research paper (scientific journal) Publisher：Organic Letters
We investigated the dehydrogenative annulation of silylated 1H-indole derivatives with alkynes to synthesize a silole-fused indole. The addition of the in situ generated silylium ion to alkynes was followed by the sila-Friedel-Crafts reaction via silyl migration, realizing regioselective dehydrogenative annulation controlled by the steric bulkiness of a base. The optical properties of the obtained siloloindoles indicated fluorescence of which the intensity depends on the location of the fused silole.
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Synthesis of Blue Flavylium Ion and Its Adsorption to Inorganic Materials for Utilization as a Repeatable pH Indicator
Tomoko Tanaka, Chie Kuroki, Hidekazu Arii
98 102 - 111 2022.3
Authorship：Corresponding author Language：Japanese Publishing type：Research paper (scientific journal)
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Preparation of Flavylium Ion Adsorbed on Zeolite as a Repeatable pH Indicator Reviewed
Chie Kuroki, Hidekazu Arii
8 ( 2 ) No5-1 - No5-7 2022.3
Authorship：Corresponding author Language：Japanese Publishing type：Research paper (scientific journal)
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Arii H., Nakao K., Masuda H., Kawashima T.
ACS Omega 7 ( 6 ) 5166 - 5175 2022.2
Authorship：Lead author Language：Japanese Publishing type：Research paper (scientific journal) Publisher：ACS Omega
A strong Lewis acid silylium ion was utilized for dehydrogenative annulation between dialkyl(1-naphthyl)silanes 1 and aldehydes 2. Silane 1a was reacted with [Ph3C][B(C6F5)4] in the presence of 2,6-di-tert-butyl-4-methylpyridine and aldehydes 2 to afford the annulation product, 1-silabenzo[d,e]isochromanes 3, in moderate isolated yields. The annulation occurred only at the 8-position on the 1-naphthyl group. The silylium ion-promoted hydrosilylation proceeded competitively to afford silyl ethers 4 via the same intermediates, silylcarboxonium ions, in the dehydrogenative annulation. The ratio of 3 and 4 was affected by solvents and the electronic properties of aromatic aldehydes; for example, the use of less polar solvents and that of benzaldehydes with an electron-withdrawing group at the para-position predominantly yielded 3. This annulation reaction was applicable to aldehydes bearing a heteroaromatic group and aliphatic alkyl groups. Judging from these results, both the formation of silylcarboxonium ions by in situ-generated silylium ions and the electrophilic aromatic substitution are important for this annulation reaction.
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Ishii T., Criniti G., Bykova E., Dubrovinsky L., Katsura T., Arii H., Kojitani H., Akaogi M.
American Mineralogist 106 ( 7 ) 1105 - 1112 2021.7
Language：Japanese Publishing type：Research paper (scientific journal) Publisher：American Mineralogist
Three single crystals of CaTi2O4 (CT)-type, CaFe2O4 (CF)-type, and new low-density CaFe2O4 (LD-CF) related MgAl2O4 were synthesized at 27 GPa and 2500 °C and also CT-type MgAl2O4 at 45 GPa and 1727 °C using conventional and advanced multi-anvil technologies, respectively.The structures of CT-type and LD-CF related MgAl2O4 were analyzed by single-crystal X-ray diffraction. The lattice parameters of the CT-type phases synthesized at 27 and 45 GPa were a = 2.7903(4), b = 9.2132(10), and c = 9.3968(12) Å, and a = 2.7982(6), b = 9.2532(15), and c = 9.4461(16) Å, respectively, (Z = 4, space group: Cmcm) at ambient conditions. This phase has an AlO6 octahedral site and an MgO8 bicapped trigonal prism with two longer cation-oxygen bonds. The LD-CF related phase has a novel structure with orthorhombic symmetry (space group: Pnma), and lattice parameters of a = 9.207(2), b = 3.0118(6), and c = 9.739(2) Å (Z = 4). The structural framework comprises tunnel-shaped spaces constructed by edge- and corner-sharing of AlO6 and a 4+1 AlO5 trigonal bipyramid, in which MgO5 trigonal bipyramids are accommodated. The CF-type MgAl2O4 also has the same space group of Pnma but a slightly different atomic arrangement, with Mg and Al coordination numbers of 8 and 6, respectively. The LD-CF related phase has the lowest density of 3.50 g/cm3 among MgAl2O4 polymorphs, despite its high-pressure synthesis from the spinel-type phase (3.58 g/cm3), indicating that the LD-CF related phase formed via back-transformation from a high-pressure phase during the recovery. Combined with the previously determined phase relations, the phase transition between CF-and CT-type MgAl2O4 is expected to have a steep Clapeyron slope. Therefore, CT-type phase may be stable in basaltic- and continental-crust compositions at higher temperatures than the average mantle geotherm in the wide pressure range of the lower mantle. The LD-CF related phase could be found in shocked meteorites and used for estimating shock conditions.
DOI： 10.2138/am-2021-7619
MISC 【 display / non-display 】
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ジヒドロジシランから誘導される多核¬白金–ケイ素錯体の合成 Invited
有井 秀和, 持田 邦夫
ケイ素化学協会誌 25 28 - 31 2010.11
Language：Japanese Publishing type：Article, review, commentary, editorial, etc. (scientific journal)
Grant-in-Aid for Scientific Research 【 display / non-display 】
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イオンの大きさや電荷を可視化する実験手法ならびに教材の開発
Grant number：23K02792 2023.04 - 2026.03
科学研究費補助金 基盤研究(C)（一般）
有井秀和
Authorship：Principal investigator Grant type：Competitive
中学校の学習指導内容の「水溶液とイオン」において、イオンは原子が電子を放出する、あるいは原子が電子を受け取ることにより生じる化学種であり、電気泳動によりイオンが帯電していることを確認している。電気泳動ではイオンが電場の中で力を受けて移動しており、イオンの大きさあるいは価数に依存して移動距離が変化することが知られている。本研究では、従来まで定性的な実験として行われていた電気泳動に定量性を加えることを目的とし、一般的な金属イオンや錯塩を利用した電気泳動実験の確立を目指す。また発色団を持つ配位子の導入により、無色イオンの可視化も試みる。