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Affiliation Department |
生命・応用化学科 生命・物質化学分野
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Title |
Associate Professor |
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Contact information |
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Homepage |
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External Link |
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HIRASHITA Tsunehisa
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Degree
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Master (Engineering) ( Nagoya Institute of Technology )
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Doctor (Engineering) ( Nagoya Institute of Technology )
Research Areas
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Nanotechnology/Materials / Structural organic chemistry and physical organic chemistry
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Nanotechnology/Materials / Synthetic organic chemistry
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Life Science / Bioorganic chemistry
From Graduate School
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Nagoya Institute of Technology Graduate School, Division of Engineering Doctor's Course Completed
- 1999.03
Country：Japan
External Career
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Delft University of Technology Biocatalysis and Organic Chemistry Department of Biotechnology Researcher
2005.02 - 2006.02
Country：Netherlands
Professional Memberships
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東海化学工業会
2009.03
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日本油化学会
2003.02
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有機合成化学協会
1995.02
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日本化学会
1994.08
Research Career
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環境調和型有機合成反応の開発
(not selected)
Project Year： 2005.04
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Organic Synthesis by Using Organometallic Compounds
(not selected)
Project Year： 2002.04
Papers
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Practical Method for the Synthesis of Mesoionic 1,3-Diaryltetrazolium Derivatives Bearing a para-substituted Phenyl Group at the 1- or 3-Position from Anilines Reviewed International journal
Yuta Matsukawa; Tsunehisa Hirashita
Synlett 2024.03
Authorship：Last author Language：English Publishing type：Research paper (scientific journal) Publisher：Georg Thieme Verlag KG
A simple, economical, and safe method for the synthesis of mesoionic 1,3-diaryltetrazolium derivatives bearing a para-substituted phenyl group at the 1- or 3-position via thiosemicarbazides was established. Such compounds were directly obtained from the corresponding para-substituted anilines instead of aryl isothiocyanates and arylhydrazines. The newly synthesized mesoionic compounds were successfully converted into the corresponding nitrosotetrazolium salts, which were utilized as catalysts for oxidation of an aliphatic alcohol and analyzed by cyclic voltammetry to determine the correlation between the catalytic efficiencies and redox potentials. The proposed method can be widely applied and is valuable for investigating the substituent effects in mesoionic and related compounds.
DOI： 10.1055/a-2283-5749
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Synthesis, Structural Characterization, and Reactions of an Adduct Formed between Mesoionic 1,3-diphenyltetrazolium-5-thiolate and Diiodine Reviewed
Yuta Matsukawa, Mirai Nakata,Tsunehisa Hirashita, and Shuki Araki
Tetrahedron Letters 138 154960 2024.02
Authorship：Corresponding author Language：English Publishing type：Research paper (scientific journal)
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Synthesis of stable class 5 mesoionic benzo[c]tetrazolo[2,3-a]cinnolinium thiolate, dicyanomethylide, and amides Reviewed
Mirai Nakata; Tsunehisa Hirashita; Yoshikazu Konishi; Shuki Araki
Organic & Biomolecular Chemistry 2023.04
Authorship：Corresponding author Language：English Publishing type：Research paper (scientific journal)
DOI： 10.1039/D3OB00362K
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Palladium-Catalyzed Selective o-Bromination of Mesoionic 1,3-Diphenyltetrazolium-5-olate: Switching the Directing Group from Nitrogen to Oxygen Reviewed International journal
Tsunehisa Hirashita, Harue Watanabe, Yuki Harada, Hideaki Kurabayashi, Yukinobu, Yamashita, Shiyogo Oizumi, Shuki Araki
ChemistrySelect 6 13414 - 13418 2021.12
Authorship：Lead author Language：English Publishing type：Research paper (scientific journal)
Pd-catalyzed bromination of mesoionic 1,3-diphenyltetrazolium-5-olate (1) was developed. In the presence of palladium acetate (5 mol%), N-bromosuccinimide (110 mol%), and p-toluenesulfonic acid (50 mol%) in 1,2-dichloroethane under reflux, olate 1 underwent bromination to give 1-(2-bromophenyl)-3-phenyltetrazolium-5-olate in a moderate yield as the major product, indicating that the 4-nitrogen atom acts as a directing group rather than the negatively charged oxygen atom. The X-ray-suitable crystals of the corresponding palladacycle were isolated from 1-mesityl-3-phentytetrazolium-5-olate and fully characterized. When both the o-positions of the 3-phenyl group were occupied by bromine atoms, o-bromination then occurred at the 1-phenyl group with the aid of the olate oxygen.
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Preparative Synthesis of 1,3-Dialkyltetrazolium-5-thiolates from 1-Alkyltetrazole-5-thiols Reviewed International journal
Hirashita, Tsunehisa; Murakami, Suguru ; Shoji, Takuo; Kurabayashi, Hideaki ; Araki, Shuki
Bulletin of the Chemical Society of Japan 2021.11
Language：English Publishing type：Research paper (scientific journal)
Mesoionic 1,3-dialkyltetrazolium-5-thiolates can be prepared in good yields by alkylation of 1-alkyltetrazole-5-thiols with secondary alcohols in concentrated sulfuric acid. The thiolates are transformed into the corresponding olates through S-alkylation followed by hydrolysis. The olates were found to be liquid at room temperature and to work effectively as polar solvents. The use of a smaller amount of sulfuric acid led to drastically different products; S-bridged dimers linked by 1,2-dimethylethylene were formed as the major products.
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The Mizoroki-Heck Reaction in Mesoionic 1-Butyl-3-methyltetrazolium-5-olate Reviewed International journal
Hideaki Kurabayashi, Tsunehisa Hirashita, Shuki Araki
Tetrahedron 99 132450 2021.10
Language：English Publishing type：Research paper (scientific journal)
1-Butyl-3-methyltetrazolium-5-olate (1), a mesoionic compound, exists as a liquid at room temperature and can be used as a polar solvent for the Mizoroki-Heck reaction, wherein it has been proven to be a superior solvent to other solvents. The reaction of iodobenzene with ethyl acrylate in the presence of palladium acetate in mesoionic liquid 1 at 40 C for 24 h gave ethyl cinnamate in 78% yield in the absence of ligands, while the use of other solvents, such as [bmim][BF4], [bmim][PF6], and DMF gave lower yields (43%, 37%, and 17%, respectively) under the same conditions. Heck-type coupling reactions of electron-deficient or electron-rich aryl iodides and bromobenzenes with olefins (15 examples, 7%–97%) were performed in 1. When a phosphine ligand was added to the reaction mixture, aryl bromides could be used, and the mesoionic liquid containing the catalysts could be reused at least five times.
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Reactions between 5-Nitroso-1,3-diphenyltetrazolium Salts and Electron-rich Arenes, Reviewed International journal
Matsukawa, Yuta; Hirashita, Tsunehisa; Araki, Shuki
Bulletin of the Chemical Society of Japan 92 540 - 544 2019.01
Language：English Publishing type：Research paper (scientific journal)
A series of reactions between 5-nitroso-1,3-diphenyltetrazolium tetrafluoroborate and methoxybenzenes, amines, thiols, sulfoxides, and sulfides, most of which are generally accepted asbeing inert to nitroso groups, is reported here. The tetrazoliumactivated nitroso functionality is capable of oxidizing the aforementioned substrates to give the corresponding oxidized products, and the nitroso tetrazolium itself is transformed into the corresponding amide or hydroxyamide, depending on the nature of the reaction partners. In the case of thioanisole, an addition product was obtained.
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Copper(I)- and Mesoionic-Hydroxyamide-Catalyzed Chemoselective Aerobic Oxidation of Primary Benzylic Alcohols Reviewed International journal
Matsukawa, Yuta; Hirashita, Tsunehisa
Synlett 30 315 - 318 2019.01
Language：English Publishing type：Research paper (scientific journal)
A new aerobic oxidation system consisting of Cu(I)I, 2,2'-bipyridine, N-methyl imidazole, and a mesoionic hydroxyamide was developed, with which selective oxidation of a broad range of benzylic alcohols was achieved.
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Tsunehisa Hirashita, Yuto Sugihara, Shota Ishikawa, Yohei Naito, Yuta Matsukawa,Shuki Araki
Synlett 29 2404 - 2407 2018.10
Authorship：Lead author Language：English Publishing type：Research paper (scientific journal)
Sodium hypochlorite pentahydrate (NaOCl·5H2O) is capable of oxidizing alcohols in acetonitrile at 20 °C without the use of catalysts. The oxidation is selective to allylic, benzylic, and secondary alcohols. Aliphatic primary alcohols are not oxidized.
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Indium-Mediated Allylation of Carbonyl Compounds in Ionic Liquids: Effect of Salts in Ionic Liquids Invited Reviewed International journal
Tsunehisa Hirashita, Fusako Takahashi, Takayuki Noda, Yuji Takagi, Shuki Araki
Molecules 2018.07
Authorship：Lead author Language：English Publishing type：Research paper (scientific journal)
The In-mediated allylation of carbonyl compounds can be performed in various types of solvents including ionic liquids. However, we have found that in [bmim][BF4] (where bmim = 1-butyl-3-methylimidazolium), the In-mediated coupling of crotyl bromide with benzaldehyde gives a complex mixture, and some additives, such as halides and amines, are crucial for the successful conversion to the corresponding γ-adduct. Instead, the addition of alcohols or water promotes the formation of the α-adduct. An asymmetric induction with up to 62% enantiomeric excess (ee) was observed employing cinchonidine as an additive in a binary solvent consisting of an ionic liquid and dichloromethane.
Books and Other Publications
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Indium compounds.（共著）
Shuki Araki, Tsunehisa Hirashita（ Role： Joint author）
Thieme Chemistry 2011.03
Language：eng Book type：Scholarly book
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Indium(III) Iodide.（共著）
Tsunehisa Hirashita, Shuki Araki（ Role： Joint author）
John Wiley & Sons 2011.03
Language：eng Book type：Dictionary, encyclopedia
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Indium and Gallium in “Comprehensive Organometallic Chemistry III”.（共著）
Shuki Araki, Tsunehisa Hirashita（ Role： Joint author）
Elsevier 2006.12
Language：eng Book type：Scholarly book
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Methyl lithium.（共著）
Shuki Araki, Tsunehisa Hirashita（ Role： Joint author）
John Wiley & Sons 2006.04
Language：eng Book type：Dictionary, encyclopedia
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In in Organic Synthesis in “Main Group Metals in Organic Synthesis” .（共著）
Araki, S. and Hirashita, T.（ Role： Joint author）
Wiley-VCH 2004.05 （ ISBN:9780080456476 ）
Language：eng Book type：Scholarly book
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Indium(I) Iodide （共著）
Shuki Araki, Tsunehisa Hirashita（ Role： Joint author）
John Wiley & Sons 2002.10
Language：eng Book type：Dictionary, encyclopedia
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Indium Trichloride.（共著）
Araki, S. and Hirashita, T.（ Role： Joint author）
John Wiley & Sons 2002.10
Language：eng Book type：Dictionary, encyclopedia
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Porous Titania Ceramics Prepared by Mimicking Silicified Woods in "Ceramic Processing Science VI".（共著）
Hirashita, T.; Miyazaki, H.; Takase, H.; Kinoshita , N.; Ota, T.（ Role： Joint author）
American Ceramic Society 2001.09 （ ISBN:978-1574981049 ）
Language：eng Book type：Scholarly book
Misc
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第30回東海地区高等学校化学研究発表交流会
平下恒久
75 ( 2 ) 124 - 124 2022.02
Authorship：Lead author, Corresponding author Language：Japanese Publishing type：Meeting report
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第30回東海地区高等学校化学研究発表交流会
平下恒久
70 ( 1 ) 48 - 48 2022.01
Authorship：Lead author, Corresponding author Language：Japanese Publishing type：Meeting report
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Concentrated Bleach Crystals
74 ( 12 ) 921 - 921 2021.11
Authorship：Lead author, Corresponding author Language：Japanese Publishing type：Article, review, commentary, editorial, etc. (scientific journal)
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メソイオン液体の設計と特性
平下恒久、荒木修喜
４０ ６ - １１ 2011.10
Authorship：Lead author Language：Japanese Publishing type：Article, review, commentary, editorial, etc. (trade magazine, newspaper, online media) Publisher：シーエムシー出版
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"jointly worked
53 939 - 943 2008.12
Authorship：Lead author Language：Japanese Publishing type：Article, review, commentary, editorial, etc. (trade magazine, newspaper, online media)
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環境調和型アルコールの酸化反応：酸化触媒ＴＥＭＰＯ
平下恒久
６ ４０９ - ４１５ 2006.06
Authorship：Lead author Language：Japanese Publishing type：Article, review, commentary, editorial, etc. (scientific journal) Publisher：日本油化学会
Presentations
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アリルインジウム反応剤によるアゾ化合物への付加反応
舟木 大翔,平下 恒久
日本化学会 第105春季年会(2025) 2025.03
Event date： 2025.03
Language：Japanese
Venue：関西大学 千里山キャンパス Country：Japan
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ヒドロキシ基を有する結晶溶媒と水素結合を形成したClass 5メソイオン性ベンゾ[c]テトラゾロ [2,3-a]シンノリニウム-2-オレートの芳香族性
中田 未来 平下 恒久
第55回中部化学関係学協会支部連合秋季大会 2024.11 中部化学関係学協会支部連合協議会
Event date： 2024.11
Language：Japanese Presentation type：Poster presentation
Venue：名古屋工業大学
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キレート剤により有機溶媒に可溶化させた次亜塩素酸ナトリウム五水和物を用いた酸化反応
手代木 怜美 平下 恒久
第55回中部化学関係学協会支部連合秋季大会 2024.11 中部化学関係学協会支部連合協議会
Event date： 2024.11
Language：Japanese Presentation type：Poster presentation
Venue：名古屋工業大学
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2-クロロ-ベンゾ[c]テトラゾロ[2,3-a]シンノリウム塩を⽤いた脱⽔縮合反応の検討
澤⽥ 永遠 平下 恒久
第55回中部化学関係学協会支部連合秋季大会 2024.11 中部化学関係学協会支部連合協議会
Event date： 2024.11
Language：Japanese Presentation type：Oral presentation (general)
Venue：名古屋工業大学
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水熱条件下におけるサリチルアルコール誘導体の分子内イプソ位置換反応による大環状エーテルの合 成
三村英里 中村亜純 平下恒久
第53回複素環化学討論会 2024.10 第53回複素環化学討論会実行委員会
Event date： 2024.10
Language：English Presentation type：Poster presentation
Venue：山口市
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亜臨界水中におけるiso-Pictet-Spengler反応
水野愛星 平下恒久
第53回複素環化学討論会 2024.10 第53回複素環化学討論会実行委員会
Event date： 2024.10
Language：English Presentation type：Poster presentation
Venue：山口市
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2-クロロ-ベンゾ[c]テトラゾロ[2,3-a]シンノリニウム塩のアミノ化反応
神谷 恵理，平下 恒久
日本化学会第104春季年会 2024.03 日本化学会
Event date： 2024.03
Language：Japanese Presentation type：Oral presentation (general)
Venue：日本大学理工学部 船橋キャンパス
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イオン液体とにせイオン液体 Invited
平下恒久
第54回中部化学関係学協会支部連合 秋季大会 2023.11
Event date： 2023.11
Language：Japanese Presentation type：Oral presentation (invited, special)
Venue：三重大学
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クラウンエーテルにより有機溶媒に可溶化させた次亜塩素酸ナトリウム五水和物を用いた酸化反応
手代木 怜美
第54回 中部化学関係学協会支部連合秋季大会 2023.11 中部化学関係学協会支部連合協議会
Event date： 2023.11
Language：Japanese Presentation type：Oral presentation (general)
Venue：三重大学工学部（三重県津市栗真町屋町1577）
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Mesoionic 1,3-Diphenyltetrazolium-5-thiolate as a Neutral Leaving Group in Allylic Substitution Reactions with Grignard Reagents
2023.09
Event date： 2023.09
Language：English Presentation type：Poster presentation
Industrial Property Rights
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マグネシウム電池用電解液、及び当該電解液を含むマグネシウム電池
平下恒久; 中本博文
Applicant：名古屋工業大学; トヨタ自動車
Application no：2013-039407 Date applied：2013.02
Country of applicant：Domestic Country of acquisition：Domestic
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電池用電解液, 及び当該電解液を備える電池
平下恒久・荒木修喜・鏡味克之・中本博文・汐月大志
Application no：PCT/JP2012/071717 Date applied：2012.08
Country of applicant：Domestic Country of acquisition：Domestic
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メソイオン化合物,当該メソイオン化合物を含む電池用電解液,及び当該 電解液を備える電池
平下恒久・荒木修喜・鏡味克之・中本博文・汐月大志
Application no：2011-18793 Date applied：2012.03
Country of applicant：Domestic Country of acquisition：Domestic
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リチウム二次電池用電解液，及び当該電解液を備えるリチウム二次電池
平下恒久・中本博文・汐月大志
Application no：PCT /IB2011/002536 Date applied：2011.10
Country of applicant：Domestic Country of acquisition：Domestic
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テトラゾリウムメソイオン構造を有する蒸留可能な室温イオン性液体
平下恒久・荒木修喜・各務友紀
Application no：2006-305434 Date applied：2006.11
Country of applicant：Domestic Country of acquisition：Domestic
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Liquid electrolyte for lithium batteries, method for producing the same, and lithium battery comprising the liquid electrolyte for lithium batteries
Tsunehisa Hirashita, Shuki Araki, Hirofumi Nakamoto, Atsushi Shirasawa
Patent/Registration no：US 9620817 B2 Date registered：2017.04 Date issued：2017.04
Country of applicant：Foreign country Country of acquisition：Foreign country
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Liquid electrolyte for batteries, method for producing the same, and battery comprising the same
Tsunehisa Hirashita, Shuki Araki, Katsuyuki Kagami, Hirofumi Nakamoto, Taishi Shiotsuki
Patent/Registration no：US 9722288 B2 Date registered：2017.08 Date issued：2017.08
Country of applicant：Foreign country Country of acquisition：Foreign country
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Battery electrolyte and method for producing same, and battery comprising electrolyte
Tsunehisa Hirashita, Shuki Araki, Katsuyuki KAGAMI, Hirofumi Nakamoto, Taishi Shiotsuki
Patent/Registration no：EP 2752933 B1 Date registered：2016.08 Date issued：2016.08
Country of applicant：Foreign country Country of acquisition：Foreign country
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用于镁电池的电解质溶液和包含该电解质溶液的镁电池
平下恒久；中本博文
Patent/Registration no：第ZL201410067164.6 Date registered：2016.08 Date issued：2016.08
Country of applicant：Foreign country Country of acquisition：Foreign country
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电池用电解液及其制造方法、以及具备该电解液的电池
平下恒久，荒木修喜，中本博文，白洋淳
Patent/Registration no：第ZL201280041985.1 Date registered：2016.08 Date issued：2016.08
Country of applicant：Foreign country Country of acquisition：Foreign country
Awards
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有機合成化学協会東海支部奨励賞
2010.10 有機合成化学協会東海支部
平下恒久
Award type：Award from Japanese society, conference, symposium, etc. Country：Japan
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東海化学工業会賞
2009.05 東海化学工業会
有機合成反応のための新規反応剤ならびに反応場の構築における研究
Award type：Award from Japanese society, conference, symposium, etc. Country：Japan
Scientific Research Funds Acquisition Results
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メソイオン性アゾジカチオン種を基盤とした有機触媒の開発
Grant number：50345948 2023.04 - 2026.03
基盤研究(C) 基盤研究(C)
平下 恒久
Authorship：Principal investigator
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リチウム電池を支えるメソイオン液体の開発
2012.04 - 2015.03
科学研究費補助金 基盤研究(C)
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メソイオン液体の開発と合成
2008.04 - 2010.03
科学研究費補助金 若手研究(B)
Other External Funds
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亜臨界水中の精密有機合成反応
2012.04 - 2013.03
民間財団等 谷川熱技術振興基金
Grant type：Competitive
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循環型金属ゼロ触媒によるアルコールの空気酸化
2011.04 - 2012.03
経済産業省 科学技術振興調整費
Grant type：Competitive
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メソイオン液体のトライボロジー
2011.04 - 2012.03
民間財団等 JKA助成
Grant type：Competitive
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フルオラスメソイオン液体の開発とバッテリー電解液への応用
2010.04 - 2011.03
経済産業省 科学技術振興調整費
Grant type：Competitive
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バッテリー電解液のための高機能性メソイオン液体の開発
2009.04 - 2010.03
民間財団等 東海産業技術振興財団研究助成
Grant type：Competitive
Committee Memberships
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第55回中部化学関係学協会支部連合秋季大会実行委員会 第55回中部化学関係学協会支部連合秋季大会実行委員
2024.04 - 2024.12
Committee type：Academic society
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日本化学会 東海支部化学教育協議会 庶務幹事
2021.04 - 2025.03
Committee type：Academic society
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日本油化学会 編集委員
2020 - 2022
Committee type：Academic society
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日本化学会 化学グランプリ東海支部実行委員長
2019.01 - 2019.12
Committee type：Academic society
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東海化学工業会 庶務幹事
2016.05 - 2017.05
Committee type：Academic society
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日本油化学会 東海支部常任幹事
2016.03
Committee type：Academic society
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日本化学会 化学グランプリ東海支部実行委員長
2016.01 - 2016.12
Committee type：Academic society
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東海化学工業会 常任幹事
2015.04
Committee type：Academic society
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日本化学会 東海支部化学教育協議会委員
2015.04
Committee type：Academic society
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日本化学会 代表正会員
2015.03 - 2022.02
Committee type：Academic society
Social Activities
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愛知県特異火災等アドバイザー
Role(s)： Informant
2024.05
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東海支部 総合講演会
Role(s)： Presenter, Planner
有機合成化学協会東海支部 web 2020.12
Audience： Graduate students, Teachers, Researchesrs
Type：Lecture
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東海支部 油化学セミナー
Role(s)： Presenter, Planner, Report writing
日本油化学会 東海支部 2019.06
Audience： College students, Graduate students, Researchesrs, Scientific, Company
Type：Lecture