Reduction of styrene compounds by hydrogen iodide

Shoji Matsumoto, Yusuke Fukaya, Motohiro Akazome, Tatsuo Kaiho

Synthetic Communications 1-9 2024年7月5日
Bathochromic Shift of Fluorescence Peak in Dipyrrolo[1,2-a:2′,1′-c]quinoxaline by Introducing Each of Electron-Donating and Electron-Withdrawing Substituent

Shoji Matsumoto, Makoto Takamori, Motohiro Akazome

Molecules 28(7) 2896-2896 2023年3月23日

Development of organic fluorophore is an important theme. Especially, the fluorophores with longer fluorescence peaks are useful to biological probes. One of the methods to change the fluorescence peak is the introduction of substituents. However, opposing characteristics of the substituents lead to different changes in the fluorescence peaks. Furthermore, the introduction of the substituent also affects their electric properties. Thus, if the materials were developed with the substituent effect on the optical and electric properties separately, it will be useful to design the functional materials related to both optical and electric properties. Herein, we investigated the substituent effect of dipyrrolo[1,2-a:2′,1′-c]quinoxalines on fluorescence properties. We synthesized the compounds bearing electron-donating or electron-withdrawing substituents at the benzene ring on dipyrrolo[1,2-a:2′,1′-c]quinoxaline, which would have more direct influence on the optical properties. By introducing each substituent at the 6 position of dipyrrolo[1,2-a:2′,1′-c]quinoxaline, the bathochromic shift was observed in the fluorescence spectra. In the case of fluorine substituent, the change of the fluorescence peak reached was about 19 nm. Using a TDDFT calculation, we explained the reason for such a substituent effect that large on the increment of LUMO energy or decrement of HOMO energy occurred by introducing electron-withdrawing or electron-donating substituents at the 6 position, respectively. The substituent effect on the change of orbital energies is typical although the different characteristics of substituents resulted in the similar tendency about the change of fluorescence peak. Furthermore, with the introduction of phenyl substituents at the 3 and 10 positions, we achieved 40–50 nm longer fluorescence peaks compared with that of the original dipyrrolo[1,2-a:2′,1′-c]quinoxaline.
Relationship between halogen-halogen interaction and electric conductivity in thiazolo[2,3-a]isoquinolin-7-ium triiodides

Shoji Matsumoto, Ryuta Sumida, Motohiro Akazome

Journal of Molecular Structure 1264 133306-133306 2022年9月
Chemoselective reduction of ¡,¢-unsaturated carbonyl and carboxylic compounds by hydrogen iodide

Shoji Matsumoto, Hayato Marumoto, Motohiro Akazome, Yasuhiko Otani, Tatsuo Kaiho

Bulletin of the Chemical Society of Japan 94(2) 590-599 2021年査読有り

The selective reduction of ¡,¢-unsaturated carbonyl compounds was achieved to produce saturated carbonyl compounds with aqueous HI solution. The introduction of an aryl group at an ¡ or ¢ position efficiently facilitated the reduction with good yield. The reaction was applicable to compounds bearing carboxylic acids and halogen atoms. Through the investigation of the reaction mechanism, it was found that Michael-type addition of iodide occurred to produce ¢-iodo compounds followed by the reduction of C-I bond via anionic and radical paths.
Change in the fluorescence of 1,1′-diaryl-2,2′-biimidazoles upon the addition of acid

Shoji Matsumoto, Seigi Tachibana, Motohiro Akazome

Heterocycles 100(10) 1666-1677 2020年査読有り

The optical properties of a series of 1,1′-diaryl-2,2′-biimidazoles were examined. Different transitions were observed in their fluorescence spectra upon changing the electronic properties of the phenyl ring at the C1 and C1′ positions. The presence of a formyl group on the phenyl ring results in fluorescence via a CT transition with a solvent effect. A bathochromic change was observed when HCl was added to a solution of compound bearing a methoxy group in CH2Cl2, whereas a hypsochromic change was observed in compound bearing a formyl group. These observations were attributed to the protonation, which causes a characteristic change in their biimidazole moieties.

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MISC

ヨウ化水素による共役エノンおよびα，β－不飽和カルボン酸誘導体の選択的オレフィン還元反応

丸本颯人, 赤染元浩, 大谷康彦, 海宝龍夫, 松本祥治

SIS Report（ヨウ素学会会報) (23) 2020年11月
環状チオアミジウム塩および環状イミダゾイソキノリニウム塩の求核試薬に対する反応性

綿貫祥汰, 高田大貴, 赤染元浩, 松本祥治

ヨウ素 (22) 2019年
Corrigendum to “Selective reaction of benzyl alcohols with HI gas: Iodination, reduction, and indane ring formations” (Tetrahedron (2017) 73(52) (7254–7259), (S0040402017311456) (10.1016/j.tet.2017.11.009))

Shoji Matsumoto, Masafumi Naito, Takehisa Oseki, Motohiro Akazome, Yasuhiko Otani

Tetrahedron 74(48) 6959-6960 2018年11月29日査読有り

© 2018 Elsevier Ltd The authors regret that, in the published article, they have represented the product from 2-(naphthalene-2-yl)propan-2-ol (1g) as 1,3,3-trimethyl-1-(naphthalen-2-yl)-2,3-dihydro-1H-cyclopenta[a]naphthalene (wrong 4m). But the product could be assigned as 1,1,3-trimethyl-3-(naphthalen-2-yl)-2,3-dihydro-1H-cyclopenta[b]naphthalene (right 4m) using 500 MHz NMR on a JEOL JNM-ECA500 spectrometer because the three singlet peaks were found at 7.83 ppm and at 7.85 ppm (as two singlet peaks) in the spectrum. Thus, they wish to correct the structure of wrong 4m into right 4m in the manuscript. The reason for the selective formation of right 4m would be caused by the less steric hinderance at 3 position of naphthalene. The reference of proton data also agreed with the structure (right 4m).1 The data of the melting point (116–117 °C) was near to the data for wrong 4m (122–124 °C2) compared with the data for right 4m (colorless viscous liquid)1. [Figure presented] Corrected data 1,1,3-trimethyl-3-(naphthalen-2-yl)-2,3-dihydro-1H-cyclopenta[b]naphthalene (4m) Colorless solid: mp 116–117 °C; 1H NMR (CDCl3, 500 MHz) δ 1.40 (s, 3H), 1.45 (s, 3H), 2.08 (s, 3H), 2.36 (d, J = 13.5 Hz, 1H), 2.47 (d, J = 13.5 Hz, 1H), 7.10 (dt, J = 1.2 and 7.2 Hz, 1H), 7.21 (dd, J = 1.9 and 8.7 Hz, 1H), 7.29 (dt, J = 0.9 and 7.0 Hz, 1H), 7.37 (d, J = 8.5 Hz, 1H), 7.41 (d, J = 8.4 Hz, 1H), 7.42 (dt, J = 1.6 Hz and 8.2 Hz, 1H), 7.46 (dt, J = 1.4 and 6.9 Hz, 1H), 7.65 (d, J = 8.6 Hz, 1H), 7.76 (d, J = 7.9 Hz, 1H), 7.80 (d, J = 8.0 Hz, 1H), 7.83 (s, 1H), 7.85 (s, 2H). Original data Colorless solid: mp 116–117 °C; 1H NMR (CDCl3, 300 MHz) δ 1.40 (s, 3H), 1.45 (s, 3H), 2.08 (s, 3H), 2.36 (d, J = 13.5 Hz, 1H), 2.47 (d, J = 13.5 Hz, 1H), 7.09 (t, J = 7.0 Hz, 1H), 7.21 (dd, J = 1.9 and 8.6 Hz, 1H), 7.29 (t, J = 7.0 Hz, 1H), 7.35–7.48 (m, 4H), 7.65 (d, J = 8.7 Hz, 1H), 7.75–7.85 (m, 5H). [Figure presented] The authors would like to apologise for any inconvenience caused.
Development of novel primer material suitable for COP film and Ag nano-ink

Taiki Yamate, Eiko Mieda, Kazuhisa Kumazawa, Hiroshi Suzuki, Motohiro Akazome

Proceedings of the International Display Workshops 1 313-316 2015年査読有り

© 2015 Society for Information Display. We have developed a unique organic-inorganic hybrid coating agent suitable for a primer which connects Ag nano-ink to COP film. This material forms the glass-like surface on the topmost surface of the hybrid layer after UV irradiation. Therefore, Ag nano-ink can adhere strongly with glass-like surface.
Development of novel primer material suitable for COP film and Ag nano-ink

Taiki Yamate, Eiko Mieda, Kazuhisa Kumazawa, Hiroshi Suzuki, Motohiro Akazome

Proceedings of the International Display Workshops 3 1781-1784 2015年査読有り

© 2015 Proceedings of the International Display Workshops. All rights reserved. We have developed a unique organic-inorganic hybrid coating agent suitable for a primer which connects Ag nano-ink to COP film. This material forms the glass-like surface on the topmost surface of the hybrid layer after UV irradiation. Therefore, Ag nano-ink can adhere strongly with glass-like surface.