5-N-Arylaminothiazoles as Highly Twisted Fluorescent Monocyclic Heterocycles: Synthesis and Characterization
- Kirara Yamaguchi ,
- Toshiaki Murai ,
- Saki Hasegawa ,
- Yohei Miwa ,
- Shoichi Kutsumizu ,
- Toshifumi Maruyama ,
- Takahiro Sasamori , and
- Norihiro Tokitoh
View Author Information
† Department of Chemistry and Biomolecular Science, Faculty of Engineering, Gifu University, Yanagido, Gifu 501-1193, Japan
‡ JST, ACT-C, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan
§ Institute for Chemical Research, Kyoto University, Uji 611-0011, Japan
*E-mail: [email protected]
Abstract
A series of 5-N-arylaminothiazoles was prepared by reacting thioamide dianions derived from secondary thioamides with thioformamides, followed by sequential oxidation with iodine. X-ray analyses demonstrated that they adopt structures that are highly twisted from planar conformations. Their orientations were tuned by the steric and/or electronic interactions of the substituents at their 2-, 4-, and 5-positions. The 5-aminothiazoles exhibited a range of fluorescent emissions, from blue to orange. Although the absorption spectra were independent of the polarity of the solvent, fluorescent emissions were influenced by the polarity of the solvent: in more polar solvents, the emissions were red-shifted. These phenomena were examined in terms of Lippert–Mataga plots and the change in the dipole moment between the ground and excited states. They also exhibited emissions in the solid state, again from blue to orange. Cyclic voltammetry of the 5-aminothiazoles showed reversible waves of one-electron oxidation. The half-potential of the oxidation was reduced by the introduction of electron-donating groups to the phenyl groups on the nitrogen atom at the 5-position. DFT calculations were carried out to determine the energy levels of the HOMO and LUMO. Finally, the results of TG-DTA showed that they are thermally stable.
Cited By
This article is cited by 30 publications.
- Nickolas A. Sayresmith, Anand Saminathan, Joshua K. Sailer, Shannon M. Patberg, Kristin Sandor, Yamuna Krishnan, Michael G. Walter. Photostable Voltage-Sensitive Dyes Based on Simple, Solvatofluorochromic, Asymmetric Thiazolothiazoles. Journal of the American Chemical Society 2019, 141 (47) , 18780-18790. https://doi.org/10.1021/jacs.9b08959
- Cristina Pérez-Caaveiro, María Moreno Oliva, Juan T. López Navarrete, José Pérez Sestelo, M. Montserrat Martínez, Luis A. Sarandeses. Synthesis of D–A–A and D–A–D Pyrimidine π-Systems Using Triorganoindium Reagents: Optical, Vibrational, and Electrochemical Studies. The Journal of Organic Chemistry 2019, 84 (14) , 8870-8885. https://doi.org/10.1021/acs.joc.9b00643
- Wei Tong, Wen-Hao Li, Yan He, Zu-Yu Mo, Hai-Tao Tang, Heng-Shan Wang, Ying-Ming Pan. Palladium-Metalated Porous Organic Polymers as Recyclable Catalysts for the Chemioselective Synthesis of Thiazoles from Thiobenzamides and Isonitriles. Organic Letters 2018, 20 (8) , 2494-2498. https://doi.org/10.1021/acs.orglett.8b00886
- Rakesh Radhakrishnan, K. G. Sreejalekshmi. Computational Design, Synthesis, and Structure Property Evaluation of 1,3-Thiazole-Based Color-Tunable Multi-heterocyclic Small Organic Fluorophores as Multifunctional Molecular Materials. The Journal of Organic Chemistry 2018, 83 (7) , 3453-3466. https://doi.org/10.1021/acs.joc.7b02978
- Toshiaki Murai, Kirara Yamaguchi, Teppei Hayano, Toshifumi Maruyama, Koji Kawai, Hayato Kawakami, and Akira Yashita . Synthesis and Photophysical Properties of 5-N-Arylamino-4-methylthiazoles Obtained from Direct C–H Arylations and Buchwald–Hartwig Aminations of 4-Methylthiazole. Organometallics 2017, 36 (14) , 2552-2558. https://doi.org/10.1021/acs.organomet.7b00128
- Kumar Godugu, Sultana Shaik, Mohammad Khaja Mohinuddin Pinjari, Trivikram Reddy Gundala, Dwaraka Viswanath Chellappa Subramanyam, Subramanyam Sarma Loka, Haranath Divi, Vemula Venkatramu, Chinna Gangi Reddy Nallagondu. Solid state thiazole-based fluorophores: Promising materials for white organic light emitting devices. Dyes and Pigments 2021, 187 , 109077. https://doi.org/10.1016/j.dyepig.2020.109077
- Alexander K. Eltyshev, Timur H. Dzhumaniyazov, Polina O. Suntsova, Artem S. Minin, Varvara A. Pozdina, Wim Dehaen, Enrico Benassi, Nataliya P. Belskaya. 3-Aryl-2-(thiazol-2-yl)acrylonitriles assembled with aryl/hetaryl rings: Design of the optical properties and application prospects. Dyes and Pigments 2021, 184 , 108836. https://doi.org/10.1016/j.dyepig.2020.108836
- Hao-Yuan Wang, Kang-Kang Yu, Chong-Yun Tan, Kun Li, Yan-Hong Liu, Lei Shi, Kai Lu, Xiao-Qi Yu. Three-in-one: information encryption, anti-counterfeiting and LD-tracking of multifunctional purine derivatives. Journal of Materials Chemistry C 2021, 49 https://doi.org/10.1039/D0TC05221C
- Rakesh Radhakrishnan, Bhavya Bini Sinu, Vishnu Anilkumar, K.G. Sreejalekshmi. Discovery of full color emissive thiazole fluorophores in solution and solid states: The core is central and regulating torsional barrier does the trick!. Dyes and Pigments 2020, 181 , 108560. https://doi.org/10.1016/j.dyepig.2020.108560
- Kumar Godugu, Thrivikram Reddy Gundala, Ramakrishna Bodapati, Venkata Divya Sri Yadala, Subramanyam Sarma Loka, Chinna Gangi Reddy Nallagondu. Synthesis, photophysical and electrochemical properties of donor–acceptor type hydrazinyl thiazolyl coumarins. New Journal of Chemistry 2020, 44 (17) , 7007-7016. https://doi.org/10.1039/D0NJ00082E
- Yuki Tsuchiya, Kirara Yamaguchi, Yohei Miwa, Shoichi Kutsumizu, Mao Minoura, Toshiaki Murai. N,N -Diarylthiazol-5-amines: Structure-Specific Mechanofluorochromism and White Light Emission in the Solid State. Bulletin of the Chemical Society of Japan 2020, https://doi.org/10.1246/bcsj.20200083
- Yong Li, Cao-Cao Sun, Cheng-Chu Zeng. Electrochemical synthesis of thiazoles from 2,5-dihydrothiazolines mediated by bromide/tetrachlorohydroquinone dual redox catalysts. Journal of Electroanalytical Chemistry 2020, 861 , 113941. https://doi.org/10.1016/j.jelechem.2020.113941
- Toshiaki Murai, Yuuta Nakatsu, Yuki Tsuchiya, Kirara Yamaguchi, Toshifumi Maruyama, Yohei Miwa, Shoichi Kutsumizu. 5-Amino-2-thiazolylpyridine N-Oxides: Synthesis and Properties. HETEROCYCLES 2020, 101 (2) , 611. https://doi.org/10.3987/COM-19-S(F)51
- Toshiaki Murai. Replacement of Elements, from Unexpected Encounter to Accidental Departure. Journal of Synthetic Organic Chemistry, Japan 2019, 77 (10) , 1030-1033. https://doi.org/10.5059/yukigoseikyokaishi.77.1030
- Fumitoshi Shibahara. Direct Functionalizations of Carbon-Hydrogen Bonds Catalyzed by Palladium/Bidentate Nitrogen-based Ligand Complexes. Journal of Synthetic Organic Chemistry, Japan 2019, 77 (8) , 776-790. https://doi.org/10.5059/yukigoseikyokaishi.77.776
- Toshiaki Murai, Mari Yoshihara, Kirara Yamaguchi, Mao Minoura. 2‐(2‐Hydroxyphenyl)‐5‐aminothiazoles: Synthesis and Properties Involving Dual Emissions. Asian Journal of Organic Chemistry 2019, 8 (7) , 1102-1106. https://doi.org/10.1002/ajoc.201900194
- Polina O. Suntsova, Alexander K. Eltyshev, Tatiana A. Pospelova, Pavel A. Slepukhin, Enrico Benassi, Nataliya P. Belskaya. Design and synthesis of disubstituted and trisubstituted thiazoles as multifunctional fluorophores with large Stokes shifts. Dyes and Pigments 2019, 166 , 60-71. https://doi.org/10.1016/j.dyepig.2019.02.051
- Nadine Weyer, Robin Guthardt, Bruno A. Correia Bicho, Jan Oetzel, Clemens Bruhn, Ulrich Siemeling. Stable N-Heterocyclic Germylenes of the Type [Fe{(η 5 -C 5 H 4 )N R } 2 Ge] and Their Oxidation Reactions with Sulfur, Selenium, and Diphenyl Diselenide. Zeitschrift für anorganische und allgemeine Chemie 2019, 645 (3) , 188-197. https://doi.org/10.1002/zaac.201800449
- Toshiaki Murai. Reaction of Thioamides. 2019,,, 75-101. https://doi.org/10.1007/978-981-13-7828-7_4
- . Chemistry of Thioamides. 2019,,https://doi.org/10.1007/978-981-13-7828-7
- Saravanakumar Manickam, Umamahesh Balijapalli, Kulathu Iyer Sathiyanarayanan. SnCl 2 -catalyzed synthesis of dihydro-5 H -benzo[ f ]pyrazolo[3,4- b ]quinoline and dihydroindeno[2,1- b ]pyrazolo[4,3- e ]pyridine with high fluorescence and their photophysical properties. New Journal of Chemistry 2018, 42 (2) , 860-871. https://doi.org/10.1039/C7NJ03654J
- Shin-ichiro Kato, Satoshi Jin, Terutaka Kimura, Naoki Yoshikawa, Daiki Nara, Kenji Imamura, Yoshihito Shiota, Kazunari Yoshizawa, Ryo Katoono, Takeshi Yamanobe, Hiroki Uehara, Yosuke Nakamura. . Organic & Biomolecular Chemistry 2018,,, 3584. https://doi.org/10.1039/C8OB00471D
- Toshiaki Murai, Hidenori Furukawa, Kirara Yamaguchi. Synthesis and Photophysical Properties of 5-N-Arylaminothiazoles with Sulfur-Containing Groups on the Aromatic Ring at the 2-Position. HETEROCYCLES 2018, 97 (1) , 409. https://doi.org/10.3987/COM-18-S(T)28
- Kseniya I. Lugovik, Aleksandra V. Popova, Alexander K. Eltyshev, Enrico Benassi, Nataliya P. Belskaya. Synthesis of Thiazoles Bearing Aryl Enamine/Aza-enamine Side Chains: Effect of the π-Conjugated Spacer Structure and Hydrogen Bonding on Photophysical Properties. European Journal of Organic Chemistry 2017, 2017 (28) , 4175-4187. https://doi.org/10.1002/ejoc.201700518
- Sònia Abás, Ulrike Moens, Carmen Escolano. Facile microwave-assisted synthesis of thioformamides from isocyanides and carbon disulfide. Tetrahedron Letters 2017, 58 (28) , 2768-2770. https://doi.org/10.1016/j.tetlet.2017.06.001
- Kirara Yamaguchi, Toshiaki Murai, Shoichi Kutsumizu, Yohei Miwa, Masahiro Ebihara, Jing-Dong Guo, Norihiro Tokitoh. Experimental and Theoretical Examination of the Radical Cations Obtained from the Chemical and Electrochemical Oxidation of 5-Aminothiazoles. ChemistryOpen 2017, 6 (2) , 282-287. https://doi.org/10.1002/open.201700016
- Kirara Yamaguchi, Toshiaki Murai, Yuki Tsuchiya, Yohei Miwa, Shoichi Kutsumizu, Takahiro Sasamori, Norihiro Tokitoh. Pyridinium 5-aminothiazoles: specific photophysical properties and vapochromism in halogenated solvents. RSC Advances 2017, 7 (29) , 18132-18135. https://doi.org/10.1039/C7RA01896G
- Kirara Yamaguchi, Toshiaki Murai, Jing-Dong Guo, Takahiro Sasamori, Norihiro Tokitoh. Acid-Responsive Absorption and Emission of 5- N -Arylaminothiazoles: Emission of White Light from a Single Fluorescent Dye and a Lewis Acid. ChemistryOpen 2016, 5 (5) , 434-438. https://doi.org/10.1002/open.201600059
- Łukasz G. Łukasiewicz, Irena Deperasińska, Yevgen M. Poronik, Yong Woong Jun, Marzena Banasiewicz, Bolesław Kozankiewicz, Kyo Han Ahn, Daniel T. Gryko. Dipolar Dyes with a Pyrrolo[2,3- b ]quinoxaline Skeleton Containing a Cyano Group and a Bridged Tertiary Amino Group: Synthesis, Solvatofluorochromism, and Bioimaging. Chemistry - An Asian Journal 2016, 11 (11) , 1718-1724. https://doi.org/10.1002/asia.201600257
- Rakesh Radhakrishnan, Kumaran G. Sreejalekshmi. Expanding the donor–acceptor toolbox with a minimal 5-(thiophen-2-yl)-1,3-thiazole core: transition metal-free synthesis and molecular design for HOMO–LUMO energy modulations. New Journal of Chemistry 2016, 40 (4) , 3036-3039. https://doi.org/10.1039/C6NJ00418K