Convenient Synthesis of Benzo[b]thiophene-5,6-dicarboximide Derivatives and Their Photophysical Properties
Modern Chemistry
Volume 4, Issue 5, October 2016, Pages: 45-51
Received: Oct. 5, 2016; Accepted: Oct. 18, 2016; Published: Nov. 10, 2016
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Naoki Kobayashi, Department of Chemistry, Faculty of Science, Shinshu University, Nagano, Japan
Shinya Yamamoto, Department of Chemistry, Faculty of Science, Shinshu University, Nagano, Japan
Haruki Shimosasa, Department of Chemistry, Faculty of Science, Shinshu University, Nagano, Japan
Mitsunori Oda, Department of Chemistry, Faculty of Science, Shinshu University, Nagano, Japan
Ryuta Miyatake, Centre for Environmental Conservation and Research Safety, University of Toyama, Toyama, Japan
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Phosphine-assisted annulation of thiophene-2,3-dicarbaldehyde with N-substituted maleimides provided the N-substituted benzo[b]thiophene-5,6-dicarboximides in good to high yields. Introduction of cyano and aryl groups to the thiophene moiety of the N-cyclohexyl product was achieved by metal-catalyzed coupling reactions via its bromo derivative. Photophysical properties of the products were also reported.
Annulation, Phosphine, Copper-Mediated Cyanation, Mizoroki-Heck Reaction, Emission
To cite this article
Naoki Kobayashi, Shinya Yamamoto, Haruki Shimosasa, Mitsunori Oda, Ryuta Miyatake, Convenient Synthesis of Benzo[b]thiophene-5,6-dicarboximide Derivatives and Their Photophysical Properties, Modern Chemistry. Vol. 4, No. 5, 2016, pp. 45-51. doi: 10.11648/
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This article is an open access article distributed under the Creative Commons Attribution License ( which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
P. Nandhikonda and M. D. Heagy, “Dual fluorescent N-aryl-2,3-naphthalimides: applications in ratiometric DNA detection and white organic light-emitting devices”, Org. Lett. 2010, 12, 4796–4799.
X. Zhan, A. Facchetti, S. Barlow, T. J. Marks, M. A. Ratner, M. R. Wasielewski, and S. R. Marde, “Rylene and diimides for organic electronics”, Adv. Mater. 2011, 23, 268–284.
P. Nandhikonda and M. D. Heagy, “An abiotic fluorescent probe for cardiac troponin l”, J. Am. Chem. Soc., 2011, 133, 14972–14974.
K. Hutt, R. Hernadez, and M. D. Heagy, “Toward intrinsically fluorescent proteomimetics: Fluorescent probe response to alpha helix structure of poly--benzyl-L-glutamate”, Tetrahedron Lett. 2006, 16, 5436–5438.
N. Sakai, J. Mareda, E. Vauthey, and S. Matile, “Core-substituted naphthalenediimides”, Chem. Commun. 2010, 46, 4225-4237.
Y. Zhou, L. Ding, K. Shi, Y.-Z. Dai, N. Ai, J. Wang, and J. Pei, “A non-fullerene small bulk heterojunction solar cells”, Adv. Mater. 2012, 24, 957–961.
T. V. Pho, F. M. Toma, M. L. Chabinyc, and F. Wudl, “Self-assembling decacyclene triimides prepared through a regioselective hextuple Freidel-Crafts carbamylation”, Angew. Chem. Int. Ed. 2013, 52, 1446–1451.
Y. Zhong, B. Kumar, S. Oh, M. T. Trinh, Y. Wu, K. Elbert, P. Li, X. Zhu, S. Xiao, F. Ng, M. L. Steigerwald, and C. Nuckolls, “Helical ribbons for molecular electronics”, J. Am. Chem. Soc. 2014, 136, 8122–8130.
M. Oda, H. Shimosasa, Y. Kumai, A. Ohta, and R. Miyatake, “An improved synthesis of arenedicarboximides by phosphine-assisted annulation of arene-1,2-dicarbaldehyde with N-substituted maleimide”, Modern Chem. 2014, 2 (4), 29–35.
H. Shimosasa, R. Miyatake, N. Kobayashi, and M. Oda “Synthesis and emission behavior of 1,3-diarylisobenzofuran- 5,6-dicarboximides and their transformation into naphthalene-2,3:6,7-bis(diacboximide)s”, Modern Chem. 2016, 4 (6), 16–23.
T. Yanagisawa, N. Kobayashi, H. Shimosasa, Y. Kumai, R. Miyatake, and M. Oda, “Synthesis and fluorescence property of 2,3-naphthalimie deriveatives bearing phenyl substituents on the naphthalene skeleton”, Dyes Pigments in press,
M. J. Haddadin, B. J. Agha, and R. F. Tabri, “Syntheses of some furans and naphtho[2,3-c] derivatives of furan, pyrrole, and thiophene”, J. Org. Chem. 1979, 44, 494–497.
S.-M. Yang and J.-M. Fang, “Coupling reactions and coupling-alkylations of thiophenecarbaldehydes promoted by samarium diiodide”, J. Org. Chem. 1999, 64, 394–399.
P. Valat, V. Wintgens, J. Kossanyi, L. Biczók, A. Demeter, and T. Bérces, “Influence of geometry on the emitting properties of 2,3- naphthalimides”, J. Am. Chem. Soc. 1992, 114, 946–953.
For examples, an emission quantum yield of N-ethylnaphthlene-2,3-dicarboximide, corresponding to 6b, in chloroform is 0.37 and that of N-phenylnaphthalene- 2,3-dicarboximide, corresponding to 6d, is 0.10.
The low quantum yields of 6e and 6f are ascribed also to a heavy atom effect of the bromine and iodine atoms.
J. F. D. Chabert, L. Joucla, E. David and M. Lemaire, “An efficient phosphine-free palladium coupling for the synthesis of new 2-arylbenzo[b]thiophenes”, Tetrahedron 2004, 60, 3221–3230.
Although Lemaire et al. reported cyanation of 3-bromobenzo[b]thiophene with CuCN in N,N-dimthylacetamide in ref 9, cyanation of 12 under the similar conditions yielded 13 in low yield.
M. P. Cava, A. A. Deana, K. Muth, and M. J. Mitchell, “N-Phenylmaleimide”, Org. Synth. Coll. Vol. 5, 1973, 944–946.
R. Tona and R. Häner, “Crosslinking of diene-modified DNA with bis-maleimides”, Mol. BioSyst. 2005, 1, 93–98.
H. Shen, K. C. Vollhardt, and C Peter, “Remarkable switch in the regiochemistry of the iodination of anilines by N-iodosuccinimide: synthesis of 1,2-dichloro-3,4-diiodo- benzene”, Synlett 2012, 23, 208–214.
Although the 13C NMR spectrum of 20b in CDCl3 shows only 19 signals, which are short for the structure of 20b, the spectrum in CD2Cl2 indicates 20 signals enough for the structure of 20b.
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