Abstract
A solvent-free microwave-assisted method for the synthesis of 2-substituted-4,5-di(2-furyl)-1H-imidazoles was developed. Imidazoles with moderate to good yields were produced by condensation of furil with aldehydes over acidic alumina impregnated with ammonium acetate, and they were characterized by FT-IR, HRMS, 1H NMR and 13C NMR spectroscopy. Crystal structure of 2,4,5-tri-2-furyl-1H-imidazole (I) in the orthorhombic space group Pbca was reported, which showed more coplanarity than the reported crystal structure of I in the monoclinic space group Cc. Moreover, their luminescent properties were investigated. It was found that the organic small molecule compounds synthesized possess higher fluorescence quantum efficiency (up to 0.508) in a 0.1 M H2SO4 aqueous solution dissolved in 0.5 mL of CH3OH; along with higher stability; also the emission of some compounds synthesized in the solution was sensitive to the polarity of the solvents.
Similar content being viewed by others
References
Balalaie, S., & Arabanian, A. (2000) One-pot synthesis of tetra-substituted imidazoles catalyzed by zeolite HY and silica gel under microwave irradiation. Green Chemistry, 2, 274–276. DOI: 10.1039/b006201o.
Benhabbour, S. R., Chapman, R. P., Scharfenberger, G., Meyer, W. H., & Goward, G. R. (2005) Study of imidazole-based proton-conducting composite materials using solid-state NMR. Chemistry of Materials, 17, 1605–1612. DOI: 10.1021/cm048301l.
Bernstein, J., Davis, R. E., Shimoni, L., & Chang, N. L. (1995) Patterns in hydrogen bonding: Functionality and graph set analysis in crystals. Angewandte Chemie International Edition, 34, 1555–1573. DOI: 10.1002/anie.199515551.
Bräse, S., Gil, C., & Knepper, K. (2002) The recent impact of solid-phase synthesis on medicinally relevant benzoannelated nitrogen heterocycles. Bioorganic & Medicinal Chemistry, 10, 2415–2437. DOI: 10.1016/s0968-0896(02)00025-1.
Chandra, A. K., Turro, N. J., Lyons, A. L., & Stone, P. (1978) The intramolecular external heavy atom effect in bromo-, benzo- and naphthonorbornenes. Journal of the American Chemical Society, 100, 4964–4968. DOI: 10.1021/ja00484a007.
Chen, G. Z., Huang, X. Z., Zhang, Z. Z., Xu, J. G., & Wang, Z. B. (1990) The methods of fluorescence analysis (2nd ed., pp. 43–58). Bei**, China: Science Press.
Chen, H. Z., **, Y. D., Xu, R. S., Peng, B. X., Desseyn, H., Janssens, J., Heremans, P., Borghs, G., & Geise, H. J. (2003) Synthesis, optical and electroluminescent properties of a novel indacene. Synthetic Metals, 139, 529–534. DOI: 10.1016/s0379-6779(03)00338-2.
Chen, J. J., Fang, H. Y., Du, C. Y., & Chen, I. S. (2005) New indolopyridoquinazoline, benzo[c]phenanthridines and cytotoxic constituents from Zanthoxylum integrifoliolum. Planta Medica, 71, 470–475. DOI: 10.1055/s-2005-864144.
Chen, Y., Gu., Q., Li, B. Z., Chen, Q., Chen, X. D., Zhang, Y. M., & Liu, J. X. (2013) Efficient synthesis of 1-R1-2-R-4,5-di(furan-2-yl)-1H-imidazoles and their luminescence properties. Comptes Rendus Chimie, 16, 1103–1110. DOI: 10.1016/j.crci.2013.05.014.
Chen, X. T., & Tong, A. J.(2014) Halogenated salicylaldehyde azines: The heavy atom effect on aggregation-induced emission enhancement properties. Journal of Luminescence, 145, 737–740. DOI: 10.1016/j.jlumin.2013.08.051.
Claiborne, C. F., Liverton, N. J., & Nguyen, K. T. (1998) An efficient synthesis of tetrasubstituted imidazoles from N-(2-oxo)amides. Tetrahedron Letters, 39, 8939–8942. DOI: 10.1016/s0040-4039(98)02058-9.
Consonni, R., Croce, P. D., Ferraccioli, R., & La Rosa, C. (1991) ChemInform Abstract: A new approach to imidazole derivatives. ChemInform, 22(40). DOI: 10.1002/chin.199140143.
Costantino, L., & Barlocco, D. (2006) Privileged structures as leads in medicinal chemistry. Current Medicinal Chemistry, 13, 65–85. DOI: 10.2174/092986706775197999.
Evans, D. A., & Lundy, K. M. (1992) Synthesis of diphthamide: The target of diphtheria toxin catalyzed ADP-ribosylation in protein synthesis elongation factor 2. Journal of the American Chemical Society, 114, 1495–1496. DOI: 10.1021/ja00030a063.
Fang, Z. J., Wang, S. M., Zhao, L., Xu, Z. X., Ren, J., Wang, X. B., & Yang, Q. F. (2007) A novel polymerizable imidazole derivative for blue light-emitting material. Material Letters, 61, 4803–4806. DOI: 10.1016/j.matlet.2007.03.038.
Fantini, M., Zuliani, V., Spotti, M. A., & Rivara, M. (2010) Microwave assisted efficient synthesis of imidazole-based privileged structures. Journal of Combinatorial Chemistry, 12, 181–185. DOI: 10.1021/cc900152y.
Fletcher, A. N. (1969) Quinine sulfate as a fluorescence quantum yield standard. Photochemistry and Photobiology, 9, 439–444. DOI: 10.1111/j.1751-1097.1969.tb07311.x.
Frazén, R. G. (2000) Recent advances in the preparation of heterocycles on solid support: A review of the literature. Journal of Combinatorial Chemistry, 2, 195–214. DOI: 10.1021/cc000002f.
Gao, D. W., Yu, H. F., Jia, J. L., Hua, S. Y., & Chen, X. D. (1998) The synthesis of furil. Acta Scientiarium Naturalium Universitatis Jilinensis, 1, 107–109.
Gao, Z. Q., Lee, C. S., Bello, I., Lee, S. T., Wu, S. K., Yan, Z. L., & Zhang, X. H. (1999) Blue organic electroluminescence of 1,3,5-triaryl-2-pyrazoline. Synthetic Metals, 105, 141–144. DOI: 10.1016/s0379-6779(99)00090-9.
Gill, J. E. (1969) The fluorecsence excitation spectrum of quinine bisulfate. Photochemistry and Photobiology, 9, 313–322. DOI: 10.1111/j.1751-1097.1969.tb07295.x.
Han, L., Zhang, Y. M., Kang, J., Tang, J. L., & Zhang, Y. H. (2011) Determination Co2+ in vitamin B12 based on enhancement of 2-(4-substituted-phenyl)-4,5-di(2-furyl) imidazole and H2O2 chemiluminescence reaction. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 82, 146–152. DOI: 10.1016/j.saa.2011.07.025.
Horton, D. A., Bourne, G. T., & Smyth, M. L. (2003) The combinatorial synthesis of bicyclic privileged structures or privileged substructures. Chemical Reviews, 103, 893–930. DOI: 10.1021/cr020033s.
Jayabharathi, J., Thanikachalam, V., Srinivasan, N., & Perumal, M. V. (2012a) Fluorescenece spectral studies of some imidazole derivatives. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 90, 125–130. DOI: 10.1016/j.saa.2012.01.030.
Jayabharathi, J., Thanikachalam, V., & Jayamoorthy, K. (2012b) Photophysical studies of some heterocyclic chromophores as potential NLO materials. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 89, 301–307. DOI: 10.1016/j.saa.2011.12.031.
Joshi, A. A., & Viswanathan, C. L. (2006) Docking studies and development of novel 5-heteroarylamino-2,4-diamino-8-chloropyrimido-[4,5-b]quinolines as potential antimalarials. Bioorganic & Medical Chemistry Letters, 16, 2613–2617. DOI: 10.1016/j.bmcl.2006.02.038.
Kang, J., Zhang, Y. M., Han, L., Tang, J. L., Wang, S., J., & Zhang, Y. H. (2011) Utilizing the chemiluminescence of 2-substituted-4,5-di(2-furyl)-1H-imidazole-H2O2-Cu2+ system for the determination of Cu2+. Journal of Photochemistry and Photobiology A: Chemistry, 217, 376–382. DOI: 10.1016/j.jphotochem.2010.11.009.
Langa, F., de la Cruz, P., de la Hoz, A., Díaz-Ortiz, A., & Díez-Barra, E. (1997) Microwave irradiation: More than just a method for accelerating reactions. Contemporary Organic Synthesis, 4, 373–386. DOI: 10.1039/co9970400373.
Li, Y. Z., Zhang, F., Jia, X. F., Gao, D. W., Sun, J. K., Zhang, Y. M., & Zhao, T. Q. (2006) Synthesis of 2,3-di(furan-2-yl)-5,6-dihydro-1,4-dioxine. Heterocyclic Communications, 12, 361–364. DOI: 10.1515/hc.2006.12.5.361.
Li, B. Z., Gu, Q., He, Y. H., Zhao, T. Q., Wang, S. J., Kang, J., & Zhang, Y. M. (2012) Facile synthesis of trisubstituted imidazoles from 1,2-di(furan-2-yl)-2-oxoethyl carboxylates and their chemiluminescence. Comptes Rendus Chimie, 15, 784–792. DOI: 10.1016/j.crci.2012.06.005.
Lipshutz, B. H., & Morey, M. C. (1983) An approach to the cyclopeptide alkaloids (phencyclopeptines) via heterocyclic diamide/dipeptide equivalents. Preparation and N-alkylation studies of 2,4(5)-disubstituted imidazoles. The Journal of Organic Chemistry, 48, 3745–3750. DOI: 10.1021/jo00169a027.
Loiseau, F., Campagna, S., Hameurlaine, A., & Dehaen, W. (2005) Dendrimers made of porphyrin cores and carbazole chromophores as peripheral units. Absorption spectra, luminescence properties, and oxidation behavior. Journal of the American Chemical Society, 127, 11352–11363. DOI: 10.1021/ja0514444.
Loupy, A., Petit, A., Hamelin, J., Texier-Boullet, F., Jacquault, P., & Mathé, D. (1998) New solvent-free organic synthesis using focused microwaves. Synthesis, 1998, 1213–1234. DOI: 10.1055/s-1998-6083.
Mi, B. X., Wang, P. F., Liu, M. W., Kwong, H. L., Wong, N. B., Lee, C. S., & Lee, S. T. (2003) Thermally stable hole-transporting material for organic light-emitting diode: An isoindole derivative. Chemistry of Materials, 15, 3148–3151. DOI: 10.1021/cm030292d.
Molard, Y., Bassani, D. M., Desvergne, J. P., Moran, N., & Tucker, J. H. R. (2006) Structural effects on the ground and excited-state properties of photoswitchable hydrogen-bonding receptors. The Journal of Organic Chemistry, 71, 8523–8531. DOI: 10.1021/jo061528a.
Nefzi, A., Ostresh, J. M., & Houghten, R. A. (1997) The current status of heterocyclic combinatorial libraries. Chemical Reviews, 97, 449–472. DOI: 10.1021/cr960010b.
Nicolaou, K. C., Baran, P. S., Zhong, Y. L., & Sugita, K. (2002) Iodine(V) reagents in organic synthesis. Part 1. Synthesis of polycyclic heterocycles via Dess-Martin periodinane-mediated cascade cyclization: Generality, scope and mechanism of the reaction. Journal of the American Chemical Society, 124, 2212–2220. DOI: 10.1021/ja012124x.
Parveen, A., Ahmed, M. R. S., Shaikh, K. A., Deshmukh, S. P., & Pawar, R. P. (2007) Efficient synthesis of 2,4,5-triaryl substituted imidazoles under solvent free conditions at room temperature. ARKIVOC, 2007, 12–18. DOI: 10.3998/ark.5550190.0008.g02.
Schubert, H., & Stodolka, H. (1963) Diimidazole. II. Synthese von Aliphatisch und Aromatisch Überbrückten N, N′-Diimidazolen. Journal für Praktische Chemie, 22, 130–139. DOI: 10.1002/prac.19630220303. (in German)
Schuster, M. F. H., Meyer, W. H., Schuster, M., & Kreuer, K. D. (2004) Toward a new type of anhydrous organic proton conductor based on immobilized imidazole. Chemistry of Materials, 16, 329–337. DOI: 10.1021/cm021298q.
Sheldrick, G. M. (1997) SHELXS-97. Program for crystal structure solution [computer software]. Göttingen, Germany: University of Göttingen.
Soh, C. H., & Lam, Y. (2010) Microwave-assisted synthesis of substituted 2-(benzylthio)imidazo[1,2a]pyrimidin-5-ones. Journal of Combinatorial Chemistry, 12, 286–291. DOI: 10.1021/cc900176x.
Stoeck, V., & Schunack, W. (1974) N-substituted imidazoles from aldehydes, 1,2-diketones, primary amines and liquid ammonia. Archiv der Pharmazie, 307, 922–925. DOI: 10.1002/ardp.19743071206.
Tsuji, J., Sakai, K., Nemoto, H., & Nagashima, H. (1983) Iron and copper catalyzed reaction of benzylamine with carbon tetrachloride: Facile formation of 2,4,5-triphenylimidazoline derivatives. Journal of Molecular Catalysis A, 18, 169–176. DOI: 10.1016/0304-5102(83)80116-3.
Usyatinsky, A. Y., & Khmelnitsky, Y. L. (2000) Microwave-assisted synthesis of substituted imidazoles on a solid support under solvent-free conditions. Tetrahedron Letters, 41, 5031–5034. DOI: 10.1016/s0040-4039(00)00771-1.
Varma, R. S. (1999) Solvent-free organic syntheses using supported reagents and microwave irradiation. Green Chemistry, 1999, 43–55. DOI: 10.1039/a808223e.
Wang, J., Mason, R., VanDerveer, D., Feng, K., & Bu, X. R. (2003) Convenient preparation of a novel class of imidazo[1,5a]pyridines: Decisive role by ammonium acetate in chemoselectivity. The Journal of Organic Chemistry, 68, 5415–5418. DOI: 10.1021/jo0342020.
Wang, S. J., Gu, Q., Su, Q., Chen, X. D., & Zhang, Y. M. (2009) 2,4,5-Tri-2-furyl-1H-imidazole. Acta Crystallographica Section E: Structure Reports Online, 65, o3194. DOI: 10.1107/s1600536809049514.
Wang, S. J., Gu, Q., Chen, X. D., Zhao, T. Q., & Zhang, Y. M. (2011) Research on the reaction of furil with ammonium acetate. European Journal of Chemistry, 2, 173–177. DOI: 10.5155/eurjchem.2.2.173-177.283.
Yang, X. C., Lu, R., Zhou, H. P., Xue, P. C., Wang, F. Y., Chen, P., & Zhao, Y. Y. (2009) Aggregation-induced blue shift of fluorescence emission due to suppression of TICT in a phenothiazine-based organogel. Journal of Colloid and Interface Science, 339, 527–532. DOI: 10.1016/j.jcis.2009.07.033.
Zhao, L., Li, S. B., Wen, G. A., Peng, B., & Huang, W. (2006) Imidazole derivatives: Thermally stable organic luminescence materials. Materials Chemistry and Physics, 100, 460–463. DOI: 10.1016/j.matchemphys.2006.01.025.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Zhang, J., Zhao, TQ., Chen, Y. et al. Microwave-assisted solvent-free synthesis and luminescence properties of 2-substituted-4,5-di(2-furyl)-1H-imidazoles. Chem. Pap. 69, 325–338 (2015). https://doi.org/10.1515/chempap-2015-0014
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1515/chempap-2015-0014