One-pot synthesis of benzopyranophenazines using graphene oxide dichlorotriazine (GO-DCT) under microwave irradiations

Document Type : Article


1 Department of Organic Chemistry, Faculty of Chemistry, University of Kashan, Kashan, P.O. Box 87317-51167, I. R. Iran

2 Department of Organic Chemistry, Faculty of Chemistry, University of Kashan, Kashan, P.O. Box 87317-51167

3 Department of Organic Chemistry, Faculty of Chemistry, University of Kashan, Kashan,


An efficient synthesis of benzopyranophenazines has been presented by one-pot four-component reaction of hydroxynaphthoquinone, o-phenylenediamine, benzaldehydes and malononitrile with graphene oxide dichlorotriazine (GO-DCT) as an efficient nanocatalyst under microwave irradiation in ethanol. The catalyst has been characterized by Fourier-transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), Energy Dispersive Spectroscopy (EDS), Atomic force microscopy (AFM) and scanning electron microscopy (SEM). Atom economy, experimental simplicity, wide range of products, low amount of catalyst loading, the reusability of the catalyst, excellent yields in short reaction times and applying the microwave methodology as an efficient and green method are some of the substantial features of this method.


Main Subjects

1. Tarui, M., Doi, M., Ishida, T., Inoue, M., Nakaike, S.,
and Kitamurat, K. DNA-binding characterization of a
novel anti-tumour benzo [a] phenazine derivative NC-
182: spectroscopic and viscometric studies", Biochem.
J., 304, pp. 271-279 (1994). DOI: 10.1042/bj3040271
2. Jardim, G.A.M., Cruz, E.H.G., Valenca, W.O., Resende,
J.M., Rodrigues, B.L., Ramos, D.F., Oliveira,
R.N., Silva, P.E.A., and Junior, E.N.S. On the
search for potential antimycobacterial drugs: synthesis
of naphthoquinoidal, phenazinic and 1,2,3-triazolic
compounds and evaluation against mycobacterium tuberculosis",
J. Braz. Chem. Soc., 26, pp. 1013-1027
(2015). DOI: 10.5935/0103-5053.20150067
3. Terenzi, A., Tomasello, L., Spinello, A., Bruno,
G., Giordano, C., and Barone, G. (Dipyrido[3,2-
a:20,30-c]phenazine)(glycinato)copper(II) perchlorate:
A novel DNA-intercalator with anti-proliferative activity
against thyroid cancer cell lines", J. Inorg.
Biochem., 117, pp. 103-110 (2012). DOI:
4. Price-Whelan, A., Dietrich, L.E.P., and Newman, D.K.
Rethinking 'secondary' metabolism: physiological
roles for phenazine antibiotics", Nat. Chem. Boil., 2,
pp. 71-78 (2006). DOI: 10.1038/nchembio764
5. Park, J.Y., Oh, S.A., Anderson, A.J., Neiswender,
J., Kim, J.C., and Kim, Y.C. Production of the
antifungal compounds phenazine and pyrrolnitrin from
Pseudomonas chlororaphis O6 is di erentially regulated
by glucose", Lett. Appl. Microbiol., 52, pp. 532-
537 (2011). DOI: 10.1111/j.1472-765X.2011.03036.x
6. Kondratyuk, T.P., Park, E.J., Yu, R., Van Breemen,
R.B., Asolkar, R.N., Murphy, B.T., Fenical, W., and
Pezzuto, J.M. Novel marine phenazines as potential
cancer chemopreventive and anti-in
agents", Mar. Drugs., 10, pp. 451-464 (2012). DOI:
7. Gilpin, M.L., Fulston, M., Payne, D., Cramp, R., and
Hood, I. Isolation and structure determination of two
novel phenazines from a streptomyces with inhibitory
activity against metallo-enzymes, including metallo-
-lactamase", J. Antibiot., 48, pp. 1081-1085 (1995).
DOI: 10.7164/antibiotics.48.1081
8. Gebhardt, K., Schimana, J., Krastel, P., Dettner,
K., Rheinheimer, J., Zeeck, A., and Fiedler, H.P.
Endophenazines A-D, new phenazine antibiotics from
the Arthropod associated endosymbiont streptomyces
anulatus", J. Antibiot., 55, pp. 794-800 (2002). DOI:
9. Yun, B.S., Ryoo, I.J., Kim, W.G., Kim, J.P., Koshino,
H., Seto, H., and Yoo, I.D. Structures of phenazostatins
A and B, neuronal cell protecting substances of
microbial origin", Tetrahedron Lett., 37, pp. 8529-8530
(1996). DOI: 10.1016/0040-4039(96)01983-1
10. Laursen, J.B. and Nielsen, J. Phenazine natural products:
biosynthesis, synthetic analogues, and biological
activity", Chem. Rev., 104, pp. 1663-1685 (2004).
DOI: 10.1021/cr020473j
11. Khurana, J.M., Chaudhary, A., Lumb, A., and Nand,
B. An expedient four-component domino protocol
for the synthesis of novel benzo [a] phenazine annulated
heterocycles and their photophysical studie",
Green. Chem., 14, pp. 2321-2327 (2012). DOI:
12. Saluja, P., Chaudhary, A., and Khurana, J.M. Synthesis
of novel
uorescent benzo [a] pyrano [2, 3-c]
phenazine and benzo [a] chromeno [2, 3-c] phenazine
J. Safaei-Ghomi et al./Scientia Iranica, Transactions C: Chemistry and ... 25 (2018) 3322{3330 3329
derivatives via facile four-component domino protocol",
Tetrahedron Lett., 55, pp. 3431-3435 (2014). DOI:
13. Hasaninejad, A. and Firoozi, S. One-pot, sequential
four-component synthesis of benzo[c]pyrano[3,2-
a]phenazine, bis-benzo[c]pyrano[3,2-a]phenazine and
oxospiro benzo[c]pyrano[3,2-a]phenazine derivatives
using 1,4-diazabicyclo[2.2.2]octane (DABCO) as an
ecient and reusable solid base catalyst", Mol. Diversity,
17, pp. 499-513 (2013). DOI: 10.1007/s11030-013-
14. Mahdavinia, G.H., Mirzazadeh, M., and Notash,
B. A rapid and simple diversity-oriented synthesis
of novel 3-amino-20-oxospiro [benzo[c]pyrano[3,2-
derivatives via a one-pot, four-component domino
reaction", Tetrahedron Lett., 54, pp. 3487-3492
(2013). DOI: 10.1016/j.tetlet.2013.04.082
15. Bharti, R. and Parvin, T. Multicomponent synthesis
of diverse pyrano-fused benzophenazines using
bifunctional thiourea-based organocatalyst in aqueous
medium", Mol. Divers, 20, pp. 867-876 (2016). DOI:
16. Abadi, A.Y.E., Maghsoodlou, M.T., Heydari, R., and
Mohebat, R. An ecient four-component domino
protocol for the rapid and green synthesis of functionalized
benzo[a]pyrano[2,3-c]phenazine derivatives
using ca eine as a homogeneous catalyst", Res.
Chem. Intermed., 42, pp. 1227-1235 (2016). DOI:
17. Yazdani-Elah-Abadi, A., Mohebat, R., and
Maghsoodlou, M.T. Theophylline as the catalyst
for the diastereoselective synthesis of trans-1,2-
dihydrobenzo[a]furo[2,3-c]phenazines in water",
RSC. Adv., 6, pp. 84326-8433 (2016). DOI:
18. Yazdani-Elah-Abadi, A., Mohebat, R. and Kangani,
M. Microwave-assisted and L-proline catalysed
domino cyclisation in an aqueous medium: a
rapid, highly ecient and green synthesis of benzo [a]
phenazine annulated", J. Chem. Res., 40, pp. 722-726
(2016). DOI: 10.3184/174751916X14787124908891
19. Shaterian, H.R. and Mohammadnia, M. Mild basic
ionic liquid catalyzed four component synthesis of
functionalized benzo [a] pyrano [2, 3-c] phenazine
derivatives", J. Mol. Liq., 177, pp. 162-166 (2013).
DOI: 10.1016/j.molliq.2012.11.006
20. Shaabani, A., Ghadari, R., and Arabieh, M. Synthesis
of a new library of pyrano-phenazine derivatives via a
novel three-component protocol", Helv. Chim. Acta,
97, pp. 228-236 (2014). DOI: 10.1002/hlca.201300006
21. Mohebat, R., Yazdani-Elah-Abadi, A., and Maghsoodlou,
M.T. A rapid and ecient domino protocol for
the synthesis of functionalized benzo [a] pyrano [2, 3-
c] phenazine and benzo [f] pyrano [2, 3-h] quinoxaline
derivatives", Res. Chem. Intermed., 42, pp. 6039-6048
(2016). DOI: 10.1007/s11164-016-2437-7
22. Mohebat, R., Yazdani-Elah-Abadi, A., Maghsoodlou,
M.T., Mohammadi, M., and Heydari, R. A
green and ecient four-component sequential protocol
for the synthesis of novel 16-(aryl)benzo[a]indeno
[20,10:5,6]pyrano[2,3-c] phenazin-15(16H)-one derivatives
using oxalic acid as a reusable and cost-e ective
organic catalyst", Res. Chem. Intermed., 42, pp. 7121-
7132 (2016). DOI: 10.1007/s11164-016-2522-y
23. Gao, Y., Tang, P., Zhou, H., Zhang, W., Yang,
H., Yan, N., Hu, G., Mei, D., Wang, J., and Ma,
D. Graphene oxide catalyzed C-H bond activation:
The importance of oxygen functional groups for biaryl
construction", Angew. Chem. Int. Ed., 55, pp. 3124-
3128 (2016). DOI: 10.1002/anie.201510081
24. Khodabakhshi, S., Marahel, F., Rashidi, A. and
Abbasabadi, M.K. A green synthesis of substituted
coumarins using nano graphene oxide as recyclable
catalyst", J. Chin. Chem. Soc., 62, pp. 389-392 (2015).
DOI: 10.1002/jccs.201400349
25. Gao, L., Guest, J.R., and Guisinger, N.P. Epitaxial
graphene on Cu(111)", Nano Lett., 10, pp. 3512-3516
(2010). DOI: 10.1021/nl1016706
26. Stankovich, S., Dikin, D.A., Piner, R.D., Kohlhaas,
K.A., Kleinhammes, A., Jia, Y., Wu, Y., Nguyen,
S.T., and Ruo , R.S. Synthesis of graphenebased
nanosheets via chemical reduction of exfoliated
graphite oxide", Carbon, 45, pp. 1558-1565 (2007).
DOI: 10.1016/j.carbon.2007.02.034
27. Mohanty, N. and Berry, V. Graphene-based singlebacterium
resolution biodevice and DNA transistor:
interfacing graphene derivatives with nanoscale and
microscale biocomponents", Nano Lett., 8, pp. 4469-
4476 (2008). DOI: 10.1021/nl802412n
28. Mazloum-Ardakani, M., Farbod, F., and Hosseinzadeh,
L. Enhanced electro-oxidation of urea
based on nickel nanoparticle decorated reduced
grapheme oxide/PEDOT:PSS composite", Scientia
Iranica, Trans. F., 24, pp. 1678-1685 (2017). DOI:
29. Sadeghzadeh, S. Impact dynamics of graphene
nanosheets in collision with metallic nanoparticles",
Scientia Iranica, Trans. F., 23, pp. 3153-3162 (2016).
DOI: 10.24200/sci.2016.4020
30. Stankovich, S., Piner, R., Nguyen, S.T., and Ruo ,
R.S. Synthesis and exfoliation of isocyanate-treated
graphene oxide nanoplatelets", Carbon, 44, pp. 3342-
3347 (2006). DOI: 10.1016/j.carbon.2006.06.004
31. Lu, C.H., Yang, H.H., Zhu, C.L., Chen, X., and Chen,
G.N. A graphene platform for sensing biomolecules",
Angew. Chem., Int. Ed., 48, pp. 4785-4787 (2009).
DOI: 0.1002/anie.200901479
32. Hummers, W.S. and O eman, R.E. Preparation of
graphitic oxide", J. Am. Chem. Soc., 80, pp. 1339-
1339 (1958). DOI: 10.1021/ja01539a017
33. Tien, H.N., Luan, V.H., Lee, T.K., Kong, B.S., Chung,
J.S., Kim, E.J., and Hur, S.H. Enhanced solvothermal
reduction of graphene oxide in a mixed solution of
3330 J. Safaei-Ghomi et al./Scientia Iranica, Transactions C: Chemistry and ... 25 (2018) 3322{3330
sulfuric acid and organic solvent", Chem. Eng. J., 211,
pp. 97-103 (2012). DOI: 10.1016/j.cej.2012.09.046
34. Wang, S.L., Wu, F.Y., Cheng, C., Zhang, G., Liu,
Y.P., Jiang, B., Shi, F., and Tu, S.J. Multicomponent
synthesis of poly-substituted benzo[a]pyrano[2,3-
c]phenazine derivatives under microwave heating",
ACS Comb. Sci., 13, pp. 135-139 (2011). DOI: