A multi-component reaction for the direct access to 4,4'-(phenylmethylene)bis(1H-pyrazol-5-ol)-3-carboxylates using nano-NiZr4(PO4)6 in water

Document Type : Article


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

2 School of Chemistry, College of Science, University of Tehran, Tehran 14155-6455, Iran


An efficient synthesis of 4,4'-(phenylmethylene)bis(1H-pyrazol-5-ol)-3-carboxylates is achieved by one pot pseudo five-component reaction of phenylhydrazine, acetylenedicarboxylates and aromatic aldehydes in the presence ofnano-NiZr4(PO4)6 at 60°C in water. Nano-NiZr4(PO4)6  has been characterized by powder X-ray diffraction (XRD) and scanning electronic microscopy (SEM). Use of simple and readily available starting materials, excellent yields in short times, reusability of the catalyst, little catalyst loading and simple operational procedures are some of the important features of this protocol.


Main Subjects

1. Wei, F., Zhao, B.X., Huang, B., Zhang, L., Sun,
C.H., Dong, W.L., Shin, D.S., and Miao, J.Y. \Design,
synthesis, and preliminary biological evaluation of
novel ethyl 1-(20-hydroxy-30-aroxypropyl)-3-aryl-1Hpyrazole-
5-car boxylate", Bioorg. Med. Chem. Lett.,
J. Safaei-Ghomi et al./Scientia Iranica, Transactions C: Chemistry and ... 25 (2018) 3288{3294 3293
16(24), pp. 6342-6347 (2006).
2. Bailey, D.M., Hansen, P.E., Hlavac, A.G., Baizman,
E.R., Pearl, J., DeFelice, A.F., and Feigenson, M.E.
\3,4-diphenyl-1H-pyrazole-1-propanamine antidepressants",
J. Med. Chem., 28(2), pp. 256-260 (1985).
3. Sujatha, K., Shanthi, G., Panneer Selvam, N.,
Manoharan, S., Perumal, P.T., and Rajendran,
M. \Synthesis and antiviral activity of 4,40-
(arylmethylene)bis(1H-pyrazol-5-ols) against peste
des petits ruminant virus (PPRV)", Bioorg. Med.
Chem. Lett., 19(15), pp. 4501-4503 (2009).
4. Bandgar, B.P., Chavan, H.V., Adsul, L.K., Thakare,
V.N., Shringare, S.N., Shaikh, R., and Gacche, R.N.
\Design, synthesis, characterization and biological
evaluation of novel pyrazole integrated benzophenones",
Bioorg. Med. Chem. Lett., 23(3), p. 912 (2013).
5. Bekhit, A.A., Hymete, A., Asfaw, H., and Bekhit,
A.E.D.A. \Synthesis and biological evaluation of some
pyrazole derivatives as anti-malarial agents", Arch.
Pharm. Chem., 345(2), pp. 147-154 (2012).
6. Zhang, D., Wang, G., Tan, C., Xu, W., Pei, Y., and
Huo, L. \Synthesis and biological evaluation of 3-(1Hindol-
3-yl) pyrazole-5-carboxylic", Arch. Pharm. Res.,
34(3), pp. 343-355 (2011).
7. Hurtado, I., Urbina, C., Suarez, C., Beyer, B.,
and Magro, A.M. \Preparation and evaluation of
a soluble derivative of the antiallergic compound
trans-2,3b,4,5,7, 8b,9, 10-octahydronaphtho [1,2-c:5,6-
c0] dipyrazole (LC-6)", Int. J. lmmunopharmac., 7(5),
pp. 635-638 (1985).
8. Domling, A. \Recent developments in isocyanide
based multicomponent reactions in applied chemistry",
Chem. Rev., 106(1), pp. 17-89 (2006).
9. Domling , A., Wang, W., and Wang, K. \Chemistry
and biology of multicomponent reactions", Chem.
Rev., 112(6), pp. 3083-3135 (2012).
10. Tejedor, D. and Garcia-Tellado, F. \Chemodi
erentiating ABB0 multicomponent reactions.
Privileged building blocks", Chem. Soc. Rev., 36(3),
pp. 484-491 (2007).
11. Dekamin, M.G., Mokhtari, Z., and Karimi, Z. \Nanoordered
B-MCM-41: An ecient and recoverable solid
acid catalyst for three component Strecker reaction of
carbonyl compounds, amines and TMSCN", Sci. Iran.,
18(6), pp. 1356-1364 (2011).
12. Estevez, V., Villacampa, M., and Menendez, J.C.
\Recent advances in the synthesis of pyrroles by
multicomponent reactions", Chem. Soc. Rev., 43(13),
pp. 4633-4657 (2014).
13. Hassankhani, A. \A rapid, one-pot, multi-component
route to 4,40-(arylmethylene)bis(3-methyl-1-phenyl-
1H-pyrazol-5-ols)", J. Mex. Chem. Soc., 59(1), pp. 1-4
14. Niknam, K., Saberi, D., Sadegheyan, M., and Deris,
A. \Silica-bonded S-sulfonic acid: an ecient
and recyclable solid acid catalyst for the synthesis
of 4,40 (arylmethylene)bis(1H-pyrazol-5-ols)", Tetrahedron
Lett., 51(4), pp. 692-694 (2010).
15. Karimi-Jaberi, Z., Pooladian, B., Moradi, M.,
and Ghasemi, E. \1,3,5-tris(hydrogensulfato) benzene:
a new and ecient catalyst for synthesis of
4,40-(arylmethylene)bis(1H-pyrazol-5-ol) derivatives",
Chin. J. Catal., 33(11-12), pp. 1945-1949 (2012).
16. Moosavi-Zare, A.R., Zol gol, M.A., Zarei, M., Zare,
A., Khakyzadeh, V., and Hasaninejad, A. \Design,
characterization and application of new ionic liquid
1-sulfopyridinium chloride as an ecient catalyst for
tandem Knoevenagel-Michael reaction of 3-methyl-1-
phenyl-1H-pyrazol-5(4H)-one with aldehydes", Appl.
Catal. A: Gen., 467(2), pp. 61-68 (2013).
17. Tu, X.C., Feng, H., Tu, M.S., Jiang, B., Wang,
S.L., and Tu, S.J. \Multicomponent domino reactions
of acetylenedicarboxylates: divergent synthesis
of multi-functionalized pyrazolones and C-tethered
bispyrazol-5-ols", Tetrahedron Lett., 53(25), pp. 3169-
3172 (2012).
18. Safaei-Ghomi, J., Asgari-Keirabadi, M.,
Khojastehbakht-Koopaei, B., and Shahbazi-
Alavi, H. \Multicomponent synthesis of C-tethered
bispyrazol-5-ols using CeO2 nanoparticles as an
ecient and green catalyst", Res .Chem. Intermed.,
42(2), pp. 827-837 (2016).
19. Kuarm, B.S. and Rajitha, B. \Xanthan sulfuric
acid: An ecient, biosupported, and recyclable
solid acid catalyst for the synthesis of 4,40-
(arylmethylene)bis(1H-pyrazol-5-ols)", Synth. Commun.,
42(16), pp. 2382-2387 (2012).
20. Sobhani, S., Hasaninejad, A.R., Maleki, M.F., and
Parizi, Z.P. \Tandem knoevenagel-michael reaction
of 1-phenyl-3-methyl-5-pyrazolone with aldehydes using
3-aminopropylated silica gel as an ecient and
reusable heterogeneous catalyst", Synth. Commun.,
42(15), pp. 2245-2255 (2012).
21. Sei , M. and Sheibani, H. \High surface area MgO as a
highly e ective heterogeneous base catalyst for threecomponent
synthesis of tetrahydrobenzopyran and 3,4-
dihydropyrano[c]chromene derivatives in aqueous media",
Catal. Lett., 126(3-4), pp. 275-279 (2008).
22. Polshettiwar, V., Decottignies, A., Len, C., and Fihri,
A. \Suzuki-Miyaura cross-coupling reactions in aqueous
media: green and sustainable syntheses of biaryls",
Chem. Sus. Chem., 3(5), pp. 502-522 (2010).
23. Lipshutz, B.H., Ghorai, S., Leong W.W.Y., Taft,
B.R., and Krogstad, D.V. \Manipulating micellar
environments for enhancing transition metal-catalyzed
cross-couplings in water at room temperature", J. Org.
Chem., 76(12), pp. 5061-5073 (2011).
3294 J. Safaei-Ghomi et al./Scientia Iranica, Transactions C: Chemistry and ... 25 (2018) 3288{3294
24. Gorodylova, N., Kosinova, V., Dohnalova, Z., Belina,
P., and Sulcova, P. \New purple-blue ceramic pigments
based on CoZr4(PO4)6", Dyes Pigm., 98(3), pp. 393-
404 (2013).
25. Liu, D.M. \Thermal di usivity of porous (Ca1􀀀xMgx)
Zr4(PO4)6 ceramic", Mater. Chem. Physic., 36(3-4),
pp. 350-353 (1994).
26. Li, Y. and Somorjai, G.A. \Nanoscale advances in
catalysis and energy applications", Nano Lett., 10(7),
pp. 2289-2295 (2010).
27. Safaei-Ghomi, J., Hatami, A., Shahbazi-Alavi H., and
Ziarati, A. \CuFe2O4 and ZrP2O7 nanoparticles as
highly e cient catalysts for the one-pot synthesis of
phthalazine derivatives under solvent-free conditions",
Sci. Iran., 23(6), pp. 2705-2716 (2016).
28. Safaei-Ghomi, J., Shahbazi-Alavi, H., and Heidari-
Baghbahadorani, E. \ZnFe2O4 nanoparticles as a
robust and reusable magnetically catalyst in the
four component synthesis of [(5-hydroxy-3-methyl-
1H-pyrazol-4yl) (phenyl) methyl]propanedinitriles
and substituted 6-amino-pyrano[2,3-c]pyrazoles",
J. Chem. Res., 39(7), pp. 410-413 (2015). DOI:
29. Safaei-Ghomi, J., Javidan, A., Ziarati, A., and
Shahbazi-Alavi, H. \Synthesis of new 2-amino-4Hpyran-
3,5-dicarboxylate derivatives using nanocrystalline
MIIZr4(PO4)6 ceramicsas reusable and robust
catalysts under microwave irradiation", J. Nanopart
Res., 17(8), pp. 338-350 (2015).
30. Safaei-Ghomi, J. and Shahbazi-Alavi, H. \A
one-pot synthesis of pyrazolopyridines catalyzed by
Fe3O4@SiO2-SO3H nanocatalyst under microwave irradiation",
Sci. Iran., 24(3), pp. 1209-1219 (2017).