Synthesis of 4,4′-(arylmethylene)bis(3-carboxymethyl-1-phenyl-1H-pyrazol-5-ol)s using ionic liquid attached to colloidal silica nanoparticles in water

Article abstract of DOI:10.3184/174751917X15000317104529

An efficient synthesis of 10 4,4′-(arylmethylene)bis(3-carboxymethyl-1-phenyl-1H-pyrazol-5-ol)s, eight of which are novel, was achieved by a one-pot three-component reaction of phenylhydrazine, dimethyl acetylenedicarboxylate and an arylaldehyde using bis

Full text of DOI:10.3184/174751917X15000317104529

JOURNAL OF CHEMICAL RESEARCH 2017
VOL. 41 AUGUST, 457–459
RESEARCH PAPER 457
Synthesis of 4,4´-(arylmethylene)bis(3-carboxymethyl-1-phenyl-1H-pyrazol-5-
ol)s using ionic liquid attached to colloidal silica nanoparticles in water
Hossein Shahbazi-Alavia,b*, Javad Safaei-Ghomia, Samane Esmailia and Seyed Hadi Nazemzadeha
aDepartment of Organic Chemistry, Faculty of Chemistry, University of Kashan, Kashan, PO Box 87317-51167, Iran
bYoung Researchers and Elite Club, Kashan Branch, Islamic Azad University, Kashan, Iran
An efficient synthesis of 10 4,4´-(arylmethylene)bis(3-carboxymethyl-1-phenyl-1H-pyrazol-5-ol)s, eight of which are novel, was achieved
by a one-pot three-component reaction of phenylhydrazine, dimethyl acetylenedicarboxylate and an arylaldehyde using bis(1(3-
methoxysilylpropyl)-3-methyl-imidazolium) copper tetrachloride tethered to colloidal silica nanoparticles as catalyst under microwave
irradiation in water. The advantages of the present process are atom economy, high catalytic activity, excellent yields, short reaction times
and utilisation of microwave heating as a clean procedure. The catalyst was recyclable.
Keywords: ionic liquid, colloidal silica nanoparticles, multi-component reaction, bispyrazoles
Introduction
Results and discussion
Pyrazoles represent biological properties including anti-cancer,1
antidepressants,2 antiviral,3 anti-inflammatory,4 anti-malarial,5
antibacterial,6 and antiallergic,7 activities. Efficient creation of
complex molecules with chemical and biological importance
is a challenging point and has gained substantial interest in
recent years.8,9. A number of methods have been developed
for the synthesis of 1-phenyl-1H-pyrazol-5-ols in the presence
of diverse catalysts such as K2CO3,10 silica-bonded S-sulfonic
acid,11 1,3,5-tris(hydrogensulfato) benzene,12 1-sulfopyridinium
chloride,13 and acetic acid.14 Some of the reported procedures
endure drawbacks such as long reaction times, use of toxic and
non-reusable catalyst and undesirable reaction conditions. Hence,
to avoid these disadvantages, the finding of an effective method
for the preparation of pyrazoles is still desirable. In recent years,
synthesis and immobilisation of nanoparticles in ionic liquids
(ILs) have been widely studied.15,16 Ionic liquids can be considered
as valuable key precursor compounds for catalysts.17,18 The nature
of cation–anion interactions in ambient temperature ionic liquids
is an issue of increasing interest.19,20 The structures of 1-ethyl-
3-methylimidazolium (Emim) and 1-butyl-3-methylimidazolium
(Bmim) with transition metal chloride anions including NiCl42-,
CoCl42-, and PdCl42- were investigated.21-23 Here we report the use
of bis(1-(3-methoxysilylpropyl)-3-methyl-imidazolium) copper
tetrachloride (CuCl42-) tethered to colloidal silica nanoparticles
as an efficient catalyst for the synthesis of 4,4´-(arylmethylene)
bis(3-carboxymethyl-1-phenyl-1H-pyrazol-5-ol)s.
Our plan was to react dimethyl acetylenedicarboxylate 1 (2
equiv) and phenylhydrazine 2 (2 equiv.) with an arylaldehyde
3 (1 equiv.) under microwave irradiation in a solvent in
the presence of a nanocatalyst (Scheme 1). We chose
phenylhydrazine (2 mmol), dimethyl acetylenedicarboxylate
(2 mmol) and 4-nitrobenzaldehyde 3 (Ar = 4-NO2–C6H4) (1
mmol) as the standard substrates to search for the optimum
reaction conditions. Various catalysts, solvents and microwave
microwave (MW) conditions were evaluated and the results
are shown in Table 1. Yields were determined for reaction in
the presence of various catalysts such as oxides of Zn, Mg,
Ni, Cu and Sn in water, MeCN, EtOH, or CHCl3, but yields of
4,4'-(4-nitrophenylmethylene)bis(3-carboxymethyl-1-phenyl-
1H-pyrazol-5-ol) 4 (Ar = 4-NO2–C6H4) were moderate 19–43%
(entries 1–7). CoAl2O4 NPs were a slight improvement at 55%
(entry 8), but much improved yields were obtained using a
nanocatalyst composed of the IL propyl-3-methyl-imidazolium
chloride and CuCl42- tethered to colloidal silica nanoparticles
(IL/nano-colloidal silica) (Scheme 1) (entries 9–15). Water
was a better solvent than MeCN or EtOH (entries 8–10), and
the best yield of 96% was obtained using a loading of 14 mg
of IL/nano-colloidal silica (not improved using 16 mg) and a
MW power of 400 W (entry 12). Thus we had established the
optimum conditions.
Using these optimised conditions, we examined the scope of
this multicomponent reaction by using various easily available
CO2Me
Ar
CO2Me
MeO2C
Ar
NH2
nanocatalyst
N
HN
Ph
+
CO2Me
1
2
2
+
O
N
N
solvent, MWI
N
OH
Ph
OH
Ph
3
2
4
O
N
O
O
N
N
S
i
2-
CuCl4
nanocatalyst =
O
O
Si
N
O
Scheme 1 One-pot syntheses of 4,4´-(phenylmethylene)bis(1H-pyrazol-5-ol)-3-carboxylates using nanocatalyst (IL/nano-colloidal silica).
* Correspondent. E-mail: hossien_shahbazi@yahoo.com

458 JOURNAL OF CHEMICAL RESEARCH 2017
Table 1 Optimisation of the reaction conditions (catalyst, catalyst
loading, solvent, duration of reaction) for the synthesis of
4,4´-(4-nitrophenylmethylene)bis(3-carboxymethyl-1-phenyl-1H-pyrazol-
Table 2 Yields of a series of 4,4´-(arylmethylene)bis(3-carboxymethyl-
1-phenyl-1H-pyrazol-5-ol)s 4 (Ar = various) prepared from dimethyl
acetylenedicarboxylate 1, phenyl hydrazine 2, and an araldehyde 3 (Ar
= various) using IL/nano-colloidal silica under microwave irradiation in
water (Scheme 1)a
5-ol) 4 (Ar = 4-NO2–C6H4) from dimethyl acetylenedicarboxylate 1, phenyl
a
hydrazine 2, and 4-nitrobenzaldehyde 3 (Ar = 4-NO2–C6H4) (Scheme 1)
Time Yieldb
M. p.
(°C)
M.p. (°C)
[ref.]
Time Yieldb
Entry Aldehyde (Ar) Product
Entry Conditions
Catalyst
(min)
10
10
10
15
10
10
15
10
10
15
(%)
96
94
90
84
88
87
82
92
90
82
(min)
100
50
65
45
55
45
45
40
15
(%)
19
35
44
31
34
55
43
55
60
73
87
96
94
89
96
1
2
3
4
5
6
7
8
9
10
4-NO2–C6H4 4a
4-Cl–C6H4 4b
2-3-Cl–C6H3 4c
215–216 216–217 [14]
223–225 226–228 [14]
1
2
CHCl3 (300 W) ZnO (3 mol%)
EtOH (400 W) MgO (4 mol%)
204–205
186–187
285–286
267–269
192–194
248–250
230–232
217–219
—
—
—
—
—
—
—
—
3
H2O (600 W)
NiO (3 mol%)
2-Me–C6H4
C6H5
2-Cl–C6H4
4-Me–C6H4
4d
4e
4f
4
EtOH (500 W) CuO (4 mol%)
5
6
H2O (500 W)
H2O (400 W)
SnO (3 mol%)
ZnO (3 mol%)
4g
7
CH3CN (400 W) ZnO (3 mol%)
3-NO2–C6H4 4h
2-Br–C6H4 4i
4-OMe–C6H4 4j
8
H2O (400 W)
CoAl2O4 NPs (3 mol%)
9
CH3CN (300 W) IL/nano-colloidal silica (16 mg)
EtOH (400 W) IL/nano-colloidal silica (16 mg)
10
11
12
13
14
15
15
10
10
10
a Reaction conditions: a mixture of dimethyl acetylenedicarboxylate 1 (2 mmol), phenyl
hydrazine 2 (2 mmol), an araldehyde 3 (Ar = various) (1 mmol) and IL/nano-colloidal silica
(14 mg) in water (15 mL) was heated for periods of 10–15 min under microwave irradiation
(400 W).
bIsolated yield.
H2O (300 W)
H2O (400 W)
H2O (500 W)
H2O (400 W)
H2O (400 W)
IL/nano-colloidal silica (14 mg)
IL/nano-colloidal silica (14 mg)
IL/nano-colloidal silica (14 mg)
IL/nano-colloidal silica (12 mg)
IL/nano-colloidal silica (16 mg)
10
10
aReaction conditions: a mixture of dimethyl acetylenedicarboxylate 1 (2 mmol), phenyl
hydrazine 2 (2 mmol), 4-nitrobenzaldehyde 3 (Ar = 4-NO2–C6H4) (1 mmol) and a catalyst
in a solvent (15 mL) was irradiated (MW) for various times and at various wattages.
b Isolated yield.
IR Magna 550 apparatus using with KBr plates. Melting points were
determined on Electro thermal 9200, and are not corrected. The
elemental analyses (C, H, N) were obtained from a Carlo ERBA Model
EA 1108 analyser. We used the Milestone microwave (Microwave
Labstation, MLS GmbH- ATC-FO 300) for synthesis.
aldehydes and the results are shown in Table 2. Aldehydes
containing electron-withdrawing groups generally gave yields
of the corresponding bispyrazole 4 of 87–96% in 10 min
(entries 1–3, 6, 8, 9), but those with electron-donating groups
gave slightly lower yields 82–84% in a longer reaction time of
15 min (entries 4, 7, 10). Two of the compounds prepared 4a,b
were known, but eight 4c–j were novel.
We also considered reusability of the IL/nano-colloidal
silica as catalyst under microwave irradiation in water for the
synthesis of product 4a and it was found that product yields
reduced to a small extent on each reuse (runs 1–5: 96, 96,
95, 95, 94%). After completion of the reaction (TLC), ethyl
acetate was added. The catalyst was insoluble in ethyl acetate
and it could therefore be recycled by an easy filtration. The
solvent was evaporated and the solid obtained recrystallised
from ethanol to afford the pyrazoles. The recovered IL/nano-
colloidal silica was washed four to six times with ethanol and
dried at room temperature for 14 h.
In conclusion, we have described an efficient and one-
pot synthesis of 4,4'-(phenylmethylene)bis(1H-pyrazol-
5-ol)-3-carboxylates by the three-component reaction of
phenylhydrazine, acetylenedicarboxylates, and aromatic
aldehydes in the presence of bis (1(3-methoxysilylpropyl)-3-
methyl-imidazolium) copper tetrachloride tethered to colloidal
silica nanoparticles under microwave irradiation in water. The
advantages offered by this method include short reaction times,
utilising microwave as a clean procedure, high atom economy,
excellent yields, use of non toxic organic solvent, and the
employment of a cost-effective catalyst.
Synthesis of ionic liquid/nano-colloidal silica
In a typical procedure, based on a reported method,24,25 colloidal
silica nanoparticles (LUDOX SM colloidal silica 30 wt% suspension
in H2O) (0.098 mL) were diluted in deionised water (3 mL), and
1-(3-trimethoxysilylpropyl)-3-methyl-imidazolium chloride (IL)
(1.8 mmol) was added slowly with continuous stirring during one
hour. Then, CuCl2.2H2O (0.15 g) was added and the mixture refluxed
for 24 h. IL functionalised silica nanoparticles were separated by
centrifugation and washed with acetone and methanol four times and
dried by lyophilisation/freeze-drying. The purity of the resultant IL/
Cu2+/SiO2 was confirmed using 1H NMR spectroscopy. The Cu loading
(4.7 wt%) was measured using XRF.
Synthesis of 4,4'-(phenylmethylene)bis(1H-pyrazol-5-ol)3-carboxy-
lates; general procedure
A mixture of dimethyl acetylenedicarboxylate (2 mmol)
phenylhydrazine (2 mmol), arylaldehydes (1 mmol) and bis
(1(3-methoxysilylpropyl)-3-methyl
imidazolium)
copper
tetrachloride tethered to silica nanoparticles (nanocatalyst)
(14 mg) in 15 mL of water were added and the mixture was
irradiated in microwave oven at 50°C and 400 W. After
completion of the reaction (TLC), ethyl acetate was added. The
catalyst was insoluble in ethyl acetate and it could therefore be
recycled by an easy filtration. The solvent was evaporated and the
solid obtained recrystallised from ethanol to afford the pyrazoles.
Physical and spectroscopic data
Methyl 4-((3-(methoxycarbonyl)-5-hydroxy-1-phenyl-1H-pyrazol-4-yl)
(4-nitrophenyl)methyl) -5-hydroxy-1-phenyl-1H-pyrazole-3-carboxylate
(4a): Golden powder; m.p. 215–216 °C; IR (KBr): ν = 3432, 3073,
Experimental
1
2954, 1731, 1600, 1515, 1443, 1344, 1213, 1113, 842 cm-1 ; H NMR
Reagent grade chemicals were purchased from Sigma-Aldrich or
Merck and were used without further purification. The products were
isolated and characterised by physical and spectral data. NMR spectra
were obtained on a Bruker Avance 400 MHz spectrometer (1H NMR at
400 Hz, 13C NMR at 100 Hz) in CDCl3 or DMSO-d6 using TMS as an
internal standard. Chemical shifts (δ) are given in ppm and coupling
constants (J) are given in Hz. The IR spectra were recorded on FT-
(DMSO-d6): δ (ppm) = 3.85 (s, 6H, 2OCH3), 4.83 (2OH exchanged
with water of DMSO-d6), 6.92 (s, 1H, CH), 7.29-7.43 (t, J = 7.6 Hz,
6H, ArH), 7.52 (d, J = 8Hz, 2H, ArH), 7.77–7.86 (m, 4H, ArH), 8.14
(d, J = 7.6 Hz, 2H, ArH); 13C NMR (DMSO-d6): δ (ppm) = 31.2, 51.4,
107.3, 122.2, 125.3, 127.6, 128.0, 129.9, 130.5, 137.3, 139.7, 142.2,
159.5, 165.3; Anal. calcd for C29H23N5O8: C, 61.16; H, 4.07; N, 12.30;
found: C, 61.10; H, 4.12; N, 12.43%.

JOURNAL OF CHEMICAL RESEARCH 2017 459
Methyl 4-((3-(methoxycarbonyl)-5-hydroxy-1-phenyl-1H-pyrazol-4-yl)
(4-chlorophenyl) methyl)-5-hydroxy-1-phenyl-1H-pyrazole-3- carboxy-
late (4b): White powder; m.p. 223–225 °C; IR (KBr): ν = 3429, 3068,
2952, 1718, 1599, 1492 cm-1; 1H NMR (CDCl3 ): δ (ppm) = 3.94 (s, 6H,
2OCH3), 6.17 (s, 1H, CH), 7.23 (m, 2H, ArH), 7.26 (m, 2H, ArH), 7.35 (m,
2H, ArH), 7.46 (m, 4H, ArH), 7.84 (m, 4H, ArH), 10.59 (2OH); 13C NMR
(DMSO-d6): δ (ppm) = 32.2, 52.3, 106.3, 123.2, 124.3, 127.6, 128.1, 129.9,
133.5, 138.3, 139.7, 144.2, 159.4, 164.9; Anal. calcd for C29H23ClN4O6: C,
62.31; H, 4.15; N, 10.02; found: C, 62.22; H, 4.25; N, 9.87%.
Methyl4-((3-(methoxycarbonyl)-5-hydroxy-1-phenyl-1H-pyrazol-4-
yl)(2,3-dichloro phenyl) methyl)-5-hydroxy-1-phenyl-1H-pyrazole-3-
carboxylate (4c): White powder; m.p. 204–205 °C; IR (KBr): ν = 3443,
2925, 1725, 1593, 1499, 1208, 1112 cm-1;1HNMR (DMSO-d6): δ (ppm) =
3.76 (s, 6H, 2OCH3), 4.65 (2OH exchanged with water of DMSO-d6), 6.73
(s, 1H, CH), 7.12-7.75 (m, 13 H, ArH); 13CNMR (DMSO-d6): δ (ppm) =
31.1, 52.0, 105.2, 122.4, 122.6, 126.8, 127.0, 129.1, 129.2, 129.5, 131.5,
131.9, 133.8, 138.3, 157.2, 162.8; Anal. calcd for C29H22Cl2N4O6: C, 58.70;
H, 3.74; N, 9.44; found: C, 58.63; H, 3.80; N, 9.51%.
1594, 1554, 1206, 1132, 764 cm-1; 1HNMR (DMSO-d6): δ (ppm) = 3.77
(s, 6H, 2OCH3), 4.64 (2OH exchanged with water of DMSO-d6), 7.365 (s,
1H, CH), 7.522 (m, 6H, ArH), 7.740 (m, 8H, ArH); 13C NMR(DMSO-d6):
δ (ppm) = 31.2, 52.6, 104.1, 122.1, 122.9, 128.3, 128.8, 129.4, 130.5, 131.4,
131.9, 134.2, 137.7, 142.1, 153.9, 158.9; Anal. calcd for C29H23BrN4O6: C,
57.72; H, 3.84; N, 9.28; found: C, 57.58; H, 3.73; N, 9.15%.
Methyl 4-((3-(methoxycarbonyl)-5-hydroxy-1-phenyl-1H-pyrazol-4-yl)
(4-methoxyphenyl) methyl)-5-hydroxy-1-phenyl-1H-pyrazole-3-carboxy-
late (4j): Green powder; m.p. 217–219 °C; IR (KBr): ν = 3429, 3052, 2950,
1727, 1600, 1508, 1444, 1206, 1125 cm-1;1H NMR (DMSO-d6): δ (ppm) =
3.70 (s, 6H, 2OCH3), 3.92 (s, 3H, OCH3) 4.38 (2OH exchanged with water
of DMSO-d6), 6.702 (s, 1H, CH), 6.755-7.865 (m, 14H, ArH); 13C NMR
(DMSO-d6): δ (ppm) = 31.4, 51.6, 54.3, 109.8, 121.8, 124.3, 124.8, 125.3,
126.5, 127.4, 128.5, 129.7, 138.5, 142.6, 162.4; Anal. calcd for C30H26N4O7:
C, 64.98; H, 4.73; N, 10.10; found: C, 64.78; H, 4.65; N, 10.02%.
Electronic Supplementary Information
Some characteristics of the nanocatalyst are described in the
ESI available through: http://ingentaconnect.com/content/stl/
jcr/2017/00000041/00000008
Methyl
4-((3-(methoxycarbonyl)-5-hydroxy-1-phenyl-1H-pyrazol-
4-yl)(2-methyl phenyl) methyl)-5-hydroxy-1-phenyl-1H-pyrazole-3-
carboxylate (4d): Green powder; m.p. 186–187 °C; IR (KBr): ν = 3429,
3027, 2954, 1722, 1600, 1494, 1122, 863, 762 cm-1;1H NMR (DMSO-d6):
δ (ppm) = 2.20 (s, 3H, CH3), 3.88 (s, 6H, 2OCH3), 4.86 (2OH exchanged
with water of DMSO-d6), 6.75 (s, 1H, CH), 6.93-7.76 (m,14H, ArH);
13CNMR (DMSO-d6): δ (ppm) = 31.0, 31.9, 52.3, 107.9, 122.8, 123.3, 124.8,
126.9, 127.4, 128.3, 128.4, 129.3, 137.4, 137.5, 138.5, 142.6, 162.4; Anal.
calcd for C30H26N4O6: C, 66.91; H, 4.87; N, 10.40; found: C 66.98, H, 4.96;
N 10.32%.
Received 12 May 2017; accepted 4 July 2017
Paper 170464
https://doi.org/10.3184/174751917X15000317104529
Published online: 1 August 2017
References
Methyl 4- ((3- (methoxycarbonyl) -5- hydroxy-1- phenyl-1H
-pyrazol-4-yl)(phenyl)methyl)-5-hydroxy-1-phenyl-1H-pyrazole-3-
carboxylate (4e): Brown powder; m.p. 285–286°C; IR (KBr): ν = 3427,
2954, 1707, 1599, 1575, 759, 697 cm-1;1H NMR (DMSO-d6): δ (ppm) 3.36
(s, 6H, 2OCH3), 3.78 (2OH, exchanged with water of DMSO-d6), 6.67 (s,
CH, 1H), 7.08-7.93 (m, 15H, ArH); 13C NMR (DMSO-d6): δ (ppm) = 32.2,
51.4, 105.3, 121.2, 125.3, 125.6, 128.0, 128.9, 130.5, 137.3, 139.7, 140.2,
158.5, 164.3; Anal. calcd for C29H24N4O6: C, 66.41; H, 4.61; N, 10.68;
found: C, 66.46; H, 4.72; N, 10.58%.
1
2
3
4
5
6
7
F. Wei, B.X. Zhao, B. Huang, L. Zhang, C.H. Sun, W.L. Dong, D.S. Shin and
J.Y. Miao, Bioorg. Med. Chem. Lett., 2006, 16, 6342.
D. M. Bailey, P. E. Hansen, A. G. Hlavac, E. R. Baizman, J. Pearl, A. F.
DeFelice and M. E. Feigenson, J. Med. Chem., 1985, 28, 256.
K. Sujatha, G. Shanthi, N. Panneer Selvam, S. Manoharan, P.T. Perumal and
M. Rajendran, Bioorg. Med. Chem. Lett., 2009, 19, 4501.
B.P. Bandgar, H.V. Chavan, L.K. Adsul, V.N. Thakare, S.N. Shringare, R.
Shaikh and R.N. Gacche, Bioorg. Med. Chem. Lett., 2013, 23, 912.
A.A. Bekhit, A. Hymete, H. Asfaw and A.E.D.A. Bekhit, Arch. Pharm. Chem.,
2012, 345, 147.
D. Zhang, G. Wang, C. Tan, W. Xu, Y. Pei and L. Huo, Arch Pharm Res., 2011,
34, 343.
I. Hurtado, C. Urbina, C. Suarez, B. Beyer and A.M. Magro, Int. J.
lmmunopharmac. 1985, 7, 635.
Methyl
4-yl)(2-chlorophenyl)
4-((3-(methoxycarbonyl)-5-hydroxy-1-phenyl-1H-pyrazol-
methyl)-5-hydroxy-1-phenyl-1H-pyrazole-3-
carboxylate (4f): White powder; m.p. 267–269 °C; IR (KBr): ν = 3420,
2957, 1723, 1595, 1552, 1207, 1131, 765 cm-1; 1HNMR (DMSO-d6):
δ (ppm) = 3.75 (s, 6H, 2OCH3), 4.65 (2OH exchanged with water of
DMSO-d6), 7.362 (s, 1H, CH), 7.512 (m, 6H, ArH), 7.770 (m, 8H, ArH);
13C NMR (DMSO-d6): δ (ppm) = 31.1, 51.6, 102.0, 122.5, 122.8, 127.3,
127.8, 129.3, 129.5, 131.4, 131.9, 133.2, 138.7, 141.0, 151.9, 162.9; Anal.
calcd for C29H23ClN4O6: C, 62.31; H, 4.15; N, 10.02; found: C, 62.25; H,
4.08; N, 10.08%.
Methyl 4-((3-(methoxycarbonyl) -5-hydroxy-1-phenyl-1H-pyrazol-4-yl)
(4-methylphenyl) methyl)-5-hydroxy-1-phenyl-1H-pyrazole-3-carboxy-
late (4g): Green powder; m.p. 192–194 °C; IR (KBr): ν = 3432, 3063,
2952, 1729, 1602, 1506, 1447, 1207, 1122 cm-1; 1H NMR (DMSO-d6): δ
(ppm) = 2.17 (s, 3H, CH3), 3.74 (s, 6H, 2OCH3), 4.35 (2OH exchanged with
water of DMSO-d6), 6.68 (s, 1H, CH), 6.75-7.76 (m, 14H, ArH); 13C NMR
(DMSO-d6): δ (ppm) = 29.3, 31.5, 51.6, 113.8, 122.8, 123.3, 124.8, 125.6,
126.9, 127.4, 128.4, 129.3, 138.5, 142.6, 162.4; Anal. calcd for C30H26N4O6:
C, 66.91; H, 4.87; N, 10.40; found: C, 66.97; H, 4.95; N, 10.34%.
Methyl4-((3-(methoxycarbonyl)-5-hydroxy-1-phenyl-1H-pyrazol-4-yl)
(3-nitrophenyl)methyl)-5-hydroxy-1-phenyl-1H-pyrazole-3-carboxylate
(4h): White powder; m.p. 248–250 °C; IR (KBr): ν = 3423, 2949, 1720,
1590, 1555, 1320, 1207, 1131 cm-1; 1HNMR (DMSO-d6): δ (ppm) = 3.78
(s, 6H, 2OCH3), 4.64 (2OH exchanged with water of DMSO-d6), 7.42 (s,
1H, CH), 7.515 (m, 6H, ArH), 7.784 (m, 8H, ArH); 13C NMR(DMSO-d6):
δ (ppm) = 32.1, 52.6, 105.0, 123.5, 123.8, 127.3, 128.8, 129.3, 129.5, 132.4,
133.9, 134.2, 139.6, 141.2, 151.9, 165.0; Anal. calcd for C29H23N5O8: C,
61.16; H, 4.07; N, 12.30; found: C, 61.03; H, 3.95; N, 12.14%.
8
9
D. Tejedor and F. Garcı´a-Tellado, Chem. Soc. Rev., 2007, 36, 484.
M.G. Dekamin, Z. Mokhtari and Z. Karimi, Scientia Iranica C., 2011, 18,
1356.
10 D. Banerjee, R. Karmakar, U. Kayal and G. Maiti, Synth. Commun., 2017,
10, 1006.
11 K. Niknam, D. Saberi, M. Sadegheyan and A. Deris, Tetrahedron Lett., 2010,
51, 692.
12 Z. Karimi-Jaberi, B. Pooladian, M. Moradi and E. Ghasemi, Chin. J. Catal.,
2012, 33, 1945.
13 A.R. Moosavi-Zare, M.A. Zolfigol, M. Zarei, A. Zare, V. Khakyzadeh and A.
Hasaninejad, Appl. Catal. A: Gen., 2013, 467, 61.
14 X.C. Tu, H. Feng, M.S. Tu, B. Jiang, S.L. Wang and S.J. Tu, Tetrahedron Lett.,
2012, 53, 3169.
15 P.S.V. Kumar, L. Suresh and G.V.P. Chandramouli, J. Saudi Chem. Soc., 2017,
21, 306.
16 S.S. Moganty, S. Srivastava, Y. Lu, J.L. Schaefer, S.A. Rizvi and L.A. Archer,
Chem. Mater. 2012, 24, 1386.
17 N.L. Lancaster, J. Chem. Res., 2005, 7, 413.
18 S.M.S. Chauhan and N. Jain, J. Chem. Res., 2004, 10, 639.
19 J. Safaei-Ghomi, R. Sadeghzadeh and H. Shahbazi-Alavi, RSC Adv., 2016, 6,
33676.
20 M. Armand, F. Endres, D.R. MacFarlane, H. Ohno and B. Scrosati, Nature
Mater., 2009, 8, 621.
21 J.E.L. Dullius, P.A.Z. Suarez, S. Einloft, R.F. de Souza and J. Dupont,
Organometallics, 1998, 17, 815.
22 C.A. Angell, N. Byrne and J.P. Belieres, Acc. Chem. Res., 2007, 40, 1228.
23 C. Zhong, T. Sasaki, M. Tada and Y. Iwasawa, J. Catal., 2006, 242, 357.
24 T. Sasaki, C. Zhong, M. Tada and Y. Iwasawa, Chem. Commun., 2005, 19,
2506.
Methyl4-((3-(methoxycarbonyl)-5-hydroxy-1-phenyl-1H-pyrazol-4-yl)
(2-bromophenyl) methyl) -5-hydroxy-1-phenyl-1H-pyrazole-3-carboxy-
late (4i): White powder; m.p. 230–232 °C; IR (KBr): ν = 3424, 2955, 1720,
25 Y. Lu, S.S. Moganty, J.L. Schaefer and L.A. Archer, J. Mater. Chem., 2012,
22, 4066.