Application of Fe3O4@SiO2@sulfamic acid magnetic nanoparticles as recyclable heterogeneous catalyst for the synthesis of imine and pyrazole derivatives in aqueous medium

Article abstract of DOI:10.1007/s11164-015-2204-1

Sulfamic acid supported on Fe₃O₄@SiO₂ superpara magnetic nanoparticles was successfully applied as a recyclable solid acid catalyst with a large density of sulfamic acid groups for the synthesis of pyrazole derivatives, an important class of potentially bioactive compounds. The products are obtained in high yield from the one-pot reaction procedure involving dicarbonyl compounds and hydrazines/hydrazides. This new method totally avoids the use of toxic or expensive solvents and organic acids in this reaction.

Full text of DOI:10.1007/s11164-015-2204-1

Res Chem Intermed
DOI 10.1007/s11164-015-2204-1
Application of Fe O @SiO @sulfamic acid magnetic
3
4
2
nanoparticles as recyclable heterogeneous catalyst
for the synthesis of imine and pyrazole derivatives
in aqueous medium
1
1
2
•
B. Zakerinasab
M. M. Samieadel
•
M. A. Nasseri
•
H. Hassani
1
Received: 5 July 2015 / Accepted: 3 August 2015
Ó Springer Science+Business Media Dordrecht 2015
Abstract Sulfamic acid supported on Fe O @SiO superpara magnetic nanopar-
3
4
2
ticles was successfully applied as a recyclable solid acid catalyst with a large
density of sulfamic acid groups for the synthesis of pyrazole derivatives, an
important class of potentially bioactive compounds. The products are obtained in
high yield from the one-pot reaction procedure involving dicarbonyl compounds
and hydrazines/hydrazides. This new method totally avoids the use of toxic or
expensive solvents and organic acids in this reaction.
Keywords Heterogeneous catalyst Á Fe O @SiO Á Superparamagnetic
3
4
2
nanoparticle Á Pyrazoles
Introduction
In recent years, magnetic nanoparticles (MNPs) have gained an increasing interest
because of their potential applications such as their uses for cell separation [1],
magnetic resonance imaging [2], drug delivery systems [3], protein separation [4]
and cancer treatments through hyperthermia [5]. Also, MNPs can be a good
candidate as a support material for heterogeneous catalysts, because of easy
synthesis, high surface area, facile separation by magnetic forces, and low toxicity
and cost [6–29]. According to these attractive properties, many MNP-supported
catalysts have been designed and widely applied as novel magnetically separated
Electronic supplementary material The online version of this article (doi:10.1007/s11164-015-2204-1)
contains supplementary material, which is available to authorized users.
&
B. Zakerinasab
bzakerinasab@birjand.ac.ir
1
2
Department of Chemistry, College of Sciences, University of Birjand, Birjand 97175-615, Iran
Department of Chemistry, Payam Noor University, Birjand, Iran
123

B. Zakerinasab et al.
catalysts in traditional metal catalysis, [30–38] organocatalysis, [39–41] and even
enzyme catalysis [42].
On a different note, the development of new methodologies for the synthesis of
pyrazoles is a subject of continuous interest to synthetic organic/medicinal chemists,
as pyrazole and their derivatives have versatile biological activities [43]. These
compounds are known to exhibit a wide spectrum of therapeutic and pharmaco-
logical properties such as antitumor cyclin-dependent kinase (CDK) inhibitors,
monoamine oxidase-B (MAO-B) inhibitor, antiinflammatory agents and a typical
antipsychotics property [44–46].
In continuation of our work on the synthesis of efficient and nontoxic nano-
catalysts and their application in the synthesis of biologically important compounds
[
47–52], in this work, we used Fe O @SiO @sulfamic acid as a nanometer-scale,
3 4 2
magnetic, supported, acidic catalyst for the synthesis of pyrazoles by the
condensation of dicarbonyl compounds and hydrazines/hydrazides. Pyrazole and
imine derivatives were produced with good to high yields (78–98 %) in aqueous
medium (Scheme 1).
Experimental
Chemicals
Reagents and solvents were purchased from Merck or Fluka chemical companies.
Purity determinations of the products were accomplished by TLC on silica-gel
polygram SILG/UV 254 plates. Melting points were measured on an Electro thermal
9
100 apparatus. IR spectra were taken on a Perkin Elmer 781 spectrometer in KBr
-
1
1
13
pellets and reported in cm . H NMR and C NMR spectra were measured on a
Bruker DPX-250 Avance instrument at 250 and 62.9 MHz in CDCl or DMSO-d
3
6
with chemical shift given in ppm relative to TMS as internal standard. The
morphology of the products were determined by using CMPhilips10 model
Transmission Electron Microscopy (TEM) at an accelerating voltage of 100 kV.
Power X-ray diffraction (XRD) was performed on a Bruker D -advance X-ray
8
diffractometer with Cu Ka (k = 0.154 nm) radiation. The thermo-gravimetric
analysis (TGA) curves were recorded under air atmosphere using a TGA/DTA
Shimadzu-50 with a platinum pan. The samples were heated in air from 25 to
8
00 °C with a heating rate of 10 °C/min. The weight losses as a function of
temperature were recorded. The magnetic properties were determined by using a
vibrating sample magnetometer (VSM) leak shore 7200 at 300 KVsm leak shore.
Catalyst preparation
Preparation of Fe O nanoparticles
4
3
First, 15 g sodium hydroxide (NaOH) was dissolved into 25 mL deionized water.
Then, the mixture of 2 g FeCl Á4H O, 5.2 g FeCl Á6H O, 25 mL deionized water
2
2
3
2
and 0.85 mL HCl was added drop by drop with vigorous stirring to make a black
1
23

Application of Fe
3
O
4
@SiO
2
@sulfamic acid magnetic…
R2
N
O
N
R3
R1
O
R1
R2
NHNH2
O N
2
R3
N N
N
O
N
H
NO2
NO
O N
2
2
R3
R1
R2
O
NH
H N
2
NH2
HN
R3
O
O
R1
R2
NH2
HN
R3
NHNH2
NO2
O
NH2
R1
R3=Ph
O N
2
HN
N N
O
R3
R3
OH
R1
R2
R1
O N
2
N
N
NO2
N
N N
N
H
H
R3
O
NO2
O N
2
R1
R2
O
N
O
N
R3
H
Scheme 1 Synthesis of pyrazole and imine derivatives
solid product. The resultant mixture was heated in a water bath for 4 h at 80 °C. The
black magnetite solid MNPs were isolated by an external magnet and washed with
deionized water and ethanol three times and then dried at 80 °C for 10 h.
Preparation of Fe O @SiO core-shell
2
3
4
Fe O (0.50 g, 2.1 mmol) was dispersed in the mixture of ethanol (100 mL) and
3
4
deionized water (20 mL) for 10 min, Then, 2.5 mL of NH was added followed by
3
the addition of tetraethoxysilane (TEOS) (1.5 mL) drop by drop. This solution was
stirred mechanically for 6 h at room temperature. Then, the product Fe O @SiO
2
3
4
123

B. Zakerinasab et al.
was separated by an external magnet and was washed with deionized water and
ethanol three times and dried at 80 °C for 10 h.
Preparation of Fe O @SiO bonded propyl chloride (Fe O @SiO @PC)
3
4
2
3
4
2
Fe O @SiO (1.0 g) was suspended in dry toluene (30 mL) and then 3-chloropropyl
3
4
2
trimethoxysilane (30.0 mL) was added followed by triethyl amine (1 mL) as a
catalyst. The suspension was mechanically stirred as it was heated under reflux
under Ar atmosphere for 48 h. Fe O @SiO bonded propyl chloride MNPs were
3
4
2
isolated by an external magnet. The collected powder was washed using toluene and
ethanol and dried under vacuum at 80 °C for 4 h to give Fe O @SiO bonded N-
3
4
2
propyl chloride (Fe O @SiO @PC). (Fe O @SiO @PC).
3
4
2
3
4
2
Preparation of Fe O @SiO bonded N-propyldiethylenetriamine
2
3
4
(
Fe O @SiO @PDETA)
3 4 2
To a mixture of Fe O @SiO bonded N-propyl chloride (1 g) in dry toluene
3
4
2
(30 mL), diethylenetriamine (30 mL) was added and the mixture was heated under
Ar atmosphere under reflux with stirring for 36 h. The reaction was cooled to room
temperature and the Fe O @SiO bonded N-propyl diethylenetriamine MNPs were
2
3
4
isolated by an external magnet. The collected compound was washed using toluene
and methanol and dried for 6 h at 80 °C to give Fe O @SiO @PDETA.
3
4
2
Preparation of Fe O @SiO bonded N-propyl diethylenetrisulfamic acid
3
4
2
(
Fe O @SiO @PDETSA)
3 4 2
To a magnetically stirred mixture of Fe O @SiO @PDETA (0.5 g) in CHCl
3
3
4
2
(10 mL) at 0 °C, chlorosulfonic acid (3.5 g) was added dropwise over 1 h. After the
addition was complete, the mixture was stirred for 12 h until all HCl was removed
from the reaction vessel. Fe O @SiO bonded N-propyl diethylenetrisulfamic acid
2
3
4
MNPs were isolated by an external magnet and were washed with methanol and
diethyl ether (30 mL) and then dried at room temperature to give
Fe O @SiO @PDETSA.
3
4
2
Catalytic activity
General procedure for the preparation of pyrazol derivatives
To a mixture of dicarbonyl compounds (1.0 mmol) and hydrazines/hydrazides
1.0 mmol) Fe O @SiO @PDETSAMNPs (0.005 g) was added in water (2 mL).
3 4 2
(
The mixture was stirred for the appropriate time at rt, as shown in Tables 3, 4 and 5.
Completion of the reaction was indicated by TLC monitoring. After completion of
the reaction, Fe O @SiO @PDETSAMNPs were separated by external magnet.
3
4
2
Then, the product was extracted with ethyl acetate (2 9 10 mL). The organic layer
was dried (Na SO ) and evaporated, and the crude product was purified by flash
column chromatography (ethyl acetate/n-hexane, 1:20) to provide the pure product.
2
4
1
23

3 4 2
Application of Fe O @SiO @sulfamic acid magnetic…
1
13
Structural assignments of the products are based on their H NMR, C NMR, mass
and IR spectra.
Results and discussion
Due to the reasonable needs for clean and green recovery of the heterogenous
catalyst, we synthesized Fe O @SiO bonded N-propyl diethylene tetra sulfamic
3
4
2
acid (Fe O @SiO @PDETSA) as a nanomagnetic heterogeneous system with a
2
3
4
large density of sulfamic acid groups. First, Fe O MNPs were prepared by the
3
4
reaction of FeCl Á4H O, FeCl Á6H O with sodium hydroxide in deionized water.
2
2
3
2
For coating silica on Fe O MNPs, NH was added to a mixture of Fe O and
3 4
3
4
3
tetraethoxysilane (TEOS) and was stirred mechanically for 6 h at room temperature
to produce Fe O @SiO MNPs. Then, Fe O @SiO propyl chloride was prepared
by the reaction of Fe O @SiO with (3-chloropropyl) trimethoxy silane in dry
3
4
2
3
4
2
3
4
2
toluene for 48 h. Then resulting compound was treated with diethylene triamine in
dry toluene for 36 h to give Fe O @SiO bonded N-propyl diethylene triamine
3
4
2
(
Fe O @SiO @PDETA). Finally, the reaction of (Fe O @SiO @PDETA) with
3 4 2 3 4 2
chlorosulfonic acid at 0 °C gave Fe O @SiO bonded N-propyl diethylene
3
4
2
tetrasulfamic acid (Fe O @SiO @PDETSA) (Scheme 2). The structural properties
of the synthesized Fe O , Fe O @SiO and Fe O @SiO @PDETSA MNPs were
3
4
2
3
4
3
4
2
3
4
2
analyzed by XRD and TEM. According to the result calculated by Scherrer
equation, it was found that the diameter of the Fe O nanoparticles obtained was
about 8 nm, while Fe O @SiO microspheres were obtained with a diameter of
3
4
3
4
2
about 10 nm due to the agglomeration of Fe O inside the nanospheres and the
3
4
surface growth of silica on the shell. The average sizes of Fe O @SiO @PDETSA
3
4
2
nanoparticles are calculated to be 12 nm, which is in good accordance with the
TEM results. Elemental analysis of Fe O @SiO @PDETSA gave the following
3
4
2
results: N and S, 1.54 and 4.69 %, respectively. A ratio N:S of 3:4 was obtained,
determined from elemental analysis. The content of S obtained from elemental
?
analysis showed that, typically, a loading of 1.4 mmol/g H was obtained.
In order to show the merits of synthesized heterogeneous catalyst in organic
reactions, Fe O @SiO bonded N-propyl diethylene tetrasulfamic acid (Fe O @-
3
4
2
3 4
SiO @PDETSA) was used for the synthesis of pyrazol from the condensation of
2
dicarbonyl compounds with hydrazine/hydrazide compounds. At the onset of this
work, the reaction of pentane-2,4-dione (1 mmol) and phenyl hydrazine (1 mmol)
as the model substrates was studied under different experimental variants
(
Scheme 3).
In preliminary experiments, this reaction was carried out in various solvents, with
Fe O @SiO @PDETSA (0.005 g) as a catalyst under ambient condition. The
3
4
2
reaction proceeded in polar and non-polar solvents in good to excellent yields. The
reaction proceeded in excellent yields (98 %) in aqueous medium (Table 1, entry 1).
Then, we changed the amount of catalyst. The results are summarized in Table 2.
Consequently, among the tested catalyst amounts, the condensation of pentane-2,4-
dione (1 mmol) and phenyl hydrazine (1 mmol) was best catalyzed by 0.005 g of
Fe O @SiO @PDETSA at room temperature. To illustrate the need for
3
4
2
123

B. Zakerinasab et al.
O
OH
Si
Si
O
OH OH
OH
Si
HO
O
O
O
OH
O
FeCl3.6H2O
+
FeCl2.4H2O
O
Si
HO
HO
NaOH, Ar
TEOS/ NH3
SiO
O
O
NanoFe3O4
OH
OH
Si O NanoFe
3
O
4
O Si
HSi
OH
H O/ EtOH
2
HO
O
O
O
O
OH
Si
O
O
HO
OH
O
Si
Si
OH
Si
O
O
O
O
Cl
Si
O
O
O
O
Cl
O
Si Si
O
O
Si
O
Si
O
2
H N
O
O
O
O
(
MeO)3Si
Si
Cl
HN
Si
O
O
NH2
Toluene, reflux
Si O NanoFe
3
O
4
O Si
O
O
Si
O
O
Si
Si
Si
Cl
N
NH2
O
NH
O
O
O
Si
O
H
Si
O
O
O
Si
O
O
O
O
N
N
NH
H
H
2
O
Si Si
Si
O
Si
O
O
O
O
O
Si
Si
O
N
NX2
O
O
NX
X
NanoFe O
Si O
3
4
O Si
Si
O
O
O
O
O
O
Si
NH
H
N
Si
O
N
H
2
O
O
Si
Si
Si
Si
O
O
O
O
O
O
O
N
NX2
O
NX
NX
X
O
Si Si
Si
O
Si
O
O
O
O
O
O
Si
Si
O
O
O
Si O
NanoFe
3
O
4
O Si
O
O
Si
O
O
X
NX2
Si
O
Si
N
O
O
O
Si
O
Si
Si
O
O
O
Scheme 2 Preparation of Fe
[Fe @SiO @PDETSA]
3 4 2
O @SiO bonded N-propyl diethylene tetrasulfamic acid MNPs
3
O
4
2
Fe O @SiO @PDETSA for this condensation, we examined the model reaction in
4
3
2
the absence of a catalyst. In this case, the reaction gives pyrazol in a rather low yield
Table 2, entry 5). Obviously, Fe O @SiO @PDETSA is an important component
of the reaction. The optimal amount of Fe O @SiO @PDETSA was 0.005 g per
(
3
4
2
3
4
2
1
mmol of reagents in 2 mL of water at room temperature.
To further explore the scope and limitation of this protocol under the optimized
conditions, particularly in regard to library construction, it was evaluated using
various hydrazines/hydrazides and diketone compounds. The results are summa-
rized in Table 3. In all cases, the reaction proceeded readily at rt to afford the
corresponding pyrazoles in good to excellent yields (78–98 %) in very short
reaction times (5–50 min). When pentane-2,4-dione was employed, the reaction
proceeded readily and the desired pyrazole was afforded in high yields (Table 3,
entries 1–5). It is excellent that some less reactive carbon electrophiles such as 1,3-
diphenyl propane-1,3-dione can serve as good substrates in this reaction (Table 3,
entries 10–13); however, the reaction time of 1,3-diphenyl propane-1,3-dione was
1
23

3 4 2
Application of Fe O @SiO @sulfamic acid magnetic…
Scheme 3 Synthesis of 3,5-
dimethyl-1-phenyl-1H-pyrazole
N
Ph
O
O
H
N
N
NH2
Ph
Table 1 Effect of solvents on
the synthesis of pyrazol
catalyzed by
a
Solvent no
Solvent
Yield (%)
1
2
3
4
5
6
7
8
9
H
2
O
98
95
95
93
93
87
87
85
80
76
83
3 4 2
Fe O @SiO @PDETSA
EtOH
MeOH
EtOAc
DMSO
DMF
Reaction conditions: pentane-
,4-dione (1 mmol), phenyl
hydrazine (1 mmol), catalyst
0.005 g), solvent (2 mL),
stirred at room temperature for
ClCH
2
2
CH Cl
2
THF
(
CHCl3
CH Cl
1
1
0
1
2
2
5
min
Solvent-free
a
Isolated yields
Table 2 The effect of amounts of catalyst on the synthesis of pyrazol
a
Entry
Amounts of catalyst (g)
Yield (%)
1
2
3
4
5
0.001
0.005
0.007
0.01
80
98
98
98
38
None
Reaction conditions: pentane-2,4-dione (1 mmol), phenyl hydrazine (1 mmol), Water (2 mL), stirred at
room temperature for 5 min
a
Isolated yields
longer than those of acethylaceton, which is probably due to the low reactivity of the
carbonyl groups. Also, it was found that both hydrazines and hydrazides could be
used. The reaction time of hydrazides and 1,3-dicarbonyl compounds was longer
than those of hydrazines. This behaviour could result from the low reactivity of
hydrazides.
b-Ketoester has been used with similar success to provide the corresponding
pyrazole derivatives which are also of much interest with respect to their biological
activities (Table 4). As shown in Tables 3 and 4, it was found that this method
works with a wide variety of substrates. A series of different substituted diketons,
including electron-withdrawing or electron-donating groups, and different substi-
tuted b-ketoesters were used in this reaction. Additionally, the reaction with various
hydrazines or hydrazides also proceeded. It is noteworthy that phenylhydrazine
123

B. Zakerinasab et al.
Table 3 Preparation of pyrazol derivatives catalyzed by Fe
3
O
4
@SiO
2
@PDETSA
R1
N
R3
O
O
nano Fe
3
O
4
@SiO
2
@PDETSA
H
N
N
R3
NH
2
R1
R2
2
H O, r.t
R2
a
Entry
1
Diketone
Hydrazines/hydrazides
Time (min)
Yield (%)
O
O
H
N
5
98
89
Ph
NH
O
2
O
O
O
2
3
4
7
O
NH
H N
2
O
O
10
5
87
95
NH
2
N
H
H
N
O
O
O
O
NH
2
Cl
NH
2
5
6
5
92
88
H N
2
O
O
O
H
N
15
Ph
CF3
CF3
Ph
NH
O
2
O
O
O
7
8
9
30
30
82
82
O
NH
H N
2
Ph
Ph
Ph
O
O
NH
N
2
CF3
CF3
H
H
N
O
O
O
O
NH
2
15
30
50
50
90
87
78
78
Cl
O
H
1
1
1
0
1
2
N
Ph
NH
2
Ph
Ph
Ph
Ph
Ph
Ph
O
O
O
O
NH
H N
2
O
NH
2
N
H
H
N
O
O
1
3
NH
2
35
85
Ph
Ph
Cl
Reaction conditions: hydrazines/hydrazides (1 mmol), diketone (1 mmol), Fe
0.005 g), H O(2 mL), stirred at room temperature
Isolated yields
3 4 2
O @SiO @PDETSA
(
a
2
1
23

Application of Fe
3
O
4
@SiO
2
@sulfamic acid magnetic…
3 4 2
Table 4 Preparation of pyrazol derivatives catalyzed by Fe O @SiO @PDETSA
a
Entry
1
β-Ketoester
Hydrazines
Time (min)
10
Yield (%)
92
O
O
H N
NH2
2
O
O
O
O
2
3
H N
2
NH2
15
15
88
85
H
O
O
N
NH2
O
Cl
O
O
O
O
H
4
5
N
15
25
88
82
Ph
Ph
NH2
O
O
H
N
NH2
H
O
O
N
6
NH2
35
82
O
Cl
Reaction conditions: hydrazines (1 mmol), b-ketoester (1 mmol), Fe
O(2 mL), stirred at room temperature
3
O
4
@SiO
2
@PDETSA (0.005 g),
H
2
a
Isolated yields
R1
R =Me, R =OEt, OMe
O
1
2
N
N
R =Ph
3
O
O
R3
H
N
R1
R2
R3
NH2
R =H
3
R1
R =Me, R =OEt, OMe
OH
1
2
N
N
R3
Scheme 4 Synthesis of analogues of pyrazole
reacted with b-ketoester to form the product containing the carbonyl group on ring
systems (Scheme 4; Table 4, entries 3–6). But it is interesting that, when hydrazine
and b-ketoester were used as the substrates, the reaction failed to afford the
expected product. In this case, another type of pyrazole analogue, 3-methyl-1H-
pyrazole-5-ol, was obtained in 88 and 92 % isolated yield (Scheme 4 and Table 4,
123

B. Zakerinasab et al.
Table 5 Preparation of imine derivatives catalyzed by Fe
3
O
4
@SiO
2
@PDETSA
H
N
O
O
O
O
N
NH2
nano Fe3O4@SiO2@PDETSA
N
Me
R
H
O
H O, r.t
2
R
R = OMe , OEt
a
Entry β-Ketoester
Hydrazides
Time (min)
45
Yield (%)
O
O
O
1
2
76
80
O
NH
O
H N
2
O
O
O
O
O
O
45
O
O
NH
H N
O
2
O
3
4
45
40
72
82
NH2
N
H
O
O
O
NH2
N
H
O
O
O
5
6
30
30
77
78
S
S
NH
H N
O
2
O
O
O
NH
H N
O
2
3 4 2
Reaction conditions: hydrazide (1 mmol), b-ketoester (1 mmol), Fe O @SiO @PDETSA (0.005 g),
H
2
O(2 mL), stirred at room temperature
a
Isolated yields
entries 1 and 2). This result clearly showed that the groups on nitrogen could lead to
different structures of pyrazole.
When hydrazides were employed with b-ketoester, the reaction did not give any
pyrazole-products and the imine adducts was only isolated product (Table 5).
Nevertheless, diketones led to the desired pyrazole in an excellent yield (Table 3,
entry 2, 7 and 11).
Following this procedure, we tested 2,4-dinitrophenylhydrazine in the reaction in
order to obtain the same pyrazole but without different substituents on the N-atom.
Surprisingly, the products were not the desired pyrazole (the expected products of
the reaction of acethylaceton and phenylhydrazine are shown in Scheme 3). We
1
23

Application of Fe
3
O
4
@SiO
2
@sulfamic acid magnetic…
R1
R2
O2N
NO2
N
N
N
H
R1=R2=Me
N
H
NO2
O2N
O
O
O2N
NHNH2
R1
R2
NO2
R1
R2
O2N
N
O
N
R =Me, R =OEt, OMe
1
2
H
NO2
Scheme 5 Synthesis of imine
Fig. 1 Recycle of the catalyst for the synthesis of pyrazol
have found that the condensation of 2,4-dinitrophenylhydrazine with diketon or b-
ketoester leads to the formation of imine compounds (Scheme 5). The low reactivity
of 2,4-dinitrophenylhydrazine containing electron-withdrawing groups (NO ) can
2
be attributed to their relatively weak nucleophilicity and therefore decreased activity
in this reaction. The use of stoichiometric quantities (1:1) of 2,4-dinitrophenylhy-
drazine and diketone gave product 6 in 35 % yield relative to the diketone.
Treatment 1 eq. of diketone with 2 eq. of 2,4-dinitrophenylhydrazine improved the
yield to 87 %.
At the end of the reaction, the catalyst could be recovered by an external magnet.
The recycled catalyst was washed with dichloromethane and subjected to a second
reaction process. The results show that the yield ofthe product after seven runs was
only slightly reduced (Fig. 1).
Conclusion
In conclusion, the present work provided a new type of heterogeneous compound
for potential synthetic application. Fe O @SiO @PDETSA MNPs are an efficient
3
4
2
and reusable catalyst for the synthesis of pyrazol and imine derivatives. The product
has been achieved by a one-pot coupling reaction of dicarbonyl compounds and
123

B. Zakerinasab et al.
hydrazines/hydrazides at ambient condition in a short period of time in aqueous
medium. In addition, it is easy to separate and recover the catalyst for another
catalytic recycling.
Acknowledgment We gratefully acknowledge the support of this work by the Birjand University
Research Council.
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