Using magnetic nanoparticles Fe3O4 as a reusable catalyst for the synthesis of pyran and pyridine derivatives via one-pot multicomponent reaction

Article abstract of DOI:10.1007/s13738-015-0684-y

An atom-economical, efficient and mild protocol is described for the synthesis of 2-amino-3-cyanopyridine and 2-amino-3-cyano-4H-pyran derivatives in the presence of high surface area Fe₃O₄ as a highly effective heterogeneous catalys

Full text of DOI:10.1007/s13738-015-0684-y

J IRAN CHEM SOC
DOI 10.1007/s13738-015-0684-y
ORIGINAL PAPER
Using magnetic nanoparticles Fe3O4 as a reusable catalyst
for the synthesis of pyran and pyridine derivatives via one‑pot
multicomponent reaction
Majid M. Heravi1 · S. Yahya Shirazi Beheshtiha1 · Mahzad Dehghani1 ·
Nastaran Hosseintash1
Received: 14 February 2015 / Accepted: 13 June 2015
© Iranian Chemical Society 2015
Abstract An atom-economical, efficient and mild proto-
col is described for the synthesis of 2-amino-3-cyanopyr-
idine and 2-amino-3-cyano-4H-pyran derivatives in the
presence of high surface area Fe3O4 as a highly effective
heterogeneous catalyst via one-pot multicomponent cyclo-
condensation reaction.
In recent years, several methods and developments have
been reported for the synthesis of pyran and pyridine [13–17]
derivatives; each has its own merits and drawbacks. Many
of the standard procedures require long reaction times,
harsh reaction conditions, expensive and toxic reagents,
solvents, and tedious work-up procedures. Moreover in
some cases, a mixture of products is obtained, needing
cost-effective column chromatography, naturally result-
ing in low yields. Heterogeneous catalysis is of supreme
importance in many areas of the chemical and energy con-
suming industries [18, 19].
Keywords Pyran · Pyridine · Magnetic nanoparticles
Fe3O4 · Multicomponent reaction · Recyclable catalyst ·
Green chemistry
Conducting the reactions, using heterogenous catalysts
should compensate some of drawbacks observed in previ-
ously reported reactions. In this kind of reaction, the cata-
lyst can be separated by filtration. However, it is worthy to
mention in spite of several advantages, experienced, practi-
cally in using of heterogenous catalysts, due to the nano-
sized particles used, few limitations to the sustainability are
observed [20].
To get around these problems, the use of a heterogene-
ous catalyst which can be separated practically other than
filtration is desirable. Magnetite nanoparticles (Fe3O4)
have attracted much attention in the past decade, due to
their unique features, including, low preparation cost, high
thermal and mechanical stability, and adaptability for large-
scale production. In addition, their paramagnetic nature
allows their facile and effective separation from the reac-
tion mixture, without using standard filtration, required in
separation of heterogeneous catalysts. Magnetite nanoparti-
cles (Fe3O4) can be easily separated from reaction mixture
by using just an external magnet [21].
Introduction
The development of efficient methods for the construction
of poly-functionalized heterocyclic compounds has allo-
cated a broad area of organic and medicinal chemistry [1].
Among heterocyclic compounds, 2-amino-3-cyano deriva-
tives have recently received considerable attention due to
their potential biological and pharmaceutical activities [2,
3]. 2-amino-3-cyanopyridine and 2-amino-3-cyano-pyran
derivatives are one of the most prevalent heterocyclic
molecular frame works found in natural products, pharma-
ceuticals, vitamins, and functional materials [4–7].
Besides, they are useful intermediates [8, 9] and exhibit
significant activity as potential antitumor agents, smooth
muscle cell proliferation inhibitors, and useful for treat-
ment for intestinal cystitis [10–12].
* Majid M. Heravi
Thus, in recent years, nano-Fe3O4 [22] has attracted
a great attention as heterogeneous catalyst [23] due to its
simple handling, easy of recovery with an external mag-
netic field [24, 25]. Magnetic nanoparticles (MNPs) have
mmh1331@yahoo.com
1
Department of Chemistry, School of Science,
Alzahra University, Vanak, Tehran, Iran
1 3

J IRAN CHEM SOC
emerged as viable alternatives to conventional materials,
as robust, readily available, oxidative stability, biologi-
cal compatibility, and high catalytic activities in various
organic transformations [26–31].
a Barnstead Electrothermal 9200 apparatus. FT-IR spectra
were recorded using KBr disks on FT-IR Bruker Tensor
27 instrument in the 500–4000 cm−1 region. The vibra-
tional transition frequencies are reported in wave numbers
(cm−1). Band intensities are assigned as weak (w), medium
(m), and strong (s). All yields refer to isolated products.
The nano-sized particles increase the exposed surface
area of the active component of the catalyst [32, 33], thereby
enhancing the contact between reactants and catalyst dramat-
ically [34–38]. These nano-catalyst bridge the gap between
homogeneous and heterogeneous catalysis [39], thus pre-
serving the desirable attributes of both systems [40, 41].
Multicomponent reactions (MCRs) [42, 43] have
received substantial consideration from the organic com-
munity for their innumerable advantages over conventional
multistep synthesis [44, 45]. The formation of C–N [46]
and C–O [47] bonds by MCRs, which are becoming pow-
erful tools in the modern synthetic chemistry due to their
efficiency, atom economy, and convenience in one-pot pro-
cesses [48].
Recently, we have used nano-Fe3O4 as an efficient and
easily separable catalyst in different organic reactions
[49–51].
In this paper, we wish to report a convenient, green,
practical and efficient approach for the synthesis of
2-amino-3-cyanopyridine and 2-amino-3-cyano-4H-pyran
derivatives via one-pot MCRs using nano-sized magnetic
Fe3O4 as heterogeneous catalyst.
Synthesis of catalyst
Magnetic nanoparticles Fe3O4 were synthesized via a co-
precipitation method as described previously [52–55] and
applied to the following MCRs as a catalyst.
Synthesis of 2‑amino‑3‑cyano‑4H‑pyran derivatives
(4a–4e): general procedure
A mixture of an appropriate aromatic aldehyde (1.0 mmol),
pyruvic acid (1.0 mmol), and malononitrile (1.2 mmol) was
dissolved in ethanol (15 ml). Fe3O4 nano-catalyst (0.03 g)
was then added to this mixture. This mixture was stirred
under reflux. The progress of reaction was monitored by
TLC (7:3, n-hexane/ethyl acetate). Upon completion of
the reaction, the mixture was cooled to room temperature.
Then the catalyst was separated from this mixture by an
external magnet and washed with hot acetic acid (5 ml) and
ethanol (5 ml), dried in oven, and stored for use in subse-
quent run under the same conditions. The remaining solu-
tion is concentrated to give of 2-amino-3-cyano-4H-pyrans
as a crude. This crude was crystallized from acetic acid to
obtain the pure products. (4b–e) (Table 4) (Scheme 1).
Experimental
General
Synthesis of 2‑amino‑3‑cyanopyridine derivatives
(7a–7g): general procedure
Chemicals and solvents were purchased from Merck–
Aldrich and used directly with high-grade quality, with-
out any purification. TLC analyses were done using pre-
coated TLC silica gel 60 F254 (Merck) plates. Melting
points were measured using a capillary tube method with
A mixture of an appropriate aromatic aldehyde (1.0 mmol),
acetophenone (1.0 mmol), malononitrile (1.0 mmol),
ammonium acetate (1.5 mmol), and Fe3O4 (0.04 g) was
Scheme 1 Synthesis of 2-amino-3-cyano-4H-pyran derivatives (4a–e)
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J IRAN CHEM SOC
Scheme 2 Synthesis of 2-amino-3-cyanopyridine derivatives (7a–g)
heated under stirring at 80 °C in an oil bath in solvent-free
conditions. The progress of the reaction was monitored by
TLC (7:3, n-hexane/ethyl acetate). After completion of the
reaction (as indicated in Table 7), the mixture was cooled
to room temperature. Then the catalyst was separated from
this mixture by an external magnet and washed with hot
acetic acid (5 ml) and ethanol (5 ml), dried in oven, and
stored for use in subsequent run under the same conditions.
The remaining solution is concentrated under reduced pres-
sure to give of 2-amino-3-cyanopyridine as a crude. This
crude was crystallized from ethanol to afford the pure prod-
ucts. (7b–g) (Table 7) (Scheme 2).
the influence of amount of catalyst and temperature on the
progress of model reaction was investigated (Table 3). Con-
sequently, as it can be seen in Table 3, the best result was
obtained when 0.03 g of catalyst was used (Table 3, entry
2). Under the optimized reaction conditions concluded,
various substituted benzaldehydes were reacted with pyru-
vic acid and malononitrile in the presence of nano-Fe3O4
in refluxing ethanol. All reactions proceeded to completion
within 1–1.5 h, and 4H-pyrans were isolated in excellent
yields. The selected 2-amino-3-cyano-4H-pyran derivatives
Table 1 Synthesis of 4a in the presence of different catalysts in
reflux condition
Entry
Catalyst (0.05 g)
Time (min)
Yield (%)a
Results and discussion
1
2
3
4
5
6
Sulfamic acid
H6P2Mo18O62
Fe3O4 NPS
Fe3O4 bulk
SMI-SO3H
–
180
60
81
85
Initially, for the optimization of the reaction conditions,
the reaction of benzaldehyde (1a), pyruvic acid (2), and
malononitrile (3) was chosen as a model and was examined
under a variety of conditions. Firstly, we used diverse cata-
lysts such as SMI-SO3H, sulfamic acid, H6P2Mo18O62, and
nano-Fe3O4 and also tested the un-catalyzed reaction. The
un-catalyzed reaction proceeded sluggishly, monitored the
reaction by TLC analysis, and after long reaction time gave
4a in low yield. Among the catalysts tested, nano-Fe3O4
gave the highest yield of 4a (Table 1, entries 3). The other
catalysts examined such as sulfamic acid and H6P2Mo18O62
were also effective (Table 1, entries 1 and 2). As a result,
Fe3O4 nano-catalyst was considered as a catalyst of choice
to synthesize different derivatives in order to establish the
generality of the method. It shows a higher reactivity, and
requiring short reaction time. We next investigated the
effect of solvents, such as H2O, CH3CN, EtOH, and also
solvent-free condition for the synthesis of 4a (Table 2).
As it can be seen in Table 2, ethanol was the best solvent
regarding the reaction yield (Table 2, entry 2). Additionally,
60
91
80
60
180
240
59
Trace
1.0 mmol (1a), 1.0 mmol (2), and 1.2 mmol (3) in the presence of
0.05 g of catalyst and 4 ml of EtOH
a
Refers to the isolated yield
Table 2 Synthesis of 4a in the presence of different solvents
Entry Solvent
Time (min) Temperature (°C) Yield (%)a
1
2
3
4
H2O
180
60
Reflux
Reflux
Reflux
100
80
CH3CH2OH
CH3CN
–
91
360
180
Trace
69
1.0 mmol (1a), 1.0 mmol (2), and 1.2 mmol (3) in the presence of
0.05 g of catalyst and 4 ml of solvent
a
Refers to the isolated yield
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J IRAN CHEM SOC
Table 3 Synthesis of 4a in the presence of different amounts of cata-
Table 5 Synthesis of 7a in the presence of different catalysts at
lyst and temperatures
80 °C
Entry
Catalyst (g)
Temperature (°C)
Yield (%)a
Entry
Catalyst (0.05 g)
Time (h)
Yield (%)a
1
2
3
4
5
6
7
0.02
0.03
0.04
0.05
0.03
0.03
0.03
Reflux
Reflux
Reflux
Reflux
70–80
79
91
91
91
70
78
81
1
2
3
4
5
6
Sulfamic acid
H6P2Mo18O62
Fe3O4 NPS
Fe3O4 bulk
SMI-SO3H
–
4
79
1
83
0.5
3
90
60
3
56
90–100
110–120
6
Trace
1.0 mmol (1a), 1.0 mmol (5a), 1.0 mmol (3), and 1.5 mmol (6) in the
presence of 0.05 g catalyst
1.0 mmol (1a), 1.0 mmol (2) and 1.2 mmol (3)
a
a
Refers to the isolated yield
Refers to the isolated yield
Table 4 Synthesis of 2-amino-3-cyano-4H-pyran derivatives (4a–e)
under optimized conditions
5, malononitrile 6, ammonium acetate 7 as a model reaction
under optimal conditions, concluded from nano-Fe3O4 cata-
lyzed synthesis of pyran derivatives. Delightfully, the model
reaction in optimal conditions gave 90 % yield for the corre-
sponding pyridine derivative, 7a (Table 5, entry 3). It is signifi-
cant to note that when the amount of catalyst was decreased
from 0.04 to 0.02 g, an appreciable decrease in the yield was
observed (Table 6, entries 4–6). Interestingly, the increment
in the amount of catalyst did not show any significant effect
on the product yield and reaction time. The analysis of the
obtained results indicated that the best condition was achieved
by carrying out the reaction in the presence of 0.04 g catalyst
in solventless conditions (Table 6, entry 4). To study the influ-
ence of temperature, the model reaction was carried out at
different temperatures (Table 6). The best yield was observed
when the reaction was heated at 80 °C in solvent-free con-
ditions (Table 6, entry 4). To establish, the generality of this
methodology, we used various substituted benzaldehydes to
obtain (7a–g). All compounds were known and their structures
were confirmed by comparison of physical and spectral data
with those of already reported (Table 7) [58–60].
Entry Product Time (min) Yield (%)a Mp (°C)/Lit. Mp [ref]
1
2
3
4
5
4a
4b
4c
4d
4e
60
55
80
50
65
91
79
80
68
70
210–214/216–218 [26]
274–276/279 [26]
256–259/260–262 [26]
236–238/240–241 [27]
215–217/218–220 [26]
1.0 mmol (1a), 1.0 mmol (2), and 1.2 mmol (3) in the presence of
0.03 g of catalyst and 4 ml EtOH at reflux condition
a
Refers to the isolated yield
(4a–e) were fully characterized, and their physical data
were compared with those of authentic compounds and
found to be identical (Table 4) [56, 57].
Encouraged by these results, we also examined the cata-
lytic activity of nano-Fe3O4 in the synthesis of 2-amino-
3-cyanopyridine derivatives 7a. We performed a one-pot
four component reaction of benzaldehyde, 1a, acetophenone
Table 6 Optimization
Entry
Product
Solvent
Catalyst (g)
Temperature (°C)
Time (h)
Yield (%)a
conditions for the synthesis of
7a in the presence of Fe3O4
catalyst
1
7a
7a
7a
7a
7a
7a
7a
7a
7a
7a
7a
H2O
0.04
0.04
0.04
0.04
0.02
0.03
0.05
0.04
0.04
0.04
0.04
Reflux
Reflux
Reflux
80
2.15
2
80
75
80
90
83
85
90
86
87
90
90
2
CH3CH2OH
3
CH3CN
2.5
0.5
1.45
1.30
0.5
3
4
–
–
–
–
–
–
–
–
5
80
6
80
7
80
8
60
9
70
0.5
0.5
0.5
10
11
100
120
1.0 mmol (1a), 1.0 mmol (5a), 1.0 mmol (3), and 1.5 mmol (6)
a
Refers to the isolated yield
1 3

J IRAN CHEM SOC
Table 7 Synthesis of 2-amino-3-cyanopyridine derivatives (7a–g)
under optimized conditions
malononitrile). Next via route A, the intermediate III,
formed by the 1,4-Michael addition of tautomerized ace-
tophenone II to alkylidene malononitrile I. Intermolecu-
lar cyclization of this created intermediate III affords the
desired pyrans (4a–e) (Scheme 3) [61].
In similar way, via route B, imine V (formed from the
reaction of an appropriate ketone and ammonium acetate)
is added to alkylidene malononitrile I via 1,4-Michael addi-
tion to give intermediate VI, followed by tautomerization
and intramolecular cyclization, to afford the intermediate
VII which is subjected to oxidative the aromatization of to
give the corresponding pyridines (7a–g) (Scheme 3) [58].
In practical applications of heterogeneous catalysis, the
reusability of the catalyst is important. In this work, we
examined the possible recovery and reusability of nano-
Fe3O4 in the aforementioned reactions.
Entry Product Time (h) Yield (%)a Mp (°C)/Lit. Mp [ref]
1
2
3
4
5
6
7
7a
7b
7c
7d
7e
7f
2
90
83
83
87
86
83
82
186–187/187–189 [28]
233–235/234–235 [28]
181–182/179–181 [29]
207/209–210 [29]
2.15
2.5
2.5
2.15
2
230–233/230–232 [30]
223–225/224–226 [30]
212–213/210–212 [28]
7 g
3
1.0 mmol (1a), 1.0 mmol (5a), 1.0 mmol (3), and 1.5 mmol (6) in the
presence of 0.04 g catalyst at 80 °C
a
Refers to the isolated yield
A proposed mechanism for the nano-Fe3O4-catalyzed
formation of 2-amino-3-cyano derivatives is shown in
Scheme 3. According to this suggested mechanism, nano-
Fe3O4 acts as a Lewis acid, playing a significant role
in increasing the electrophilic character of the electro-
philes. The reaction may proceed via alkylidene malon-
onitrile I (generated from condensation of aldehyde with
After completion of the model reactions, the catalyst
was recovered from the reaction mixture simply by using
an external magnet. The recovered catalyst was suspended
in (5 ml) hot acetic acid. This suspension was filtered and
washed with diethyl ether and dried. This recovered cata-
lyst was used in both aforementioned reactions. As shown
in Fig. 1, the recovered catalyst could be re-used at least 4
Scheme 3 Proposed mechanism of the synthesis of (4a–e), (7a–g)
1 3

J IRAN CHEM SOC
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In summary, an extremely efficient, mild, facile and eco-
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pyridine and pyran derivatives has been developed, via a
one-pot MCR, in the presence of high surface area Fe3O4
(MNPs) as a highly effective heterogeneous catalyst. The
catalysts show environmental friendly character and recy-
clability, being re-used at least in four consecutive runs
without significant loss of catalytic activity. This develop-
ment in the synthesis of two important heterocyclic sys-
tems, in comparison with previously reported methods, not
only affords the desired products in excellent yields but
also required shorter reaction times. The most important
advantage of our protocol is the convenient separation of
the commercially purchasable or readily available nano-
Fe3O4 catalyst from reaction mixture and reusing it in sev-
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