Three-component synthesis of pyrano[2,3-d]pyrimidinone derivatives catalyzed by Ni2+ supported on hydroxyapatite-core–shell-γ-Fe2O3 nanoparticles in aqueous medium

Article abstract of DOI:10.1007/s11164-016-2555-2

Pyrano[2,3-d]pyrimidine derivatives were synthesized via one-pot, three-component condensation reaction of aromatic aldehydes, malononitrile, and barbituric acid in aqueous ethanol catalyzed by Ni²⁺ supported on hydroxyapatite-core–shell-γ-Fe

Full text of DOI:10.1007/s11164-016-2555-2

Res Chem Intermed
DOI 10.1007/s11164-016-2555-2
Three-component synthesis of pyrano[2,3-d]
pyrimidinone derivatives catalyzed by Ni supported
2
+
on hydroxyapatite-core–shell-c-Fe O nanoparticles
2
3
in aqueous medium
1
2
3
•
Sobhan Rezayati
Rahimeh Hajinasiri
•
Zahra Abbasi
1
•
Eshagh Rezaee Nezhad
2
•
Abdolhadi Farrokhnia
Received: 24 February 2016 / Accepted: 19 April 2016
Ó Springer Science+Business Media Dordrecht 2016
Abstract Pyrano[2,3-d]pyrimidine derivatives were synthesized via one-pot, three-
component condensation reaction of aromatic aldehydes, malononitrile, and barbi-
2
turic acid in aqueous ethanol catalyzed by Ni supported on hydroxyapatite-
?
2
?
core–shell-c-Fe O nanoparticles (c-Fe O @HAp-Ni NPs) as Lewis acid. The
2
3
2 3
nontoxic nature and easy handling of the catalyst, environmentally friendly and
facile work-up procedure, short reaction time, low catalyst loading, and high
effectiveness to give products in good to excellent yield are advantages of this
2
?
approach. Also, c-Fe O @HAp-Ni NPs can be easily recovered and reused for at
2
3
least six runs.
2?
Keywords Nanoparticles Á Lewis acid catalyst Á Supported Ni Á Multicomponent
reaction Á Pyrano[2,3-d]pyrimidinone Á Knoevenagel reaction
Introduction
Multicomponent reactions (MCRs) have attracted considerable interest due to their
ease of performance, high yield, and especially synthetic feasibility and efficiency
[
1–3]. MCRs include three or more starting materials reacting in a single flask to
Electronic supplementary material The online version of this article (doi:10.1007/s11164-016-2555-2)
contains supplementary material, which is available to authorized users.
&
Sobhan Rezayati
sobhan.rezayati@yahoo.com
1
Chemistry Department, Qaemshahr Branch, Islamic Azad University,
P.O. Box 163, Qaemshahr, Iran
2
3
Chemistry Department, College of Science, Shahid Chamran University, Ahvaz, Iran
Department of Chemistry, Payame Noor University, P.O. Box 19395-4697, Tehran, Iran
123

S. Rezayati et al.
form a new product, where basically all the atoms contribute to the newly formed
product. Pyrano[2,3-d]pyrimidine derivatives are examples where multicomponent
synthesis can be used. Due to the diverse biological activity of compounds in this
class, there is great interest in their synthesis.
Pyrano[2,3-d]pyrimidine structures have a wide range of biological activities
such as spasmolytic, diuretic, anticoagulant, antitumor, antiallergic, anticoagulant,
anticancer, and antianaphylactic activity, as well as acting as potassium channel
activators [4–6]. Synthesis of pyrano[2,3-d]pyrimidines has been achieved by
many methods, including microwave condition [7, 8], ultrasonic irradiation [9], in
absence of catalysts [10], Zn[(L)proline]2 [11], 1,4-diazabicyclo[2.2.2]octane
(
DABCO) [12], alum [13], and ionic liquids [11]. Reported methods appearing in
literature usually involve forcing conditions, long reaction time, waste creation,
need for complex synthetic procedures, and involvement of organic solvents as
well as high energy to proceed. So, due to environmental concerns associated with
aspects of organic solvents, development of aqueous-phase synthesis of
pyrano[2,3-d]pyrimidines is of considerable interest in such research to achieve
short reaction time, environmentally friendly procedures, and excellent yield by
such new methods. Recently, application of nanoparticles (NPs) has attracted
considerable attention in both industrial and academic research due to their unique
properties based on their high surface area and unique magnetic properties. Also,
they have a wide range of uses in various fields such as biology and medical
applications [14], magnetic resonance imaging [15], environmental remediation
[16], data storage [17], and magnetic fluids [18], while recent studies have also
shown that magnetic nanoparticles are excellent supports for various catalysts
[
19, 20].
As part of our current studies aimed at identifying ecofriendly methods for
synthesis of pyrano[2,3-d]pyrimidinones (4a–p), we report herein a one-pot, three-
component reaction between aromatic aldehydes, malononitrile, and barbituric acid
2
?
catalyzed by Ni supported on hydroxyapatite-core–shell-c-Fe O NPs in aqueous
2
3
ethanol at room temperature, achieving good to excellent isolated yields (85–95 %)
(
Scheme 1).
H
O
R
γ-Fe O @HAp-Ni2+NPs
2
3
R
1
O
CN
NH2
NC
CN
HN
EtOH (10 ml)
15-35 min
2
O
O
N
H
O
NH
4
(a-p)
O
N
H
3
O
Scheme 1 Synthesis of pyrano[2,3-d]pyrimidine derivatives
1
23

Three-component synthesis of pyrano[2,3-d]pyrimidinone…
Experimental
Materials and methods
All chemicals were purchased from Merck or Fluka chemical companies. All
13
1
products are known compounds and were characterized by comparing H and
C
nuclear magnetic resonance (NMR) spectroscopic data and melting points with
literature values. Uncorrected melting points of all compounds were measured in an
1
open capillary in a paraffin bath. H and C NMR spectra were recorded using a
13
1
13
Bruker instrument ( H at 400 MHz and C at 100 MHz) in dimethyl sulfoxide
DMSO)-d solvent with tetramethylsilane (TMS) as internal standard. Infrared (IR)
(
6
spectra were recorded on a Frontier FT-IR (PerkinElmer) spectrometer using a KBr
disk. Thin-layer chromatography (TLC) was performed with silica gel 60 F254
plates with ultraviolet (UV) light for visualization. The phases present in the
magnetic materials were analyzed by powder XRD (model X0 Pert with X’Pert;
˚
Philips, The Netherlands) with Cu Ka1 radiation (k = 1.5401 A), operating the
X-ray generator at 40 kV and 30 mA. Diffraction patterns were collected in the 2 h
range of 20–80°.
2
1
Preparation of c-Fe O @HAp-Ni NPs
2
3
2
?
In this study, c-Fe O @HAp-Ni
NPs were prepared according to literature
2
3
2?
procedure. Then, the mean size and surface morphology of the c-Fe O @HAp-Ni
2
3
NPs were characterized by transmission electron microscopy (TEM), scanning electron
microscopy (SEM), vibrating-sample magnetometry (VSM), X-ray diffraction (XRD)
analysis, and Fourier-transform infrared (FTIR) spectroscopy techniques [21–23].
General procedure for synthesis of pyrano[2,3-d]pyrimidinone derivatives
4
a–p
Substituted aromatic aldehydes 1 (1 mmol), malononitrile 2 (1 mmol), barbituric
2
?
acid 3 (1 mmol), and c-Fe O @HAp-Ni NPs (10 mg) in EtOH (10 mL) was
2
3
stirred at room temperature for appropriate time (see Table 4). After reaction
completion as monitored by TLC (ethyl acetate:n-hexane 7:3), the filtrate mixture
was recrystallized to provide pure crystals of pyrano[2,3-d]pyrimidinone derivatives
with excellent yields (85–95 %). The products were known compounds and were
characterized based on IR and NMR spectroscopic data. Their melting points (m.p.)
were compared with reported values.
Results and discussion
In continuation of our studies toward development of new and cleaner methods for
2
organic transformations [23–32], in this study, we prepared Ni supported on
?
hydroxyapatite-core–shell-c-Fe O nanoparticles, according to reported procedures
2
3
(
Scheme 2), and then used them for one-pot, three-component condensation
123

S. Rezayati et al.
FeCl
2 2
. 4H O
FeCl
3
2
. 6H O
NH
4
OH (25%)
2
Ca (NO3)2 4H O
O
2
(
4 2
NH ) HPO
o
300 οC, 3h
90 οC, 2 h
2
5 C
2 2
FeCl . 4H O
2
5 οC, 48 h
Scheme 2 Synthesis of catalyst
Table 1 Effect of various
b
2
?
Entry
Amount of catalyst (mg)
Time (min)
Yield (%)
2 3
loadings of c-Fe O @HAp-Ni
NPs for synthesis of 4a in
solvent-free conditions at room
temperature
a
1
2
3
4
5
6
7
No catalyst
2 h
50
50
40
35
45
45
39
65
72
88
79
68
55
1
5
10
15
20
30
a
In hours
b
Isolated yield
reaction of aromatic aldehydes with malononitrile and barbituric acid in EtOH as
green solvent at room temperature (Scheme 1). The structure of the c-Fe O @HAp-
2
3
2
?
Ni NPs was characterized by FTIR spectroscopy, XRD analysis, VSM, SEM, and
TEM (see supporting information for experimental procedures for synthesis of
2
?
c-Fe O @HAp-Ni NPs) [22, 23].
2
3
To optimize the catalyst loading, the reaction of benzaldehyde 1 (1 mmol) with
malononitrile 2 (1 mmol) and barbituric acid 3 (1 mmol) was investigated as a model,
and its behavior studied under solvent-free conditions at room temperature (Table 1).
As shown in Table 1, in absence of catalyst, the reaction was slow and resulted in poor
yield (39 %), even after long reaction time (2 h) (Table 1, entry 1). The best result was
2?
obtained when the reaction was carried out in presence of 10 mg c-Fe O @HAp-Ni
2
3
NPs under solvent-free conditions at room temperature (Table 1, entry 4). Higher
1
23

Three-component synthesis of pyrano[2,3-d]pyrimidinone…
Table 2 Synthesis of
a
Entry
Solvent
Time (min)
Yield (%)
compound 4a in presence of c-
2
?
2 3
Fe O @HAp-Ni NPs (10 mg)
1
2
3
4
5
6
7
MeCN
EtOH
45
25
60
60
60
60
60
50
in various solvents
95
MeOH
71
CHCl
Ethyl acetate
CH Cl
PhCH
3
Trace
Trace
65
2
2
3
Trace
a
Isolated yield
catalyst loading (20–30 mg) neither increased the yield nor shortened the conversion
time (Table 1, entries 6, 7). Hence, the optimum concentration of c-Fe O @HAp-
Ni NPs was chosen as 10 mg in the model reaction.
2
3
2?
In the next step, to improve the yield of 4a, we carried out the test reaction in
presence of polar and nonpolar solvents such as acetonitrile, ethanol, methanol,
chloroform, ethyl acetate, dichloromethane, and acetone; the results are presented in
Table 2, indicating that the solvent had a significant effect on product yield and
reaction time. As shown in Table 2, it was found that ethanol was a solvent of
choice for the reaction, with product 4a obtained after 25 min in excellent yield
(
Table 2, entry 2). When the reaction proceeded in other solvents, the desired
products were obtained in low yield even after 60 min (Table 2, entries 1, 3, and 6).
No reaction occurred when ethyl acetate or chloroform was used as solvent
(
Table 2, entries 5, 6). Therefore, this reaction was developed with other aldehydes;
the results are summarized in Table 4. Use of aqueous ethanol as solvent in the
reaction medium showed remarkable benefits, such as environmental safety, lack of
carcinogenic effects, comparatively low cost to operate, and simple work-up.
Then, we examined the catalytic activity of various acids such as citric acid,
0
0
tartaric acid, cyanuric chloride, N,N,N ,N -tetrabromobenzene-1,3-disulfonamide
0
(
TBBDA), and poly(N,N -dibromo-N-ethylbenzene-1,3-disulfonamide) (PBBS) in
the model reaction of benzaldehyde 1 (1 mmol) with malononitrile 2 (1 mmol) and
Table 3 Synthesis of compound 4a using various catalysts
c
Entry
Catalyst
Time (min)
Yield (%)
1
2
3
4
5
6
7
a
Citric acid
120
120
120
180
180
120
25
51
45
55
63
65
NR
95
Tartaric acid
Cyanuric chloride
a
TBBDA
b
PBBS
Silica gel
2
?
2 3
c-Fe O @HAp-Ni NPs
0
0
N,N,N ,N -tetrabromobenzene-1,3-disulfonamide
0
b
c
Poly(N,N -dibromo-N-ethylbenzene-1,3-disulfonamide)
Isolated yield
123

S. Rezayati et al.
2
?
2 3
Table 4 Synthesis of pyrano[2,3-d]pyrimidinones catalyzed by c-Fe O @HAp-Ni NPs
m.p. (°C)
Found
Entry
1
Product
Time (min) Yield (%)a
Reported
O
CN
25
15
95
90
205–207
235–237
206–208 [34]
HN
O
N
H
O
NH2
4
a
Cl
O
2
CN
234–235 [34]
HN
O
N
H
O
NH2
4b
Cl
O
CN
HN
3
4
25
17
92
93
241–243
238–240
242–244 [34]
239–241 [34]
O
N
H
O
NH2
4
c
Cl
O
Cl
CN
HN
O
N
H
O
NH2
4d
Cl
O
Cl
CN
HN
5
6
25
15
85
95
225–226
237–240
227–228 [35]
239–241 [34]
O
N
H
O
NH2
4
e
NO2
O
CN
HN
O
N
H
O
NH2
4
f
1
23

Three-component synthesis of pyrano[2,3-d]pyrimidinone…
Table 4 continued
m.p. (°C)
Found
Entry
Product
Time (min) Yield (%)a
Reported
NO2
O
CN
HN
7
20
17
93
91
272–274
226–228
271–272 [34]
O
N
H
O
NH2
4
4
g
Me
O
8
9
CN
226–227 [34]
HN
O
N
H
O
NH2
h
Me
O
CN
HN
20
25
90
91
225–227
280–282
224–225 [34]
280–284 [34]
O
N
H
O
NH2
4
i
OMe
O
1
0
CN
HN
O
N
H
O
NH2
4
j
OMe
O
CN
HN
1
1
2
20
15
88
93
223–225
252–254
200–202 [34]
252–253 [34]
O
N
H
O
NH2
4
k
CN
O
1
CN
HN
O
N
H
O
NH2
4
l
123

S. Rezayati et al.
Table 4 continued
m.p. (°C)
Found
Entry
Product
Br
Time (min) Yield (%)a
Reported
O
13
CN
15
92
235–236
235–236 [34]
HN
O
N
H
O
NH2
4
m
OH
O
CN
HN
1
4
5
30
20
90
90
161–163
269–271
160–162 [34]
268–270 [34]
O
N
H
O
NH2
4
n
F
O
1
CN
HN
O
N
H
O
NH2
4
o
CHO
O
16
CN
35
88
332–334
335–337 [34]
HN
O
N
H
O
NH2
4
p
a
Isolated yield
barbituric acid 3 (1 mmol) in EtOH as green solvent at room temperature (Table 3).
As can be seen in Table 3, various catalysts such as citric acid (entry 1), tartaric
acid (entry 2), and cyanuric chloride (entry 3) were less efficient. Also, it is also
clearly seen from these data that no yield of the corresponding 4a was obtained
when amorphous silica gel was employed as catalyst (Table 3, entry 6). The
reaction was very slow when using TBBDA (Table 3, entry 4) or PBBS (Table 3,
entry 5), with the corresponding product isolated in only 63 or 65 % yield,
respectively, after 180 min (Table 1, entry 8). Excellent product yield (95 %) was
2
?
obtained in short reaction time (25 min) when c-Fe O @HAp-Ni
NPs was
2
3
utilized as catalyst (Table 3, entry 7). This study clearly showed that c-Fe O @
2
3
2
HAp-Ni NPs exhibit higher activity under the same reaction conditions and
?
1
23

Three-component synthesis of pyrano[2,3-d]pyrimidinone…
2
?
catalyst loading. c-Fe O @HAp-Ni NPs are a good catalyst for synthesis of
2
3
pyrano[2,3-d]pyrimidinone derivatives. Therefore, this reaction was developed with
other aldehydes; the results are summarized in Table 4.
As shown in Table 4, various pyrano[2,3-d]pyrimidinone derivatives (4a–p) were
prepared from aromatic aldehydes (with electron-withdrawing as well as electron-
donating groups such as Cl, Br, F, CH , OCH , CN, OH, and NO ) with malononitrile
3
3
2
and barbituric acid in EtOH as green solvent at room temperature in good to excellent
yields (85–95 %) in short reaction times (15–35 min). In general, the results given in
Table 4 reveal that excellent yield and short reaction time of pyrano[2,3-d]pyrim-
idinone derivatives were obtained under mild conditions. The data obtained from IR,
1
13
H NMR, and C NMR spectra confirmed all of the proposed products. The
1
13
structures of compounds 4a–p were deduced from IR, H and C NMR spectra,
confirming all of the proposed products.
Catalyst recycling is one of the most important advantages of our method. For
this purpose, the reaction of benzaldehyde 1 (1 mmol) with malononitrile 2
(
Fe O @HAp-Ni NPs (10 mg) at room temperature. After reaction completion as
1 mmol) and barbituric acid 3 (1 mmol) was performed in presence of c-
2?
2
3
monitored by TLC, the mixture was filtered, and complete separation of the product
from the surface of the catalyst was achieved by washing the catalyst with hot
ethanol (2 9 5 mL). Finally, the recovered catalyst was washed with acetone and
dried before use for six consecutive runs (Fig. 1).
Although we have not established the reaction mechanism, a possible explanation
is given in Scheme 3. The reaction may proceed first via Knoevenagel condensation
of aryl aldehyde 5 with malononitrile 6 to afford Michael acceptor 8. Intramolecular
cyclization condensation of 10 gives 11. Finally, intermediate 11 converts to
product 12 after proton transfer and tautomerization. The reaction mechanism is
assumed to be the same as that proposed by Rezaee Nezhad et al. in 2009 for
synthesis of dihydropyrimidinone derivatives [33].
To show the efficiency of the present method, we compare the results of
pyrano[2,3-d]pyrimidinone derivative synthesis from benzaldehyde 1 (1 mmol),
malononitrile 2 (1 mmol), and barbituric acid 3 (1 mmol) in presence of
1
00
8
0
6
0
Time (min)
Yield (%)
40
2
0
6
5
0
4
3
2
Rum
1
2
?
Fig. 1 Recyclability of c-Fe
2
O
3
@HAp-Ni NPs
123

S. Rezayati et al.
O
NH
O
2
N
N
H
H
C
C
C
Cat.
Ar
H
HC
Ar
H
C
N
6
5
3
Knoevenagel
condensation
-
H O
2
O
OH
O
Ar
H
CN
Ar
H
CN
CN
HN
HN
Michael
N
CN
O
O
N
H
O
O
N
H
O
O
N
H
1
7
8
9
Cat.
O
Ar
O
O
Ar
O
O
Ar
CN
NH
CN
CN
N
N
N
O
N
H
NH2
O
N
H
O
N
H
OH
1
2
11
10
Fe O
3
4
2+
Cat. γ-Fe O @HAp-Ni NPs
2
3
Scheme 3 Proposed mechanism for one-pot synthesis of pyrano[2,3-d]pyrimidinones catalyzed by c-
2
?
2 3
Fe O @HAp-Ni NPs
[
KAl(SO ) ], [BMIm]BF , Zn[(l)proline] , diammonium hydrogen phosphate
4 2 4 2
(
SO H with respect to catalyst reusability, reaction time, product yield, and reaction
DAHP), dibutylamine, L-proline, 1,4-dioxane, H [NaP W O110, and SBA-Pr-
1
4
5
30
3
condition in Table 5. Recently, use of [BMIm]BF (Table 5, entry 2), Zn[(l)pro-
4
line] (Table 5, entry 3), and DAHP (Table 5, entry 4) was reported for preparation
2
of pyrano[2,3-d]pyrimidine derivatives. These methods have longer reaction times
and lower product yields. Also, slightly longer reaction times (30–120 min) are
found when using L-proline (Table 5, entry 6) as catalyst, with the corresponding
1
23

Three-component synthesis of pyrano[2,3-d]pyrimidinone…
Table 5 Comparison of results for synthesis of pyrano[2,3-d]pyrimidinone derivatives catalyzed by our
new catalyst with those obtained by recently reported catalysts
a
Entry
Catalyst
Condition
Time (min)
Yield (%)
Ref.
1
2
3
4
5
6
7
8
9
[KAl(SO
4
)
2
]
H
2
O/80 °C
30–45
3–5 h
0.5–12 h
2 h
81–88
82–95
80–92
71–81
83–94
68–85
60–70
85–90
30–91
85–95
[13]
[BMIm]BF
4
[BMIm] BF
4
/90 °C
[11]
Zn[(l)proline]
DAHP
2
EtOH/reflux
EtOH/r.t.
[35]
[36]
Dibutylamine
L-Proline
Aq. EtOH/reflux
Aq. EtOH/reflux
43–129
30–120
1–2
[37]
[38]
1,4-Dioxane
H
2
O/reflux
[39]
H
14[NaP
SBA-Pr-SO
c-Fe @HAp-Ni NPs
Isolated yield
5
W
30
O
110
EtOH/reflux
30–60
10–45
15–35
[40]
3
H
Solvent-free/140 °C
EtOH/r.t.
[34]
2?
10
2
O
3
This work
a
Table 6 Scalability of synthesis of pyrano[2,3-d]pyrimidinone derivatives by reaction of aromatic
@HAp-
aldehydes (15 mmol), malononitrile (15 mmol), and barbituric acid (15 mmol) using c-Fe
2
O
3
2
Ni NPs (10 mg) in EtOH as green solvent at room temperature
?
a
Entry
Product
Time (min)
Yield (%)
1
2
3
4
a
4a
4f
40
15
25
19
91
92
87
91
4h
4m
Isolated yield
product isolated in only 68–85 % yield. Use of 1,4-dioxane (Table 5, entry 7) as
catalyst for synthesis of pyrano[2,3-d]pyrimidinone derivatives has been reported,
requiring reaction time of almost 1–2 h with low product yields (60–70 %). Use of
SBA-Pr-SO H (Table 5, entry 9) as catalyst for synthesis of pyrano[2,3-d]pyrim-
3
idinone derivatives has also been reported. This method relies on use of high
temperature (140 °C) and also has low product yields (30–91 %). As indicated by
2
?
Table 5, c-Fe O @HAp-Ni
NPs show remarkably improved synthesis of
pyrano[2,3-d]pyrimidinone, with shorter reaction times (15–35 min) and higher
2
3
yields (85–95 %).
In subsequent work, to determine the scalability of our method, we examined
some reactions at larger scale (15 mmol of each reactant); the results are
summarized in Table 6, revealing that the reactions were successfully performed
at larger scale without significant loss of yield.
Conclusions
We report an efficient and green method for one-pot, three-component synthesis of
pyrano[2,3-d]pyrimidinones (4a–p) catalyzed by an efficient and heterogeneous
2
?
nanocatalyst of Ni supported on hydroxyapatite-core–shell-c-Fe O as reusable
2
3
123

S. Rezayati et al.
Lewis acid catalyst in EtOH at room temperature. The catalyst is stable and can
promote yields and reaction times over six runs without significant loss of activity.
Furthermore, short reaction time, solvent-free reaction condition, high product
yield, nonchromatographic product purification, i.e., simple recrystallization from
ethanol, easy work-up, and clean procedure make this approach a useful addition to
available methods. The new catalyst was fully characterized by several techniques
including FTIR spectroscopy, XRD analysis, VSM, TEM, and SEM.
Acknowledgments We gratefully acknowledge funding from the National Elites Foundation of Iran for
this research.
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