Use of sodium molybdate dihydrate as an efficient heterogeneous catalyst for the synthesis of benzopyranopyrimidine derivatives

Article abstract of DOI:10.1080/15533174.2012.740717

Sodium molybdate dihydrate (Na₂MoO₄.2H₂O) has been investigated as a heterogeneous catalyst for the one-pot pseudo-four-component synthesis of the benzopyranopyrimidine derivatives. This efficient and facile technique avoids the use of difficult workup and harsh reaction conditions. Copyright Taylor & Francis Group, LLC.

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Synthesis and Reactivity in Inorganic, Metal-Organic,
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Use of Sodium Molybdate Dihydrate as an Efficient
Heterogeneous Catalyst for the Synthesis of
Benzopyranopyrimidine Derivatives
Majid M. Heravi a & Masoumeh Zakeri b
a Department of Chemistry, School of Sciences, Alzahra University, Vanak, Tehran, I. R. Iran
b Young Researchers Club, North Tehran Branch, Islamic Azad University, Tehran, I. R. Iran
Published online: 28 Dec 2012.
To cite this article: Majid M. Heravi & Masoumeh Zakeri (2013): Use of Sodium Molybdate Dihydrate as an Efficient
Heterogeneous Catalyst for the Synthesis of Benzopyranopyrimidine Derivatives, Synthesis and Reactivity in Inorganic, Metal-
Organic, and Nano-Metal Chemistry, 43:2, 211-216
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 43:211–216, 2013
Copyright ꢀ Taylor & Francis Group, LLC
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ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2012.740717
Use of Sodium Molybdate Dihydrate as an Efficient
Heterogeneous Catalyst for the Synthesis of
Benzopyranopyrimidine Derivatives
Majid M. Heravi1 and Masoumeh Zakeri2
1Department of Chemistry, School of Sciences, Alzahra University, Vanak, Tehran, I. R. Iran
2Young Researchers Club, North Tehran Branch, Islamic Azad University, Tehran, I. R. Iran
non-available reagents, drastic reaction conditions, and longer
time with difficult workup. Therefore, it has attracted continuous
interest to develop methods for the synthesis of benzopyranopy-
rimidine compounds.
Sodium molybdate was first synthesized by the method of
hydration. A more convenient synthesis is done by dissolving
MoO3 in sodium hydroxide at 50–70◦C and crystallizing the
filtered product.[9] The anhydrous salt is prepared by heating to
100◦C.
Sodium molybdate dihydrate (Na2MoO4.2H2O) has been inves-
tigated as a heterogeneous catalyst for the one-pot pseudo–four-
component synthesis of the benzopyranopyrimidine derivatives.
This efficient and facile technique avoids the use of difficult workup
and harsh reaction conditions.
Keywords benzopyranopyrimidine, multicomponent reaction, sali-
cylaldehyde, sodium molybdate dihydrate
MoO3 + 2NaOH → Na2MoO4.2H2O
[1]
INTRODUCTION
In multicomponent reactions (MCRs), three or more reac-
tants come together in a single reaction vessel to form new
products that contain structural units of all the components.
This type of reaction becomes increasingly important in organic
and medicinal chemistry because it allows obtaining highly so-
phisticated poly functional molecules through simple one-pot
procedures.[1–3] The chemistry of pyrimidines and their deriva-
tives has been studied for over a century due to the associa-
tion of these systems with a variety of biological properties.
Benzopyranopyrimidines have been reported to possess signif-
icant pharmacological activities and several papers have fo-
cused on their synthesis and physiological activities.[4–6] Re-
cently, a rapid progress has been done in the field of 4H-1-
benzopyran-2-ones and related pyrimidine, due to the interac-
tion of several drugs, receptor binding models, which enabled
a systematic and rational design of novel inhibitors of various
enzymes, such as HIV protease[7] and DNA gyrase or topoi-
somerase[8] tetrahydro-2H-benzopyran-2-ones. Though many
synthetic strategies have been applied for preparation of fused
pyrimidine derivatives, most of these methods suffer from some
drawbacks, which include use of expensive or commercially
The agriculture industry uses 1 million pounds sodium
molybdate per year as a fertilizer.[10] In particular, its use
has been suggested for treatment of whiptail in broccoli and
cauliflower in molybdenum-deficient soils.[11] It is used in in-
dustry for corrosion inhibition, as it is a non-oxidizing anodic
inhibitor.[9] The addition of sodium molybdate significantly re-
duces the nitrite requirement of fluids inhibited with nitrite-
amine, and improves the corrosion protection of carboxylate
salt fluids.[12] Moreover, sodium molybdate is used as an effi-
cient heterogeneous catalyst for soybean oil methanolysis.[13]
However, to the best of our knowledge; there are no reports
about multicomponent reactions with Na2MoO4.2H2O as a cat-
alyst. In continuation of our investigations of the synthesis of
heterocyclic compounds and designing procedures in multi-
component reactions,[14] we have developed an efficient pro-
tocol for the synthesis of benzopyranopyrimidine derivatives,
through the pseudo–four-component condensation of salicy-
laldehyde derivatives, malononitrile, and amines in the presence
of Na2MoO4.2H2O as a catalyst, in ethanol at room temperature
(Scheme 1).
EXPERIMENTAL
Received 8 November 2011; accepted 13 October 2012.
The authors gratefully acknowledge partial financial support from
Alzahra University Research Council.
Address correspondence to Majid M. Heravi, Department of Chem-
istry, School of Sciences, Alzahra University, Vanak, Tehran, I. R. Iran.
E-mail: mmh1331@yahoo.com
All the chemicals were purchased from Merck Company
(Germany). Melting points were measured, using a capillary
tube method with an electrothermal engineering LTD 9200
apparatus (United Kingdom). H and 13C NMR spectra were
1
recorded on a Bruker AQS-AVANCE spectrometer (Germany)
211

212
M. M. HERAVI AND M. ZAKERI
SCH. 1. Pseudo–four-component synthesis of benzopyranopyrimidine derivatives.
at 500 and 125 MHz, using TMS as an internal standard (DMSO NMR (500 MHz, DMSO-d6): δ 3.52 (t, 4H, J = 4.3 Hz, 2CH2),
solution). FTIR spectra were recorded using KBr disks on FT- 3.80 (t, 4H, J = 4.2 Hz, 2CH2), 4.01 (s, 2H, CH2), 6.91–6.94 (2
IR Bruker Tensor 27 instrument (Germany). Mass spectra were overlapped doublets, 2H, J = 7.9 and 7.8 Hz, ArH), 7.15–7.20
documented on an Agilent Technology (HP) mass spectrometer (m, 2H, ArH), 7.28 (t, 1H, J = 7.2 Hz, ArH), 7.35 (d, 1H,
(USA) operating at an ionization potential of 70 eV. Elemental J = 7.5 Hz, ArH), 7.38–7.39 (dd, 1H, J = 7.5 and 1.6 Hz,
analyses were performed using a Perkin-Elmer 2004 (II) CHN ArH), 8.26 (d, 1H, J = 7.8 Hz, ArH), 13.09 (s, 1H, OH) ppm;
analyzer (USA).
13C NMR (125 MHz, DMSO-d6): δ 25.56, 48.95, 66.86, 98.42,
116.95, 117.18, 118.93, 119.67, 120.70, 125.43, 128.98, 129.52,
129.89, 131.09, 150.60, 160.65, 161.41, 164.00, 164.86 ppm;
MS (EI) m/z: 361(M+); Anal. Calcd. for C21H19N3O3: C,
69.79; H, 5.30; N, 11.63. Found: C, 69.75; H, 5.45; N,
11.81.
For 2-methoxy-6-(9-methoxy-4-morpholino-5H-benzopy-
rano[2,3-d]pyrimidin-2-yl)phenol (4d), IR (KBr): 3445, 3035,
2945, 1600 cm−1; 1H NMR (500 MHz, DMSO-d6): δ 3.51(brs,
4H, 2CH2), 3.76–3.80 (brs, 7H, 2CH2, OCH3), 3.87 (s, 3H,
OCH3), 3.99 (s, 2H, CH2), 6.83 (t, 1H, J = 7.8 Hz, ArH), 6.87 (d,
1H, J = 7.5 Hz, ArH), 6.98 (d, 1H, J = 8.0 Hz, ArH), 7.05–7.10
(m, 2H, ArH), 7.85 (d, 1H, J = 8.0 Hz, ArH), 13.30 (s, 1H, OH)
ppm; 13C NMR (125 MHz, DMSO-d6): δ: 25.65, 48.97, 56.60,
56.66, 66.85, 98.30, 111.71, 115.76, 118.78, 119.00, 120.95,
121.50, 125.26, 131.34, 139.89, 148.30, 149.41, 151.19, 161.67,
164.03, 164.75 ppm; MS (EI) m/z: 421(M+); Anal. Calcd. for
C23H23N3O5: C, 65.55; H, 5.50; N, 9.97. Found: C, 65.48; H,
5.55; N, 10.01.
For 2-methoxy-6-(9-methoxy-4-(piperidin-1-yl)-5H-benzo-
pyrano[2,3-d]pyrimidin-2-yl)phenol (4e), IR (KBr): 3420,
3045, 2930, 1605 cm−1; 1H NMR (500 MHz, DMSO-d6): δ 1.69
(brs, 6H, 3CH2), 3.47 (brs, 4H, 2CH2), 3.80 (s, 3H, OCH3), 3.87
(s, 3H, OCH3), 3.96 (s, 2H, CH2), 6.84 (t, 1H, J = 7.9 Hz, ArH),
6.88 (d, 1H, J = 7.5 Hz, ArH), 6.98 (d, 1H, J = 8.0 Hz, ArH),
7.05–7.10 (m, 2H, ArH), 7.85 (d, 1H, J = 7.9 Hz, ArH), 13.49
(s, 1H, OH) ppm; 13C NMR (125 MHz, DMSO-d6): δ 24.70,
25.78, 26.35, 49.65, 56.60, 56.66, 98.00, 111.68, 115.70, 118.70,
119.08, 120.91, 121.71, 125.18, 131.34, 140.05, 148.30, 149.41,
151.26, 161.65, 164.20, 165.01 ppm; MS (EI) m/z: 419(M+);
Anal. Calcd. for C24H25N3O4: C, 68.72; H, 6.01; N, 10.02.
Found: C, 68.78; H, 6.15; N, 9.91.
For 2-(4-(dimethylamino)-9-methoxy-5H-benzopyrano[2,3-
d]pyrimidin-2-yl)-6-methoxyphenol (4f), IR (KBr): 3428, 3040,
2930, 1608 cm−1; 1H NMR (500 MHz, DMSO): δ 3.18 (s, 6H,
2CH3), 3.78 (s, 3H, OCH3), 3.85 (s, 3H, OCH3), 3.95 (s, 2H,
CH2), 6.81–6.87 (m, 2H, ArH), 6.98 (d, 1H, J = 8.0 Hz, ArH),
7.12–7.14 (m, 2H, ArH), 7.66 (d, 1H, J = 7.9 Hz, ArH), 13.39 (s,
1H, OH) ppm; 13C NMR (125 MHz, DMSO): δ 24.72, 40.60,
Typical Procedure for the Synthesis of Compound 4a
A mixture of 2-hydroxybenzaldehyde (2 mmol), malonon-
itrile (1 mmol), morpholine (1 mmol), and Na2MoO4.2H2O
(10 mol%) in ethanol (10 mL) was stirred at room tempera-
ture for 10 h (the progress of the reaction was monitored by
TLC). After completion, the reaction mixture was filtered and
the precipitate washed with H2O (3 × 5 mL) to afford pure
4a. Catalyst is soluble in water and simply separated from the
products.
Reusability of the Na2MoO4.2H2O
One of the advantages of the heterogeneous catalysts is its
ability to be recyclable. We were able to separate catalyst from
the reaction medium easily by extraction with water. The catalyst
was recovered by evaporation of the water of the aqueous layer
in a vacuum oven. Then, the catalyst was dried under vacuum for
1 h, and reused in subsequent runs. In Table 1, the comparison
of efficiency of the Na2MoO4.2H2O in synthesis of 4a after
four times is reported. As shown in Table 1, the first reaction
using recovered Na2MoO4.2H2O afforded a similar yield to that
obtained in the first run. In the second, third and fourth runs, the
yields were gradually decreased.
Spectroscopic Data for the Some Products
For 2-(4-morpholino-5H-benzopyrano[2,3-d]pyrimidin-2-
yl)phenol (4a), IR (KBr): 3440, 3045, 2965, 1605 cm−1; H
1
TABLE 1
Reuseability of the Na2MoO4.2H2O for synthesis of
2-(4-morpholino-5H-benzopyrano[2,3-d]pyrimidin-2-yl)
phenol 4a
Entry
Time (h)
Yielda (%)
1
2
3
4
12
13
15
20
85
70
60
55
aIsolated yield.

THE SYNTHESIS OF BENZOPYRANOPYRIMIDINE
213
TABLE 2
Effect of solvent on the synthesis of
2-(4-morpholino-5H-benzopyrano[2,3-d]pyrimidin-2-yl)
phenol 4a
56.63, 56.66, 98.05, 110.68, 114.79, 118.73, 119.18, 120.95,
121.78, 125.21, 129.49, 140.15, 148.33, 149.47, 151.27, 161.65,
164.22, 165.09 ppm; MS (EI) m/z: 379(M+); Anal. Calcd. for
C21H21N3O4: C, 66.48; H, 5.58; N, 11.08. Found: C, 66.48; H,
5.69; N, 10.99.
Entry
Solvent
Time (h)
Yield (%)a
For 3-(8-hydroxy-4-(piperidin-1-yl)-5H-benzopyrano[2,3-
d]pyrimidin-2-yl)benzene-1,2-diol (4h), IR (KBr): 3465, 3210,
1
2
3
4
CH3CN
CH2Cl2
Toluene
C2H5OH
24
24
48
10
55
10
Very low
90
1
3185, 2970, 1615 cm−1; H NMR (500 MHz, DMSO): δ 3.44
(brs, 4H, 2CH2), 3.80 (brs, 4H, 2CH2), 3.98 (s, 2H, CH2),
6.72–6.75 (m, 2H, ArH), 6.79 (d, 1H, J = 7.8 Hz, ArH), 6.90 (d,
1H, J = 7.5 Hz, ArH), 6.94 (t, 1H, J = 7.7 Hz, ArH), 7.74 (d,
1H, J = 7.9 Hz, ArH), 8.94 (brs, 1H, OH), 9.80 (brs, 1H, OH),
13.26 (s, 1H, OH) ppm; 13C NMR (125 MHz, DMSO): δ 25.53,
48.92, 66.81, 98.42, 113.85, 116.28, 117.98, 119.67, 121.79,
122.43, 125.98, 129.12, 141.89, 150.09, 153.60, 157.65, 161.81,
164.12, 164.80 ppm; MS (EI) m/z: 391(M+); Anal. Calcd. for
C21H19N3O5: C, 64.12; H, 4.87; N, 10.68. Found: C, 64.00; H,
4.95; N, 10.71.
aYields refer to isolated pure products.
as a catalyst[15] and microwave-assisted reactions[16] our method
gives a straightforward procedure and mild reaction conditions
at room temperature with a new catalyst.
In order to achieve suitable conditions for the synthesis
of the benzopyranopyrimidines 4, several classes of hetero-
geneous catalysts have been investigated. Heterogeneous cat-
alysts are advantageous because they are usually recyclable and
products purification is greatly facilitated. Catalysts based on
molybdenum compounds showed high efficiency in multicom-
ponent reactions.[17,18] We studied this reaction with heteropoly-
acids including Mo, such as H3[PMo12O40], H6[PMo9V3O40],
H14[NaP5W29MoO110], MoO3, and Na2MoO4.2H2O. The
Brønsted acids such as H3[PMo12O40], H6[PMo9V3O40] and
H14[NaP5W29MoO110] promoted the reaction in 30–65% yields.
(Table 3, entries 2–4). Under the same conditions, MoO3 gave
benzopyranopyrimidine 4a in 45% yield after 13 h (Table 3,
entry 5). The best overall yield was obtained using 10 mol%
Na2MoO4.2H2O in ethanol at room temperature (Table 3, entry
1).
For 4-(8-hydroxy-4-(piperidin-1-yl)-5H-benzopyrano[2,3-
d]pyrimidin-2-yl)benzene-1,3-diol (4i), IR (KBr): 3460, 3215,
1
3185, 2965, 1615 cm−1; H NMR (500 MHz, DMSO): δ 3.46
(brs, 4H, 2CH2), 3.82 (brs, 4H, 2CH2), 4.01 (s, 2H, CH2),
6.32 (d, 1H, J = 7.9 Hz, ArH), 6.56 (s, 1H, ArH), 6.77–6.80
(m, 2H, ArH), 7.13 (d, 1H, J = 7.9 Hz, ArH), 7.63 (d, 1H,
J = 8.0 Hz, ArH), 8.94 (brs, 1H, OH), 9.85 (brs, 1H, OH),
13.31 (s, 1H, OH) ppm; 13C NMR (125 MHz, DMSO): δ 25.50,
48.95, 66.86, 98.40, 116.85, 117.27, 118.94, 119.67, 120.82,
125.41, 129.01, 130.12, 130.76, 131.11, 150.63, 160.65, 161.81,
164.18, 164.82 ppm; MS (EI) m/z: 391(M+); Anal. Calcd. for
C21H19N3O5: C, 64.12; H, 4.87; N, 10.68. Found: C, 64.08; H,
5.01; N, 10.75.
RESULTS AND DISCUSSION
We herein report the use of Na2MoO4.2H2O catalyst for the
one-pot pseudo–four-component synthesis of the benzopyra-
nopyrimidine derivatives at room temperature with good yields.
To choose the best reaction conditions, first a model reaction
was selected, using 2 mmol salicylaldehyde with 1 mmol mal-
ononitrile and 1 mmol morpholine in the presence of catalytic
amounts of Na2MoO4.2H2O at room temperature. We evalu-
ated the amount of Na2MoO4.2H2O required for the model
reaction. It was found that when increasing the amount of
the Na2MoO4.2H2O from 5 to 7 and 10 mol%, the yields in-
creased from 70 to 85 and 90, respectively. Using 10 mol%
Na2MoO4.2H2O at room temperature is sufficient to push this
reaction forward. More amounts of the catalyst did not improve
the yields. In another investigation, the model reaction was ex-
amined in various solvents commonly used in organic synthetic
procedures (Table 2). Polar solvent such as ethanol was much
better than nonpolar solvents in terms of better yields and shorter
reaction times, due to the better solubility of the reagents in po-
lar solvent. In comparison with the recently reported method for
preparation of benzopyranopyrimidine derivatives with LiClO4
TABLE 3
Effect of catalyst on the pseudo–four-component synthesis of
2-(4-morpholino-5H-benzopyrano[2,3-d]pyrimidin-2-yl)
phenol 4a
Time
(h)
Yielda
(%)
Entry
Catalyst
1
2
3
4
5
Na2MoO4.2H2O (10 mol%)
H3[PMo12O40] (10 mol%)
H6[PMo9V3O40] (10 mol%)
H14[NaP5W29MoO110] (10 mol%) 10
MoO3 (10 mol%) 13
10
15
13
90
30
40
65
45
aThe yields refer to isolated products.

214
M. M. HERAVI AND M. ZAKERI
TABLE 4
Synthesis of benzopyrano[2,3-d]pyrimidine derivatives 4a
Mp (◦C)
Found (Lit.)
Entry
4a
Aldehyde
Amine
Productb
Time (h)
10
Yieldc (%)
90
200–204
210[16]
4b
11
178–180
187[16]
80
4c
4d
12
8
174–176
70
90
177–179[15]
217–219
231[16]
4e
8.30
193–196
80
181–183[15]
4f
10
18
201–204 —
75
60
4g
195–198
196–198[15]
4h
4i
8
171–173 —
175–177 —
75
70
10
aAll reactions were carried out using 2 mmol of 2-hydroxybenzaldehyde derivatives, 1 mmol malononitrile and 1 mmol amine in the presence
of Na2MoO4.2H2O as a catalyst, in ethanol at room temperature.
bAll products were characterized by IR, 1H and 13C NMR, mass spectroscopy, and CHN.
cThe yields refer to isolated products.
As shown in Table 4, to establish the generality of the method, electron-withdrawing groups such as Br result in a low amount
a wide variety of suitable substrates were employed. Various sal- of yield with long reaction time. All structures were fully charac-
icylaldehydes and amines were used and the reactions afforded terized by FTIR, 1H, 13C NMR, mass, and CHN. The treatment
the corresponding products. Salicylaldehydes bearing different of 2 mmol 2-hydroxybenzaldehyde with 1 mmol morpholine
substitutes, such as OMe, Br, and OH on the aryl rings were and 1 mmol malononitrile in ethanol in the presence of catalyst
suitable to the reaction. In the investigation of various salicy- afforded 2-(4-morpholino-5H-benzopyrano[2,3-d]pyrimidin-2-
laldehydes, it was found that electron-donating substituents such yl) phenol 4a. For instance, the IR spectrum of compound 4a
as OMe and OH are the most active in the reaction. However, showed absorption band at region 3440 cm−1 (OH). In 1HNMR

THE SYNTHESIS OF BENZOPYRANOPYRIMIDINE
215
O
N
N
H
CHO
OH
CN
CN
3
NC
CN
OH
O
NH
2
1
5
6
O
N
O
N
O
N
CHO
OH
H
[1,5] proton shift
N
OH
1
NH
NH
N
H
OH
O
N
O
7
O
N
4a
SCH. 2. Investigation of a possible reaction mechanism for 2-(4-morpholino-5H-benzopyrano[2,3-d]pyrimidin-2-yl) phenol 4a.
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In summary, we have developed benzopyranpyrimidine com-
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ence of a catalytic amount of Na2MoO4.2H2O in ethanol. The
low toxicity of the catalyst, simple experimental procedure, het-
erogeneous catalyst, and good yields of the products are the
advantages.

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