Nano-ZnO Impregnated on Starch—A Highly Efficient Heterogeneous Bio-Based Catalyst for One-Pot Synthesis of Pyranopyrimidinone and Xanthene Derivatives as Potential Antibacterial Agents

Article abstract of DOI:10.1134/S1070428020070234

Abstract: A new method has been proposed for the synthesis of pyranopyrimidinone andxanthene derivatives using zinc oxide–starch nanocomposite as catalyst undermicrowave irradiation. The ZnO–starch nanocomposite was characterized by X-raydiffraction and s

Full text of DOI:10.1134/S1070428020070234

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2020, Vol. 56, No. 7, pp. 1279–1288. © Pleiades Publishing, Ltd., 2020.
Nano-ZnO Impregnated on Starch—A Highly Efficient
Heterogeneous Bio-Based Catalyst for One-Pot Synthesis
of Pyranopyrimidinone and Xanthene Derivatives
as Potential Antibacterial Agents
A. Amininiaa, K. Pourshamsiana,*, and B. Sadeghia
a Department of Chemistry, Tonekabon Branch, Islamic Azad University, Tonekabon, 46841-61167 Iran
*e-mail: Kshams49@gmail.com
Received January 25, 2020; revised February 5, 2020; accepted February 11, 2020
Abstract—A new method has been proposed for the synthesis of pyranopyrimidinone and xanthene derivatives
using zinc oxide–starch nanocomposite as catalyst under microwave irradiation. The ZnO–starch nanocomposite
was characterized by X-ray diffraction and scanning electron microscopy data, and the size of the ZnO-starch
nanocomposite particles was estimated at 70–90 nm. The catalyst was used in the three-component condensation
of aromatic aldehydes with barbituric acid and malononitrile and the 1:2 condensation of aromatic aldehydes
with naphthalen-2-ol to obtain pyranopyrimidinone and xanthene derivatives, respectively. The catalyst can be
reused several times without loss of catalytic activity. The proposed procedure utilizes affordable and
inexpensive materials, provides excellent yields in short reaction time, and is eco-friendly, which makes it more
economic than conventional methods. The antibacterial activity of the synthesized compounds was evaluated
against M. luteus and P. aeruginosa.
Keywords: ZnO–starch nanocomposite, microwave-assisted synthesis, pyranopyrimidinone, xanthene, antibac-
terial activity
DOI: 10.1134/S1070428020070234
INTRODUCTION
environmentally benign procedures is essential for
the synthesis of pyranopyrimidinone and xanthene
derivatives.
Pyranopyrimidinone and xanthene derivatives con-
stitute important classes of organic compounds used in
pharmaceutical chemistry [1]. They have various
pharmacological activities such as antiviral [2], anti-
bacterial [3], antitumor [4], hepatoprotective [5], anti-
fungal [6], and anti-inflammatory activities [7] and are
used as food additives [8]. Several synthetic protocols
have been reported for the synthesis of pyranopyrimi-
dinone and xanthene derivatives, including cycliza-
tions catalyzed by palladium compounds [9–11],
various Lewis acids such as NbCl2 [12–14], and
Brønsted acids [15–18].
Many organic reactions are carried out at elevated
temperature on heating on an oil or sand bath. These
old methods can cause problems such as by-product
formation, product decomposition, and so on. Micro-
wave heating, in addition to solving these problems,
provides very rapid reactions and generates a heat
system that cannot be easily accessed by other methods
[22, 23]. The main advantage of using microwave
radiation in the synthesis of organic compounds is
much shorter reaction time than in conventional
thermal method.
Many of the reported methods for synthesis of the
pyranopyrimidinone and xanthene derivatives utilize
expensive reagents and catalysts, strongly acidic con-
ditions, inert atmosphere, and toxic organic solvents
and are characterized by long reaction times and low
yields [19–21]. In order to avoid these restrictions, the
development of new highly effective catalysts and
In continuation of our research aimed at finding
efficient catalysts for the synthesis of pyranopyrimi-
dinone and xanthene, we focused on another suitable
substrate for the synthesis of nanocomposite catalysts.
Such a substrate is starch which is an affordable, inex-
pensive, and environmentally friendly material.
1279

AMININIA et al.
1280
RESULTS AND DISCUSSION
because of its empty orbitals. In recent years, a variety
of polymers have been studied as lightweight matrices
for coating and modifying nanoparticles [31]. In addi-
tion, the polymer shell inhibits nanoparticle aggrega-
tion, increases stability, reduces toxicity, and increases
shelf life [32]. According to [33], the viscosity of water
and starch is high. By adding a solution of zinc salt
a solution with lower viscosity is obtained. Presumably,
zinc ions interact with hydroxy oxygen atoms of starch,
thus weakening the intermolecular hydrogen bonding
of the starch and disrupting its crystalline structure,
which gives a solution with lower viscosity.
We were interested in the synthesis of pyrano-
[2,3-d]pyrimidine and xanthene derivatives via
a domino Knoevenagel–Michael condensation [24–29]
catalyzed by ZnO&starch in aqueous ethanol under
microwave irradiation at a power of 230 W. The cata-
lytic significance of ZnO&starch has been highlighted
in increasing the yield of the products. The catalyst was
prepared according to the reported procedure [30].
Previous investigations have shown that Lewis
acids reduce the potential barrier to reactions. We
decided to investigate the catalytic activity of ZnO–
starch nanocomposite, which can act as a Lewis acid
The morphology of ZnO&St nanocomposite was in-
vestigated by scanning electron microscopy. Figure 1a
(a)
(b)
Fig. 1. SEM images of ZnO&St nanocomposite at different magnifications: (a) view field 2.97 μm; (b) view field 10.9 μm.
(a)
(b)
8000
6000
Zn
4000
O
2000
0
Zn
C
Zn
10
0
10
20
30
40
2θ, deg
50
60
70
Energy, keV
Fig. 2. (a) EDX and (b) XRD patterns of ZnO&St.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 7 2020

NANO-ZnO IMPREGNATED ON STARCH
1281
Scheme 1.
O
O
Ar
O
ZnO@starch
H2O–EtOH, MW
CN
O
NH
HN
NC
CN
+
+
Ar
H
O
N
H
O
O
N
H
NH2
1
2
3
4a–4i
4, Ar = 4-BrC6H4 (a), 3-ClC6H4 (b), 2-ClC6H4 (c), 2,3-Cl26H4 (d), 4-NCC6H4 (e), 2,4-Cl2C6H4 (f),
3-HOC6H4 (g), 4-O2NC6H4 (h), 4-F3CC6H4 (i).
Scheme 2.
Ar
ZnO@starch
H2O–EtOH
OH
O
+ 2
Ar
H
O
2
5
6a–6k
6, Ar = 2,4-Cl2C6H4 (a), 3-MeOC6H4 (b), Ph (c), 4-BrC6H4 (d), 3-O2NC6H4 (e), 3-MeC6H4 (f),
4-ClC6H4 (g), 4-MeOC6H4 (h), 3-ClC6H4 (i), 3-BrC6H4 (j), 4-FC6H4 (k).
shows that the ZnO&St particles are spherical in shape
with an average size of 75 nm. The SEM image at
higher magnification completely confirmed the infor-
mation obtained from the catalytic morphology
(Fig. 1b). The chemical purity of ZnO&St samples was
checked by energy-dispersive X-ray spectroscopy
(EDX). The X-ray diffraction pattern (XRD) of
ZnO&St is shown in Fig. 2. The obtained pattern corre-
Table 1. Synthesis of pyranopyrimidine 4a in the presence of ZnO–starch nanocomposite under different conditions
Catalyst amount, mg
Solvent
Temperature conditions
Reaction time, min
Yield, %
–
2
5
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
MW
10
10
10
10
10
10
10
10
10
10
10
10
10
45
25
35
45
60
60
MW
33
54
72
75
80
86
87
89
89
7
MW
10
15
20
22
25
30
22
22
22
22
22
22
22
22
22
22
MW
MW
MW
MW
MW
MW
EtOH
MW
DMF
MW
65
CH2Cl2
MW
72
EtOH/H2O (1/1)
H2O
MW
Reflux
Reflux
Reflux
Reflux
Reflux
MW
94
90
EtOH/H2O (1/1)
EtOH/H2O (1/1)
EtOH/H2O (1/1)
EtOH/H2O (1/1)
No solvent
77
81
87
92
38
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 7 2020

AMININIA et al.
Table 2. Synthesis of xanthene 6c in the presence of ZnO–starch nanocomposite under different conditions
1282
Catalyst amount, mg
Solvent
Temperature conditions
Reaction time, min
Yield, %
38
5
10
15
20
25
30
35
30
30
30
30
30
30
30
30
30
30
H2O
H2O
H2O
H2O
H2O
H2O
H2O
MW
15
15
15
15
15
15
15
15
15
15
15
45
25
35
45
60
60
MW
57
MW
71
MW
78
MW
89
MW
90
MW
91
EtOH
MW
85
DMF
MW
65
CH2Cl2
MW
72
EtOH/H2O (1/1)
H2O
MW
Reflux
Reflux
Reflux
Reflux
Reflux
MW
92
90
EtOH/H2O (1/1)
EtOH/H2O (1/1)
EtOH/H2O (1/1)
EtOH/H2O (1/1)
Solvent free
67
74
87
92
38
sponds to the hexagonal (wurtzite) crystal structure of
the nanocatalyst. These results confirmed the presence
of ZnO in ZnO&St.
the best yields were obtained in aqueous ethanol at
a ratio of 1:1. The amount of the catalyst was varied
from 2 to 35 mg. It was found that the catalyst amount
22 mg in the synthesis of 4a and 30 mg in the synthesis
of 7c provided the highest product yields. Further
increase of the catalyst amount did not lead to a signif-
icant increase in the yield. The optimal reaction con-
ditions are highlighted in bold red in Tables 1 and 2.
The ZnO&St nanocomposite was used to catalyze
the three-component condensation of barbituric acid
(1) with aromatic aldehydes 2 and malononitrile (3) to
obtain pyranopyrimidine derivatives 4a–4i (Scheme 1),
as well as the 1:2 condensation of aromatic aldehydes 2
with naphthalen-2-ol (5) to produce xanthenes 6a–6k
(Scheme 2). The model reactions were performed
under various conditions with variation of the solvent
(water, ethanol, dimethylformamide, methylene chlo-
ride, 1:1 aqueous ethanol, and solvent-free) at different
temperature conditions (reflux or microwave irradia-
tion) with different amounts of the catalyst and dif-
ferent reaction times (Tables 1, 2). The results showed
that the product yield was higher in protic solvents, and
Thus, the use of ZnO&St nanocomposite together
with microwave irradiation significantly accelerated
the reactions and provided good yields and simple
workup in the preparation of pyranopyrimidinone and
xanthene derivatives.
Plausible catalytic mechanisms for both reactions
are depicted in Scheme 3. In the synthesis of pyrano-
pyrimidinone derivatives, yellowish arylidenemalono-
nitrile was initially formed via Knoevenagel condensa-
tion of malononitrile and activated aromatic aldehyde
in quantitative yield. The subsequent Michael addition,
followed by intramolecular cyclization, afforded the
final product.
Yield, %
4a
6c
100
80
60
40
Various aromatic aldehydes reacted with malono-
nitrile and barbituric acid in the synthesis of pyrano-
pyrimidinone derivatives and with β-naphtol in the
synthesis of xanthene derivatives under the optimized
conditions to give the corresponding products in high
yields and in short reaction times. The obtained results
are summarized in Tables 3 and 4.
20
0
1
2
3
4
5
6
7
Run no.
Fig. 3. Reusability of ZnO&St in the synthesis of pyranopy-
rimidinone 4a and xanthene 6c.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 7 2020

NANO-ZnO IMPREGNATED ON STARCH
1283
Scheme 3.
OH
NC
CN
O
O
Ar
Ar
H
Ar
Ar
H
NC
O
CN
O
NH
O
Ar
O
Ar
CN
O
N
H
O
HN
O
N
H
N
OH
O
OH
O
Ar
Ar
CN
HN
O
N
O
NH2
O
H
Table 3. Reaction times, yields, and melting points of compounds 4a–4i
Melting point, °C
Reaction time,
Compound no.
Ar
Yield, %
Reference
min
reported
230–231
240–241
240–241
240–242
254–256
241–242
158–160
239–240
250–251
found
4a
4b
4c
4d
4e
4f
4-BrC6H4
12
13
14
19
11
18
17
11
12
91
92
85
81
95
85
90
91
93
235–237
245–247
247–249
250–251
265–266
238–239
165–166
241–242
260–261
[34]
[34]
[34]
[35]
[35]
[36]
[36]
[36]
[36]
3-ClC6H4
2-ClC6H4
2,3-Cl2C6H4
4-NCC6H4
2,4-Cl2C6H4
3-HOC6H4
4-O2NC6H4
4-F3CC6H4
4g
4h
4i
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 7 2020

AMININIA et al.
1284
Table 4. Reaction times, yields, and melting points of compounds 6a–6k
Melting point, °C
found
Reaction time,
Compound no.
Ar
Yield, %
Reference
min
14
15
12
17
17
11
14
13
14
12
15
reported
255–257
179–181
187–189
310–312
217–220
190–192
295–297
219–221
225–227
201–202
265–266
6a
6b
6c
6d
6e
6f
2,4-Cl2C6H4
3-MeOC6H4
Ph
88
91
92
88
95
95
90
89
88
85
89
251–252
181–183
184–185
303–305
213–215
197–200
288–290
215–217
217–220
198–200
255–258
[37]
[37]
[37]
[37]
[38]
[39]
[40]
[40]
[40]
[41]
[41]
4-BrC6H4
3-O2NC6H4
3-MeC6H4
4-ClC6H4
4-MeOC6H4
3-ClC6H4
3-BrC6H4
4-FC6H4
6g
6h
6i
6j
6k
Table 5. In vitro antibacterial activity of compounds 4a–4i and 6a–6k against M. luteus
Concentration, μg/mL
Compound no.
MBC, μg/mL
2000
1000
500
250
125
62.5
4a
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Inhibition
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Inhibition
250
250
250
250
250
250
250
250
250
500
500
500
500
500
500
500
500
500
500
500
< 62.5
4b
4c
4d
4e
4f
4g
4h
4i
6a
6b
Growth
6c
Growth
6d
Growth
6e
Growth
6f
Growth
6g
Growth
6h
Growth
6i
Growth
6j
Growth
6k
Growth
Tetracycline
Inhibition
One of the most important features of a solid cata-
lyst is its recyclability. The recyclability of ZnO&St
NCs was investigated using the model reaction. After
completion of the reaction, the catalyst was filtered off,
washed well with acetone and ethyl acetate, and used
in the next reaction cycle. The results showed that the
catalyst retained its activity after three runs (Fig. 3).
All the synthesized compounds were evaluated for
their in vitro antibacterial activity against Micrococcus
luteus (M. luteus) and Pseudomonas aeruginosa
(P. aeruginosa) by determining their minimum inhib-
itory (MIC) and minimum bactericidal concentrations
(MBC) in comparison to tetracycline used as standard
drug. All the synthesized compounds showed good
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 7 2020

NANO-ZnO IMPREGNATED ON STARCH
1285
Table 6. In vitro antibacterial activity (MBC, μg/mL) of compounds 4a–4i and 6a–6k against P. aeruginosa
Concentration, μg/mL
Compound
no.
MBC, μg/mL
2000
1000
500
250
125
62.5
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Inhibition
4a
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Inhibition
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Inhibition
Inhibition
Inhibition
Inhibition
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Inhibition
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Growth
Inhibition
500
500
4b
4c
500
4d
1000
1000
1000
1000
1000
1000
1000
1000
1000
1000
1000
1000
1000
1000
500
4e
4f
4g
4h
4i
6a
6b
6c
6d
6e
6f
6g
6h
6i
6j
500
6k
500
Tetracycline
< 62.5
antibacterial activity. Pyranopyrimidinone derivatives
4a–4i were generally more active than xanthenes 6a–
6k (Tables 5, 6).
(400 and 100 MHz, respectively) using CDCl3–
DMSO-d6 as solvent and tetramethylsilane as internal
standard. The catalyst was prepared using a Tecno-Gaz
Astra 3D ultrasound device (9.5 L, frequency 45 kHz,
305 W input power with heating, 2 transducers). All
microwave-assisted reactions were carried out in
a microwave oven.
In conclusion, we have proposed a convenient and
efficient procedure for the synthesis of pyranopyrim-
idine and xanthene derivatives in the presence of
ZnO&St nanocomposite under microwave irradiation.
The procedure is advantageous due to short reaction
time, low cost, simple operation, and recyclability of
the catalyst. In many cases, the products crystallized
directly from the reaction mixture in high purity.
Preparation of ZnO–starch nanocomposite.
A reaction vessel was charged with 40 mL of distilled
water, 0.2 g of starch and 1.2 g (4 mmol) of ZnNO3·
6H2O were added, and the mixture was heated under
ultrasound irradiation (20 kHz) at 40°C for 5 min. The
mixture was then adjusted to pH 9 by adding dropwise
a dilute solution of sodium hydroxide and ultrasonically
irradiated for 15 min more. The white precipitate of
ZnO&St was separated by centrifugation, washed
several times with deionized water to remove im-
purities, and dried at 70°C for 24 h.
EXPERIMENTAL
The chemicals and solvents (all of analytical grade)
used in the synthesis of pyranopyrimidine and xanthene
derivatives were obtained from Merck and Aldrich.
The progress of reactions was monitored by thin-layer
chromatography on 0.2-mm silica gel F-252 plates
(Merck). The melting points were determined in open
capillaries using an Electrothermal 9100 melting point
General procedure for the preparation of pyrano-
pyrimidines 4a–4i. A mixture of aromatic aldehyde 2
(1 mmol), malononitrile (1.2 mmol, ~80 mg), barbituric
acid (1 mmol, 156 mg), and 22 mg of ZnO&St in
1
apparatus and are uncorrected. The H and 13C NMR
spectra were recorded on a Bruker 3000 spectrometer
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 7 2020

AMININIA et al.
1286
aqueous ethanol (2 mL + 2mL) was irradiated in a mi-
crowave oven at a power of 230 W. After completion
of the reaction, the resulting solid (crude product)
was filtered off and recrystallized from ethanol. The
physical data (melting points and NMR and IR spectra)
of the known compounds were found to be identical
with those reported in the literature. Spectral data for
selected compounds are given below.
1H NMR spectrum, δ, ppm: 6.53 s (1H, 14-H), 7.04 t
(1H, J = 7.2 Hz, Harom), 7.18 t (2H, J = 7.2 Hz,
Harom), 7.45 t (2H, J = 7.5 Hz, Harom), 7.53–7.60 m
(6H, Harom), 7.62 t (4H, J = 8 Hz, Harom), 8.44 d (2H,
J = 8 Hz, Harom).
14-(3-Methylphenyl)-14H-dibenzo[a,j]xanthene
(6f). Yellow solid, mp 197–200°C. IR spectrum (KBr),
ν, cm–1: 3018, 2921, 1623, 1591, 1512, 1457,1400,
1
1249, 960, 806, 806, 743. H NMR spectrum, δ, ppm:
7-Amino-5-(3-chlorophenyl)-2,4-dioxo-1,3,4,5-
tetrahydro-2H-pyrano[2,3-d]pyrimidine-6-carbo-
nitrile (4b). Dark yellow powder, mp 240–241°C. IR
spectrum (KBr), ν, cm–1: 3419, 3300 (NH2), 3186
(NH), 2192 (C≡N), 1689, 1654 (C=O). 1H NMR spec-
2.07 s (3H, CH3), 6.67 s (1H, 14-H), 6.77 d (1H, J =
7.6 Hz, Harom), 7.04 t (1H, J = 7.6 Hz, Harom), 7.31 s
(1H, Harom), 7.45 m (2H, Harom), 7.54 s (1H, Harom),
7.56 d (2H, J = 8.8 Hz, Harom), 7.63 m (2H, Harom),
7.91–7.94 m (4H, Harom), 8.67 d (2H, J = 8.4 Hz,
Harom).
trum, δ, ppm: 4.47 s (1H, 5-H), 7.28 br.s (2H, Harom
,
NH2), 7.61 t (1H, 3J = 7.6 Hz, Harom), 7.74 d (1H, 3J =
7.6 Hz, Harom), 8.06 br.s (1H, Harom), 8.08–8.13 m (1H,
Harom), 11.11 s (1H, NH), 12.16 br.s (1H, NH).
14-(4-Methoxyphenyl)-14H-dibenzo[a,j]xanthene
(6h). White solid, mp 215–217°C. IR spectrum (KBr),
ν, cm–1: 3072, 2834, 1622, 1592, 1509, 1458, 1438,
7-Amino-5-(2-chlorophenyl)-2,4-dioxo-1,3,4,5-
tetrahydro-2H-pyrano[2,3-d]pyrimidine-6-carbo-
nitrile (4c). Dark yellow powder, mp 240–241°C. IR
spectrum (KBr), ν, cm–1: 3410, 3370 (NH2), 3158
(NH), 2185 (C≡N), 1689 (C=O). 1H NMR spectrum, δ,
ppm: 4.72 s (1H, 5-H), 7.153 br.s (2H, NH2), 7.21–
7.28 m (3H, Harom), 7.36 d (1H, Harom), 11.06 s (1H,
NH), 12.08 br.s (1H, NH).
1
1399, 1249, 1082. H NMR spectrum, δ, ppm: 3.38 s
(3H, CH3), 6.68 s (1H, 14-H), 6.69 d (2H, J = 8.4 Hz,
Harom), 7.46 t (2H, J = 7.2 Hz, Harom), 7.53 t (4H,
J = 7.5 Hz, Harom), 7.62 t (2H, Harom), 7.93 t (4H, J =
8.4 Hz, Harom), 8.66 d (2H, J = 8.4 Hz, Harom).
14-(3-Chlorophenyl)-14H-dibenzo[a,j]xanthene
(6i). White solid, mp 217–220°C. IR spectrum (KBr),
ν, cm–1: 3467, 3057, 1658, 1622, 1591, 1514, 1473,
7-Amino-5-(4-nitrophenyl)-2,4-dioxo-1,3,4,5-
tetrahydro-2H-pyrano[2,3-d]pyrimidine-6-carbo-
nitrile (4h). White powder, mp 239–240°C. IR spec-
trum (KBr), ν, cm–1: 3477, 3238 (NH2), 3127 (NH),
2192 (C≡N), 1677, 1645 (C=O). 1H NMR spectrum, δ,
ppm: 4.42 s (1H, 5-H), 7.21 br.s (2H, NH2), 7.52 d (2H,
1
1458, 1431, 1400, 1240, 1238. H NMR spectrum, δ,
ppm: 6.73 s (1H, 14-H), 7.00 t (1H, J = 8.4 Hz, Harom),
7.07 t (1H, J = 7.2 Hz, Harom), 7.31 d (1H, J = 8 Hz,
Harom), 7.43 s (1H, Harom), 7.46 t (2H, Harom), 7.53 d
(2H, J = 8.4 Hz, Harom), 7.62 d (2H, J = 7.2 Hz, Harom),
7.93 d (4H, J = 8.4 Hz, Harom), 8.59 d (2H, J = 8.4 Hz,
Harom).
3
3J = 8.8 Hz, Harom), 8.16 d (2H, J = 8.8 Hz, Harom),
11.12 br.s (1H, NH), 12.17 br.s (1H, NH).
14-(3-Bromophenyl)-14H-dibenzo[a,j]xanthene
(6j). White solid, mp 198–200°C. IR spectrum (KBr),
ν, cm–1: 3065, 2923, 1622, 1590, 1566, 1514, 1472,
General procedure for the synthesis of xanthene
derivatives 6a–6k. A reaction vessel was charged with
water (5 mL) and ethanol (5 mL), 288 mg of naphtha-
len-2-ol (5, 2 mmol), benzaldehyde 2 (1 mmol), and
30 mg of ZnO&St were added, and the mixture was
irradiated in a microwave oven at a power of 230 W.
The progress of the reaction was monitored by TLC.
After completion of the reaction, the mixture was
cooled to room temperature, the catalyst was separated
by filtration, the filtrate was evaporated, and the crude
product was purified by recrystallization from ethanol.
All products were characterized by comparison of their
melting points and FT-IR spectra with published data.
Spectral data of selected compounds are given below.
1
1456, 1432, 1392, 1239. H NMR spectrum, δ, ppm:
6.76 s (1H, 14-H), 7.11 t (1H, J = 7.6 Hz, Harom), 7.17–
7.19 m (1H, Harom), 7.47 t (2H, J=7.2 Hz, Harom),
7.57 d (2H, J = 8.8 Hz, Harom), 7.63–7.67 m (3H,
Harom), 7.81 br.s (1H, Harom), 7.94 d (4H, J = 8.8 Hz,
Harom), 8.70 d (2H, J = 8.4, Harom).
Antibacterial activity. A liquid culture medium
was prepared by adding 0.8 g of nutrient broth into
100 mL of distilled water, and test tubes were charged
with 1 mL of the medium and autoclaved at 115°C for
15 min. Solutions of compounds 4 and 6 in DMSO at
six concentrations of each sample were prepared (1000,
500, 250, 125, 62.5, and 31.25 μg/mL), and 1 mL of
the solution was added to the autoclaved test tubes.
14-Phenyl-14H-dibenzo[a,j]xanthene (6c). White
solid, mp 184–185°C. IR spectrum (KBr), ν, cm–1:
3069, 3041, 2927, 1614, 1581, 1508, 1474, 1361.
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NANO-ZnO IMPREGNATED ON STARCH
1287
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CONFLICT OF INTEREST
The authors declare that they have no conflict of interest.
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