Synthesis of 2,3-dihydroquinazolin-4(1H)-ones catalyzed by nano-Fe3O4/TiCl2/cellulose as a bio-based magnetic catalyst

Article abstract of DOI:10.1007/s13738-016-0956-1

Abstract: Nano-Fe₃O₄/TiCl₂/cellulose as a new, green, bio-based and recyclable catalyst was synthesized by bonding TiCl₄ to hydroxyl groups of nano-cellulose and Fe₃O₄ nanoparticles. This catalyst was characterized by FT-IR, FESEM, TEM, XRF, BET, VSM, EDX and XRD. As a first report, the catalytic activity of nano-Fe₃O₄/TiCl₂/cellulose was investigated in the synthesis of 2,3-dihydroquinazolin-4(1H)-ones in good to excellent yields under mild conditions. Graphical abstract: [Figure not available: see fulltext.]

Full text of DOI:10.1007/s13738-016-0956-1

J IRAN CHEM SOC
DOI 10.1007/s13738-016-0956-1
ORIGINAL PAPER
Synthesis of 2,3‑dihydroquinazolin‑4(1H)‑ones catalyzed
by nano‑Fe O /TiCl /cellulose as a bio‑based magnetic catalyst
3
4
2
1
2
1
Bi Bi Fatameh Mirjalili · Abdolhamid Bamoniri · Sara Azad
Received: 10 June 2016 / Accepted: 28 July 2016
©
Iranian Chemical Society 2016
Abstract Nano-Fe O /TiCl /cellulose as a new, green, bio-
TEM, XRF, BET, VSM, EDX and XRD. As a first report, the
catalytic activity of nano-Fe O /TiCl /cellulose was investi-
gated in the synthesis of 2,3-dihydroquinazolin-4(1H)-ones
3
4
2
based and recyclable catalyst was synthesized by bonding
TiCl to hydroxyl groups of nano-cellulose and Fe O nano-
3
4
2
4
3
4
particles. This catalyst was characterized by FT-IR, FESEM,
in good to excellent yields under mild conditions.
Graphical abstract
Keywords 2,3-dihydroquinazolin-4(1H)-ones · Nano-
Fe O /TiCl /cellulose · Solid acid · Supported Lewis acid ·
3
4
2
Magnetic catalyst
Introduction
Electronic supplementary material The online version of this
article (doi:10.1007/s13738-016-0956-1) contains supplementary
material, which is available to authorized users.
In recent years, research trends have been oriented toward
magnetic nanoparticles as heterogeneous supporting cata-
lyst, because of their large surface area, high dispersion of
the active accessible centers and easy recovery from reac-
tion media by external magnet [1]. The most used and
accessible magnetic particle is magnetite (Fe O ) owing to
*
Bi Bi Fatameh Mirjalili
fmirjalili@yazd.ac.ir
1
2
Department of Chemistry, College of Science, Yazd
University, Yazd 89195-741, Islamic Republic of Iran
3
4
its potential applications in magnetic resonance imaging
(MRI), hyperthermia, drug targeting and catalysis [2–10].
Department of Organic Chemistry, Faculty of Chemistry,
University of Kashan, Kashan, Islamic Republic of Iran
1
3

J IRAN CHEM SOC
Various strategies have been developed for the preparation
of magnetic catalyst using Fe O nanoparticle [9–13].
(XRD) pattern was obtained by a Philips Xpert MPD dif-
fractometer equipped with a Cu Ka anode (k = 1.54 Å)
in the 2θ range from 10° to 80°. Field emission scanning
electron microscopy (FESEM) was obtained on a Mira
3-XMU. Transmission electron microscopy (TEM) was
obtained using a Philips CM120 with a LaB6 cathode and
accelerating voltage of 120 kV. XRF analysis was done
with Bruker, S4 Explorer instrument. VSM measurements
were performed by using a vibrating sample magnetom-
eter (Meghnatis Daghigh Kavir Co., Kashan Kavir, Iran).
Brunauer–Emmett–Teller (BET) surface area analysis of
catalyst was done with Micromeritics, Tristar II 3020 ana-
lyzer. Energy-dispersive X-ray spectroscopy (EDS) of BF3/
nano-γ-Al O was measured by EDS instrument, Phenom
3
4
On the other hand, recently biopolymers such as cel-
lulose [14], starch [15], chitosan (CS) [16] or wool [17]
have been used as heterogeneous catalytic systems. In this
context, cellulose can play a major role as a natural, bio-
compatible and biodegradable polymer containing free OH
groups with nucleophilic character. It has been used for
synthesis of some compounds which used in enantiose-
lective chromatography [18], protein immobilization [19],
antibodies [20], retarded drug release [21] and synthesis of
cellulose sulfuric acid [14]. 2,3-Dihydroquinazolin-4(1H)-
ones are an important class of fused heterocyclic com-
pounds which have drawn much attention because of their
biological potential and pharmaceutical activities such as
anti-inflammatory [22], antibacterial [23], antiplasmodial
2
3
pro X.
[24], antitumor [25], antimicrobial and antioxidant [26].
Preparation of nano‑cellulose from cotton
Recently, a number of classical methods for the synthesis
of 2,3-dihydroquinazolin-4(1H)-ones have been reported
in the literature involving the condensation of 2-amin-
obenzamide with aldehydes in the presence of various
catalysts. Previously, Wang-OSO H [27], CAN. SiO [28],
Cotton fibers were washed with distilled water for several
times and dried in an air-circulated oven at 100 ± 2 °C until
constant weight. Then, they were chopped to an approxi-
mate length of 5–10 mm. The fibers were then treated
with a 17.5 w/v NaOH solution at 100 °C for 12 h under
mechanical stirring. This treatment allowed purifying cel-
lulose by removing other constituents such as lignin, hemi-
cellulose, wax and organic acids present in the fibers. Sub-
sequently, fibers were filtered and washed with distilled
water until the alkali was completely eliminated. It was then
bleached with 100 ml of a mixture of 3.5 % w/v sodium
hypochlorite:water (1:1) at 80 °C for 3 h under mechanical
stirring. The resulting alpha cellulose was hydrolyzed par-
tially using 65 % sulfuric acid aqueous solution with a ratio
cotton:acid (1:10 w/w) at 45 °C. After 1 h, the obtained sus-
pension was diluted with water fivefold to stop the hydroly-
sis reaction. The suspension was centrifuged at 12,000 rpm
to separate the nano-cellulose from acid solution. Washing
with water and centrifuging was repeated for four to five
times to remove any remaining free acids.
3
2
2
-morpholinoethanesulfonic acid [29], Amberlyst-15 [30],
N-propylsulfamic acid supported on magnetic Fe O nano-
3
4
particles (MNPs-PSA) [31], CuCl /Fe O -TEDETA [32],
2
3
4
[
PYC SO H][HSO ]/A 300 SiO [33], [Bmim]PF [34],
4 3 4 2 6
tetrabutylammonium bromide (TBAB) [35] and NH SO H
2
3
[
36] have been used for promotion of 2,3-dihydroquina-
zolin-4(1H)-ones synthesis. Some of these catalysts have
many limitations such as inefficient separation of the cata-
lyst from reaction mixtures, unrecyclable and environmen-
tal limitations. In continuation of our efforts to synthesis
and application of supported Lewis acids in organic syn-
thesis, herein, we wish to report synthesis of nano-Fe O /
3
4
TiCl /cellulose as a new and biodegradable magnetic
2
nano-catalyst and application of it for the synthesis of
2
,3-dihydroquinazolin-4(1H)-ones.
Experimental
General
Preparation of nano‑Fe O /TiCl /cellulose
3
4
2
In a well-ventilated system, TiCl (5 mL) was added drop
4
wise to the mixture of nano-cellulose (5 g) and CH Cl
2
2
All compounds were purchased from Merck, Aldrich and
FLUKA chemical companies and used without any addi-
tional purification. A refrigerated centrifuge (Eppendorf
Centrifuge 5417R) was used for preparation of nano-
cellulose. FT-IR spectra were run on a Bruker, Equinox
(20 mL). The mixture was stirred for one hour at room tem-
perature. The resulted suspension was filtered, washed with
CH Cl and the resulted nano-TiCl /cellulose dried at room
2
2
n
temperature. Then, Fe O nanoparticles (0.25 g) were dis-
3
4
persed in 20 mL CH Cl under ultrasound irradiation. Then,
2
2
5
5 spectrometer. A Bruker (DRX-400 Avance) NMR was
0.25 g of nano-TiCl /cellulose was slowly added with vigor-
n
1
13
used to record the H-NMR and C-NMR spectra. Melt-
ing points were determined by a Buchi melting point B-540
B.V.CHI apparatus and were uncorrected. X-ray diffraction
ous stirring at 40 °C for 1 h. The resulted magnetic nano-
Fe O /TiCl /cellulose particles were isolated through filter-
3
4
2
ing, washing with CH Cl and drying at 50 °C.
2
2
1
3

J IRAN CHEM SOC
Scheme 1 Synthesis protocol for nano-Fe O /TiCl /cellulose
3
4
2
1
General procedure for the synthesis
H NMR (Acetone-d , 400 MHz): δ 7.79 (brs, 2H), 7.53
6
of 2,3‑dihydroquinazolin‑4(1H)‑ones
(brs, 1H), 7.46 (brs, 1H), 7.33 (m, 2H), 6.84 (d, J = 7.2 Hz,
1
H), 6.80 (d, J = 6.8 Hz, 1H), 6.29–6.32 (m, 2H). IR (KBr,
1
−
Nano-Fe O /TiCl /cellulose (0.03 g) was added to a
cm ): 3339, 3183, 1656, 1609, 1472, 1147, 1094, 1053.
3
4
2
solution of 2-aminobenzamide (1 mmol) and aldehyde
1 mmol) in EtOH (3 mL). The mixture was stirred at
(
room temperature for an appropriate time as indicated in
Table 5. After completion of the reaction, as indicated by
TLC (EtOAc:n-Hexane, 1:4), the catalyst was removed by
external magnet and then the product was precipitated by
addition of 4 mL water. The precipitate was filtered off and
washed with water. Finally, the crude product was puri-
fied by re-crystallization from EtOH and water to afford
the corresponding 2,3-dihydroquinazolin-4(1H)-ones in
Results and discussion
In this work, we have prepared nano-cellulose by partial
hydrolysis of cotton, and so, magnetic nanoparticles Fe O
3
4
via co-precipitation method [37]. Since cotton is contain-
ing cellulose with other substances such as lignin, hemi-
cellulose, wax and organic acids which caused leaching in
organic mediums, the cotton substances except cellulose
must be removed. For this purpose, the cotton was treated
with NaOH and NaOCl, respectively. For preparation of
nano-cellulose, the obtained cellulose has been treated
with concentrated H SO for partial hydrolysis of its acetal
7
5–96 % yields.
Physical and spectroscopic data for selected compounds
2
4
2
-Phenyl-2,3-dihydroquinazolin-4(1H)-one (Table 5, III )
linkages. After, partial hydrolysis, the free OH groups in
nano-cellulose have been increased and could be used to
synthesis of nano-cellulose supported catalysts. Then, we
have synthesized nano-Fe O /TiCl /cellulose as a new
a
1
H NMR (DMSO-d , 400 MHz): δ 8.45 (brs, 1H), 8.16
6
(
m, 1H), 8.02 (m, 2H), 7.83 (d, J = 7.6 Hz, 3H), 7.69 (brs,
1
1
1
H), 7.37 (brs, 1H), 7.26 (d, J = 6.4 Hz, 1H), 7.15 (brs,
3
4
2
−
1
H), 6.27 (s, 1H). IR (KBr, cm ): 3303, 3176, 3060, 1652,
magnetic catalyst in two steps. In the first step, TiCl was
4
610, 1507, 1481.
added to nano-cellulose/CH Cl mixture at room tempera-
2
2
2
-(4-Nitrophenyl)-2,3-dihydroquinazolin-4(1H)-one
ture to result nano-TiCl /cellulose as a white solid. In the
n
(
Table 5, III )
second step, dry solid of nano-TiCl /cellulose was added to
b
n
1
H NMR (Acetone-d , 400 MHz): δ 8.26(d, J = 8 Hz,
nano-Fe O /CH Cl mixture to obtain a brown solid. In the
6
3
4
2
2
2
7
1
3
H), 7.87 (d, J = 8 Hz, 2H), 7.78 (m, 1H), 7.52 (brs, 1H),
first step, the OH functional groups in nano-cellulose act as
.30 (m, 1H), 6.84 (d, J = 8 Hz, 1H), 6.79 (d, J = 6.8 Hz,
nucleophile and react with TiCl to form C-O-Ti moieties.
4
−
1
H), 6.51 (brs, 1H), 6.11 (s, 1H). IR (KBr, cm ): 3283,
Some of Ti–Cl bonds in TiCl were remained which react,
4
−
1
172, 1641, 1606, 1515, 1460, 1346 cm .
-(3-Bromophenyl)-2,3-dihydroquinazolin-4(1H)-one
in second step, with surface OH groups in nano-Fe O to
3
4
2
form nano-Fe O /TiCl /cellulose (Scheme 1). The parti-
3 4 2
(
Table 5, III )
cle size nano-TiCl /cellulose and nano-Fe O /TiCl /cellu-
i
n 3 4 2
1
H NMR (Acetone-d , 400 MHz): δ 7.76 (d, J = 8 Hz,
lose were investigated by field emission scanning electron
microscopy (FESEM) and transmission electron micros-
copy (TEM) in which dimensions of catalyst were achieved
below 50 nm (Fig. 1). To investigate the elemental compo-
nent of nano-Fe O /TiCl /cellulose, XRF analysis of cata-
6
2
6
H), 7.59 (m, 2H), 7.36 (d, J = 8 Hz, 2H), 7.30 (m, 1H),
.82 (d, J = 8 Hz, 1H), 6.78 (m, 1H), 6.34 (brs, 1H), 5.93
−
1
(
brs, 1H). IR (KBr, cm ): 3273, 3178, 3060, 1646, 1611,
1
473.
-(2,4-Dichlorophenyl)-2,3-dihydroquinazolin-4(1H)-
one (Table 5, IIIj)
3
4
2
2
lyst was done by comparison of its kilo counts per second
(KCPS) with pure samples. In our catalyst, nano-Fe O /
3
4
1
3

J IRAN CHEM SOC
Fig. 1 a FESEM images of nano-TiCl /cellulose, b FESEM images of nano-Fe O /TiCl /cellulose, c TEM images of nano-Fe O /TiCl /cellulose
n
3
4
2
3
4
2
Table 1 XRF analysis of nano-Fe O /TiCl /cellulose
3
4
2
Sample
TiO2
NaCl
Fe
1820.6 (Fe O )
Catalyst
KCPS
2318.4 (TiO2)
60 (Ti)
516.5 (Cl)
60 (Cl)
149.8 (TiO2)
3.9 (Ti)
58.1 (Cl)
6.75 (Cl)
1321.4 (Fe O )
2
3
2
3
Amount of element (%)
97.2 (Fe)
70 (Fe)
The signal at 802 is assigned to C-O-Ti stretching vibration
which is observed in nano-TiCl /cellulose and nano-Fe O /
n
3
4
TiCl /cellulose.
2
X-ray diffraction (XRD) patterns of nano-TiCl /cellu-
n
lose and nano-Fe O /TiCl /cellulose are shown in Fig. 3.
3
4
2
The values of 2θ and FWHM are shown in Table 2. Accord-
ing to XRD pattern of nano-TiCl /cellulose (Fig. 3a), the
n
three signals in 2θ, 15.13, 16.74 and 22.93 with FWHM,
0
.4723, 0.9446 and 0.4723, respectively, show the exist-
ence of cellulose. Other signals in 2θ, 20.55, 28.56, 34.63
and 41.84 prove the bonding of Ti to cellulose backbone.
XRD pattern of nano-Fe O /TiCl /cellulose (Fig. 3b) shows
3
4
2
a diffraction peak at 2θ = 22.53 corresponding to cellulose
in addition to other signals at 35.55, 43.22, 57.29 and 62.85
degree which are related to the presence of Fe O moiety in
Fig. 2 FT-IR (ATR) spectra of a nano-cellulose, b nano-Fe O /TiCl /
3
4
2
cellulose and c nano-TiCl /cellulose
n
3
4
catalyst.
The magnetic properties of Fe O and nano-Fe O /
3
4
3
4
TiCl /cellulose, the percentage of elements, Ti, Cl and Fe,
TiCl /cellulose were characterized using vibrating sample
2
2
were determined via comparison with KCPS of pure TiO2,
NaCl and iron metal as shown in Table 1. The amount of
magnetometer (VSM) (Fig. 4a). Two measured samples
demonstrate a superparamagnetic behavior, as confirmed
by zero coercivity and remanence on the magnetization
loop. The saturation magnetization values of Fe O and
3
0
.9 g of Ti and 6.75 g of Cl is equal to 0.08 mol of Ti and
.19 mol of Cl; thus, the ratio of Ti:Cl is 1:2.
3
4
−
nano-Fe O /TiCl /cellulose are ~50 emu g and ~30 emu
3 4 2
1
Comparison of nano-Fe O /TiCl /cellulose with nano-
3
4
2
−
g , respectively. The results show that bonding Fe O to
3 4
1
TiCl /cellulose and nano-cellulose was demonstrated by
n
their FT-IR (ATR) spectra (Fig. 2). As shown in Fig. 2,
nano-Fe O /TiCl /cellulose has a characteristic signal at
nano-TiCl /cellulose has insignificant effect on the mag-
n
netic properties of Fe O . Thermal gravimetric analysis
3
4
2
3
4
−
1
5
80 cm , which is assigned to Fe–O stretching vibration.
(TG–DTA) pattern of nano-Fe O /TiCl /cellulose was
3 4 2
1
3

J IRAN CHEM SOC
Fig. 3 XRD pattern of: a nano-TiCl /cellulose and b nano-Fe O /TiCl /cellulose
n
3
4
2
Table 2 Reflexes in XRD
diffractogram of: (A) nano-
No
1
2
3
4
5
6
7
TiCl /cellulose and (B) nano-
n
(A)
B)
Pos. [°2Ɵ]
FWHM [°2Ɵ]
Pos. [°2Ɵ]
15.130
0.472
16.748
0.944
20.553
0.472
22.935
0.472
28.563
0.708
34.634
0.295
41.846
Fe O /TiCl /cellulose
3
4
2
1.728
(
22.537
1.102
30.265
0.787
35.553
0.787
43.221
0.944
57.299
0.787
62.850
0.768
–
–
FWHM [°2Ɵ]
Fig. 4 a Magnetization loops of (a) Fe O (blue color) and (b) nano-Fe O /TiCl /cellulose (red color), b thermal gravimetric analysis (TG-
3
4
3
4
2
DTG) pattern of nano-Fe O /TiCl /cellulose
3
4
2
detected by heating from 50 to 400 °C and then cooling
until 166 °C (Fig. 4b). The catalyst is stable until 200 °C,
and only 6 % of its weight was reduced due to the removal
of catalyst moisture. Heating the catalyst until 352 °C
caused 32 % of its mass to be reduced. The char yield of
the catalyst in 352 °C is 68 %. According to the TG–DTA
diagram of nano-Fe O /TiCl /cellulose and our study, it
3 4 2
was revealed that this catalyst is suitable for the promotion
of organic reactions below 200 °C.
Single-point surface area at P/Po = 0.290975024 is
2
2
40.3972 m /g, and BET surface area is 40.7778 m /g. The
N adsorption isotherm of catalyst is depicted in Fig. 5.
2
1
3

J IRAN CHEM SOC
the efficiency of present nano-catalyst with other catalysts,
the model reaction was also performed using the reported
catalysts for the synthesis of 2,3-dihydroquinazolin-4(1H)-
ones. As Table 4 indicates, in comparison with other cata-
lysts, we observed good and high yields of products in
very mild and green conditions using nano-Fe O /TiCl /
3
4
2
cellulose.
Finally, the above optimized reaction conditions were
explored for the synthesis of 2,3-dihydroquinazolin-4(1H)-
one derivatives and the results are summarized in Table 5.
The reusability of the catalyst was also investigated
on the model reaction. The magnetic nature of the cata-
lyst allowed its facile recovery by simple separation by
an external magnet, washing with ethanol and drying at
room temperature to provide an opportunity for recycling
experiments. The separated nano-catalyst was reused in the
above-mentioned reaction for the synthesis of IIIc for seven
times without considerable loss of its catalytic activity
Fig. 5 Nitrogen adsorption isotherms on nano-Fe O /TiCl /cellulose
at 77.15 °K
3
4
2
(Fig. 7). Partial loss of activity may be due to active sites
Meanwhile, energy-dispersive X-ray spectroscopy
EDS) of nano-Fe O /TiCl /cellulose was measured by
blockage of the catalyst and/or partial leaching of titanium
from the catalyst.
(
3
4
2
EDS instrument (Fig. 6). According to this data, the weight
percentage of C, O, Cl, Ti and Fe is 21.2, 36.6, 2.44, 3.09
and 36.67, respectively.
Conclusion
After characterization of nano-Fe O /TiCl /cellulose,
3
4
2
the activity of catalyst was evaluated for the synthesis of
,3-dihydroquinazolin-4(1H)-ones. For optimization of the
reaction conditions, the reaction of 2-aminobenzamide and
-chlorobenzaldehyde as a model reaction was investigated
Table 3). As shown in Table 3, entry 14, it was found that
.03 g of nano-Fe O /TiCl /cellulose at room temperature
We have demonstrated the preparation and characteriza-
tion of nano-Fe O /TiCl /cellulose as a novel magnetite
2
3
4
2
recoverable, eco-friendly, inexpensive and efficient nano-
catalyst. The catalytic activity of the prepared catalysts
was investigated in the synthesis of 2,3-dihydroquinazo-
lin-4(1H)-one derivatives through two-component reac-
tion of aldehydes and 2-aminobenzamide. This protocol
4
(
0
3
4
2
in EtOH is the best reaction condition. In order to compare
Fig. 6 EDS analysis diagram of
nano-Fe O /TiCl /cellulose
3
4
2
1
3

J IRAN CHEM SOC
Table 3 Synthesis of 2-(4-chlorophenyl)-2,3-dihydroquinazolin-4(1H)-one in the presence of nano-Fe O /TiCl /cellulose under various condi-
3
4
2
tions
Entry
Solvent
Catalyst (g)
Condition
Time
Yield (%)Ref.,a
b
1
2
3
4
5
6
7
8
9
–
–
Catalyst (0.05)
R. T
6 h
3 h
2 h
3 h
3 h
3 h
2 h
2 h
3 h
–
b
Catalyst (0.05)
100 °C
R. T
60
41
53
59
60
50
70
45
85
92
30
70
96
60
b
H O
Catalyst (0.05)
2
b
H O
Catalyst (0.05)
Reflux
Reflux
R. T
2
b
CH CN
Catalyst (0.05)
3
b
CH Cl
Catalyst (0.05)
2
2
b
CHCl3
Catalyst (0.05)
Reflux
R. T
b
MeOH
MeOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
Catalyst (0.05)
b
Catalyst (0.05)
Reflux
Reflux
R. T
b
1
1
1
1
1
1
0
1
2
3
4
5
Catalyst (0.05)
15 min
9 min
4 h
b
Catalyst (0.05)
–
R. T
b
Catalyst (0.04)
R. T
6 min
6 min
45 min
b
Catalyst (0.03)
R. T
b
Catalyst (0.02)
R. T
The amounts of 4-chlorobenzaldehyde (1 mmol), 2-aminobenzamide (1 mmol)
a
Isolated yield
b
Nano-Fe O /TiCl /cellulose
3
4
2
Table 4 Comparison of
Entry
Solvent
EtOH
Catalyst (g)
Condition
Time
Yield
nano-Fe O /TiCl /cellulose
Ref.,a
3
4
2
(
%)
with reported catalysts for the
synthesis of 2-(4-chlorophenyl)-
b
1
2
3
4
5
6
7
Catalyst (0.03)
R. T
6 min
96
2
,3-dihydroquinazolin-4(1H)-
H O
Wang-OSO H
100 °C
R. T
24 min
10 min
180 min
1 h
84 [27]
86 [28]
89 [29]
85 [30]
90 [31]
98 [32]
2
3
one
CH CN
CAN. SiO2
3
c
EtOHl/H O
X (0.1 mmol)
60 °C
80 °C
70 °C
Reflux
2
CH CN
Amberlyst-15
MNPs-PSAd
CuCl /Fe O -
3
H O
25 min
45 min
2
EtOH
2
3
4
TEDETA
Ye
8
9
–
–
–
110 °C
75 °C
10 min
40 min
60 min
35 min
90 [33]
90 [34]
75 [35]
89 [36]
[Bmim]PF6
TBABf
1
1
0
1
100 °C
70 °C
H O
NH SO H
2
2
3
a
b
c
d
e
f
Isolated yield
Nano-Fe O /TiCl /cellulose
3
4
2
X:2-morpholinoethanesulfonic acid
N-propylsulfamic acid supported on magnetic Fe O nanoparticles
3
4
Y: [PYC SO H][HSO ]/A 300 SiO
2
4
3
4
Tetrabutylammonium bromide
1
3

J IRAN CHEM SOC
Table 5 Synthesis of
,3-dihydroquinazolin-4(1H)-
2
ones (IIIa–k) in the presence of
nano-Fe O /TiCl /cellulose
3
4
2
Entry
R
Product
Time (min)
Yield (%)b
M.P.[Ref]
1
2
3
4
5
6
7
8
9
H
IIIa
IIIb
IIIc
IIId
IIIe
IIIf
IIIg
IIIh
IIIi
IIIj
IIIk
10
10
6
92
95
96
95
85
90
95
90
93
88
79
219–220 [28]
309–312 [35]
193–194 [27]
199–200 [32]
158–161 [28]
191–192 [29]
206–208 [27]
193–195 [29]
223–224 [33]
166–169 [38]
185–187 [36]
4-NO2–
4-Cl–
4-Br
6
4-(CH ) CH–
15
12
8
3
2
2-NO2–
2-Cl–
3-NO2–
3-Br–
10
10
15
15
10
1
2, 4-(Cl)2–
1
2, 4-(MeO)2–
a
2
-Aminobenzamide (1.0 mmol), aldehyde (1.0 mmol) and nano-Fe O /TiCl /cellulose (0.03 g) were used
3 4 2
in EtOH at room temperature
b
Isolated yield
2.
3.
4.
5.
S. Laurent, D. Forge, M. Port, A. Roch, C. Robic, L. Vander Elst,
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2010)
T. Zeng, W.-W. Chen, C.M. Cirtiu, A. Moores, G. Song, C.-J. Li,
Green Chem. 12, 570 (2010)
6
7
.
.
T. Zeng, G. Song, A. Moores, C.-J. Li, Synlett 2010, 2002 (2010)
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1
28, 5279 (2006)
8
.
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Fig. 7 Recycling of nano-Fe O /TiCl /cellulose for the synthesis of
IIIc
9. M.B. Gawande, P.S. Branco, R.S. Varma, Chem. Soc. Rev. 42,
3
4
2
3371 (2013)
1
0. B. Movassagh, A. Takallou, A. Mobaraki, J. Mol. Catal. A-Chem.
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96, 90 (2015)
4
includes some important advantages such as short reac-
tion times, high yields, simple methodology and easy
work-up procedure. The nano-catalyst could be recycled
and reused without significant loss of its catalytic activity.
(
1
1
3
3. M.B. Gawande, Y. Monga, R. Zboril, R. Sharma, Coord. Chem.
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Acknowledgments The Research Council of Yazd University grate-
fully acknowledged for the financial support for this work.
1
1
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