Supported N-propylsulfamic acid on magnetic nanoparticles used as recoverable and recyclable catalyst for the synthesis of 2,3-dihydroquinazolin- 4(1H)-ones in water

Article abstract of DOI:10.1016/j.cclet.2013.01.032

An efficient and eco-friendly method is reported for the synthesis of 2-substituted-2,3-dihydroquinazolin-4(1H)-ones from direct cyclocondensation of anthranilamide with aldehydes and ketones using N-propylsulfamic acid supported onto magnetic Fe₃O₄ nanoparticles (MNPs-PSA) as a recoverable and recyclable nanocatalyst in good to excellent yields in water at 70 °C. The catalyst was readily separated using an external magnet and reusable without significant loss of their catalytic efficiency.

Full text of DOI:10.1016/j.cclet.2013.01.032

Chinese Chemical Letters 24 (2013) 211–214
Contents lists available at SciVerse ScienceDirect
Chinese Chemical Letters
journal homepage: www.elsevier.com/locate/cclet
Original article
Supported N-propylsulfamic acid on magnetic nanoparticles used as recoverable
and recyclable catalyst for the synthesis of 2,3-dihydroquinazolin-4(1H)-ones in
water
a,
b
b
b
Amin Rostami *, Bahman Tahmasbi , Hoshyar Gholami , Hajir Taymorian
a
Young Researchers and Elites Club, Sanandaj Branch, Islamic Azad University, Sanandaj, Iran
b
Department of Chemistry, Faculty of Science, University of Kurdistan, Zip Code 66177-15175, Sanandaj, Iran
A R T I C L E I N F O
A B S T R A C T
Article history:
An efficient and eco-friendly method is reported for the synthesis of 2-substituted-2,3-dihydroqui-
Received 7 September 2012
Received in revised form 5 December 2012
Accepted 10 December 2012
nazolin-4(1H)-ones from direct cyclocondensation of anthranilamide with aldehydes and ketones using
3 4
N-propylsulfamic acid supported onto magnetic Fe O nanoparticles (MNPs-PSA) as a recoverable and
recyclable nanocatalyst in good to excellent yields in water at 70 8C. The catalyst was readily separated
using an external magnet and reusable without significant loss of their catalytic efficiency.
ß 2013 Amin Rostami. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights
reserved.
Keywords:
Magnetic nanoparticles
N-Propylsulfamic acid
Nanocatalyst
2
,3-Dihydroquinazolin-4(1H)-ones
Cyclocondensation
Anthranilamide
1
. Introduction
Magnetic nanoparticles are efficient, readily available, high-
2,3-dihydroquinazolin-4(1H)-ones involves the condensation re-
action of anthranilamide with aldehyde or ketone in the presence
of various promoting agents [16–23]. Although reported methods
produce good results in many instances, the development of
efficient, simple, easy work-up and environmentally benign
protocols using recyclable catalysts and green solvents for the
synthesis of these important compounds is still desirable and in
demand.
surface-area resulting in high catalyst loading capacity and
outstanding stability heterogeneous supports for catalysts [1].
More importantly, magnetic separation of the magnetic nanopar-
ticles is more effective than filtration or centrifugation [2], simple,
economical and promising for industrial applications [3]. Among
the various magnetic nanoparticles used as the core magnetic
2 3
Sulfamic acid (H NSO H, SA), a common inorganic acid, is
support, Fe
3
O
4
nanoparticles are arguably the most extensively
nonvolatile, noncorrosive, stable, water resistance and incapable of
forming complexes, making it an outstanding alternative to metal
catalysts in different areas of organic synthesis as an efficient and
green reagent [24,25]. The main drawback of SA just like any
heterogeneous or homogeneous catalyst is its separation from the
reaction mixture by filtration or liquid–liquid techniques which
cause the loss of catalyst in many reactions. To overcome this
drawback, SA can be immobilized on magnetic nanoparticles. In
recent years, organic reactions in aqueous media have received
high priority in view of green methodology [26].
studied [4] because of their simple synthesis, low cost, and
relatively large magnetic susceptibility [5]. Recently, preparation
and application of several supported catalysts on magnetic Fe
nanoparticles have been reported [6–11].
3 4
O
2
,3-Dihydroquinazolin-4(1H)-ones are an important class of
fused heterocycles with a wide range of pharmaceutical and
biological activities [12]. These compounds can easily be oxidized
to their quinazolin-4(3H)-one analogues [13], which also include
important pharmacologically active compounds [14]. Various
methods have already been proposed for the synthesis of these
compounds [15]. A general procedure for the synthesis of
2. Experimental
General procedure for the synthesis of 2,3-dihydroquinazolin-
*
Corresponding author.
4(1H)-ones: The MNPs-PSA (10 mg) was added to a mixture of
E-mail address: a.rostamir@uok.ac.ir (A. Rostami).
anthranilamide (1 mmol, 0.136 g) and aldehyde or ketone
1
001-8417/$ – see front matter ß 2013 Amin Rostami. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
http://dx.doi.org/10.1016/j.cclet.2013.01.032

2
12
A. Rostami et al. / Chinese Chemical Letters 24 (2013) 211–214
Scheme 1. MNPs-PSA catalyzes the synthesis of 2,3-dihydroquinazolin-4(1H)-ones
in water.
Fig. 2. Image showing MNPs-PSA can be separated by applied magnetic field. A
reaction mixture in the absence (right) or presence of a magnetic field (left).
Scheme 2. Synthesis of MNPs-PSA: (a) 3-aminopropyltriethoxysilane, ethanol/
water, rt, 8 h and (b) chlorosulfuric acid, dichloromethane, rt, 2 h.
3 4
differentiates from that of the unfunctionalized Fe O nano-
magnets and aminopropyl-functionalized magnetic nanoparticles
(Fig. 1B). XRD pattern of MNPs-PSA is shown in Fig. 1C, the position
and relative intensities of all peaks confirm well. To determine the
acid amount on the surface, the prepared catalyst (100 mg) was
added to an aqueous NaCl solution (1 mol/L, 10 mL) with an initial
pH 5.93. The mixture was stirred for 0.5 h after which the pH of
solution decreased to 1.72, indicating an ion exchange between
sulfamic acid protons and sodium ions, this is equal to a loading of
1.9 mmol/g of sulfamic acid group. This result confirmed by back-
titration of the catalyst.
(
1 mmol) in water (2 mL). Then the mixture was stirred for the
appropriate time at 70 8C. The progress was monitored by TLC.
After completion of the reaction, the reaction mixture was cooled
to room temperature. CH
catalyst was separated by an external magnet. The resulting
mixture was washed with brine (10 mL) and dried over anhydrous
2
Cl
2
(2 Â 5 mL) was added and the
2 4 2 2
Na SO . CH Cl was evaporated under reduced pressure to afford
the essentially pure products. In some cases, the product was
recrystalized from ethanol for further purification.
Subsequently, in order to optimize the reaction conditions, we
evaluated the influence of different amounts of catalyst on the
model cyclocondensation reaction of anthranilamide (1 mmol)
and 4-methoxybenzaldehyde (1 mmol) in water at 70 8C on
reaction time and yield of product (Table 1). When adding catalyst,
the reaction times were reduced, however 10 mg of MNPs-PSA was
chosen as the desired condition.
3
. Results and discussion
In continuation of our efforts in the development of green
synthetic methodologies [27–30], herein we report catalytic
application of MNPs-PSA as magnetically heterogeneous nanoca-
talysts for the synthesis of 2-substituted-2,3-dihydroquinazolin-
4
(1H)-ones from direct cyclocondensation of anthranilamide with
In order to extend the scope of this cyclocondensation reaction,
the various benzaldehyde derivatives, including electron-donating
and electron-withdrawing groups on aromatic ring, terephthalde-
hyde and aliphatic ketones were investigated in the presence of the
catalytic amount of MNPs-PSA in water at 70 8C, the results are
summarized in Table 2.
aldehydes or ketones in water at 70 8C (Scheme 1).
Initially, the MNPs-PSA was synthesized according to the
method reported recently with some modifications as shown in
Scheme 2 [31]. Magnetite (Fe
coprecipitation of iron (II) and iron (III) ions in basic solution at
3 4
O ) nanoparticles were prepared by
8
5 8C using the method described [32].
The catalyst has been characterized by scanning electron
As shown in Table 2, aromatic aldehydes electron-donating
group yielded corresponding 2-substituted-2,3-dihydroquinazo-
lin-4(1H)-ones in shorter reaction time and higher yield, whereas
aromatic aldehydes with electron-withdrawing groups gave
longer reaction times. For aliphatic ketones such as acetone and
cyclohexanone, relatively slower reactions were observed (Table 2,
entries 15 and 16). We have developed this synthetic method for
the preparation of bis-2,3-dihydroquinazolin-4(1H)-one in a 2:1
microscopy (SEM), Fourier transform infrared spectroscopy (FT-
IR), X-ray diffraction (XRD) and by comparisons with authentic
sample. A SEM image of MNPs-PSA is shown in Fig. 1A. It was
confirmed that the catalyst was made up of nanometer-sized
particles. The IR spectrum of MNPs-PSA shows peaks that are
characteristic of
a functionalized SA group, which clearly
Fig. 1. (A) SEM images of MNPs-PSA, (B) the comparative FT-IR spectra for (a) MNPs, (b) MNPs–APTMs and (c) MNPs-PSA, and (C) the XRD pattern of MNPs-PSA.

A. Rostami et al. / Chinese Chemical Letters 24 (2013) 211–214
213
Table 1
4
. Conclusion
Optimization of the amounts of MNPs-PSA for cyclocondensation reaction of
anthranilamide (1 mmol) and 4-methoxybenzaldehyde (1 mmol) in water at 70 8C.
In summary, MNPs-PSA as
a
eco-friendly, efficient and
Entry
Catalyst (mg)
Time (min)
Yield (%)
magnetically recoverable catalyst was used in synthesis of 2,3-
dihydroquinazolin-4(1H)-ones by direct cyclocondensation of
anthranilamide and aryl aldehydes or ketones with good to high
yields in water. The characteristic advantages of this catalyst are
rapid, simple and efficient separation by using an appropriate
external magnet, which minimizes the loss of catalyst during
separation, and reusable without significant loss of activity up to
1
2
3
4
5
5
7
60
45
25
20
17
89
96
97
95
97
10
20
30
10 cycles. In addition, MNPs-PSA couples the advantages of
Table 2
heterogeneous and homogeneous SA-based systems, which make
it as a promising material for industry.
MNPs-PSA catalyzed the synthesis of 2,3-dihydroquinazolin-4(1H)-ones in water at
a
7
0 8C.
Entry
Aldehyde
Time
Yields
Mp (8C) [Ref.]
b
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min)
(%)
1
2
3
4
5
6
7
8
9
C
6
H
5
CHO
4-OH-C
4-CH OC
35
50
25
50
30
30
60
25
35
30
97
95
97
94
95
93
91
90
91
87
86
88
86
89
71
79
220–222 [17]
275–277 [17]
191–193 [17]
187–189 [17]
214–216 [18]
231–233 [17]
198–200 [19]
204–206 [17]
210–211 [23]
199–200 [17]
190–193 [17]
204–206 [17]
222–224 [20]
245–247 [16]
184–186 [21]
223–225 [22]
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