Synthesis of some novel 2-aryl-substituted 2,3-dihydroquinazolin-4(1 H)-ones under solvent-free conditions using MCM-41-SO3H as a highly efficient sulfonic acid

Article abstract of DOI:10.1055/s-0029-1218676

MCM-41-SO₃H, ordered mesoporous silica material MCM-41 with covalently anchored sulfonic acid groups located inside the mesochannels, was used as an acid catalyst for the rapid and green synthesis of 2,3-dihydroquinazolin-4(1H)-one derivatives

Full text of DOI:10.1055/s-0029-1218676

1356
PAPER
Synthesis of Some Novel 2-Aryl-Substituted 2,3-Dihydroquinazolin-4(1H)-
ones under Solvent-Free Conditions Using MCM-41-SO3H as a Highly
Efficient Sulfonic Acid
Synthesis of
2
h
-Aryl-2,3-dih
a
ydroquina
h
z
olin-4(1
H
)
-o
n
nes Using MaCM-41-S 3
O
z
H
Rostamizadeh,*a Ali Mohammad Amani,a Gholam Hossein Mahdavinia,*b Hamid Sepehrian,c
Samira Ebrahimia
a
Department of Chemistry, K. N. Toosi University of Technology, P.O. Box 15875-4416, Tehran, Iran
Fax +98(21)22853650; E-mail: shrostamizadeh@yahoo.com
Department of Chemistry, Islamic Azad University-Marvdasht Branch, Marvdasht, Iran
b
E-mail: Email: hmahdavinia@gmail.com
c
Jaber Ibn Hayan Research Laboratories Science and Technology Research Institute, AEOI, P.O. Box 11365-8486, Tehran, Iran
Received 15 December 2009
widely used organic compounds from readily available re-
Abstract: MCM-41-SO3H, ordered mesoporous silica material
agents is a major challenge in organic synthesis. Thus, a
reaction that uses a catalytic amount of nanosized MCM-
41-SO3H as a catalyst, should greatly contribute to the
MCM-41 with covalently anchored sulfonic acid groups located in-
side the mesochannels, was used as an acid catalyst for the rapid and
‘green’ synthesis of 2,3-dihydroquinazolin-4(1H)-one derivatives
under solvent-free condition. This novel synthetic method offers creation of environmentally benign processes. To the best
several advantages, such as excellent yields, simple procedure,
short reaction times, and mild reaction conditions.
of our knowledge, no examples of MCM-41-SO3H-cata-
lyzed synthesis of quinazolinones have been reported in
Key words: MCM-41-SO3H, nanocatalyst, 2,3-dihydroquinazoli-
none, multicomponent reactions, solvent-free conditions
the literature. Herein, we report, for the first time, the
preparation of 2,3-dihydroquinazolin-4(1H)-ones via
multicomponent reactions catalyzed by MCM-41-SO3H
as a catalyst under very mild conditions.
Atom-economic multicomponent reactions and the identi-
fication of catalytic procedures that can be run under sol-
vent-free conditions both play important roles in organic
synthesis, especially for the synthesis of bioactive hetero-
cycles.1 Accordingly, the development of efficient meth-
ods for the synthesis of heterocyclic compounds has posed
a real challenge to organic chemists for over a century.2,3
Fused nitrogen-containing heterocycles are structural
fragments of many natural compounds and they are im-
portant for various vital processes. Quinazolinones have
been frequently used in medicine because of their wide
spectrum of biological activity.4–9 Several quinazolinone
derivatives have been synthesized as potential antimicro-
bial,10 anticancer,11 and antimalarial agents.12 One of the
main groups of quinazolinones, dihydroquinazolinones,
influence numerous cellular processes; they display a
broad range of biological, medicinal, and pharmacologi-
cal properties and they are constituents of antitumor, anti-
O
H
N
N
N
Figure 1
In recent years, organically functionalized ordered meso-
porous silicas15–18 with a tunable pore structure and tai-
lored composition have received considerable interest
with broad application ranging from adsorbent,19–22 gas
separation,23 and catalysis24–28 to biological uses.15,29
Some properties of these materials are: mechanically sta-
ble structure, high surface area, and large, ordered pores
with narrow size distribution of an inorganic backbone.
Therefore, it would be reasonable to consider these mate-
rials as numerous combined nanosize vessels with the
same properties. One of the best-known nanosize inorgan-
ic backbones is MCM-41, which is a structurally well-
ordered mesoporous material with a narrow pore size dis-
tribution between 1.5 and 10 nm, depending on the surfac-
tant cation and a very high surface area of up to 1500 m2
g–1.30 It has been shown that Si-MCM-41 lacks Brönsted
acid sites and exhibits only weak hydrogen-bonded-type
sites.31,32 Herein, we wish to report the preparation of
MCM-41-SO3H as a new, modified sulfonic acid. While
several types of solid sulfonic acids, based on ordered me-
soporous silicas, have been created in recent years,28 there
have been only a few reports of their applications as cata-
lysts in chemical transformations. In the present work
MCM-41 was modified to contain covalently bonded sul-
biotic,
antidefibrillatory,
antipyretic,
analgesic,
antihypertonic, diuretic, antihistamine, antidepressant,
and vasodilating agents.13 For example, luotonin A
(Figure 1), a novel pyrroloquinazolinoquinoline alkaloid,
shows cytotoxic activity against mouse leukemia cells (P-
388) and inhibitory activity against topoisomerase I and
II.14
In view of these useful properties, development of a sim-
ple, efficient, and general synthetic method for these
SYNTHESIS 2010, No. 8, pp 1356–1360
x
x
.
x
x
.2
0
1
0
Advanced online publication: 15.03.2010
DOI: 10.1055/s-0029-1218676; Art ID: Z13809SS
© Georg Thieme Verlag Stuttgart · New York

PAPER
Synthesis of Some Novel 2-Aryl-Substituted 2,3-Dihydroquinazolin-4(1H)-ones Using MCM-41-SO3H
1357
fonic groups on the inside surface of the channels and pro-
vide the silica supported material with Brönsted acid
properties. MCM-41 was synthesized according to a pre-
viously described method using cetyltrimethylammonium
bromide [(C16H33)Me3N+Br–], as the templating agent.33
The surfactant template was then removed from the syn-
thesized material by calcination at 540 °C for six hours.
Then MCM-41 was reacted with chlorosulfonic acid to
give a white powder that was named ‘MCM-41-SO3H’. It
is interesting to note that the reaction is easy and clean
without any workup procedure, because HCl gas is
evolved from the reaction vessel immediately
(Scheme 1).
Figure 3
2-aryl-substituted 2,3-dihydroquinazolin-4(1H)-ones 4
catalyzed by MCM-41-SO3H under solvent-free condi-
tions.
During our investigation, as a model we chose the reaction
of isatoic anhydride (1, 1 mmol), ammonium acetate (2,
1.2 mmol), and 4-chlorobenzaldehyde (3j, 1 mmol) and
examined the effect of the amount of MCM-41-SO3H as
catalyst in the absence of solvent under various tempera-
tures on the yield of 4j (Scheme 2, Table 1). Initial screen-
ing studies confirmed that solvent-free conditions were
optimal for this reaction. The results obtained during this
optimization showed some interesting points. First of all,
increasing the amount of MCM-41-SO3H did not obvi-
ously improve the yield of 4j, while decreasing the
amount of nanocatalyst decreased the yield of 4j and in-
creased reaction time; the optimum amount of the catalyst
was found to be 5 mg. The second important point that
could be elicited from these results is that raising the reac-
tion temperature from 75 °C stepwise to 115 °C increased
the yield of 4j and also improved the reaction rate, but an
increase from 115 to 120 °C did not improve the reaction
rate. Therefore, the optimum temperature was 115 °C.
Also in order to evaluate and show the high catalytic ac-
tivity of MCM-41-SO3H, the effect of other Lewis acids,
such as ZrOCl2/K10 and NaHSO4/SiO2, was investigated
in this model reaction. As shown in Table 1 (entries 15
and 16) when the mixture was reacted under solvent-free
condition in the presence of these Lewis acids, the yield
was lower, which further shows the superior catalytic ac-
tivity of MCM-41-SO3H in this transformation. More-
over, application of solvents (such as EtOH, MeOH,
CH2Cl2, MeCN, and H2O) did not lead to better results.
Under these conditions, longer reaction times and very
low yields can be clearly observed (Table 2, entries 1–5).
Scheme 1
MCM-41-SO3H was characterized by thermogravimetric
analysis (TGA), scanning electron microscopy (SEM), X-
ray diffraction (XRD), and acid-base titration. The SEM
image of mesoporous MCM-41-SO3H that had been coat-
ed with gold for two minutes was taken to show the sur-
face at high magnification (Figure 2). XRD analysis was
performed from 1.5° (2q) to 10.0° (2q) at a scan rate of
0.02° (2q)/sec. The XRD patterns of the synthesized
MCM-41-SO3H sample are presented in Figure 3. The
sample of MCM-41-SO3H showed relatively well-defined
XRD patterns, with one major peak along with three small
peaks identical to those of MCM-41 materials.34
In continuation of our search for new synthetic methodol-
ogies for biologically important heterocycles,35 we herein
report a ‘green’ approach to the synthesis of some novel
O
CHO
O
catalyst
NH
O
NH + OAc–
+
+
4
solvent, temperature
N
H
N
H
O
Cl
Cl
1
3j
2
4j
Figure 2
Scheme 2
Synthesis 2010, No. 8, 1356–1360 © Thieme Stuttgart · New York

1358
S. Rostamizadeh et al.
PAPER
MCM-41-SO3H is an efficient and green catalyst for the
synthesis of 2,3-dihydroquinazolinones. Very recently,
formation of 2,3-disubstituted quinazolin-4(3H)-ones via
multicomponent reactions has been reported in the litera-
ture.36–39 We believe that many biologically active deriv-
atives could be synthesized by this multicomponent
reaction with high atomic economy. Herein, a three-com-
ponent, one-step synthesis of 2,3-dihydroquinazolin-
4(1H)-ones using MCM-41-SO3H, which is relatively
safe and inexpensive, is at the center of our study. In the
course of our work on the applications of MCM-41-SO3H
in organic reactions, we have found that it is an effective
promoter as well as an ecofriendly and efficient catalyst
for the synthesis of 2,3-dihydroquinazolin-4(1H)-ones.
Furthermore, one of the most interesting point in this work
is due to very large specific surface areas, highly ordered
pore systems and moreover, the surface properties (inside
the channels) of the modified sulfonic acid (MCM-41-
SO3H), which shows high activity. A plausible mechanis-
tic pathway to 2-aryl-substituted 2,3-dihydroquinazolin-
4(1H)-ones is illustrated in Scheme 3. In the initial step,
reaction of isatoic anhydride (1), and ammonium acetate
(2) within the MCM-41-SO3H tunnels, together with de-
carboxylation, gives 2-aminobenzamide (5). Condensa-
tion of this compound with the aromatic aldehyde 3 gives
imine 6, which undergoes cyclization to afford the dihyd-
roquinazoline product 4.
Table 1 Effect of Amount of MCM-41-SO3H, Different Catalysts,
and Temperature on the Synthesis of 4j (Scheme 2)
Entry Catalyst
Amounta (mg)
Temp Time Yieldb
(°C) (min) (%)
1
2
3
4
5
6
7
8
9
MCM-41-SO3H
100 (0.6 mmol H+)
10 (0.06 mmol H+)
100 (0.6 mmol H+)
10 (0.06 mmol H+)
5 (0.03 mmol H+)
75
75
85
85
95
300 67
350 60
150 75
210 76
20 70
45 80
55 73
14 86
MCM-41-SO3H
MCM-41-SO3H
MCM-41-SO3H
MCM-41-SO3H
MCM-41-SO3H
MCM-41-SO3H
MCM-41-SO3H
MCM-41-SO3H
100 (0.6 mmol H+) 100
10 (0.06 mmol H+) 100
5 (0.03 mmol H+)
105
200 (1.2 mmol H+) 110
100 (0.6 mmol H+) 110
7
7
90
90
10 MCM-41-SO3H
11 MCM-41-SO3H
12 MCM-41-SO3H
13 MCM-41-SO3H
14 MCM-41-SO3H
15 ZrOCl2/K10
5 (0.03 mmol H+)
10 (0.06 mmol H+) 115
115
10 92
10 91
10 92
10 93
10 70
10 80
50 (0. 3 mmol H+)
5 (0.03 mmol H+)
5 mg
115
120
115
115
O
16 NaHSO4/SiO2
5 mg
O
O
a Reactions were performed with 1 mmol of reactants.
b Isolated yield.
NH2
N
O
1
+
H
NH2
5
NH4+OAc–
3
2
OSO3H
Table 2 Synthesis of 4j Using MCM-41-SO3Ha in Different Sol-
H
O S O
vents (Scheme 2)
O
N
O
NH2
Ar
Entry
Solvent
EtOH
Temp (°C) Time (min) Yieldb (%)
NH
N
H
Ar
1
2
3
4
5
6
reflux
reflux
reflux
reflux
reflux
115
180
210
420
45
82
70
87
85
53
92
6
H
4
MeOH
CH2Cl2
MeCN
H2O
Scheme 3
In conclusion, MCM-41-SO3H has been employed here as
an appropriate catalyst for the one-pot multicomponent
synthesis of 2,3-dihydroquinazolin-4(1H)-ones 4 on the
basis of its (a) high efficiency, (b) easy availability, (c)
low cost, (d) operational simplicity, and (e) action under
mild reaction conditions. The products were formed in ex-
cellent yields with short reaction times. The method offers
several advantages, such as omitting toxic solvents or cat-
alysts, a very simple workup procedure without chroma-
tography method, and improved yields. The starting
materials are inexpensive and commercially available.
45
solvent-free
10
a Amount of catalyst was 5 mg for 1 mmol of 1.
b Isolated yield.
With these results in hand, a variety of heterocyclic and
aromatic aldehydes, possessing both electron-donating
and electron-withdrawing groups were employed for
quinazolinones formation and, in all cases, the yields of 4
were excellent (Table 3). All known products were char-
acterized by comparing their physical and spectral (IR and
1H and 13C NMR) data with those of authentic samples re-
ported in the literature. The data for novel compounds
(Table 3, entries 1–5) are reported in this paper.
Products 4f–o are known compounds and their physical data, IR,
and 1H NMR spectra were essentially identical with those of authen-
tic samples. Other products, which are new, were characterized by
IR, 1H and 13C NMR, and MS. Melting points were measured on a
Buchi B-540 apparatus. IR spectra were obtained on an ABB
Bomem Model FTLA200-100 spectrophotometer. 1H and 13C NMR
Synthesis 2010, No. 8, 1356–1360 © Thieme Stuttgart · New York

PAPER
Synthesis of Some Novel 2-Aryl-Substituted 2,3-Dihydroquinazolin-4(1H)-ones Using MCM-41-SO3H
1359
Table 3 Synthesis of 2-Aryl-Substituted 2,3-Dihydroquinazolin-4(1H)-ones in the Presence of MCM-41-SO3H
O
O
NH
MCM-41-SO3H (5 mg)
115 °C, solvent-free
O
NH4+OAc–
ArCHO
+
+
N
H
Ar
N
H
O
1
2
3
4
(1 mmol)
(1.2 mmol)
(1 mmol)
Entry
Ar
Product
Time (min)
Yielda (%)
Mp (°C)
Found
Lit.
1
2
1H-indol-3-yl
4-AcNHC6H4
2,4-Cl2C6H4
2-HOC6H4
3-HOC6H4
4-HOC6H4
4-O2NC6H4
4-NCC6H4
4-BnOC6H4
4-ClC6H4
4a
4b
4c
4d
4e
4f
4
20
10
4
95
85
98
97
95
99
75
98
90
92
90
98
87
90
85
219–220
241–242
181–185
252–254
206–207
277–279
300–302
350–351
238–240
207–208
232–233
183–184
225–226
228–230
180–182
–
–
3
–
4
–
5
5
–
6
5
278–28040
310–31235
350–35135
238–24035
207–20835
232–23335
183–18435
225–22635
229–23135
180–18235
7
4g
4h
4i
10
10
10
10
15
5
8
9
10
11
12
13
14
15
4j
2,3-Cl2C6H3
4-MeOC6H4
Ph
4k
4l
4m
4n
4o
5
4-MeC6H4
3-O2NC6H4
15
12
a Isolated yields.
spectra were determined on a Bruker Avance DRX-300 spectrome-
ter, at 300 and 75 MHz, using TMS as an internal standard. Mass
spectra were performed on a Shimadzu QP 1100EX with an ioniza-
tion potential of 70 eV.
2-(1H-Indol-3-yl)-2,3-dihydroquinazolin-4(1H)-one (4a)
IR (KBr): 1658 (C=O), 2926 (C–H), 3068 (C–H), 3179 (N–H),
3243 cm–1 (N–H).
1H NMR (CDCl3–DMSO-d6): d = 7.17–7.30 (m, 4 H), 7.53 (m, 2
H), 7.7 (s, 1 H, NH), 8.05 (d, J = 7.7 Hz, 1 H), 8.15 (d, J = 2 Hz, 1
H), 8.23 (d, J = 7.5 Hz, 1 H), 8.68 (s, 1 H), 8.96 (s, 1 H, NH), 12.00
(s, 1 H, NH).
13C NMR (CDCl3–DMSO-d6): d = 62.01, 112.52, 114.85, 119.47,
120.73, 121.72, 123.25, 124.39, 124.72, 126.50, 130.17, 132.40,
135.75, 137.37, 151.46, 157.20, 167.08.
Synthesis and Functionalization of MCM-41-SO3H
MCM-41 was modified using a 100-mL suction flask equipped with
a constant pressure dropping funnel containing ClSO3H (81.13 g,
0.70 mol) and a gas inlet tube for conducting HCl gas over an ad-
sorbing soln. Into it was charged MCM-41 (60.0 g) and ClSO3H
was then added dropwise over a period of 30 min at r.t. HCl gas
evolved from the reaction vessel immediately. After completion of
the addition the mixture was shaken for 30 min and a white solid
(MCM-41-SO3H) was obtained (115.9 g).
MS (EI): m/z (%) = 263 (M+, 9), 262 (26), 245 (34), 146 (89), 117
(100), 90 (74), 63 (62).
2-[4-(Acetylamino)phenyl]-2,3-dihydroquinazolin-4(1H)-one
2,3-Dihydroquinazolin-4(1H)-ones 4; General Procedure
A mixture of isatoic anhydride (1, 163 mg, 1 mmol), aromatic alde-
hyde 3 (1 mmol), and NH4OAc (2, 1.2 mmol) was added to MCM-
41-SO3H (5 mg, 0.03 mmol H+); it was then stirred at 115 °C for an
appropriate period of time (Table 3). When the reaction was com-
plete (TLC, n-hexane–EtOAc, 2:1) the mixture was treated with
EtOH (10 mL) and the solid catalyst was separated by filtration.
H2O (10 mL) was added and precipitate product was filtered and fi-
nally recrystallized (EtOH).
(4b)
IR (KBr): 1647 (C=O), 1675 (C=O), 3036 (C–H), 3300 cm–1 (N–
H).
1H NMR (CDCl3–DMSO-d6): d = 2.05 (s, 3 H, CH3), 5.7 (s, 1 H),
6.68 (t, J = 7.5 Hz, 1 H), 6.75 (d, J = 8 Hz, 1 H), 7.03 (s, 1 H, NH),
7.24 (t, J = 7.5 Hz, 1 H), 7.43 (d, J = 8.5 Hz, 2 H), 7.60 (m, 3 H),
8.22 (s, 1 H, NH), 10.00 (s, 1 H, NH).
13C NMR (CDCl3–DMSO-d6): d = 24.05, 66.54, 114.49, 115.01,
117.21, 118.81, 127.45, 133.35, 135.83, 139.58, 148.07, 163.80,
168.43.
Synthesis 2010, No. 8, 1356–1360 © Thieme Stuttgart · New York

1360
S. Rostamizadeh et al.
PAPER
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J1 = 8 Hz, J1 = 2 Hz, 1 H), 7.65–7.68 (m, 3 H), 8.25 (s, 1 H, NH).
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127.43, 127.68, 128.93, 130.85, 132.93, 133.54, 133.98, 136.96,
147.55, 163.59.
MS (EI): m/z (%) = 292 (M+, 57), 291 (91), 147 (100), 120 (54), 92
(29), 65 (14).
2-(2-Hydroxyphenyl)-2,3-dihydroquinazolin-4(1H)-one (4d)
IR (KBr): 1642 (C=O), 3079 (C–H), 3205 (O–H), 3407 cm–1 (N–H).
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H), 7.35 (d, J = 7.5 Hz, 1 H), 7.64 (d, J = 7.5 Hz, 1 H), 7.97 (s, 1 H,
NH), 9.88 (s, 1 H, NH).
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2-(3-Hydroxyphenyl)-2,3-dihydroquinazolin-4(1H)-one (4e)
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H).
1H NMR (CDCl3–DMSO-d6): d = 5.65 (s, 1 H), 6.65 (t, J = 7.5 Hz,
1 H), 6.72 (t, J = 8 Hz, 2 H), 6.89 (m, 2 H, CH, OH), 7.00 (s, 1 H),
7.2 (m, 2 H), 7.51 (d, J = 7.5 Hz, 1 H), 8.24 (s, 1 H, NH), 9.50 (s, 1
H, NH).
13C NMR (CDCl3–DMSO-d6): d = 66.47, 113.66, 114.34, 114.86,
115.35, 116.99, 117.45, 127.35, 129.33, 133.29, 143.20, 147.80,
157.36, 163.54.
MS (EI): m/z (%) = 240 (M+, 14), 239 (42), 147 (100),120 (51), 92
(37), 65 (31).
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Yavari, R.; Khanchi, A. R. J. Radioanal. Nucl. Chem. 2008,
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Acknowledgment
Authors gratefully acknowledge the Research Council of K. N.
Toosi University of Technology for partial financial support of this
work.
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Synthesis 2010, No. 8, 1356–1360 © Thieme Stuttgart · New York