The first report on the preparation of boehmite silica sulfuric acid and its applications in some multicomponent organic reactions

Article abstract of DOI:10.1039/c5nj02607e

Boehmite silica sulfuric acid (boehmite-SSA) has been prepared for the first time via an efficient sequential synthetic procedure. Initially, boehmite nanoparticles were prepared, coated by silica, and then reacted with chlorosulfonic acid to obtain boehmite-SSA. A simple, inexpensive, environmentally friendly and efficient procedure for the synthesis of polyhydroquinoline and 2,3-dihydroquinazolin-4(1H)-one derivatives using this compound as an efficient and novel nanocatalyst has been described. Boehmite-SSA is a stable, heterogeneous, cost-effective, easy to handle, and recoverable catalyst and can be reused for several consecutive runs without a significant loss of catalytic activity. Its structure was characterized by FT-IR spectroscopy, thermogravimetric analysis (TGA), powder X-ray diffraction (XRD) and scanning electron microscopy (SEM).

Full text of DOI:10.1039/c5nj02607e

View Article Online
View Journal
NJC
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: A. Ghorbani-
Choghamarani and B. Tahmasbi, New J. Chem., 2015, DOI: 10.1039/C5NJ02607E.
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.
www.rsc.org/njc

Please do not adjust margins
New Journal of Chemistry
Page 1 of 9
View Article Online
DOI: 10.1039/C5NJ02607E
New Journal of Chemistry
ARTICLE
The First Report on the Preparation of Boehmite Silica Sulfuric
Acid and Its Application in Some Multicomponent Organic
Reactions
Received 00th January 20xx,
Accepted 00th January 20xx
Arash GhorbaniꢀChoghamarani* and Bahman Tahmasbi
DOI: 10.1039/x0xx00000x
Boehmite silica sulfuric acid (BoehmiteꢀSSA) has been prepared for the first time via efficient sequential
synthetic procedure. Initially, boehmite nanoparticles was prepared, coated by silica, then reacted with
chlorosulfunic acid to obtain BoehmiteꢀSSA. A simple, inexpensive, environmentally friendly and efficient
procedure for the synthesis of polyhydroquinoline and 2,3ꢀdihydroquinazolinꢀ4(1H)ꢀone derivatives using this
compound as an efficient and novel nanocatalyst. BoehmiteꢀSSA is stable, heterogeneous, costꢀeffective, easy
to handle, recoverable catalyst and can be reused for several consecutive runs without significant loss of
catalytic activity. Its structure was characterized by FTꢀIR spectroscopy, thermogravimetric analysis (TGA),
powder Xꢀray diffraction (XRD) and scanning electron microscopy (SEM).
www.rsc.org/
which presence of many OH on the nanoboehmite surface
leads to reaction with tetraethyl orthosilicate (TEOS),
1 Introduction
dopamine, alkoxysilane and other reagents for the
immobilization of other substances [9, 10].
Recently, separation and recycling of heterogeneous
catalysts is employed in the various area of research [1].
However, immobilization of homogeneous catalysts usually
decreases the catalytic activity or selectivity [2]. This
drawback can be overcome using nanomaterials as
heterogeneous supports. Since, when the size of the support is
decreased to the nanometre scale, the surface area is
substantially increased, which is combined with excellent
accessibility of the surfaceꢀbound catalytic sites [3]. Among
the various nanomaterials, nanoboehmite is oxide hydroxide
(ꢀꢀAlOOH) particles of aluminum which has recently been
used as an absorbent, opticalmmaterial, coatings, composite
reinforcement material in ceramics, cosmetic products,
vaccine adjuvants, pillared clays and sweepꢀflocculation for
fresh water treatment, and also rarely used as heterogeneous
supports in the isolation and recycling of expensive
homogeneous catalysts [4, 5]. Also boehmite was used as the
precursor material for the synthesis of alumoxanes [4].
Numerous methods have been reported for preparation of
boehmite nanoparticles; but, most of them have focused on
the morphologies, chemical and physical properties of the
prepared particles; meanwhile, modification of nanoboehmite
surface has been rarely reported as heterogeneous catalysts
[5ꢀ7]. Boehmite nanoparticles has several advantages, such as
nonꢀtoxic, easily and readily available, thermal and
mechanical stability, highꢀsurfaceꢀarea [8, 9] and also the
surface of nanoboehmite covered with hydroxyl groups,
2,3ꢀDihydroꢀ4(1H)ꢀquinazolinone and their polycyclic
derivatives are a very important class of heterocycles that
attracted much attention because they possess their potential
biological and pharmaceutical activities including antifertility,
antibacterial, antitumor, antifungal, and mono amine oxidase
inhibition [11–15]. For example, altanserin and nitro
altanserin are drugs for 5ꢀHT2A receptor antagonists [16],
also 2ꢀ(2ꢀhydroxyphenyl)ꢀ4(3H)ꢀquinazolinone was utilized
in the detection of metal ions [17]. 2,3ꢀDihydroꢀ4(1H)ꢀ
quinazolinones are also reported to possess the ability to
inhibit enzymes of biological importance [18]. Furthermore,
2,3ꢀdihydroꢀ4(1H)ꢀquinazolinones derivatives are the key
intermediate for the synthesis of 4ꢀ(3H)ꢀquinazolinones
compounds [19].
Besides, polyhydroquinoline derivatives have been
reported to possess a wide range of biological properties and
pharmaceutical
activities
such
as
vasodilator,
hepatoprotective,
antiatherosclerotic,
bronchodilator,
antitumor, geroprotective, antidiabetic activity and also their
ability to modulate calcium channels [20ꢀ24]. Thus the
synthesis of these heterocycles has become an area of great
interest.
For this reason, many methods including a variety of
supports have been developed over the years to find efficient
these multicomponent reactions. However, the mesoporouse
silicas such as MCMꢀ41 [25], SBAꢀ15 [26] or some
nanoparticles such as TiO2 NPs [27] and iron oxide [28] have
been used as catalyst supports for organic synthesis, which
requires high temperature for calcination or inert atmosphere
and a lot of time and tedious conditions to prepare. Also some
of previously reported catalysts such as heteropolyacids [29],
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1ꢀ3 | 1
Please do not adjust margins

Please do not adjust margins
New Journal of Chemistry
Page 2 of 9
View Article Online
DOI: 10.1039/C5NJ02607E
ARTICLE
Journal Name
carbon nanotubes [30] ionic liquids [31ꢀ33] or some polymers catalyst was separated using simple filtration. CH2Cl2 was
[33] are more expensive. While preparation of nanoboehmite evaporated and all products was recrystallized in ethanol for
was not air or moisture sensitive, more importance further purification.
nanoboehmite was prepared in water at room temperature
without inert atmosphere using commercial materials such as
Al(NO3)3.9H2O and NaOH. Therefore herein BoehmiteꢀSSA
as a new nano heterogeneous catalyst has been reported for
2.4 Selected spectral data
2-(4-chlorophenyl)-2,3-dihydoquinazolin-4(1H)-one
(entry 1, table 3): Mp: 202ꢀ204 °C. IR (KBr) cmꢀ1: 3309,
1655, 1611, 1435. 1H NMR (400 MHz, DMSOꢀd6): δH=
8.29 (s, 1H), 7.61ꢀ7.43 (m, 5H), 7.26ꢀ7.20 (t, J=7.5, 1H), 7.12
(s, 1H), 6.75ꢀ6.63 (m, 2H), 5.75 (s, 1H) ppm.
2-(4-ethoxyphenyl)-2,3-dihydoquinazolin-4(1H)-one
(entry 3, table 3): Mp: 168ꢀ170 °C. IR (KBr) cmꢀ1: 3301,
1650, 1613, 1443. 1H NMR (400 MHz, DMSOꢀd6): δH= 7.95ꢀ
7.94 (b, 1H), 7.52ꢀ7.50 (m, 2H), 7.34 (s, 1H), 7.26 (s, 1H),
6.95ꢀ6.90 (m, 3H), 6.68ꢀ6.67 (m, 1H), 5.85 (s, 1H), 5.75 (s,
1H), 4.07ꢀ4.05 (q, J=4, 2H), 1.46ꢀ1.44 (s, 3H) ppm.
the
synthesis
of
polyhydroquinoline
and
2,3ꢀ
dihydroquinazolinꢀ4(1H)ꢀone derivatives.
2 Experimental
2.1. Preparation of the boehmite-SSA
The solutions of 6.490 g NaOH in 50 ml of distilled water
was added to solutions of 20 g Al(NO3)3.9H2O in 30 ml
distilled water as drop to drop under vigorous stirring. The
resulting milky mixture was subjected to mixing in the
ultrasonic bath for 3 h at 25 ºC. The resulted nanoboehmite
was filtered and washed by distilled water and were kept in
the oven at 220 ºC for 4 h.
The obtained boehmite nanoparticles (1 g) was dispersed
in water (10 mL) and ethanol (50 mL) by sonication for 30
min. Under continuous stirring, PEG (5.36 g), ammonia
solution (10 mL) and TEOS (2 mL) were respectively added
into the suspension, and continuously reacted for 38 h at room
temperature. Then, the product (boehmiteꢀsilica) was filtered
and washed with ethanol and distilled water, the obtained
boehmiteꢀsilica was dried at room temperature.
The obtained boehmiteꢀsilica (0.5 g) were dispersed in dry
nꢀhexane (5 mL) by ultrasonic bath for 30 min. Subsequently,
chlorosulfunic acid (0.75 mL) was added drop wise over a
period of 30 min and the mixture was stirred for 4h at room
temperature. Then, the final product was filtered and washed
by dry nꢀhexane, ethanol and nꢀhexane respectively to remove
the unattached substrates. The product (boehmiteꢀSSA) dried
at room temperature and stored in a refrigerator to use.
2-(4-methylphenyl)-2,3-dihydroquinazolin-4(1H)-one
(entry 6, table 3): Mp: 230ꢀ232 °C. IR (KBr) cmꢀ1: 3313,
1
1658, 1611, 1439. H NMR (400 MHz, DMSOꢀd6): δH= 8.21
(s, 1H), 7.62ꢀ7.59 (d, J=7.5, 1H), 7.38ꢀ7.35 (d, J=7.5, 2H),
7.26ꢀ7.14 (m, 3H), 7.03 (s, 1H), 6.75ꢀ6.64 (m, 2H), 5.71 (s,
1H), 2.49ꢀ2.42 (s, 3H) ppm.
2-(3,4-dimethoxyphenyl)-2,3-dihydoquinazolin-4(1H)-
one (entry 7, table 3): Mp: 211ꢀ214 °C. IR (KBr) cmꢀ1: 3335,
1
1671, 1610, 1436. H NMR (400 MHz, DMSOꢀd6): δH= 8.21
(s, 1H), 7.64ꢀ7.62 (d, J=7.6, 1H), 7.28ꢀ7.24 (t, J=0.8, 1H),
7.15 (d, J=1.6, 1H), 7.04ꢀ6.97 (m, 2H), 6.95 (s, 1H), 6.78ꢀ
6.76 (d, J=8, 1H), 6.72ꢀ6.67 (t, J=1.2, 1H), 5.71 (s, 1H), 3.77
(s, 3H), 3.76 (s, 3H) ppm.
2-(4-bromophenyl)-2,3-dihydoquinazolin-4(1H)-one
(entry 8, table 3): Mp: 196ꢀ198 °C. IR (KBr) cmꢀ1: 3310,
1656, 1608, 1433. 1H NMR (400 MHz, DMSOꢀd6): δH= 8.17ꢀ
8.14 (m, 1H), 7.80ꢀ7.78 (m, 1H), 7.63ꢀ7.59 (m, 3H), 7.47ꢀ
7.44 (m, 2H), 7.30ꢀ7.24 (m, 1H), 6.77ꢀ6.72 (d, J=19.2, 1H),
6.71ꢀ6.68 (m, 1H), 5.76 (s, 1H) ppm.
Ethyl-4-(4-bromophenyl)-2,7,7-trimethyl-5-oxo-
1,4,5,6,7,8-hexahydroquinoline-3-carboxylate (entry 2,
table 5): Mp: 251ꢀ253 °C. IR (KBr) cmꢀ1: 3276, 3243, 3207,
2.2 General procedure for the synthesis of
polyhydroquinoline derivatives in the presence of
boehmite-SSA
1
1703, 1649, 1421. H NMR (400 MHz, DMSOꢀd6): δH= 9.14
(s, 1H), 7.41ꢀ7.39 (d, J=8.4, 2H), 7.13ꢀ7.11 (d, J=8, 2H), 4.84
(s, 1H), 4.01ꢀ3.96 (q, J=6.8, 2H), 2.52ꢀ2.46 (d, J=26.4 1H),
2.31ꢀ2.27 (m, 4H), 2.21ꢀ2.17 (d, J=16, 1H), 2.01ꢀ1.97 (d,
J=16, 1H), 1.15ꢀ1.12 (t, J=7.2, 3H), 1.02 (s, 3H), 0.85 (s, 3H)
ppm.
Ethyl-4-(4-methylphenyl)-2,7,7-trimethyl-5-oxo-
1,4,5,6,7,8-hexahydroquinoline-3-carboxylate (entry 4,
table 5): Mp: 250ꢀ253 °C. IR (KBr) cmꢀ1: 3276, 3276, 3246,
3208, 1702, 1648, 1423. 1H NMR (400 MHz, DMSOꢀd6): δH=
9.04 (s, 1H), 7.05ꢀ7.03 (d, J=8, 2H), 7.00ꢀ6.98 (d, J=8, 2H),
4.82 (s, 1H), 4.00ꢀ3.95 (q, J=7.2, 2H), 2.45ꢀ2.41 (d, J=16,
1H), 2.31ꢀ2.27 (m, 4H), 2.21ꢀ2.15 (m, 4H), 2.10ꢀ1.96 (d,
J=16, 1H), 1.17ꢀ1.13 (t, J=6.8, 3H), 1.02 (s, 3H), 0.86 (s, 3H)
ppm.
Ethyl-4-(4-ethoxyphenyl)-2,7,7-trimethyl-5-oxo-
1,4,5,6,7,8-hexahydroquinoline-3 carboxylate (entry 5,
table 5): Mp: 172ꢀ174 °C. IR (KBr) cmꢀ1: 3446, 3276, 3198,
1684, 1607, 1494. 1H NMR (400 MHz, DMSOꢀd6): δH= 7.28ꢀ
7.19 (m, 2H), 6.74ꢀ6.72 (d, J=8, 2H), 5.80 (s, 1H), 4.99 (s,
1H), 4.07ꢀ4.05 (t, J=4, 2H), 3.97ꢀ3.96 (t, J=3.6 ,2H), 2.39ꢀ
A mixture of aldehyde (1 mmol), dimedon (1 mmol), ethyl
acetoacetate (1 mmol), ammonium acetate (1 mmol) and
boehmiteꢀSSA (0.03 g) was stirred in ethanol under reflux
conditions and the progress of the reaction was monitored by
TLC. After completion of the reaction, catalyst was separated
by simple filtration and washed with ethyl acetate. Then, the
solvent was evaporated and all products was recrystallized in
ethanol, which the pure polyhydroquinoline derivatives were
obtained in good to excellent yields.
2.3 General procedure for the synthesis of 2,3-
dihydroquinazolin-4(1H)-ones derivatives in the presence
of boehmite-SSA
A mixture of boehmiteꢀSSA (0.03 g), anthranilamide (1
mmol) and aldehyde (1 mmol) was stirred at 80 ºC in ethanol
(2 mL). The progress was monitored by TLC. After
completion of the reaction, the reaction mixture was cooled to
room temperature. CH2Cl2 (2 ×5 mL) was added and the
2 | J. Name., 2012, 00, 1ꢀ3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 9
New Journal of Chemistry
Please do not adjust margins
View Article Online
DOI: 10.1039/C5NJ02607E
Journal Name
ARTICLE
OH
OH
2.15 (m, 7H), 1.38ꢀ1.37 (m, 3H), 1.21ꢀ1.20 (m, 3H), 1.07 (s,
3H), 0.95 (s, 3H) ppm.
HO
HO
OH
SiO2
Ethyl-4-(3,4-dimethoxyphenyl)-2,7,7-trimethyl-5-oxo-
1,4,5,6,7,8-hexahydroquinoline-3-carboxylate (entry 6,
e
l
e
OH
e
TEOS, NH3, PEG
H2O/EtOH, rt, 38 h
l
ꢀ1
c
t
e
i
i
c
t
table 5): Mp: 204ꢀ206 °C. IR (KBr) cm : 3280, 3213, 1696,
t
i
2
i
r
t
2
m
r
a
1
O
m
h
e
o
a
i
O
p
HO
1645, 1452. H NMR (400 MHz, DMSOꢀd6): δH= 9.05 (s,
h
i
p
S
o
e
S
o
n
a
n
OH
OH
o
B
a
1H), 6.79ꢀ6.76 (m, 2H), 6.65ꢀ6.63 (d, J=8, 1H), 4.80 (s, 1H),
4.04ꢀ3.99 (q, J=7.2, 2H), 3.69ꢀ3.68 (d, J=4.4, 5H), 2.47ꢀ2.42
(d, J=17.2, 2H), 2.35ꢀ2.27 (m, 4H), 2.22ꢀ2.18 (d, J=16, 1H),
2.03ꢀ1.99 (d, J=16, 1H), 1.20ꢀ1.16 (t, J=6.8, 3H), 1.03 (s,
3H), 0.90 (s, 3H) ppm.
B
n
HO
n
SiO2
OH
HO
HO
OH
Ethyl-4-(4-methoxyphenyl)-2,7,7-trimethyl-5-oxo-
1,4,5,6,7,8-hexahydroquinoline-3-carboxylate (entry 8,
table 5): Mp: 248ꢀ250 °C. IR (KBr) cmꢀ1: 3278, 3246, 3208,
1701, 1649, 1423. 1H NMR (400 MHz, DMSOꢀd6): δH= 9.04
(s, 1H), 7.08ꢀ7.06 (d, J=8.4, 2H), 6.77ꢀ6.75 (d, J=8.4, 2H),
4.80 (s, 1H), 4.02ꢀ3.96 (q, J=7.2, 2H), 3.69 (s, 3H), 2.52ꢀ2.45
(d, J=29.2, 1H), 2.31ꢀ2.29 (m, 4H), 2.20ꢀ2.16 (d, J=16, 1H),
2.01ꢀ1.97 (d, J=16.4, 1H), 1.17ꢀ1.14 (t, J=7.2, 3H), 1.02 (s,
3H), 0.87 (s, 3H) ppm.
h
H
3
2
O
,
S
e
l
n
a
C
x
e
h
ꢀ
n
OSO3H
OSO3H
HO3SO
HO3SO
OSO3H
SiO2
e
OSO3H
l
e
c
t
i
2
i
t
3 Results and discussion
2
r
O
m
a
i
O
HO3SO
h
i
p
S
e
S
o
n
a
OSO3H
OSO3H
o
B
3.1 Catalyst preparation
HO3SO
n
The boehmiteꢀSSA was prepared by the concise route
outlined in Scheme 1. Initially, boehmite nanoparticles
have been prepared via addition of NaOH to the solution
of Al(NO3)3.9H2O as the source of aluminum at room
temperature. Ultimately, after coating of boehmite
SiO2
HO3SO
HO3SO
OSO3H
OSO3H
Scheme 1. Synthesis of boehmiteꢀSSA.
nanoparticles
with
silica
using
TEOS,
the
3.2 Catalyst characterization
functionalization of terminal silanol groups with
chlorosulfunic acid (The reaction of silanol group has
been reported for the first time by Zolfigol [34]) led to
the formation of boehmite silica sulfamic acid (boehmiteꢀ
SSA). The catalyst has been characterized by scanning
electron microscopy (SEM), Xꢀray diffraction (XRD)
thermogravimetric analysis (TGA) and Fourier transform
infrared spectroscopy (FTꢀIR).
The size of the catalyst was evaluated using SEM. The
SEM image of boehmiteꢀSSA was shown that the catalyst
was formed of nanometerꢀsized particles (Figure 1). As
shown in Figure 1a, the unit cells of boehmite were obtained
in cubic orthorhombic structures.
.
a
b
Figure 1. SEM image of boehmite (a) and boehmiteꢀSSA (b).
The XRD patterns of boehmite nanoparticles was shown
in Figure 2. As seen in Figure 2, the boehmite phase was
identified from the XRD patterns by the peak positions at
14.40 (0 2 0), 28.41 (1 2 0), 38.55 (0 3 1), 46.45 (1 3 1), 49.55
(0 5 1), 51.94 (2 0 0), 56.02 (1 5 1), 59.35 (0 8 0), 65.04 (2 3
1), 65.56 (0 0 2), 68.09 (1 7 1), and 72.38 (2 5 1), which the
main peaks of the XRD pattern are consistent with the
characteristic peaks of the orthorhombic unit cell of the
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1ꢀ3 | 3
Please do not adjust margins

Please do not adjust margins
New Journal of Chemistry
Page 4 of 9
View Article Online
DOI: 10.1039/C5NJ02607E
ARTICLE
Journal Name
boehmite nanoparticles [5, 6]. The position and relative
intensities of all peaks confirm well.
0.00
20.00
40.00
60.00
80.00
2θ / degree
Figure 2. The XRD pattern of boehmite.
The FTꢀIR spectrum for boehmite nanoparticles (a),
boehmiteꢀsilica (b) and boehmiteꢀSSA (c) are shown in
Figure 3. In spectra of the IR boehmite nanoparticles, strong
bands at 3086 and 3308 cm−1 which is assigned to the OꢀH
bonds which are attached to the surface boehmite
nanoparticles [8, 35]. Several peaks in FTꢀIR spectrum of
boehmite nanoparticles at 480, 605 and 735 cm−1 can be
attributed to the characteristic absorption of AlꢀO bonds [4].
Moreover, the band at 1650 cm−1 corresponding to the nitrate
impurity vibration and the bands at 1164 and 1069 cmꢀ1
corresponding to the hydrogen bands of OH…OH surface [4,
8]. In the FTꢀIR spectra of boehmiteꢀsilica and boehmiteꢀSSA
(Figure 3b and c): The band at 1072 and 770 cmꢀ1 are due to
Si–O–Si vibrations [36]. A broad bands is present at
approximately 1070 and 770 cm−1 in boehmiteꢀsilica FTIR
spectra , which can be attributed to the an overlap of the
asymmetric and symmetric stretching vibration of the SiꢀOꢀSi
bonds with AlꢀO and OH…OH stretching vibration leads to
band broading. Reaction of boehmiteꢀsilica with
chlorosulfunic acid produces boehmiteꢀSSA in which the
presence of SO3H moiety is asserted with 938ꢀ1220 cm−1 and
3000ꢀ3400 cmꢀ1 bands in FTꢀIR spectra.
Figure 3. FTꢀIR spectra of (a) boehmite, (b) boehmiteꢀsilica and (c)
boehmiteꢀSSA.
The silica sulfuric acid loaded onto boehmite
nanoparticles was quantified using TGA. Figure 4 shows the
TGA curves for bare boehmite nanoparticles (blue curve),
boehmite coated with silica (boehmiteꢀsilica) (red curve) and
boehmiteꢀSSA (green curve). In the TGA curves, adsorbed
water mass loss occurred at temperatures below 250 ºC as
well as the endothermic weight loss at 300 ºC is attributed to
water loss from structural hydroxyl groups in the precursor
[37]. After coating of silica on boehmite (Figure 4b), the TGA
curves show loss of physically adsorbed water, residual
solvent and hydroxyl groups decomposition. In the profile of
boehmiteꢀSSA, sulfonic groups have been reported to desorb
at temperatures above 300 °C (about 25%). On the basis of
this result, the well grafting of silica sulforic acid on the
boehmite nanoparticles is verified.
100
90
80
70
60
50
40
27
227
427
627
827
Temperature(◦C)
Figure 4. TGA diagram of boehmite (blue line), boehmiteꢀsilica
(red line) and boehmiteꢀSSA (green line).
4 | J. Name., 2012, 00, 1ꢀ3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 9
New Journal of Chemistry
Please do not adjust margins
View Article Online
DOI: 10.1039/C5NJ02607E
Journal Name
ARTICLE
Entry
Substrate
Catalyst
Yield (%)a
3.3 Catalytic studies
1
2
3
4
5
4ꢀchlorobenzaldehyde
4ꢀchlorobenzaldehyde
4ꢀchlorobenzaldehyde
4ꢀchlorobenzaldehyde
4ꢀchlorobenzaldehyde
ꢀ
Traceb
43c
Herein we examined the catalytic activity of boehmiteꢀ
SSA as an efficient, stable, recyclable and commercially
viable catalyst for synthesis of Polyhydroquinoline and 2,3ꢀ
dihydroquinazolinꢀ4(1H)ꢀone derivatives. Synthesis of 2,3ꢀ
Boehmite nanoparticles
Boehmiteꢀsilica
boehmiteꢀSA
26c
64c
boehmiteꢀSSA
98
a Isolated yield after 50 min, b Reaction proceeds in the absence of the
catalyst, c Isolated yield was obtained by plate chromatography.
dihydroquinazolinꢀ4(1H)ꢀone
derivatives
using
cyclocondensation reaction of aldehydes and anthranilamide
in the present of boehmiteꢀSSA was shown in Scheme 2. In
our initial screening experiments, 4ꢀchlorobenzaldehyde and
anthranilamide were selected as model substrates to optimize
the reaction conditions, and the results are shown in Table 1.
At first, the solvent effect was examined. That good yields
were obtained in ethanol as the solvent (Table 1,entry 6),
whereas H2O, ethyl acetate, CH2Cl2, nꢀhexane and acetone
Then, a variety of aldehydes were described to explore the
scope of substrates under the optimized reaction conditions
and the results are shown in Table 3. Various electronꢀ
donating and electronwithdrawing substituents such as ꢀCH3,
ꢀOCH3, ꢀOCH2CH3, ꢀBr, ꢀCl, ꢀF, and ꢀNO2 on aldehydes were
well tolerated.
Table 3. Synthesis of 2,3ꢀdihydroquinazolinꢀ4(1H)ꢀones catalyzed
afforded low to moderate yields (Table 1, entries 1ꢀ5), by boehmiteꢀSSA in ethanol and at 80 ºC.
Time Yield Melting
therefore, ethanol was selected as the solvent. Finally, the
amount of boehmiteꢀSSA was also examined, and 30 mg of
boehmiteꢀSSA was found to be optimal, Meanwhile a lower
yield was observed when the amount of the catalyst was
decreased (Table 1, entries 6ꢀ8).
Entry
1
Product
Reference
(min) (%)a point (ºC)
50
98 202ꢀ204 [11]
2
3
4
35
120
50
94 188ꢀ190 [19]
85 168ꢀ170 [12]
96 223ꢀ225 [11]
Scheme 2. BoehmiteꢀSSA catalyzed the synthesis of 2,3ꢀ
dihydroquinazolinꢀ4(1H)ꢀone derivatives.
Table 1. Optimization of the synthesis 2,3ꢀdihydroquinazolinꢀ4(1H)ꢀ
ones conditions for the condensation of 4ꢀchlorobenzaldehyde whit
anthranilamide as a model compound in ethanol for 50 min.
Entry
Solvent
H2O
Ethyl acetate
CH2Cl2
nꢀHexane
Acetone
Ethanol
Ethanol
Ethanol
Catalyst (mg)
Yield (%)a
1
2
3
4
5
6
7
8
30
30
30
30
30
30
25
20
70
62
29
Trace
Trace
98
5
6
7
100
65
89 189ꢀ191 [14]
90 230ꢀ232 [19]
88 211ꢀ214 [12]
76
61
130
a Isolated yield.
O
NH
NH
Br
In order to show the role does boehmite or boehmiteꢀsilica and
boehmiteꢀSSA plays during the reactions, synthesis of 2ꢀ(4ꢀ
chlorophenyl)ꢀ2,3ꢀdihydroquinazolinꢀ4(1H)ꢀone was examined
8
9
70
65
90 196ꢀ198 [14]
91 194ꢀ196 [19]
in the presence of boehmiteꢀSSA compared to alone boehmite
and boehmiteꢀsilica. The results of this comparison are shown
in Table 2. As shown in Table 2, the products were obtained in
43 and 26% of yield in the presence of boehmite and boehmiteꢀ
silica, respectively. Also, direct functionalization of the
boehmite (in the absent of silica layer) by chlorosulfunic acid
(boehmiteꢀSA) has been done and its catalytic activity was
compared with boehmiteꢀSSA (Table 2, entry 4). As shown in
Table 2, the products were obtained in 64 of yield in the
presence of boehmiteꢀSA. Therefore to increase the surface area
of boehmite and make more efficient and effective acidic
catalyst, boehmite surface coated with silica.
10
45
94 204ꢀ205 [19]
11
12
50
65
96 184ꢀ186 [12]
93 243ꢀ245 [14]
Table 2. The effect of boehmite or boehmiteꢀsilica and
boehmiteꢀSA in comparison with boehmiteꢀSSA in the
condensation of 4ꢀchlorobenzaldehyde whit anthranilamide as a
model compound under optimized conditions.
a Isolated yield.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1ꢀ3 | 5
Please do not adjust margins

Please do not adjust margins
New Journal of Chemistry
Page 6 of 9
View Article Online
DOI: 10.1039/C5NJ02607E
ARTICLE
Also, we report the application of boehmiteꢀSSA as
Journal Name
OH
O
catalysts for the synthesis of polyhydroquinoline
derivatives using the condensation of aldehyde with
dimedon, ethylacetoacetate and ammonium acetate
(Scheme 3). In order to optimize the reaction conditions,
the reaction of 4ꢀchlorobenzaldehyde (1 mmol) with
dimedon (1 mmol), ethyl acetoacetate (1 mmol) and
ammonium acetate (1.2 mmol) was optimized using
various solvents such as H2O, EtOH and CH3CN (Table
4, entries 1–3) in the presence of different amount of
boehmiteꢀSSA as the catalyst (Table 4, entries 3–5). The
best results were obtained in ethanol at reflux for 180
min in the presence of 30 mg of catalyst (Table 4, entry
3). Therefore, ethanol was selected as a solvent for this
reaction.
O
3
4
210
250
88 228ꢀ230 [14]
OEt
N
H
96 250ꢀ253 [14]
90 172ꢀ174 [14]
95 204ꢀ206 [14]
95 237ꢀ239 [14]
96 248ꢀ250 [14]
5
6
7
8
250
215
180
230
Scheme 3. BoehmiteꢀSSA catalyzed the oneꢀpot synthesis of
polyhydroquinoline derivatives.
Table 4. Optimization of the synthesis polyhydroquinolines
conditions for the condensation of 4ꢀchlorobenzaldehyde, dimedon,
ethyl acetoacetate and ammonium acetate as a model compound in
ethanol at 80 ºC for 180 min.
Entry
Solvent
H2O
CH3CN
Ethanol
Ethanol
Ethanol
Catalyst (mg)
Yielde (%)a
1
2
3
4
5
30
30
30
20
15
32
41
95
68
52
a Isolated yield, bno reaction.
Using the optimized conditions, we extended the
study with different aldehydes for the synthesis of
various polyhydroquinoline derivatives using boehmiteꢀ
SSA. The results of this study are depicted in Table 5. As
shown, a variety of benzaldehydes bearing electronꢀ
donating and electronꢀwithdrawing substituents were
successfully employed to prepare the corresponding
polyhydroquinoline derivatives in excellent yields.
Table 5. Synthesis of polyhydroquinolines catalyzed by boehmiteꢀ
SSA in ethanol and at 80 ºC.
Time Yield Melting
(min)
Entry
Product
Reference
(%)a point (ºC)
9
200
320
90 183ꢀ185 [21]
1
215
94 217ꢀ219 [14]
NO2
O
O
10
91 176ꢀ179 [23]
OEt
N
H
2
270
94 251ꢀ253 [21]
aIsolated yield.
6 | J. Name., 2012, 00, 1ꢀ3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 7 of 9
New Journal of Chemistry
Please do not adjust margins
View Article Online
DOI: 10.1039/C5NJ02607E
Journal Name
ARTICLE
acid/ MW (600 W)
ZrCl4
[hnmp][HSO4]
[NMP][HSO4]
[NMP][H2PO4]
BoehmiteꢀSSA
3.4 Recyclability of the catalyst
7
8
9
4ꢀClC6H4CHO
4ꢀClC6H4CHO
4ꢀClC6H4CHO
37
28
22
38
91 [41]
83 [42]
84 [42]
79 [42]
The reusability of the boehmiteꢀSSA catalyst was studied for
the reaction between benzaldehyde with dimedon, ethyl
acetoacetate and ammonium acetate in ethanol under reflux
condition. As shown in figure 5, the catalyst was recovered by a
simple filtration and reused over 5 runs without considerable
decrease in activity even after 5 runs. The average isolated
yield for five successive runs was 93%, which clearly
demonstrates the practical recyclability of this catalyst.
10 4ꢀClC6H4CHO
11 4ꢀClC6H4CHO
a Isolated yield.
50 98 [this work]
4 Conclusions
In summary, we have developed a novel, practical and
environmentally friendly method for synthesis of 2,3ꢀ
dihydroquinazolinꢀ4(1H)ꢀone
and
polyhydroquinoline
100
90
80
70
60
50
40
derivatives using boehmiteꢀSSA as efficient and reusable
nanocatalyst. This catalyst can be prepared by a simple
procedure from commercially available and cheap materials.
In addition, the catalyst can be easily recovered and reused
for several times without any significant loss of activity.
Acknowledgements
1
2
3
4
5
This work was supported by the research facilities of Ilam
University, Ilam, Iran.
Run number
Figure 5. The recycling experiment of boehmiteꢀSSA in
condensation of 4ꢀchlorobenzaldehyde, dimedon, ethylacetoacetate References
and ammonium acetate.
1. V. Polshettiwar, R. Luque, A. Fihri, H. Zhu, M. Bouhrara,
J.M. Basset, Chem. Rev. 2011, 111, 3036.
2. Y. Zhu, L.P. Stubbs, F. Ho, R. Liu, C.P. Ship, J.A.
Maguire, N.S. Hosmane, Chemcatchem. 2010, 2, 365.
3. S. Shylesh, V. Schunemann, W. R. Thiel, Angew. Chem.
Int. Ed. 2010, 49, 3428.
4. L. Rajabi, A.A. Derakhshan, Sci. Adv. Mater. 2010, 2,
163.
5. K. Bahrami, M.M. Khodaei, M. Roostaei, New J. Chem.
2014, 38, 5515.
6. H. Liu, J. Deng, W. Li, Catal. Lett. 2010, 137, 261.
7. E. Carbonell, E. DelgadoꢀPinar, J. PitarchꢀJarque, J.
Alarcón, E. GarcíaꢀEspañ, J. Phys. Chem. 2013, 117,
14325.
8. V. Vatanpour, S.S. Madaenia, L. Rajabi, S. Zinadini,
A.A. Derakhshan, J. Membr. Sci. 2012, 401–402, 132.
3.5 Comparison of the catalyst activity
The efficiency of this nanocatalyst is demonstrated by comparison
our results on the synthesis of 2ꢀ(4ꢀchlorophenyl)ꢀ2,3ꢀ
dihydroquinazolinꢀ4(1H)ꢀone with the previous methods in the
literatures (Table 6). As it can be seen from this Table the good
reaction time and higher yield than the other reported catalysts has
been achieved. Also this new catalyst is comparable or may be better
in terms of price, nonꢀtoxicity, stability and easy separation than the
reported ones. In addition, BoehmiteꢀSSA can be reused over 5 runs.
The recyclability and reusability of the prepared catalyst is another
point, the BoehmiteꢀSSA was reused over 5 runs without any
significant loss of its activity. The average isolated yield for 5
successive runs was 93%, which clearly demonstrates the practical
recyclability of this catalyst. Moreover, the mesoporous silica or
some nanoparticles NPs have been used as catalyst supports, which
require high temperature for calcination and a lot of time and tedious
conditions to prepare. Also some of previously reported catalysts 9. Z. Wu, Y. Mao, M. Song, X. Yin, M. Zhang, Catal.
such as heteropolyacids, ionic liquids or some polymers are more
expensive, while preparation of nanoboehmite was not air, or
moisture sensitive. This nanomaterial was prepared in water at room
temperature without inert atmosphere.
Commun. 2013, 32, 52.
10. M.B. Gholivand, G. Malekzadeh, A.A. Derakhshanc,
Sensor. Actuat. B Chem. 2014, 201, 378.
11. S.D. Dindulkar, J. Oh, V.M. Arole, Y.T. Jeong, C. R.
Chimie 2014, 17, 971.
12. A. GhorbaniꢀChoghamarani, M. Norouzi, J. Mol. Catal.
A: Chem. 2014, 395, 172.
13. B.H. Chen, J.T. Li, G.F. Chen, Ultrason. Sonochem.
2015, 23, 59.
14. A. GhorbaniꢀChoghamarani, G. Azadi, RSC Adv. 2015, 5,
9752.
Table 6. Comparison of BoehmiteꢀSSA for the synthesis of 2ꢀ(4ꢀ
chlorophenyl)ꢀ2,3ꢀdihydroquinazolinꢀ4(1H)ꢀone with previously
reported procedure.
Time Yield (%)a
(min) [Reference]
Entry
Substrate
Catalyst
1
2
3
4
4ꢀClC6H4CHO
4ꢀClC6H4CHO
4ꢀClC6H4CHO
4ꢀClC6H4CHO
GSA@MNPs
[Bmim]PF6
TBAB/100 ºC
SiO2ꢀFeCl3
2ꢀ(Nꢀ
50
40
60
99 [28]
90 [32]
75 [38]
87[39]
420
15. J. Zhang, D. Ren, Y. Ma, W. Wang, H. Wu, Tetrahedron
2014, 70, 5274.
5
6
4ꢀClC6H4CHO morpholino)ethanesulfonc 180
89 [40]
92 [40]
acid
2ꢀ(Nꢀ
4ꢀClC6H4CHO
12
morpholino)ethanesulfonc
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1ꢀ3 | 7
Please do not adjust margins

Please do not adjust margins
New Journal of Chemistry
Page 8 of 9
View Article Online
DOI: 10.1039/C5NJ02607E
ARTICLE
Journal Name
16. C.H. Van Dyck, P.Z. Tan, R.M. Baldwin, L.A. Amici,
P.K. Garg, C.K. Ng, R. Soufer, D.S. Charney, R.B. Innis,
J. Nuclear Med. 2000, 41, 234.
17. M. Waibel, J. Hasserodt, Tetrahedron Lett. 2009, 50,
2767.
18. N.B. Darvatkar, S.V. Bhilare, A.R. Deorukhkar, D.G.
Raut, M.M. Salunkhe, Green Chem. Lett. Rev. 2010, 3,
301.
19. A. Rostami, B. Tahmasbi, H. Gholami, H. Taymorian,
Chin. Chem. Lett. 2013, 24, 211.
20. P.N. Kalaria, S.P. Satasia, D.K. Raval, Eur. J. Med.
Chem. 2014, 78, 207.
21. S.M. Vahdat, F. Chekin, M. Hatami, M. Khavarpour, S.
Baghery, Z. Roshan‐Kouhi, Chin. J. Catal. 2013, 34, 758.
22. M. Saha, A. Kumar Pal, Tetrahedron Lett. 2011, 52,
4872.
23. M. NasrꢀEsfahani, S. J. Hoseini, M. Montazerozohori, R.
Mehrabi, H. Nasrabadi, J. Mol. Catal. A: Chem. 2014,
382, 99.
24. L. Saikia, D. Dutta, D. Kumar Dutta, Catal. Commun.
2012, 19, 1.
25. P. Sivaguru, K. Parameswaran, M. Kiruthiga, P. Vadivel,
A. Lalitha, J. Iran. Chem. Soc. 2015, 12, 95.
26. S. Rostamnia, A. Hassankhani, H. Golchin Hossieni, B.
Gholipour, H. Xin, J. Mol. Catal. A: Chem. 2014, 395,
463.
27. A. Bharathi, S.M. Roopan, A. Kajbafvala, R.D. Padmaja,
M.S. Darsana, G. Nandhini Kumari, Chin. Chem. Lett.
2014, 25, 324.
28. M. Hajjami, B. Tahmasbi, RSC Adv. 2015, 5, 59194.
29. M.M. Heravi, S. Sadjadi, J. Iran. Chem. Soc. 2009, 6, 1.
30. Z. Zarnegar, J. Safari, Z. Mansouri Kafroudi, New J.
Chem. 2015, 39, 1445.
31. D.A. Kotadia, S.S. Soni, J. Mol. Catal. A: Chem. 2012,
353–354, 44.
32. J. Chen, W. Su, H. Wu, M. Liu, C. Jin, Green. Chem.
2007, 9, 972.
33. J. Wang, Y. Zong, R. Fu, Y. Niu, G. Yue, Z. Quan, X.
Wang, Y. Pan, Ultrason. Sonochem. 2014, 21, 29.
34. M.A. Zolfigol, Tetrahedron 2001, 57, 9509.
35. B. Atashkar, A. Rostami, B. Tahmasbi, Catal. Sci.
Technol. 2013, 3, 2140.
36. A. GhorbaniꢀChoghamarani, F. Nikpour, F. Ghorbani, F.
Havasi, RSC Adv. 2015, 5, 33212.
37. P. Liu, Y. Zhu, J. Ma, S. Yang, J. Gong, J. Xu, Prog. Nat.
Sci.: Mat. Int. 2013, 23, 145.
38. A. Davoodnia, S. Allameh, A.R. Fakhari, N. Tavakoliꢀ
Hoseini, Chin. Chem. Lett. 2010, 21, 550.
39. M. Ghashang, K. Azizi, H. MoulaviꢀPordanjani, H.R.
Shaterian, Chin. J. Chem. 2011, 29, 1617.
40. V. B. Labade, P. V. Shinde, M. S. Shingare, Tetrahedron
Lett. 2013, 54, 5778.
41. M. AbdollahiꢀAlibeik, E. Shabani, Chin. Chem. Lett.
2011, 22, 1163.
42. H.R. Shaterian and M. Aghakhanizade, Res. Chem.
Intermed. 2014, 40, 1655.
8 | J. Name., 2012, 00, 1ꢀ3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 9 of 9
New Journal of Chemistry
View Article Online
DOI: 10.1039/C5NJ02607E
The First Report on the Preparation of Boehmite Silica Sulfuric Acid and Its
Application in Some Multicomponent Organic Reactions
Arash Ghorbani-Choghamarani and Bahman Tahmasbi
Boehmite silica sulfuric acid was prepared at room temperature using commercially available materials and applied as
nanocatalyst for preparation of DHQs and PHQs.