Efficient preparation of boehmite silica dopamine sulfamic acid as a novel nanostructured compound and its application as a catalyst in some organic reactions

Article abstract of DOI:10.1039/c5nj03546e

A novel type of recoverable boehmite nanocatalyst was prepared via immobilization of dopamine on the surface of boehmite followed by coating with silica and reacting with chlorosulfunic acid to obtain boehmite silica dopamine sulfamic acid (boehmite-Si-DSA). This compound was characterized by FT-IR spectroscopy, TGA, XRD, TEM and SEM techniques. Boehmite-Si-DSA was used as an efficient, recoverable and thermally stable heterogeneous nanocatalyst for the preparation of 2,3-dihydroquinazolin-4(1H)-one, sulfoxides and disulfides. The catalyst was recovered by simple filtration and reused several times without significant loss of catalytic efficiency.

Full text of DOI:10.1039/c5nj03546e

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Efficient preparation of boehmite silica dopamine
sulfamic acid as novel nanostructured compound
and its application as catalyst in some organic
reactions
Cite this: DOI: 10.1039/x0xx00000x
Received 00th January 2012,
Accepted 00th January 2012
*
Maryam Hajjami , Arash Ghorbani-Choghamarani, Raziyeh Ghafouri-Nejad
and Bahman Tahmasbi
DOI: 10.1039/x0xx00000x
www.rsc.org/
A novel type of boehmiteꢀrecoverable nanocatalyst was prepared via immobilization of
dopamine on the surface of boehmite followed by coating with silica, then reaction with
chlorosulfunic acid to obtain boehmite silica dopamine sulfamic acid (boehmiteꢀSiꢀDSA). This
compound was characterized by FTꢀIR spectroscopy, TGA, XRD, TEM and SEM techniques.
BoehmiteꢀSiꢀDSA used as an efficient, recoverable and thermally stable heterogeneous
nanocatalyst for the preparation of 2,3ꢀdihydroquinazolinꢀ4(1H)ꢀone, sulfoxides and disulfides.
The catalyst was recovered by simple filtration and reused for several times without significant
loss of its catalytic efficiency.
antihistaminic, herbicidal activity, plant growth regulation ability
and antihypertensive agents.10ꢀ12 In addition, these compounds can
1 Introduction
be oxidized to their quinazolinꢀ4(3H)ꢀone analogues, which also are
important pharmacologically active compounds.13 For example,
based Fluorescence property of quinazolinone, 2ꢀ(2ꢀhydroxyphenyl)ꢀ
4(3H)ꢀquinazolinone was utilized in the detection of metal ions.14
Generally, 2,3ꢀdihydroquinazolinꢀ4(1H)ꢀones were prepared using
the cyclization of carbonyl groups with anthranilamide or one pot
threeꢀcomponent reaction of isatoic anhydride, aldehydes and amines
in the presence of acid catalysts.15, 16
Besides, the oxidation of sulfides to sulfoxides and oxidative
coupling of thiols into disulfides are useful in the synthesis of new
products, which play an important role in various medical and
biological applications.17, 18 Some of biologically active sulfoxides
play an important role as therapeutic agents such as antifungal,
antibacterial, antihypertensive and antiꢀatherosclerotic as well as
psychotropics and vasodilators.18, 19 Sulfoxides are also valuable in
the CꢀC bond formation and molecular rearrangements.20
Additionally, Omeprazole, and the pesticide fipronil are two typical
examples of the extensive application of these intermediates in
pharmaceutical and fine chemical industries.17ꢀ19 Likewise, disulfide
bond formation is important in peptides, in bioactive molecules as
well as oil sweetening processes.20 Disulfides are used in synthesis
of organoꢀsulfur compounds via C–S bond formation and
sulfonylation of enolates and other anions while some disulfides
have been found to be useful as vulcanizing agents for rubber and
elastomers imparting them suitable tensile strength21, 22 and they are
also essential moieties of biologically active compounds for peptide
In recent years, supported catalysts on the nanoparticles have
attracted much attention in organic reactions.1 Because, when the
size of the support is decreased to the nanometer scale, the surface
area is substantially increased and the support can be evenly
dispersed in solution, forming a homogenous emulsion.2 Some
nanomaterial such as magnetic iron oxide,3 mesoporous silica
material,4 graphene oxide,5 molecular sieve6 and etc. were applied as
support. But preparation of many supports required a lot of time or
N2 atmosphere, also mesoporous silica required high temperature for
calcination. While nanoboehmite is rarely employed as
a
heterogeneous support. Boehmite is an aluminum oxide hydroxide
(γꢀAlOOH) particles, has the orthorhombic structure, which the
surface of boehmite nanoparticles covered with hydroxyl groups,
which existence of many hydroxyl groups on the nanoboehmite
surface leads to reaction with dopamine, alkoxysilane and other
reagents which support terminal functional groups available for
immobilization of other substances.7 Nanoboehmite has several
advantages, such as nonꢀtoxicity, readily available, high dispersion
of the active phases, thermal and mechanical stability and highꢀ
surfaceꢀarea resulting in high catalysts loading capacity.8, 9
2,3ꢀDihydroquinazolinone derivatives are important bicyclic
heterocycles which have been reported to possess a wide range of
biological properties and pharmaceutical activities such as
vasodilating, diuretic, tranquilizing, Antibacterial, antitumor,
antidefibrillatory, antihistaminic, anticonvulsant, anticancer,
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and protein stabilization anions.23 For these reasons, oxidation of
sulfides and thiols has been reported using a variety of reagents in
the presence of different catalyst.17ꢀ28 Hydrogen peroxide (with only
H2O as a byproduct) has been applied for these transformations as an
inexpensive and environmentally benign oxidant.29
2 Results and discussion
2.1 Catalyst preparation
The boehmiteꢀSiꢀDSA was prepared by the concise route outlined in
Scheme 1. Initially, boehmite nanoparticles have been prepared on
addition of NaOH to the solution of Al(NO3)3.9H2O as the source of
aluminum at room temperature. After coating of boehmite
nanoparticles with silica using tetraethyl orthosilicate (TEOS), the
silanol groups were functionalized with dopamine. Ultimately, the
functionalization of terminal amines with chlorosulfunic acid led to
the boehmite dopamine sulfamic acid (boehmiteꢀSiꢀDSA). The
crystalline structure of synthesized samples was examined by Xꢀray
diffraction using GBCꢀDifftech MMA diffractometer. The nickel
filtered Cu Kα (λ= 1.54A˚) radiation was used at acceleration
voltage of 35 kV and current of 34.2 mA. The diffraction angle was
scanned from 1˚ to 80˚, 2θ at a rate of 1˚/min. Fourier transform
infrared spectroscopy (FTIR) analyses were carried in KBr on FTIR,
spectrophotometer (Bruker, Germany) Vertex 70 in the range of
400–4000 cm−1. A thermogravimetric analysis (TGA) was carried
out (PerkinElmer Pyris Diamond, U.K.) from an ambient
temperature to 840 ˚C and at N2 atmosphere, using a ramp rate of
10˚C/min. TEM analysis of catalyst was recorded using a Zeissꢀ
EM10Cꢀ80KV TEM. Also the catalyst morphology was examined
by measuring SEM and EDX study with accelerating voltage of 10
kV were using FESEMꢀTESCAN MIRA3.
Figure 1. TEM image of boehmiteꢀSiꢀDSA.
a
O
O
O
Al
Al
Al
O
O
O
O
Al OH
O
Si OH
O
Al
Al
Al
O
O
O
O
Al
Al
Al
O
O
O
TEOS, NH3, PEG
H2O/EtOH, rt, 38 h
O
O
O
Si OH
O
O
O
Al OH
O
O
b
O
Si
Al OH
Dopamine
EtOH, rt, 24 h
O
O
O
Al
Al
Al
O
O
Al O
O
Si
Si
Si
O
Si
Si
Si
O
NHSO3H
NH2
Al
Al
Al
O
O
O
O
Al
Al
Al
O
O
O
O
O
O
O
O
O
O
O
O
Al O
O
O
O
ClSO3H
O
O
O
nꢀhexane, 2 h
O
Al
O
Scheme 1. Synthesis of boehmiteꢀSiꢀDSA.
2.2 Catalyst characterization
The size and morphology of boehmite nanoparticles and boehmiteꢀ
SiꢀDSA were obtained by SEM and TEM. As shown in Figure 1, the
particle sizes of boehmiteꢀSiꢀDSA were about 86 and 30 nm in the
long and short dimension respectively. Also, the SEM image of the
boehmite and boehmiteꢀsilica showed that particles have a regular
geometric shape in comparison with nanoboehmite (Figure 2).
Figure 2. SEM image of boehmiteꢀSiꢀDSA (a) and boehmite (b).
The XRD patterns of boehmite nanoparticles (red line) and
boehmiteꢀSiꢀDSA (green line) are shown in Figure 3. As seen in
Figure 3, 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 all the peaks can be confirmed the crystallization of boehmite
with an orthorhombic structures.8, 30 Also sharp peaks around 2θ=20ꢀ
30 in boehmiteꢀSiꢀDSA XRD pattern, which is typical for dopamine
and in boehmite itself can’t be seen.31,32
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Several peaks in FTꢀIR spectrum of boehmite nanoparticles at 477,
613 and 735 cm−1 can be attributed to the characteristic absorption of
AlꢀO bonds.7 Also, the nitrate impurity vibration at 1650 cm−1 and
the vibrations of hydrogen bands OH…OH by two strong absorption
bands at 1164 and 1069 cmꢀ1 were observed in FTꢀIR spectrum [7,
34]. In the 1072 and 770 cmꢀ1 spectral region of the FTꢀIR spectra
(Figure 5bꢀd): an overlap of the asymmetric and symmetric
stretching vibration of the SiꢀOꢀSi bonds with AlꢀO and OH…OH
stretching vibration leads to band broading.35 In the FTꢀIR spectra of
boehmiteꢀSiꢀdopamine (Figure 5c), The presence of the anchored
dopamine groups are confirmed by C–H stretching vibrations that
appear at 2961 cm−1 and also NꢀH stretching vibration modes as a
broad band that appear at 3080ꢀ3343 cmꢀ1. Also, vibrations in the
range of 1100ꢀ1600 cmꢀ1 are attributed to the aromatic ring, CꢀC, Cꢀ
O and CꢀN. Reaction of boehmiteꢀSiꢀdopamine with chlorosufonic
acid produces boehmiteꢀSiꢀDSA in which the presence of SO3H
moiety is asserted with 938ꢀ1220 cm−1 bands in FTꢀIR spectra. Also,
vibrations in the range of 3000ꢀ3400 cmꢀ1 are attributed to the SO3ꢀH
groups.
5000
4000
3000
2000
1000
0
0
20
40
60
80
2θ / degree
Figure 3. The XRD pattern of boehmite (red line) and boehmiteꢀSiꢀ
DSA (green line).
The TGA was used to determine the percent of functional groups
chemisorbed onto the surface of boehmite nanoparticles. Figure 4
shows the TGA curves for bare boehmite nanoparticles (black
curve), boehmite coated with silica (boehmiteꢀsilica) (red curve),
boehmite functionalized with dopamine (boehmiteꢀSiꢀdopamine)
(blue curve) and boehmiteꢀSiꢀDSA (green curve). The initial weight
loss at below 110 ºC in the all samples, was caused by the removal
of the adsorbed water, as well as the endothermic weight loss at 300
ºC is attributed to water loss from structural hydroxyl groups in the
precursor.33 In the profile of boehmiteꢀSiꢀDSA, organic groups have
been reported to desorb at temperatures above 250 °C (about 85%).
Meanwhile, weight loss about 45% from 250 to 650 °C is occurred
for boehmiteꢀSiꢀdopamine. On the basis of this result, the well
grafting of dopamine sulfamic acid on the boehmite nanoparticles is
verified.Thermal stability of the catalyst was also determined, since
synthesis of many organic compound were usually carried out at
high temperature. As shown in Figure 4, boehmiteꢀSiꢀDSA catalyst
was stable even at 220 ºC.
100
80
60
40
20
0
25
225
425
Temperature(◦C)
625
825
Figure 5. FTꢀIR spectra of (a) boehmite nanoparticles, (b) boehmiteꢀ
silica, (c) boehmiteꢀSiꢀdopamine and (d) boehmiteꢀSiꢀDSA.
Figure 4. TGA diagram of (black line) boehmite nanoparticles, (red
line) boehmiteꢀsilica, (blue line) boehmiteꢀSiꢀdopamine and
boehmiteꢀSiꢀDSA (green line).
The energy dispersive Xꢀray spectrum (EDX) of boehmiteꢀSiꢀDSA
in Figure 6 displayed that the mass percent of C, N, O, Si and Al are
17.0, 4.7, 52.3, 10.4 and 15.6, respectively and the Si/Al ratio is
0.67. Also to determine the amount of acid in catalyst according to
the literature,13 the 0.1 g of catalyst was added to an aqueous
NaCl solution (1 mol/L, 10 mL) with an initial PH 6.89. The
mixture was stirred for 30 min until the PH of solution
decreased to 2.62 that indicating an ion exchange between sulfamic
acid protons and sodium ions and this is equal to a loading of 0.53
mmol.gꢀ1 of sulfamic acid group.
The FTꢀIR spectrum for boehmite nanoparticles (a), boehmiteꢀsilica
(b), boehmiteꢀSiꢀdopamine (c) and boehmiteꢀSiꢀDSA (c) are shown
in figure 5.
The FTꢀIR spectrum of the boehmite nanoparticles shows two strong
bands at 3086 and 3308 cm−1 which incorporates the contributions
from both symmetrical and asymmetrical modes of the OꢀH bonds
7,
8
which are attached to the surface boehmite nanoparticles.3,
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8
9
10
Acetone
Ethyl acetate
nꢀhexane
30
30
30
30
35
76
62
57
11 Dichloromethane
a Isolated yield.
After the obtimumization of the reaction condition, the various
aldehydes including aromatic aldehydes (Table 2, entries 1ꢀ13),
aliphatic aldehydes (Table 2, entries 15 and 16) and alylic
aldehyde (Table 2, entry 14) have been described in optimum
condition and the products were obtained in good to excellent
yields (Table 2). The experimental procedure is very simple and
convenient, and has the ability to tolerate a variety of aldehydes
contain electronꢀdonating (Table 2, entries 2ꢀ5) and electronꢀ
withdrawing (Table 2, entries 6ꢀ11) functional groups. Also,
terephthaldehyde and isophthaldehyde (Table 2, entries 12 and
13) were successfully employed to prepare the corresponding
products in excellent yields. Therefore, the results revealed that
this methodology is effective for a wide range of aldehydes.
Figure 6. EDX spectra of boehmiteꢀSiꢀDSA
2.3 Catalytic study
Herein we examined the catalytic activity of boehmiteꢀSiꢀDSA
in some organic reactions such as synthesis of 2,3ꢀ
dihydroquinazolinꢀ4(1
and oxidative coupling thiols into sulfoxides and disulfides
respectively. Synthesis of 2,3ꢀdihydroquinazolinꢀ4(1 )ꢀone
H)ꢀone derivatives, oxidation of sulfides
H
derivatives using cyclocondensation reaction of aldehydes and
anthranilamide in the present of boehmiteꢀSiꢀDSA was shown
in Scheme 2.
O
O
R
NH
NH
CHO
NH2
BoehmiteꢀSiꢀDSA
Ethanol, Reflux
R
+
NH2
Scheme 2. boehmiteꢀSiꢀDSA catalyzed the synthesis of 2,3ꢀ
dihydroquinazolinꢀ4(1 )ꢀone derivatives.
H
The reaction condition for the synthesis of 2,3ꢀ
dihydroquinazolinꢀ4(1 )ꢀone derivatives was optimized by
H
cyclocondensation reaction of anthranilamide and 4ꢀ
chlorobenzaldehyde in the presence of different amounts of
boehmiteꢀSiꢀDSA (Table 1, entries 1ꢀ6) and in various solvents
such as Acetonitrile, Acetone, Ethyl acetate, nꢀhexane and
Dichloromethane were used (Table 1, entries 6ꢀ11). As shown
in Table 1, the best results were obtained in ethanol using 0.03
gr of boehmiteꢀSiꢀDSA (Table 1, entry 6).
Table 1. Optimization for the synthesis of 2,3ꢀ
dihydroquinazolinꢀ4(1
H
)ꢀone
conditions
for
the
cyclocondensation of 4ꢀchlorobenzaldehyde and anthranilamide
as a model compound at 80 ºC for 150 min.
Entry
Solvent
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
Acetonitrile
Catalyst (mg)
Yielde (%)a
1
2
3
4
5
6
7
5
35
46
58
80
89
97
75
10
15
20
25
30
30
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Also, we tested the catalytic activity of boehmiteꢀSiꢀDSA in the
oxidation of sulfides to sulfoxides and oxidative coupling of
thiols into disulfides using H2O2 (Scheme 3). In order to choose
the reaction condition, we examined the oxidation of
methylphenyl sulfide as a model compound in the presence of
different amounts of boehmiteꢀSiꢀDSA (Table 3, entries 1ꢀ7)
and in various solvents (Table 3, entries 7ꢀ14). As shown in
Table 3, the best results for sulfoxidation were found under
solventꢀfree condition using 0.03 g of boehmiteꢀSiꢀDSA at
room temperature (Table 3, entry 6). The optimum reaction
conditions for the oxidative coupling of thiols were found to be
0.003 g of catalyst in ethanol at room temperature.
Table 2. Synthesis of 2,3ꢀdihydroquinazolinꢀ4(1
catalyzed by boehmiteꢀSiꢀDSA in ethanol and at 80 ºC.
Yiel
H)ꢀones
Time
(min)
Melting
Entry
Product
d
Reference
point (ºC)
(%)a
1
60
30
96 219ꢀ221
98 224ꢀ226
[13]
2
[35]
3
4
5
45
50
60
98 177ꢀ179
97 163ꢀ165
96 212ꢀ215
[13]
[13]
[35]
Scheme 3. The oxidation of sulfides into sulfoxides and
oxidative coupling of thiols into disulfides using H2O2 in the
presence of boehmiteꢀSiꢀDSA.
Table 3. Optimization of the reaction conditions for the
oxidation of methylphenyl sulfide (1 mmol) as a model
compound.
6
7
150 97 199ꢀ200
[16]
[35]
[13]
Yield
Entry
Solvent
Catalyst (mg)
Time (min)
(%)a
ꢀb
1
2
3
4
5
6
7
8
9
10
11
12
13
14
SolventꢀFree
SolventꢀFree
SolventꢀFree
SolventꢀFree
SolventꢀFree
SolventꢀFree
SolventꢀFree
Dichloromethane
Acetone
nꢀhexane
Acetonitrile
Water
Ethanol
Ethyl acetate
0
20
20
20
20
20
75
98 174ꢀ176
10
15
20
25
30
40
30
30
30
30
30
30
30
40
51
65
78
98
95
94
95
95
93
97
98
94
20
20
8
9
155 94 214ꢀ216
285
275
420
120
95
110 95 197ꢀ199 [16, 35]
60
600
10
190 93 181ꢀ183
[13]
a Isolated yield, b No reaction.
In obtained optimum condition, the wide range of sulfides and
thiols with different functional groups were converted to their
corresponding products in the present of boehmiteꢀSiꢀDSA as
catalyst at room temperature under solventꢀfree condition. The
products were obtained in high to excellent yields in a short
reaction time. The result of this study was shown in table 4 and
5. These oxidizing systems allowed the chemoselective
oxidation of 2ꢀ(phenylthio)ethanol, 2ꢀ(methylthio)ethanol and
2ꢀmercaptoethanol to the corresponding sulfoxides and
disulfide. Interestingly primary hydroxyl groups in these
substrates remained intact during the oxidation reactions (Table
4, entries 3, 4 and Table 5, entry 3). The all products were
obtained in high to excellent yields without any byproducts
such as sulfone (for oxidation of sulfides) or thiosulfinates,
disulfoxides, sulfinyl sulfones or disulfones (for the oxidative
11
12
105 97 195ꢀ197 [13, 35]
30
55
98 244ꢀ246
92 200ꢀ203
[16]
[35]
13
14
50
95 175ꢀ178
[35]
a Isolated yield.
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[17]
coupling of thiols). Therefore, the results revealed that this
methodology is effective for a wide range of sulfides.
5
6
10
20
97
98
Oil
55ꢀ56
[4]
Table 4. Oxidation of sulfides into sulfoxides using H2O2 in the
presence of boehmiteꢀSiꢀDSA at room temperature.
Entry
Product
Time (min) Yield (%)a
7
120
15
97
96
267ꢀ269
85ꢀ87
[17]
1
5
83
80
8
[17]
2
3
25
aIsolated yield.
30
10
80
80
In another study, to better clarify the importance of Boehmite
as support, we functionalized MCMꢀ41 mesoporous with
dopamine sulfamic acid and also supported dopamine sulfamic
acid on silica as new catalysts and examined the reactions at the
same conditions. First of all we prepared MCMꢀ41ꢀSiꢀDSA. In
this light mesoporous Si–MCMꢀ41 was prepared according to
the literature procedure.37 Deionized water was added to 2 M
NaOH and cetyltrimethylammoniumbromide (CTAB) as a
surfactant template and stirred intense at 80 oC, after
clarification tetraethylorthosilicate (TEOS) was added slowly
and continuously. After 2 h stirring, the synthetic solution
obtained with molar composition TEOS/CTAB/NaOH/H2O:
60/3.0/1.0/1. After cooling to room temperature, the resulting
solid was gathered by filtration, washed with deionized water,
and dried at 343 K. Then followed by calcination at 823 K for 5
h with rate of 2˚C/min to remove the residual surfactant. Then
dopamine (1.5 g) was added to the 1 g of SiꢀMCMꢀ41in
ethanol. The reaction mixture was stirred at room temperature
for 24 h. Then, the dopamineꢀSiꢀMCMꢀ41 was separated by
simple filtration and washed with ethanol and dried at room
temperature. Chlorosulfunic acid (0.75 mL) was added drop
wise over a period of 30 min to the obtained dopamineꢀSiꢀ
MCMꢀ41 (0.5 g) in nꢀhexane (5 mL) and the mixture was
stirred for 5 h at room temperature. Then, the final product was
filtered and washed by dry nꢀhexane, ethanol to remove the
unattached substrates. The product (MCMꢀ41ꢀDSA) dried at
room temperature.
4
5
6
55
10
85
98
7
45
98
8
9
65
100
15
98
98
91
10
In another effort, we immobilized sulfamic acid on silica in the
absence of boehmite. The procedures are the same as that
reported in 4.1. Preparation of the boehmiteꢀDSA but without
the first step related to boehmite synthesis. Then we examined
the synthesis of 2ꢀ(4ꢀmethylphenyl)ꢀ2,3ꢀdihydroquinazolinꢀ
11
20
98
a Isolated yield.
4(1H)ꢀone and oxidation of methylphenyl sulfide using
mesoporous catalyst (MCMꢀ41ꢀDSA) and SiꢀDSA at the same
condition of boehmiteꢀDSA. The results are presented in table
6.
Table 5. Oxidative coupling of sulfides into disulfides using
H2O2 in the presence of boehmiteꢀSiꢀDSA at room temperature.
Time Yield Melting
Table 6. Immobilization of sulfamic acid on defferent supports
Entry
Product
Ref.
(min)
(%)a point (ºC)
Time
(min)
Yield
Entry
Substrate
Catalyst
(%)a
4ꢀ
methylbenzal
dehyde
1
5
97
130ꢀ132
[17]
MCMꢀ41ꢀ
DSA
1
30 (200) 38 (65)
30 (200) 25 (60)
2
3
120
20
98
95
85ꢀ87
Oil
[17]
[17]
4ꢀ
2
3
methylbenzal
dehyde
SiꢀDSA
4ꢀ
boehmiteꢀ
DSA
methylbenzal
dehyde
30
98b
4
10
97
160ꢀ163
[36]
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New Journal of Chemistry
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DOI: 10.1039/C5NJ03546E
ARTICLE
kinds of reactions. More importance, in compared than other
catalyst, boehmiteꢀSiꢀDSA has been easily prepared using cheap and
commercially materials in short time, and can be reused for 5 times
without any significant loss of activity.
methylphenyl
sulfide
methylphenyl
sulfide
MCMꢀ41ꢀ
DSA
4
5
6
20 (180) 42 (92)b
20 (150) 30 (95)b
SiꢀDSA
methylphenyl
sulfide
boehmiteꢀ
DSA
20
98
Table 7. Comparison results of boehmiteꢀSiꢀDSA with other
catalysts
a Purification by preparative TLC. b Isolated yield.
As shown in table 6, in the synthesis of 2ꢀ(4ꢀmethylphenyl)ꢀ
2,3ꢀdihydroquinazolinꢀ4(1H)ꢀone, after 30 min the reaction did
Entry
Substrate
Catalyst Time Yield TOF
(min) (%)a (min ꢀ1)
Ref.
not completed and the yields of 38% in the presence of MCMꢀ
41ꢀDSA and 25% in the presence of SiꢀDSA obtained by
purification with preparative TLC. Even after a longer time,
200 min, reaction did not completed and product purification
performed by preparative TLC. In the oxidation of
methylphenyl sulfide, similar behavior occurred, but with much
more time (8 × compared to boehmiteꢀDSA) the reaction have
been completed.
1
4ꢀ
2ꢀ
180 91
0.05
[38]
methylbenzald morpholinoe
ehyde
thanesulfoni
c acid
2
3
4
5
4ꢀ
pꢀSAC
ZrCl4.
20 92
15 97
4.6
[39]
[40]
methylbenzald
ehyde
2.4 Recyclability of the catalyst
In order to examine ability of the catalyst recycling, the
reusability of the boehmiteꢀSiꢀDSA was examined for the
oxidation of methylphenyl sulfide and synthesis of 2ꢀ(4ꢀ
4ꢀ
3.23
0.54
2.05
methylbenzald
ehyde
chlorophenyl)ꢀ2,3ꢀdihydroquinazolinꢀ4(1H)ꢀone. For this issue,
after the completion of the reaction, the mixture was filtered
and washed with ethylacetate to remove the residual product.
The recovered catalyst was dried and subjected to the next
without any significant activation. As shown in figure 7, the
catalyst can be reused up to 5 runs without any significant loss
of activity. The average isolated yield for several successive
runs was obtained in 96 and 97%, for methylphenyl sulfoxide
4ꢀ
[hnmp][HS 28 75
O4]
[41]
methylbenzald
ehyde
4ꢀ
boehmiteꢀSiꢀ 30 98
DSA
This work
methylbenzald
ehyde
and
2ꢀ(4ꢀchlorophenyl)ꢀ2,3ꢀdihydroquinazolinꢀ4(1H)ꢀone,
respectively.
6
7
methyl(phenyl) RuII(TMP)( 100 90
sulfane CO)
4.5
[20]
[42]
methyl(phenyl) SiO2–2ꢀ
150 86
0.38
100
90
80
70
60
50
sulfane
ImSiO2–2ꢀ
Im
8
9
methyl(phenyl) Mn(III)–
sulfane salphen
32 95
2.97
3.08
9.5
[43]
This work
[44]
methyl(phenyl) boehmiteꢀSiꢀ 20 98
sulfane DSA
1
2
3
4
5
Run number
10 naphthaleneꢀ2ꢀ Fe@SBAꢀ15 10 95
thiol
Fig 7. The recycling experiment of boehmiteꢀDSA in oxidation of
methylphenyl sulfide (green column) and synthesis of 2ꢀ(4ꢀ
chlorophenyl)ꢀ2,3ꢀdihydroquinazolinꢀ4(1H)ꢀone (red column).
11 naphthaleneꢀ2ꢀ
thiol
nickel
nanoparticle
s
8
93
0.78
[45]
2.5 Comparison of the catalyst
In order to describe the catalytic activity of boehmiteꢀSiꢀDSA, we
compared the results of the synthesis of 2ꢀ(pꢀtolyl)ꢀ2,3ꢀ
dihydroquinazolinꢀ4(1H)ꢀone (Table 2, entry 2) and also oxidation
of methyl(phenyl)sulfide (Table 4, entry 11) and oxidative coupling
of naphthaleneꢀ2ꢀthiol (Table 5, entry 1) in the presence of this
catalyst with the previous methods in the literatures. This catalyst
afford good reaction time and higher yield than other catalysts
(Table 7). Also comparison of activity based on turnover frequency
(TOF) showed excellent results for boehmiteꢀSiꢀDSA in all three
12 naphthaleneꢀ2ꢀ boehmiteꢀSiꢀ
5
97
12.2
This work
thiol
DSA
3 Conclusions
In summary, we have demonstrated that boehmiteꢀDSA can be used
as a green, efficient and reusable nanocatalyst for the synthesis of a
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ARTICLE
wide range of 2,3ꢀdihydroquinazolinꢀ4(1H)ꢀone derivatives in simple filtration and washed with ethyl acetate, and next, the
ethanol under reflux condition. Also, oxidation of sulfides to product was extracted with ethyl acetate. The organic layer was
sulfoxides and oxidative coupling of thiols into disulfides was dried over anhydrous Na2SO4 (1.5 g). Finally, the organic solvents
reported at room temperature in the present of boehmiteꢀDSA as an were evaporated, and products were obtained in good to high yield.
efficient nanocatalyst. The advantages of these protocol are the use
of a commercially available, ecoꢀfriendly, cheap and chemically
stable materials, the simple methodology, practicability, easy work
up and high products yields. The product separation and catalyst
recycling are easy by simple filtration. The catalyst can be reused for
5 times without any significant loss of activity.
4.4 General procedure for the oxidative coupling of thiols into
disulfides using H2O2 in the presence of boehmite-Si-DSA
BoehmiteꢀSiꢀDSA (0.03 g) was added to a mixture of thiol (1
mmol) and H2O2 (0.4 mL) in ethanol (5 mL). Then the mixture was
stirred for the appropriate time at room temperature. The progress
was monitored by TLC. After completion of the reaction, the catalyst
was separated by simple filtration and the mixture was washed with
ethyl acetate. The product was extracted with ethyl acetate. The
organic layer was dried over anhydrous Na2SO4 (1.5 g). In some
cases, the product was recrystallized from ethanol for further
purification and products were obtained in good to high yield.
4 Experimental
4.1. Preparation of the boehmite-DSA
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.
4.5 Selected Spectral data
2-(4-Methylphenyl)-2,3-dihydroquinazolin-4(1H)-one (Table 2,
entry 2):
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.
1
Mp: 224ꢀ226 °C. IR (KBr) cmꢀ1: 3313, 1658, 1611, 1439. H NMR
(400 MHz, DMSOꢀd6): δH= 8.20 (s, 1H), 7.63ꢀ7.60 (d, J=7.5, 1H),
7.40ꢀ7.37 (d, J=7.5, 2H), 7.25ꢀ7.13 (m, 3H), 7.03 (s, 1H), 6.74ꢀ6.63
(m, 2H), 5.71 (s, 1H), 2.50ꢀ2.43 (s, 3H) ppm.
2-(4-Ethoxyphenyl)-2,3-dihydoquinazolin-4(1H)-one (Table 2,
entry 4):
The obtained boehmiteꢀsilica (1 g) was dispersed in 25 mL
ethanol, and solution by ultrasonic bath for 30 min, and then
dopamine (1.5 gr) was added to the reaction mixture. The
reaction mixture was stirred at room temperature for 24 h.
Then, the nanoparticles was separated by simple filtration and
washed with ethanol. The obtained boehmiteꢀSiꢀdopamine was
dried at room temperature.
1
Mp: 163ꢀ165 °C. IR (KBr) cmꢀ1: 3301, 1650, 1613, 1443. H NMR
(400 MHz, DMSOꢀd6): δH= 7.96ꢀ7.95 (b, 1H), 7.51ꢀ7.49 (m, 2H),
7.34 (s, 1H), 7.25 (s, 1H), 6.94ꢀ6.89 (m, 3H), 6.67ꢀ6.66 (m, 1H),
5.84 (s, 1H), 5.75 (s, 1H), 4.08ꢀ4.06 (q, J=4, 2H), 1.47ꢀ1.45 (s, 3H)
ppm.
The obtained boehmiteꢀSiꢀdopamine (0.5 g) were dispersed in
dry nꢀhexane (5 mL) by ultrasonic bath for 20 min.
Subsequently, chlorosulfunic acid (0.75 mL) was added drop
wise over a period of 30 min and the mixture was stirred for 2h
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 (boehmiteꢀDSA)
dried at room temperature and stored in a refrigerator to use.
2-(3,4-Dimethoxyphenyl)-2,3-dihydoquinazolin-4(1H)-one (Table
2, entry 5):
1
Mp: 212ꢀ215 °C. IR (KBr) cmꢀ1: 3335, 1671, 1610, 1436. H NMR
(400 MHz, DMSOꢀd6): δH= 8.20 (s, 1H), 7.65ꢀ7.63 (d, J=7.6, 1H),
7.29ꢀ7.25 (t, J=0.8, 1H), 7.16 (d, J=1.6, 1H), 7.03ꢀ6.96 (m, 2H), 6.94
(s, 1H), 6.79ꢀ6.78 (d, J=8, 1H), 6.73ꢀ6.68 (t, J=1.2, 1H), 5.71 (s,
1H), 3.78 (s, 3H), 3.76 (s, 3H) ppm.
2-(4-Chlorophenyl)-2,3-dihydoquinazolin-4(1H)-one (Table 2,
entry 6):
4.2 General procedure for the synthesis of 2,3-
dihydroquinazolin-4(1H)-ones derivatives
1
Mp: 199ꢀ200 °C. IR (KBr) cmꢀ1: 3309, 1655, 1611, 1435. H NMR
A mixture of boehmiteꢀSiꢀDSA (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 catalyst was separated using simple
filtration. CH2Cl2 was evaporated and all products was recrystalized
in ethanol for further purification.
(400 MHz, DMSOꢀd6): δH= 8.30 (s, 1H), 7.60ꢀ7.41 (m, 5H), 7.25ꢀ
7.19 (t, J=7.5, 1H), 7.11 (s, 1H), 6.76ꢀ6.64 (m, 2H), 5.76 (s, 1H)
ppm.
2-(4-Bromophenyl)-2,3-dihydoquinazolin-4(1H)-one (Table 2,
entry 9):
Mp: 197ꢀ199 °C. IR (KBr) cmꢀ1: 3310, 1656, 1608, 1433. H NMR
(400 MHz, DMSOꢀd6): δH= 8.18ꢀ8.15 (m, 1H), 7.79ꢀ7.77 (m, 1H),
7.62ꢀ7.60 (m, 3H), 7.48ꢀ7.45 (m, 2H), 7.29ꢀ7.23 (m, 1H), 6.78ꢀ6.73
(d, J=19.2, 1H), 6.70ꢀ6.67 (m, 1H), 5.77 (s, 1H) ppm.
1
4.3 General procedure for the oxidation of sulfides to sulfoxides
using H2O2 in the presence of boehmite-Si-DSA
A mixture of sulfide (1 mmol), H2O2 (0.4 mL) and boehmiteꢀSiꢀ
DSA (0.03 g) was stirred at room temperature under solventꢀfree
condition and the progress of the reaction was monitored by TLC.
After completion of the reaction, catalyst was separated using
1
Tetrahydrothiophene 1-oxide (Table 4, entry 1): H NMR (400
MHz, CDCl3): δ = 2.26 (t, J= 7.6 Hz, 2H), 3.05 (t, J= 7.6 Hz, 2H)
ppm.
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2-((Methylsulfinyl)methyl)furan (Table 4, entry 2): 1H NMR (400
MHz, CDCl3): δ = 2.58 (s, 3H), 4.06 (d, J= 14 Hz,1H), 4.15 (d, J=
14 Hz,1H), 6.43 (d, J= 3.2 Hz,1H), 7.14ꢀ7.57 (m, 2H) ppm.
17. Y. Chen, J. Zhuo, D. Zheng, S. Tian and Z. Li, J. Mol. Catal. B:
Enzym., 2014, 106, 100.
18. A. GhorbaniꢀChoghamarani, Z. Darvishnejad and M. Norouzi, Appl.
Organometal. Chem., 2015, 29, 170.
19. T. H. Chen, Z. Yuan, A. Carver and R. Zhang, Appl. Catal. A: Gen.,
2014, 478, 275.
20. D. Habibi, M. A. Zolfigol, M. Safaiee, A. Shamsian and A. Ghorbaniꢀ
Choghamarani, Catal. Commun., 2009, 10, 1257.
1
Methyl(p-tolyl)sulfane (Table 4, entry 7): H NMR (400 MHz,
CDCl3): δ = 2.23 (s, 3H), 2.56 (s, 3H), 7.18 (d, J= 3.2 Hz, 2H), 7.40
(d, J= 3.2 Hz, 2H) ppm.
21. Y. Liu, H. Wang, C. Wang, J. P. Wan and C. Wen, RSC Adv., 2013, 3,
21369.
22. D. Singh, F. Z. Galetto, L. C. Soares, O. E. D. Rodrigues and A. L.
Braga, Eur. J. Org. Chem., 2010, 2010, 2661.
23. A. K. Patra, A. Dutta, M. Pramanik, M. Nandi, H. Uyama and A.
Bhaumik, ChemCatChem., 2014, 6, 220.
24. A. A. Elkin, T. I. Kylosova, V. V. Grishkoc and I. B. Ivshina, J. Mol.
Catal. B: Enzym., 2013, 89, 82.
1
1-(Propylsulfinyl)propane (Table 4, entry 10): H NMR (400
MHz, CDCl3): δ = 1.12 (t, J= 6 Hz, 6H), 1.85ꢀ1.94 (m, 4H), 2.64ꢀ
2.96 (m, 4H) ppm.
1,2-di(naphthalen-2-yl)disulfane (Table 5, entry 1): 1H NMR (400
MHz, CDCl3): δ = 7.48 (m, 4H), 7.64 (m, 2H), 7.75 (m, 2H), 7.80
(m, 4H), 8.1 (s, 2H) ppm.
25. G. P. Romanelli, P. I. Villabrille, C. V. Cáceres, P. G. Vázquez and P.
Tundo, Catal. Commun., 2011, 12, 726.
1
1,2-bis(4-bromophenyl)disulfane (Table 5, entry 2): H NMR
(400 MHz, CDCl3): δ = 7.34 (d, J= 8.2 Hz, 4H), 7.43 (t, J= 8.2 Hz,
26. L. Villalobos and T. Ren, Inorg. Chem. Commun., 2013, 28, 52.
27. S. Thurow, V. A. Pereira, D. M. Martinez, D. Alves, G. Perin, R. G.
Jacob and E. J. Lenardão, Tetrahedron Lett., 2011, 52, 640.
28. M. Abbasi and D. Khalili, J. Iran. Chem. Soc., 2015, 12, 1425.
29. H. Zhang and G. Wang, Tetrahedron Lett., 2014, 55, 56.
30. H. Liu, J. Deng and W. Li, Catal. Lett., 2010, 137, 261.
31. M. Safari, M. Ghiaci, M. JafariꢀAsl and A. A. Ensafi, Appl. Surf. Sci.,
2015, 342, 26.
4H) ppm.
2,2'-Disulfanediyldiethanol (Table 5, entry 3): 1H NMR (400
MHz, CDCl3): δ = 2.59 (br, 2H), 2.90 (t, J= 5.6 Hz, 4H), 3.92 (t, J=
5.6 Hz, 4H) ppm.
32. K. Farhadi and N. Farnad, J. Iran. Chem. Soc., 2015, 12, 347.
33. P. Liu, Y. Zhu, J. Ma, S. Yang, J. Gong and J. Xu, Prog. Nat. Sci.:
Mat. Int., 2013, 23, 145.
1,2-bis(4,6-dimethylpyrimidin-2-yl)disulfane (Table 5, entry 4):
1H NMR (400 MHz, CDCl3): δ = 2.39 (s, 12H), 6.75 (s, 2H) ppm.
34. L. Rajabi and A. A. Derakhshan, Sci. Adv. Mater., 2010, 2, 163.
35. A. GhorbaniꢀChoghamarani and M. Norouzi, J. Mol. Catal. A: Chem.,
2014, 395, 172.
Acknowledgements
36. A. GhorbaniꢀChoghamarani, B. Ghasemi, Z. Safari and G. Azadi,
Catal. Commun., 2015, 60, 70.
37. M. Hajjami, L. Shiri and A. Jahanbakhshi, Appl. Organomet. Chem.,
2015, 29, 668.
This work was supported by the research facilities of Ilam
University, Ilam, Iran.
38. V. B. Labade, P. V. Shinde and M. S. Shingare, Tetrahedron Lett.,
Notes and references
2013, 54, 5778.
39. M. Rahman, I. Ling, N. Abdullah, R. Hashim and A. Hajra, Rsc Adv.,
Department of Chemistry, Facultu of science,Ilam university, Ilam, Iran.
Fax: +988412227022; Tel: +988412227022; E-mail: mhajjjami@yahoo.com
& m.hajjami@ilam.ac.ir.
2015, 5, 7755.
40. M. AbdollahiꢀAlibeik and E. Shabani, Chinese Chem. Lett., 2011, 22,
1163.
41. H. R. Shaterian and M. Aghakhanizadeh, Res. Chem. Intermed., 2014,
1. G. R. Patzke, Y. Zhou, R. Kontic and F. Conrad, Angew. Chem. Int.
Ed., 2011, 50, 826.
2. Y. Zhu, L. P. Stubbs, F. Ho, R. Liu, C. P. Ship, J. A. Maguire and N.
S. Hosmane, ChemCatChem., 2010, 2, 365.
3. B. Atashkar, A. Rostami and B. Tahmasbi, Catal. Sci. Technol., 2013,
3, 2140.
4. M. Nikoorazm, A. GhorbaniꢀChoghamarani, F. Ghorbani, H. Mahdavi
and Z. Karamshahi, J. Porous Mater., 2015, 22, 261.
5. Y. S. Feng, X. Y. Lin, J. Hao and H. J. Xu, Tetrahedron, 2014, 70,
5249.
40, 1655.
42. X. ꢀY. Shi and J. ꢀF. Wei, J. Mol. Catal. A: Chem., 2008, 280, 142.
43. A. Abdolmaleki and S. MalekꢀAhmadi, J. Iran. Chem. Soc., 2012, 9,
1015.
44. F. Rajabi, T. Kakeshpour and M. R. Saidi, Catal. Commun., 2013, 40,
13.
45. A. Saxena, A. Kumar and S. Mozumdar, J. Mol. Catal. A: Chem.,
2007, 269, 35.
6. A. Fodor, Z. Hella and L. PiraultꢀRoy, Appl. Catal. A: Gen., 2014,
484, 39.
7. V. Vatanpour, S. S. Madaenia, L. Rajabi, S. Zinadini and A. A.
Derakhshan, J. Membr. Sci., 2012, 401, 132.
8. K. Bahrami, M. M. Khodaei and M. Roostaei, New J. Chem., 2014,
38, 5515.
9. E. Carbonell, E. DelgadoꢀPinar, J. PitarchꢀJarque, J. Alarcón and E.
GarcíaꢀEspañ, J. Phys. Chem., 2013, 117, 14325.
10. S. D. Dindulkar, J. Oh, V. M. Arole and Y. T. Jeong, C. R. Chimie,
2014, 17, 971.
11. B. H. Chen, J. T. Li and G. F. Chen, Ultrason. Sonochem., 2015, 23,
59.
12. J. Zhang, D. Ren, Y. Ma, W. Wang and H. Wu, Tetrahedron, 2014,
70, 5274.
13. A. Rostami, B. Tahmasbi, H. Gholami and H. Taymorian, Chinese
Chem. Lett., 2013, 24, 211.
14. M. Waibel and J. Hasserodt, Tetrahedron Lett., 2009, 50, 2767.
15. M. Narasimhulu and Y. R. Lee, Tetrahedron, 2011, 67, 9627.
16. A. GhorbaniꢀChoghamarani and G. Azadi, RSC Adv., 2015, 5, 9752.
This journal is © The Royal Society of Chemistry 2013
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DOI: 10.1039/C5NJ03546E
Graphical Abstract
Efficient preparation of boehmite silica dopamine
sulfamic acid as novel nanostructured compound and
its application as catalyst in some organic reactions
Maryam Hajjami*, Arash Ghorbani-Choghamarani, Raziyeh
Ghafouri-nejad and Bahman Tahmasbi
Nanoboehmite was prepared in water at room temperature using commercially materials
and applied as support for preparation of new catalyst.