Eco-friendly synthesis of 3,4-dihydroquinoxalin-2-amine, diazepine-tetrazole and benzodiazepine-2-carboxamide derivatives with the aid of MCM-48/H5PW10V2O40

Article abstract of DOI:10.1002/aoc.3729

A heterogeneous material composed of MCM-48/H₅PW₁₀V₂O₄₀ was produced and used as an efficient, eco-friendly and highly recyclable catalyst for the one-pot and multicomponent synthesis of 3,4-dihydroquinoxalin-2-amine, diazepine-tetrazole and benzodiazepine-2-carboxamide derivatives in aqueous media and at room temperature with high yields in short reaction times (40–60?min). The recoverable catalyst was easily recycled at least five times without any loss of catalytic activity. The structures of obtained products were confirmed using ¹H NMR and ¹³C NMR spectra.

Full text of DOI:10.1002/aoc.3729

Received: 2 October 2016
DOI 10.1002/aoc.3729
Revised: 30 November 2016
Accepted: 5 December 2016
F U L L PA P E R
Eco‐friendly synthesis of 3,4‐dihydroquinoxalin‐2‐amine,
diazepine‐tetrazole and benzodiazepine‐2‐carboxamide
derivatives with the aid of MCM‐48/H5PW10V2O40
Esmail Vessally1 | Rahim Hosseinzadeh‐Khanmiri1,2 | Ebrahim Ghorbani‐Kalhor2 |
Moosa Es’haghi2 | Ladan Ejlali2
1 Department of Chemistry, Payame Noor
A heterogeneous material composed of MCM‐48/H5PW10V2O40 was produced and
used as an efficient, eco‐friendly and highly recyclable catalyst for the one‐pot and
multicomponent synthesis of 3,4‐dihydroquinoxalin‐2‐amine, diazepine‐tetrazole
and benzodiazepine‐2‐carboxamide derivatives in aqueous media and at room
University, Tehran, Iran
2 Department of Chemistry, Tabriz Branch, Islamic
Azad University, Tabriz, Iran
Correspondence
Ebrahim Ghorbani‐Kalhor, Department of
Chemistry, Tabriz Branch, Islamic Azad
temperature with high yields in short reaction times (40–60 min). The recoverable
catalyst was easily recycled at least five times without any loss of catalytic activity.
University, Tabriz, Iran.
1
Email: ekalhor@iaut.ac.ir
The structures of obtained products were confirmed using H NMR and 13C NMR
spectra.
KEYWORDS
3,4‐dihydroquinoxalin‐2‐amine, benzodiazepine‐2‐carboxamide, diazepine‐tetrazole,
green chemistry, MCM‐48/H5PW10V2O40
1
|
INTRODUCTION
It is known that high active phase dispersion or high
surface area as well as fast mass transfer of products and
Heterocyclic chemistry is one of the most important branches
in organic chemistry which accounts for nearly one‐third of
modern publications.[1]
Quinoxaline is one of the heterocyclic compounds
containing nitrogen atoms that display a broad spectrum
of biological and pharmacological activities such as
insecticidal, fungicidal, herbicidal, anthelmintic, antibacterial,
antimycobacterial, antiprotozoal, anticancer and antibiotic
properties.[2,3]
Benzodiazepines are an important class of bioactive
compounds. These compounds have been widely applied
for their anxiolytic, anticonvulsant, hypnotic, sedative,
skeletal muscle relaxant, amnestic, diabetic nephropathy,
glomerulosclerosis and peptide hormone properties.[4–6]
Catalysis based on heteropolyacids (HPAs) and related com-
pounds, especially those comprising the strongest Keggin‐type
HPAs, is an important field in which new and promising
developments are being realized in both academia and
technological fields. The major disadvantages of HPAs lie in
extremely low surface area, water solubility, difficult recovery
and recycling which always limit their practical applications.[7,8]
reactants are necessary for any active catalyst. Hence,
designing a heterogeneous catalyst involving a rigorous
control of the surface geometry and proper control of
surface chemistry at the mesoscales need to be explored
for the successful development of environmentally compati-
ble catalytic systems. New heterogeneous materials based
on mesoporous molecular sieves have attracted much
research interest and have opened new vistas for the same.
The use of these mesoporous materials from the Mobile
Composition of Matter (MCM) family has provided
attractive possibilities for development of highly active solid
catalysts and they have found a number of applications in
various industrially important classes of reactions.[9]
Mesoporous materials are widely used in various fields
according to their high surface area and tunable struc-
tures.[10–17] MCM‐48 is a type of mesoporous silica tube‐
like material with uniformly sized three‐dimensional
mesopores. These compounds have been of interest as solid
supports in catalysis and sorption. The mesoporous silica
material MCM‐48 has been considered as an ideal support
for various HPAs, because of its special pore structure and
Appl Organometal Chem. 2017;e3729.
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https://doi.org/10.1002/aoc.3729

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VESSALLY ET AL.
large surface area; moreover, this support is easy to produce
at a low cost.[18]
MCM‐48 has an interesting bicontinuous cubic structure
(with Ia3d symmetry) centred on the gyroid minimal surface
that divides available pore space into two nonintersecting
subvolumes. This three‐dimensional bicontinuous structure
is preferred over the two‐dimensional hexagonal structure
for catalytic applications, because the unique three‐dimen-
sional channel network is thought to provide a highly opened
porous host that offers easy and direct access for guest
species, thus facilitating inclusion or diffusion throughout
the pore channels without pore blocking.[19,20]
Recently, science and technology have been shifting
emphasis to environmentally friendly and sustainable
resources and processes, and for these reasons a few
heterogeneous materials with supported HPW, such as
HPW/C,[21] HPW/CNTS,[22] HPW/TiO2,[23] HPW/SnO2,[24]
HPW/C‐Al2O3,[25] HPW/Nb2O5,[26] HPW/ZrO2,[27] HPW/
hydrous zirconia,[28] HPW/SiO2
48,[30,31] have been studied.
and HPW/MCM‐
[29]
SCHEME
1
Synthesis of 3,4‐dihydroquinoxalin‐2‐amine, diazepine‐
tetrazole and benzodiazepine‐2‐carboxamide derivatives
Loading of HPAs on mesoporous silica not only allows
transfer of HPA‐catalysed reactions from homogeneous to
heterogeneous systems to avoid the difficulty in catalyst
separation, but also effectively increases the surface area of
HPAs.[32]
Heterogeneous catalytic systems have attracted world-
wide attention and have been studied extensively due to their
technological and biological applications such as in drug
delivery, bioseparation, biomolecular sensors and magnetic
resonance imaging.[33–37]
Shaabani and co‐workers reported novel routes
for the synthesis of quinoxaline and benzodiazepine
derivatives
using
isocyanide‐based multicomponent
reactions in the presence of non‐recyclable catalytic amount
of p‐toluenesulfonic acid, with long reaction times, the
reaction not occurring in the absence of this catalyst.[38]
In this paper, a novel method for the synthesis biologically
important materials is presented using MCM‐48/
H5PW10V2O40. This environmentally benign, heterogeneous
and highly reusable catalyst shows very good catalytic activity
towards the synthesis of 3,4‐dihydroquinoxalin‐2‐amine,
diazepine‐tetrazole and benzodiazepine‐2‐carboxamide deriv-
atives (Scheme 1).
FIGURE 1 FT‐IR spectrum of MCM‐48
which correspond to a significant degree of long‐range
ordering in the structure and well‐ordered hexagonal pore
system. The (100) reflection of MCM‐48 is still observed
after H5PW10V2O40 loading (Figure 2). However, modifica-
tion of MCM‐48 with H5PW10V2O40 results in a loss of
crystalline order, as is evidenced by a significant decrease
in diffraction intensities.[39]
The scanning electron microscopy (SEM) image of
MCM‐48 (Figure 3) demonstrates fine, spherical particles
of uniform diameter and particle size. The SEM image of
H5PW10V2O40/MCM‐48 depicts that the catalyst has a
homogeneous distribution of spherical particles and the
structure is not significantly affected upon introduction of
HPW, although some agglomeration and particle shape dete-
rioration are observed. Further, no change in surface mor-
phology indicates that HPW species are well dispersed
inside the three‐dimensional pores of the support, which
agrees well with the surface area and X‐ray diffraction data.
2
| RESULTS AND DISCUSSION
The Fourier transform infrared (FTIR) spectrum of MCM‐48
shows a peak at around 960 cm−1, which is related to Si─OH
(silanol) stretching vibration (Figure 1).
The powder low‐angle X‐ray scattering of calcined
mesoporous structure of MCM‐48 was studied. This
compound shows an intense peak assigned to the reflections
at (100) and two low‐intensity peaks at (200) and (110),

VESSALLY ET AL.
3 of 7
and benzodiazepine‐2‐carboxamide derivatives (Scheme 1).
To illustrate the need of a catalyst for these reactions, in a
typical experiment, 1,2‐benzenediamine (1a), acetone (2a)
and cyclohexyl isocyanide (3a) were stirred in ethanol at
room temperature in the absence of catalyst. The yield in this
case is a trace after 12 h that shows the catalyst is important
for the reaction.
Thereupon, in a pilot experiment, 1a, 2a and 3a were
stirred in ethanol at room temperature using HPA, MCM‐48
and MCM‐48/H5PW10V2O40 catalyst. Table 1 summarizes
the catalytic performance results for the synthesis of
N‐cyclohexyl‐3,3‐dimethyl‐3,4‐dihydroquinoxalin‐2‐amine
(4a). The catalytic activity is found to be in the order MCM‐48/
H5PW10V2O40 > H5PW10V2O40 > MCM‐48.
In order to obtain the best synthesis conditions, 1a, 2a
and 3a in the presence of MCM‐48/H5PW10V2O40 in
various organic solvents were allowed to react at room
temperature. As evident from Table 2, commercially absolute
ethanol, ethanol 96% and methanol 99% are the best solvents
for the synthesis of 4a with respect to yield and reaction
time.
FIGURE 2 Low‐angle X‐ray diffraction patterns of calcined MCM‐48(blue
curve) and H5PW10V2O40/MCM‐48 (black curve)
The catalytic efficiency could be influenced by the
amount of catalyst. Therefore, a set of experiments using var-
ious amounts of catalyst was considered for the reaction of 1a,
2a and 3a in ethanol 96% at room temperature (Table 3). The
optimum amount of MCM‐48/H5PW10V2O40 catalyst is
TABLE 1 Optimization of catalyst for synthesis of N‐cyclohexyl‐3,3‐
dimethyl‐3,4‐dihydroquinoxalin‐2‐amine (4a)a
Catalyst
Time (min)
Yield (%)b
MCM‐48
50
50
50
33
62
92
HPA
MCM‐48/H5PW10V2O40
aReaction conditions: 1,2‐benzenediamine (1a, 1.00 mmol), acetone (2a,
1.00 mmol), cyclohexyl isocyanide (3a, 1.00 mmol) and catalyst (0.04 g) were
stirred in ethanol 96% (3.00 ml).
FIGURE
3
SEM and TEM images of MCM‐48 and MCM‐48/
H5PW10V2O40
bIsolated yield.
The transmission electron microscopy (TEM) image of
MCM‐48 shows a very well‐ordered pore system with
pore diameter of between 2 and 4 nm (Figure 3). It is
well known in the literature, that MCM‐48 has a three‐
dimensional pore system with two nonintersecting gyroidal
pores which can assist dispersion of material having
diameters in the range 1–3 nm. The TEM image of
H5PW10V2O40/MCM‐48 (Figure 3) shows ordered three‐
dimensional channels that are well arranged over a large
scale. Furthermore, the absence of characteristic peaks of
the crystalline phase of HPW in the catalyst indicates that
HPW is highly dispersed inside the channels of MCM‐
48. The results are in good agreement with the X‐ray
diffraction data.
TABLE 2 Optimization of solvent for synthesis of N‐cyclohexyl‐3,3‐
dimethyl‐3,4‐dihydroquinoxalin‐2‐amine (4a)a
Solvent
Time (min)
Yield (%)b
H2O
50
50
50
50
50
50
50
50
50
76
71
69
85
32
62
90
92
94
CH2Cl2
CHCl3
CH3CN
C6H6
THF
MeOH 99%
EtOH 96%
EtOH 100%
aReaction conditions: 1,2‐benzodiamine (1a, 1.00 mmol), acetone (2a,
1.00 mmol), cyclohexyl isocyanide (3a, 1.00 mmol) and catalyst (0.04 g) were
stirred in ethanol 96% (3.00 ml).
The catalytic efficiency of the MCM‐48/H5PW10V2O40
heterogeneous catalytic system was studied for the prepara-
tion of 3,4‐dihydroquinoxalin‐2‐amine, diazepine‐tetrazole
bIsolated yield.

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VESSALLY ET AL.
TABLE 3 Effect of catalyst amount on reaction of 1,2‐benzodiamine, ace-
presence of MCM‐48/H5PW10V2O40, 1H–tetrazol‐5‐yl‐4‐
methyl‐1H‐benzo[b][1,4]diazepines 6a–j were obtained
(Scheme 1).
tone and cyclohexyl isocyanidea
Catalyst
Catalyst amount (g) Time (min) Yield (%)b
In a pilot experiment, 1a and 2a were stirred in the presence
of a catalytic amount of MCM‐48/H5PW10V2O40 in methanol
at room temperature. The progress of the reaction was moni-
tored by TLC. After 30 min, trimethylsilyl azide and 3a were
added to the reaction mixture and stirring was continued for
20 min. After completion of the reaction, the catalyst was
removed by filtration. The residue was crystallized from ace-
tone to give 5‐(1‐cyclohexyl‐1H‐tetrazol‐5‐yl)‐5,7,7‐trimethyl‐
4,5,6,7‐tetrahydro‐1H‐1,4‐diazepine‐2,3‐dicarbonitrile (6a) in
91% yield. This reaction does not proceed in the absence of
catalyst.
Using MCM‐48/H5PW10V2O40 as the best catalyst in
methanol, we initiated a study to explore the scope of this
reaction. Various derivatives of 1a, ketones 2 and isocyanides
3 were examined in this reaction. The results are summarized
in Table 5.
MCM‐48
0.06
0.05
0.04
0.02
0.06
0.05
0.04
0.02
0.06
0.05
0.04
0.02
50
50
50
50
50
50
50
50
50
50
50
50
38
36
33
29
66
63
62
48
96
95
92
76
MCM‐48
MCM‐48
MCM‐48
H5PW10V2O40
H5PW10V2O40
H5PW10V2O40
H5PW10V2O40
MCM‐48/H5PW10V2O40
MCM‐48/H5PW10V2O40
MCM‐48/H5PW10V2O40
MCM‐48/H5PW10V2O40
aReaction conditions: 1,2‐benzodiamine (1a, 1.00 mmol), acetone (2a,
1.00 mmol), cyclohexyl isocyanide (3a, 1.00 mmol) and catalyst were stirred in
ethanol 96% (3.00 ml).
bIsolated yield.
In view of the success of the reactions discussed above for
the synthesis of benzodiazepine derivatives, we decided to
extend our study by using water instead of TMSN3 (5) for
the preparation of 7a–g (Scheme 1). The reaction proceeds
cleanly under mild conditions at room temperature and no
undesirable side reactions are observed under these reaction
conditions.
In a pilot experiment, 4‐nitro‐1,2‐phenylenediamine and
2a were stirred in methanol at room temperature in the pres-
ence of a catalytic amount of MCM‐48/H5PW10V2O40. The
progress of the reaction was monitored by TLC. After
30 min, 3a and water were added to the reaction mixture,
and stirring was continued for 25 min. After completion of
the reaction, an aqueous workup afforded compound 7a in
92% yield.
0.04 g to reach 92% yield of compound 4a. Lower amounts of
catalyst result in a decrease in the efficacy of the reaction,
while higher amounts lead to complete conversion in a short
reaction time. Clearly, immobilizing the HPA on the MCM‐
48 increases its catalytic activity towards the condensation
reaction.
Using MCM‐48/H5PW10V2O40 in ethanol 96%, we initi-
ated a study to explore the scope of this procedure. Various
derivatives of 1a, carbonyl compounds 2 and isocyanides 3
were applied in this reaction (Table 4).
In continuation, by using a two‐step condensation reac-
tion between 1a, two moles of ketone derivatives (2), an
isocyanide (3a) and TMSN3 (5) as a nucleophile in the
TABLE 4 Synthesis of 3,4‐dihydroquinoxalin‐2‐amines with various diamines, carbonyl compounds and isocyanidesa
M.p. (°C)
Reported[22]
Time
(min)
Yield
(%)b
Entry
Amine compound
o‐Phenylenediamine
Carbonyl compound
R5
Found
4a
4b
4c
Acetone
cHex
t‐Bu
50
50
45
50
50
55
60
50
55
60
60
50
55
92
87
94
91
90
92
89
86
87
81
85
91
83
161–163
104–107
154–155
180–182
187–190
>250
160–162
106–108
153–155
181–182
187–189
>250
o‐Phenylenediamine
Cyclohexanone
Cyclohexanone
Acetone
4‐Methyl‐o‐phenylenediamine
3,4‐Diaminobenzophenone
3,4‐Diaminobenzophenone
4‐Nitro‐1,2‐phenylenediamine
4‐Nitro‐1,2‐phenylenediamine
3,4‐Diaminobenzophenone
4,5‐Dichloro‐1,2‐phenylenediamine
4‐Nitro‐1,2‐phenylenediamine
4‐Nitro‐1,2‐phenylenediamine
4‐Methyl‐o‐phenylenediamine
o‐Phenylenediamine
cHex
cHex
cHex
cHex
t‐Bu
4d
4e
Cyclohexanone
Acetone
4f
4 g
4 h
4i
Acetone
158–161
>250
158–160
>250
4‐Nitrobenzaldehyde
4‐Methylbenzaldehyde
Benzaldehyde
4‐Methoxybenzaldehyde
Acetone
cHex
t‐Bu
>250
>250
4j
cHex
cHex
cHex
177–180
176–179
171–173
>250
178–180
175–176
—
4 k
4 l
4 m
Acetone
1,1,3,3‐Tetramethylbutyl
—
aReaction conditions: diamines (1, 1.00 mmol), carbonyl compounds (2, 1.00 mmol), isocyanides (3, 1.00 mmol) and MCM‐48/H5PW10V2O40 (0.04 g) were stirred in
ethanol 96% (3.00 ml).
bIsolated yield.

VESSALLY ET AL.
5 of 7
TABLE 5 Synthesis of 1H–tetrazolylbenzo[b][1,4]diazepine derivatives with various diamines, carbonyl compounds and isocyanidesa
M.p. (°C)
Time
(min)
Yield
(%)b
Entry
Amine compound
o‐Phenylenediamine
Carbonyl compound
Acetone
R5
cHex
Found
Reported[19]
6a
6b
6c
6d
6e
6f
50
45
40
50
55
55
50
50
35
30
91
89
90
90
81
87
75
86
89
85
241–243
203–205
293–295
>300
241–242
202–204
293–295
>300
4‐Methyl‐o‐phenylenediamine
3,4‐Diaminobenzophenone
3,4‐Diaminobenzophenone
4‐Nitro‐1,2‐phenylenediamine
4‐Nitro‐1,2‐phenylenediamine
4‐Nitro‐1,2‐phenylenediamine
4,5‐Dichloro‐1,2‐phenylenediamine
o‐Phenylenediamine
Acetone
cHex
cHex
cHex
TOSMIC
cHex
cHex
cHex
cHex
t‐Bu
Acetone
Cyclohexanone
Acetone
197–199
>300
196–198
>300
Cyclohexanone
4‐tert‐Butylcyclohexanone
Cyclohexanone
Cyclohexanone
4‐tert‐Butylcyclohexanone
6 g
6 h
6i
>300
>300
>300
>300
>300
—
6j
4‐Methyl‐o‐phenylenediamine
283–285
—
aReaction conditions: diamines (1, 1.00 mmol), carbonyl compounds (2, 1.00 mmol), isocyanides (3, 1.00 mmol), TMSN3 (5, 1.3 mmol) and MCM‐48/H5PW10V2O40
(0.04 g) were stirred in methanol (3.00 ml).
bIsolated yield.
TABLE 6 Synthesis of 2,3,4,5‐tetrahydro‐1H‐1,5‐benzodiazepine‐2‐carboxamide derivatives with various diamines, carbonyl compounds and isocyanidesa
M.p. (°C)
Time
(min)
Yield
(%)b
Entry
Amine compound
Carbonyl compound
Acetone
R5
Found
Reported[23]
7a
7b
7c
7d
7e
7f
4‐Nitro‐1,2‐phenylenediamine
4‐Nitro‐1,2‐phenylenediamine
4,5‐Dichloro‐1,2‐phenylenediamine
4,5‐Dichloro‐1,2‐phenylenediamine
3,4‐Diaminobenzoic acid
cHex
t‐Bu
55
55
50
50
55
50
55
92
89
86
85
87
82
88
186–188
225–227
170–173
169–172
214–216
211–213
191–193
185–187
224–226
169–172
168–170
213–214
—
Acetone
Acetone
cHex
t‐Bu
Cyclohexanone
Cyclohexanone
Cyclohexanone
4‐tert‐Butylcyclohexanone
cHex
cHex
cHex
o‐Phenylenediamine
7g
o‐Phenylenediamine
—
aReaction conditions: diamines (1, 1.00 mmol), carbonyl compounds (2, 1.00 mmol), isocyanides (3, 1.00 mmol), H2O (1.00 ml) and MCM‐48/H5PW10V2O40 (0.04 g)
were stirred in methanol (3.00 ml).
bIsolated yield.
TABLE 7 Recycling of catalysta
Under optimal conditions, various derivatives of 1a,
ketones 2 and isocyanides 3 were examined in this reaction.
The results are summarized in Table 6.
Cycle
Catalyst (g)
Yield (%)
1
2
3
4
5
6
0.040
0.040
0.040
0.037
0.037
0.036
92
92
92
91
91
90
The catalyst is very active, stable, nontoxic and inexpen-
sive. To explore the reusability of MCM‐48/H5PW10V2O40,
it was easily separated from the reaction medium by filtration
and washed thoroughly with ethanol. Then, the catalyst was
dried in air and then was activated in a vacuum oven at
70 °C for 3 h. Finally, the recycled catalyst was reused for
another condensation reaction. Findings exhibited the same
catalytic activity as the fresh catalyst, without any loss of its
activity. In addition, to ensure reproducibility of the transfor-
mation, repeated typical experiments were carried out under
identical reaction conditions (Table 7).
The changes in the structure of the recovered MCM‐48/
H5PW10V2O40 were determined using FT‐IR methods. As
depicted in Figure 4, the structure of the recycled catalyst
does not change and a very slight decrease in the reaction
yield may be due to the covering of the surface of catalyst
by impurities.
aReaction conditions: 1,2‐benzodiamine (1a, 1.00 mmol), acetone (2a,
1.00 mmol), cyclohexyl isocyanide (3a, 1.00 mmol) and catalyst were stirred in
ethanol 96% (3.00 ml).
the formation intermediate 8 from condensation between
diamine 1 and 2 mol of ketone 2. Then, an intramolecular
imine–enamine cyclization of 9 affords seven‐membered ring
10. On the basis of the well‐established chemistry of the reac-
tion of isocyanides with imines,[19] intermediate 11 is pro-
duced by nucleophilic attack of isocyanide 3 to iminium 10
followed by nucleophilic attack of an azide molecule on the
nitrilium moiety and production of compound 12. Finally,
the [2 + 3] intermolecular cycloaddition reaction between
A possible mechanism for the formation of products 6a–j
is shown in Figure 5. It is conceivable that the initial event is

6 of 7
VESSALLY ET AL.
4
| EXPERIMENTAL
4.1 | Preparation of Supported MCM‐48/
H5PW10V2O40 Catalyst
MCM‐48 and H5PW10V2O40⋅30H2O were synthesized
according to a previously reported procedure.[26] MCM‐48‐
supported H5PW10V2O40⋅30H2O was prepared by
mixing dried MCM‐48 (2.00 g) with a solution of
H5PW10V2O40⋅30H2O (0.50 g) in the minimum amount of
deionized water. The resulting mixture was stirred continu-
ously with a magnetic stirrer for 15 h. After removal of water,
the solid powder was first dried at 100 °C for 4–5 h, and then
dried at 140 °C for 3 h.
FIGURE 4 FT‐IR spectra of MCM‐48/H5PW10V2O40 before and after
reaction
4.2 | General Procedure for Preparation of Products
4a–m
A solution of 1,2‐benzenediamine (1.00 mmol), carbonyl
compound (1.00 mmol) and isocyanide (1.00 mmol) was
stirred for 40–60 min in the presence of MCM‐48/
H5PW10V2O40 (0.04 g) in 3.00 ml of ethanol 96% at room
temperature. After completion of the reaction, as indicated
by TLC (ethyl acetate–n‐hexane, 3:1), the precipitate was fil-
tered off and the product was dissolved in acetone. The cata-
lyst was removed by filtration and the filtrate solution was
crystallized to afford pure crystalline products 4a–m.
4.3 | General Procedure for Preparation of Products
6a–j
A solution of 1,2‐benzenediamine (1.00 mmol) and carbonyl
compound (2.20 mmol) was stirred for 30 min in the presence
of MCM‐48/H5PW10V2O40 (0.04 g) in 3.00 ml of methanol
at room temperature. After completion of the reaction, as
indicated by TLC (ethyl acetate–n‐hexane, 2:1), isocyanide
(1.00 mmol) and trimethylsilyl azide (1.30 mmol) were added
to the reaction mixture and stirred at room temperature. After
completion of the reaction, as indicated by TLC (ethyl ace-
tate–n‐hexane, 3:1), the precipitate was filtered off and the
product was dissolved in acetone. The catalyst was removed
by filtration. Then, the solution crystallized to afford products
6a–j.
FIGURE 5 Possible mechanism for the formation of products 6a–j
the C═N and N3 group of the intermediate 12 leads to 6a–j
(Figure 5).
3
| CONCLUSIONS
Mesoporous silica‐supported HPAs have attracted much
attention in heterogeneous catalysis. HPA anchored to
MCM‐48 proved to be an excellent solid acid catalyst for
the synthesis of 3,4‐dihydroquinoxalin‐2‐amine, diazepine‐
tetrazole and benzodiazepine‐2‐carboxamide derivatives
upon mixing readily available substrates in short reaction
times at room temperature. Recyclability of the catalyst with
no loss in its activity, mild reaction conditions, ease of prod-
uct isolation, use of nontoxic substrates and excellent yields
are important features of this new protocol to prepare 3,4‐
dihydroquinoxalin‐2‐amine, diazepine‐tetrazole and benzodi-
azepine‐2‐carboxamide derivatives.
4.4 | General Procedure for Preparation of Products
7a–g
A solution of 1,2‐benzenediamine (1.00 mmol) and carbonyl
compound (2.20 mmol) was stirred for 30 min in the presence
of MCM‐48/H5PW10V2O40 (0.04 g) in 3.00 ml of methanol
at room temperature. After completion of the reaction, as
indicated by TLC (ethyl acetate–n‐hexane, 2:1), isocyanide
(1.00 mmol) and water (1 ml) were added to the reaction mix-
ture and stirred at room temperature. After completion of the
reaction, as indicated by TLC (ethyl acetate–n‐hexane, 3:1),
the precipitate was filtered off and the product was dissolved

VESSALLY ET AL.
7 of 7
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solution crystallized to afford products 7a–g.
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