Efficient synthesis of α-aminonitriles over homopiperazine sulfamic acid functionalized mesoporous silica nanoparticles (MSNs-HPZ-SO3H), as a reusable acid catalyst

Article abstract of DOI:10.1007/s13738-019-01654-x

Abstract: Good to excellent yields of α-aminonitriles are achieved through three-component Strecker reaction of aldehydes or ketones with amines and trimethylsilyl cyanides over homopiperazine sulfamic acid functionalized mesoporous silica nanoparticles (MSNs-HPZ-SO₃H). The advantages of this protocol include: simplicity, short reaction time, high yields, ease of product isolation and reusability of the catalyst. Graphical abstract: MSNs-HPZ-SO₃H is prepared as an acid catalyst and successfully used for three-component Strecker reaction of aldehydes or ketones with amines and trimethylsilyl cyanides (TMSCN) under solvent-free conditions, a straightforward strategy for the synthesis of α-aminonitriles.[Figure not available: see fulltext.].

Full text of DOI:10.1007/s13738-019-01654-x

Journal of the Iranian Chemical Society
https://doi.org/10.1007/s13738-019-01654-x
ORIGINAL PAPER
Efcient synthesis of α‑aminonitriles over homopiperazine sulfamic
acid functionalized mesoporous silica nanoparticles (MSNs‑HPZ‑SO3H),
as a reusable acid catalyst
Zahra Nasresfahani1 · Mohamad Z. Kassaee1,2 · Esmaiel Eidi1
Received: 30 September 2018 / Accepted: 18 March 2019
© Iranian Chemical Society 2019
Abstract
Good to excellent yields of α-aminonitriles are achieved through three-component Strecker reaction of aldehydes or ketones
with amines and trimethylsilyl cyanides over homopiperazine sulfamic acid functionalized mesoporous silica nanoparticles
(MSNs-HPZ-SO3H). The advantages of this protocol include: simplicity, short reaction time, high yields, ease of product
isolation and reusability of the catalyst.
Graphical abstract
MSNs-HPZ-SO3H is prepared as an acid catalyst and successfully used for three-component Strecker reaction of aldehydes
or ketones with amines and trimethylsilyl cyanides (TMSCN) under solvent-free conditions, a straightforward strategy for
the synthesis of α-aminonitriles.
Mohamad Z. Kassaee: Visiting Scholar (sabbatical).
Electronic supplementary material The online version of this
article (https://doi.org/10.1007/s13738-019-01654-x) contains
supplementary material, which is available to authorized users.
Extended author information available on the last page of the article
Vol.:(0123456789)
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Journal of the Iranian Chemical Society
Keywords α-Aminonitriles · Homopiperazine · Mesoporous silica · Nanocatalyst · One-pot synthesis
[31], [VO(TPPA)][C(CN)3]4 [32] and montmorillonite
KSF clay [33].
Introduction
During the last few years, acid catalysts have played
an important role in organic transformations. Despite the
high activity and selectivity, the use of homogeneous acidic
catalysts has been somewhat limited because of drawbacks
which have led to economical and environmental problems.
Therefore, heterogeneous acidic catalysts may overcome
these problems. The immobilization of homogeneous cata-
lysts on a solid support has advantages such as simple sepa-
ration, minimization of waste and less contamination.
Mesoporous material properties include high surface
area, tunable pore size distribution, high hydrothermal and
mechanical stability which make them a potential candidate
as a catalyst support in the feld of heterogeneous catalysis
[34–36]. Recently, we have prepared MSNs-HPZ-SO3H and
used it as a catalyst for synthesis of 1-amidoalkyl-2-naph-
thols [37]. Herein, we wish to report an efcient procedure
for synthesis of α-aminonitriles via one-pot three-component
condensation of aldehydes or ketones, amines and TMSCN
in the presence of MSNs-HPZ-SO3H as an efcient solid
acid catalyst (Scheme 1).
A fundamental aspect of the green chemistry is adoption of
multi-component reactions (MCRs) with atom efciency
and signifcant diversity plus straightforward design, and
formation of multi-bonds in one pot [1]. An important
multi-component reaction is the one-pot three-component
synthesis of α-aminonitriles, which are valuable synthons
in synthesis of various nitrogen-containing heterocycles
such as imidazoles, thiadiazoles [2], 4-amino-2,3-dihy-
droisothiazole-1,1-dioxides [3] and aza spiro nucleoside
analogous of TSAO [4]. They are also regarded as possible
precursors to corrins, porphyrins, nucleic and nicotinic
acids [5] and saframycin A [6]. In fact, α-aminonitriles
have been considered as key intermediates for the syn-
thesis of natural, unnatural α-amino acids [7] and the
chiral building blocks in the pharmaceutical industry [8].
The Strecker reaction is one of the known methods for
preparation of α-aminonitriles [9]. This classical proce-
dure involves a direct multi-component reaction using an
aldehyde or ketone, an amine or its equivalent and a cya-
nide reagent. Among cyanide sources for the synthesis of
α-aminonitriles, trimethylsilyl cyanide (TMSCN) [10] is a
safer reagent. Due to the importance of the Strecker reac-
tion products (α-aminonitriles), numerous modifcations
and improvements have been done to perform this reaction
with various protocols which often require a Bronsted or
Lewis acid catalytic system. Thus, various homogeneous
catalysts have been developed in recent years including:
vanadyl trifate [11], Sc(OTf)3 [12], NiCl2 [13], InI3 [14],
RhI3 [15] and GdCl3.6H2O [16]. On the other hand, to
overcome the problems associated with homogeneous cat-
alysts, several heterogeneous catalysts have been reported
including: silica-based scandium(III) [17], SO42−/ZrO2
[18], [bmim]BF4 [19], sulfamic acid functionalized mag-
netic Fe3O4 nanoparticles [20], MNPs functionalized
with urea or urethane moieties [21], SBA-15-supported
sulfonic acid [22], NHC–amidate Pd(II) complex [23],
mesoporous aluminosilicate [24], guanidine hydrochloride
[25], K2PdCl4 [26], chitosan [27], β-cyclodextrine [28],
Sn–montmorillonite [29], Co/SBA-15 [30], PEG-OSO3H
Results and discussion
The MSNs-HPZ-SO3H is prepared using the following pro-
cedure (Scheme 2) [37]. In the frst step, mesoporous silica
nanoparticles (MSNs) are prepared via the sol–gel method
[38]. In the second step, 3-chloropropyl-functionalized
(MSNs-Cl) is obtained from reaction of MSNs with 3-chlo-
ropropyltrimethoxysilane (CPTMS). Reaction of MSNs-Cl
with homopiperazine gives MSNs-HPZ. Finally, reaction of
the latter with chlorosulfonic acid (ClSO3H) gives the nano-
catalyst (MSNs-HPZ-SO3H).
The synthesized catalyst is characterized by Fourier
transform infrared spectroscopy (FT-IR), X-ray difraction
(XRD), scanning electron microscopy (SEM), thermogravi-
metric/diferential thermal analyses (TGA-DTA) and nitro-
gen adsorption–desorption analysis.
The XRD pattern of pure MSNs is assigned to (100),
(110) and (200) planes with values of d-spacing at 40.01,
Scheme 1 Solvent-free Strecker reaction of carbonyl compounds (1), amines (2) and TMSCN (3) over MSNs-HPZ-SO3H, at room temperature
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Journal of the Iranian Chemical Society
Scheme 2 Preparation of the nanocatalyst (MSNs-HPZ-SO3H)
26.97 and 22.46 Å, respectively. For MSNs-HPZ and
MSNs-HPZ-SO3H, only a refection associated with (100)
plan of the ordered 2D hexagonal mesophase is observed.
The intensity of this refection after functionalizing with
organic groups is lower than that of the original MSNs
(Fig S1, Supporting Information).
these results, the well grafting of organic functional groups
on the MSNs is verifed.
The textural properties of MSNs and MSNs-HPZ are
probed (Fig S5, Supporting Information). The isotherms of
these two materials exhibit type IV curve, showing the char-
acteristic of uniform mesoporous materials. The calculated
Brunauer–Emmett–Teller (BET) surface area, pore volume
and pore diameter of MSNs are 783 m2/g, 0.767 cm3/g and
3.9 nm, respectively. After being grafted, the correspond-
ing parameters for MSNs-HPZ are decreased to 313 m2/g,
0.175 cm3/g and 2.2 nm, respectively. These observations
suggest that the organic groups are successfully anchored
on the primary mesopores.
The FT-IR spectra of MSNs, MSNs-Cl, MSNs-HPZ
and MSNs-HPZ-SO3H are compared (Fig S2, Supporting
Information). In the spectrum of starting MSNs, charac-
teristic absorption bands at 1086 cm−1 and 801 cm−1 are
assigned to asymmetric and symmetric stretching vibra-
tions of Si–O–Si. Also, stretching of Si–OH at 962 cm−1
and bending of Si–O–Si at 461 cm−1 are observed. The
broadband of 3450 cm−1 is related to the stretching vibra-
tions of silanol groups, and the peak at 1635 cm−1 is
assigned to the H–O–H bending vibration of the absorbed
water molecules on surface. Stretching vibrations of
anchored alkyl groups appear as weak C–H symmet-
ric and asymmetric absorptions at 2930 and 2960 cm−1,
respectively. In addition, N–SO2, O–SO2 and S=O bonds
stretching vibrations cannot be resolved due to the over-
lap with the Si–O–Si stretching at 960–1350 cm−1. Broad
peak in the range of 2500–3600 cm−1 indicates the acidic
OH vibration signal of SO3H group. Also, a new band at
approximately 580 cm−1 is due to the presence of a SO2
group in MSNs-HPZ-SO3H.
Catalytic ability of MSNs-HPZ-SO3H is tested for the
exclusive synthesis of α-aminonitrile derivatives. To explore
the optimized conditions, the reaction of benzaldehyde with
aniline and TMSCN is chosen as a model reaction, and the
efects of various solvents and catalyst amounts are investi-
gated. The initial screening of the reaction in the presence
of diferent amounts of catalyst in various times shows that
the best result is obtained in the presence of 10 mg catalyst
when reaction reaches 92% yield in 10 min under solvent-
free conditions. In the absence of the catalyst, reactivity is
poor and provides low yield for the model reaction (Table 1).
To compare the efects of solvents with that of solvent-free
conditions, we evaluate the reaction in the absence and pres-
ence of solvents such as EtOH, CH3CN, CH2Cl2 and H2O.
SEM image provides more accurate information about
the morphology and particle size of the MSNs-HPZ-SO3H
nanocatalyst (Fig S3, Supporting Information). This micro-
graph indicates that the particle morphology is relatively
semi-spherical. Also, the obtained histogram of the SEM
image confrms that the size distribution is narrow with a
23 nm average value and a 17 nm standard deviation.
Thermogravimetric/diferential thermal analyses (TGA/
DTA) of MSNs-HPZ-SO3H display the thermal stability
of the synthesized material (Fig S4, Supporting Informa-
tion). The initial weight loss from 25 to 120 °C is due to
the removal of physically adsorbed water and solvent on
the external surface of the nanoparticles. The weight loss
between temperature ranges of 200–670 °C in the TGA
curve may be associated with oxidative decomposition of
organic and inorganic functional groups. On the basis of
Table 1 Efect of the catalyst amount in the reaction of benzaldehyde,
aniline and TMSCN at room temperature
Entry
Catalyst (mg)
Time (min)
Yield (%)a
1
2
3
4
5
6
0
5
5
10
15
20
300
20
30
10
10
10
Trace
60
75
92
92
93
Bold row indicate the best result obtain by using 10 mg catalyst
aIsolated yields
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Journal of the Iranian Chemical Society
Table 2 Solvent efects and temperature on reaction of benzaldehyde,
electron-withdrawing groups in the ortho, meta and para
positions are used to react with aniline. Yields of the prod-
ucts are good to excellent (Table 3, entries 1–9). Also, acid-
sensitive aldehydes such as cinnamaldehyde work well
without the formation of any side products and give the
α-aminonitrile derivatives in 90% yield (Table 3, entry 4).
Diferent types of amines such as 4-bromoaniline, 4-chloro-
aniline, p-toluidine, benzyl amine and secondary amine such
as morpholine are used in one-pot three-component con-
densation reactions with very good yields (Table 3, entries
10–16). Next, we direct our attention to use some ketones as
carbonyl components. Pleasantly, it is found that the reac-
tions of acetophenone, acetone and cyclohexanone with ani-
line and TMSCN are very efcient and the corresponding
α-aminonitriles are obtained rapidly in quantitative yields
(Table 3, entries 17–19). On the other hand, benzophenone
is found to be unreactive under same conditions, and no
product formation is detected (Table 3, entry 20).
aniline and TMSCN
Entry
Solventa
Tempera-
ture (°C)
Time (min)
Yield (%)b
1
2
3
4
5
6
7
EtOH
CH3CN
CH2Cl2
H2O
Solvent-free
Solvent-free
Solvent-free
RT
RT
RT
RT
RT
50
120
120
120
120
10
65
50
45
70
92
91
93
10
80
10
Bold row indicate the best result obtain under solvent-free conditions
a2 ml solvent is used
bIsolated yields
Solvent-free conditions are found more suitable, on the basis
of reaction time and yield at room temperature (Table 2).
Optimal reaction conditions are established to show
the scope and generality of this process. So, three-com-
ponent condensation of other substituted aldehydes and
amines, with TMSCN over MSNs-HPZ-SO3H, is carried
out under the same reaction conditions. The results show a
highly efective performance of the catalyst in the prepara-
tion of α-aminonitriles (Table 3). Various benzaldehydes
with substituents carrying either electron-donating or
A plausible mechanism is described for the synthesis
of α-aminonitriles in the presence of MSNs-HPZ-SO3H
(Scheme 3). According to this mechanism, the catalyst active
carbonyl group of aldehyde or ketone 1 through hydrogen
bonding for nucleophilic attack of amine 2. After exchange
of hydrogen, intermediate (III) obtains. The removal of
water from intermediate (III) produces the corresponding
imine (IV), and the activated imine carbon is attacked by
cyanide 3 to give product 4.
Table 3 Synthesis of α-aminonitriles in the presence of MSNs-HPZ-SO3H under solvent-free conditions
Entry
Aldehyde/ketone
Amine
Time (min)
Yield (%)a
TON
TOF (min−1
)
M.p (°C)
M.p (°C) [Ref.]
1
2
3
4
5
6
7
8
C6H5CHO
C6H5NH2
C6H5NH2
C6H5NH2
C6H5NH2
C6H5NH2
C6H5NH2
C6H5NH2
C6H5NH2
10
10
15
10
20
20
25
20
15
30
15
10
15
10
20
25
30
15
10
60
92
93
95
90
92
91
89
88
90
80
90
92
93
90
85
85
46.0
46.5
47.5
45.0
46.0
45.5
44.5
44.0
45.0
40
45.0
46
46.5
45
42.5
42.5
42.5
41
42
–
4.60
4.65
3.16
4.50
2.30
2.27
1.78
2.20
3.0
1.33
3.0
4.6
3.1
4.5
78–80
112–113
77–80
117–119
95–96
109–111
Oil
122–124
68–70
112–114
107–108
105–106
107–108
88–91
Oil
80–82 [39]
109–112 [33]
76–78 [33]
117–119 [39]
94–96 [40]
–
4-ClC6H4CHO
4-MeC6H4CHO
C6H4CH=CHCHO
4-OMeC6H4CHO
2-OH-5-BrC6H3CHO
3-OHC6H4CHO
4-OHC6H4CHO
2-ClC6H4CHO
2-ClC6H4CHO
C6H5CHO
Oil [39]
121–122 [40]
67–70 [27]
112–116 [39]
106–108 [40]
107–109 [27]
104–106 [27]
87–90 [39]
Oil [33]
68–69 [41]
150–151 [39]
[42]
69–71 [39]
–
9
C6H5NH2
10
11
12
13
14
15
16
17
18
19
20
4-BrC6H4NH2
4-ClC6H4NH2
4-MeC6H4NH2
4-MeC6H4NH2
4-MeC6H4NH2
C6H5CH2NH2
Morpholine
C6H5NH2
C6H5CHO
4-MeC6H4CHO
4-ClC6H4CHO
C6H5CHO
C6H5CHO
C6H5COCH3
CH3COCH3
Cyclohexanone
Benzophenone
2.12
1.7
1.41
2.73
4.2
65–66
148–150
89–91
68–70
–
85
82
84
C6H5NH2
C6H5NH2
C6H5NH2
No reaction
–
aIsolated yields
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Journal of the Iranian Chemical Society
Scheme 3 Plausible mechanism for the synthesis of α-aminonitriles using MSNs-HPZ-SO3H
morphology and size of the recovered catalyst in comparison
100
90
80
70
60
50
40
30
20
10
0
with fresh catalyst (Fig S6, Supporting Information).
To further evaluate the overall utility of the current meth-
odology, the catalytic activity of MSNs-HPZ-SO3H in syn-
thesis of α-aminonitriles is compared with several previ-
ously reported methods (Table 4). It is clear that the present
method reduces the reaction time and provides a higher yield
of the product.
1
2
3
4
5
Experimental
Number of cycles
Materials and methods
Fig. 1 Reusability of MSNs-HPZ-SO3H in the model reaction
Chemical reagents in high purity are purchased from Merck
and Aldrich. Melting points are determined in open capil-
laries using an Electrothermal 9100 apparatus and uncor-
rected. Fourier transform infrared (FT-IR) spectra are
recorded using KBr pellets in the range 400–4000 cm−1 on
a Nicolet IR-100 infrared spectrometer. The NMR spectra
are recorded using a Brucker DRX 500-Avance spectrometer
operating at 500 MHz for 1HNMR in CDCl3 with TMS as
an internal standard. X-ray difraction (XRD) is performed
using Philips XPert (1710 difractometer). The latter appears
The possibility of recycling the catalyst MSNs-HPZ-
SO3H is also evaluated in the model reaction. Upon com-
pletion, hot ethanol is added to the reaction mixture, and the
catalyst is fltered and washed with ethanol several times,
dried and reused for the subsequent run. This procedure is
repeated fve times. The results indicate that catalyst activ-
ity changes only slightly after fve catalytic cycles (Fig. 1).
Also, an SEM image of the recovered catalyst after fve
runs is also taken, and there is no obvious change in the
Table 4 Comparison of
Entry Catalyst
Conditions
Time
24 h
90 min 93
96
10 min 91
30 min 95
6 h
Yield (%) [Ref.]
catalytic activity of MSNs-
HPZ-SO3H with other known
catalysts in running the model
reaction
1
2
3
4
5
6
7
8
NHC–amidate Pd(II) complex
SO42−/ZrO2
SiO2
PEG-OSO3H
Fe3O4@ZrO2/SO4
CH2Cl2, rt
THF, rt
Ball milling, 700 rpm 3 h
Water, rt
EtOH, rt
79
[23]
[18]
[43]
[31]
2−
[39]
[42]
Nafon-H
CH2Cl2, 60 °C
80
Fe3O4@SiO2@Me&Et-PhSO3H Solvent-free, rt
MSNs-HPZ-SO3H Solvent-free, rt
13 min 95
10 min 92
[44]
Present work
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Journal of the Iranian Chemical Society
with Co Kα (α = 1.79285 A) one voltage of 40 kV. Ther-
mogravimetric/diferential thermal analyses (TGA/DTA)
are done on a thermal analyzer with a heating rate of 10 °C
min−1 over a temperature range of 25–800 °C. The particle
morphology is examined by scanning electron microscopy
using SEM (HITACHI S-4160), on gold-coated samples.
of phenolphthalein indicator solution is added. The acidic
solution is titrated to neutrality using 0.1 M NaOH solution
to determine the loading of acid sites on the MSNs-HPZ-
SO3H catalyst. The results reveal that samples of MSNs-
HPZ-SO3H possess 2 mmol H+ g−1. This process is repeated
for recovered catalyst; after reaction, the results show no
substantial change in amount of acid loading of catalyst.
Hence, no leaching of the acid occurred during the course
of the reaction.
General procedure for preparation of the MSNs
The MSNs is synthesized according to the sol–gel method
[38]. Specifcally, 0.5 g of the CTAB and 0.14 g of NaOH
are mixed in 240 mL deionized water. The solution is stirred
vigorously at 80 °C for 2 h, then 2.5 mL of tetraethyl ortho-
silicate (TEOS) is added, and the reaction is continued for
another 2 h. The as-prepared product (MSNs-CTAB) is
washed three times with ethanol and re-dispersed in 200 mL
of ethanol containing 2 g of NH4NO3, at 80 °C. The remain-
ing mixture is refuxed for 6 h. Then, the resulting precipitate
is centrifuged and washed with ethanol repeatedly to give a
white powder which is dried under vacuum.
General procedure for preparation of α‑aminonitrile
The catalyst (10 mg) is added to a mixture of aldehyde (or
ketone) (1 mmol), amine (1 mmol) and TMSCN (1.2 mmol).
The mixture is stirred at ambient temperature for the appro-
priate time. After completion of the reaction (monitored by
TLC), the reaction mixture is diluted with hot ethanol and
stirred for 5 min. The catalyst is removed by centrifugation
or fltration. The solution is evaporated to aford the product
which is recrystallized from ethanol.
General procedure for preparation of the MSNs‑Cl
Spectral data of the selected products
The MSNs-Cl is prepared by refuxing 0.5 g of MSNs with
0.5 g of 3-chloropropyltrimethoxysilane (CPTMS) in tolu-
ene, under a nitrogen atmosphere, for 24 h. The resulting
solid is fltered, washed with toluene and then dried under
vacuum.
2‑(p‑tolyl)‑2‑(p‑tolylamino)acetonitrile (Table 3, Entry
13) 1H NMR (500 MHz, CDCl3): δH (ppm)=2.30 (3H, s,
CH3), 2.40 (3H, s, CH3), 5.37 (1H, s, CH), 6.72 (2H, d,
J=5.0 Hz, H–Ar), 7.09 (2H, d, J=5.0 Hz, H–Ar), 7.27(2H,
d, J = 5.0 Hz, H–Ar), 7.49 (2H, d, J= 5.0 Hz, H–Ar); 13C
NMR (125 MHz, CDCl3); δC (ppm) = 20.6, 50.5, 114.7,
118.4, 126.7, 127.2, 127.7, 130.0, 131.0, 139.5, 142.1.
General procedure for preparation of the MSNs‑HPZ
A solution of 1 g (10 mmol) of homopiperazine, in dry tolu-
ene and propyl amine, is added dropwise to a suspension of
0.5 g of the MSNs-Cl in toluene. This mixture is refuxed for
24 h under a nitrogen atmosphere. Then, the solid is fltered
and washed in Soxhlet. After this treatment, the MSNs-HPZ
powder is dried under vacuum.
2‑Methyl‑2‑(phenylamino)propanenitrile (Table 3, Entry
1
18) H NMR (500 MHz, CDCl3): δH (ppm)=1.72 (6H, s,
2CH3), 6.95–6.98 (3H, m, H–Ar), 7.27–7.30 (2H, m, H–Ar);
13C NMR (125 MHz, CDCl3); δC (ppm)=28.2, 49.2, 117.7,
121.0, 122.0, 129.3, 143.5.
General procedure for preparation
of the MSNs‑HPZ‑SO3H
Conclusions
To a solution of MSNs-HPZ (0.5 g) in n-hexane (2 mL),
Et3N (0.1 mL) is added. After 5 min, chlorosulfonic acid
(0.1 mL) is added to the mixture and stirred for 3 h. Finally,
the residue is fltered and washed with toluene, ethanol and
water and dried under vacuum.
In this work, acid functionalized mesoporous silica nanopar-
ticles (MSNs-HPZ-SO3H) is synthesized and fully character-
ized; because of good surface area and acidity, this catalyst
can be utilized efciently for synthesis of α-aminonitriles
via three-component coupling reactions of aldehydes (or
ketones), amines and trimethylsilyl cyanide. The corre-
sponding products are obtained in high yields. This protocol
is a useful and attractive process for Strecker reaction due
to several advantages, such as the simple experiment, short
reaction times, excellent yields of products and recyclable
catalyst.
Acidity of MSNs‑HPZ‑SO3H
Titrations are done to determine the acid loading of the cata-
lysts. At frst, 100 mg of MSNs-HPZ-SO3H is dispersed in
20 ml H2O by sonicating for 40 min at room temperature
after which the pH of solution becomes acidic; two drops
1 3

Journal of the Iranian Chemical Society
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Compliance with ethical standards
Conflict of interest The authors declare that there is no confict of in-
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Afliations
Zahra Nasresfahani1 · Mohamad Z. Kassaee1,2 · Esmaiel Eidi1
2
* Mohamad Z. Kassaee
Chemical and Biomolecular Engineering, Vanderbilt
mohamad.z.kassaee@vanderbilt.edu;
kassaeem@modares.ac.ir
University, Nashville, TN 37240, USA
1
Department of Chemistry, Tarbiat Modares University,
P.O.Box 14155-175, Tehran, Iran
1 3