Design of BNPs-TAPC Palladium Complex as a Reusable Heterogeneous Nanocatalyst for the O-Arylation of Phenols and N-Arylation of Amines

Article abstract of DOI:10.1007/s10562-018-2627-6

The thermally stable new heterogenous nanocatalyst BNPs@SiO₂(CH₂)₃-TAPC-O-CH₂CH₂NH₂-Pd(0) was synthesized, characterized and successfully applied in carbon-heteroatom (C–O and C–N) coupling reactions of aryl halides with phenols and amines. The formation of resultant nanocatalyst was approved by FT-IR, XRD, TGA, XPS and EDX techniques. The morphology of BNPs@SiO₂(CH₂)₃-TAPC-O-CH₂CH₂NH₂-Pd(0) was characterized using scanning and transmission electron microscopes. The leaching of palladium from the surface of the catalyst was studid by ICP-OES technique. Noteworthy, the highly active BNPs@SiO₂(CH₂)₃-TAPC-O-CH₂CH₂NH₂-Pd(0) can be easily recycled and reused for six times with negligible loss in its activity. Some remarkable advantages of this method are the shorter reaction times, milder conditions, no needs for an inert atmosphere, high yields and easy separation. Graphical Abstract: [Figure not available: see fulltext.].

Full text of DOI:10.1007/s10562-018-2627-6

Catalysis Letters
https://doi.org/10.1007/s10562-018-2627-6
Design of BNPs-TAPC Palladium Complex as a Reusable Heterogeneous
Nanocatalyst for the O-Arylation of Phenols and N-Arylation of Amines
Kiumars Bahrami1,2 · Minoo Khodamorady1
Received: 24 September 2018 / Accepted: 26 November 2018
© Springer Science+Business Media, LLC, part of Springer Nature 2018
Abstract
The thermally stable new heterogenous nanocatalyst BNPs@SiO2(CH2)3-TAPC-O-CH2CH2NH2-Pd(0) was synthesized,
characterized and successfully applied in carbon-heteroatom (C–O and C–N) coupling reactions of aryl halides with phenols
and amines. The formation of resultant nanocatalyst was approved by FT-IR, XRD, TGA, XPS and EDX techniques. The
morphology of BNPs@SiO2(CH2)3-TAPC-O-CH2CH2NH2-Pd(0) was characterized using scanning and transmission electron
microscopes. The leaching of palladium from the surface of the catalyst was studid by ICP-OES technique. Noteworthy, the
highly active BNPs@SiO2(CH2)3-TAPC-O-CH2CH2NH2-Pd(0) can be easily recycled and reused for six times with negligible
loss in its activity. Some remarkable advantages of this method are the shorter reaction times, milder conditions, no needs
for an inert atmosphere, high yields and easy separation.
Graphical Abstract
Keywords Boehmite nanoparticles · Cross coupling reactions · Buchwald-Hartwig reactions · Heterogeneous nanocatalyst
1 Introduction
Electronic supplementary material The online version of this
article (https://doi.org/10.1007/s10562-018-2627-6) contains
Palladium-catalyzed cross coupling reactions have been
supplementary material, which is available to authorized users.
found a special place in organic reactions [1, 2]. Within
the previous couple of decades, various economical
Extended author information available on the last page of the article
Vol.:(0123456789)
1 3

K. Bahrami, M. Khodamorady
heterogeneous and homogenous palladium catalysts have
been used for cross-coupling reactions, particularly, C–N
and C–O cross coupling reactions [3].
Boehmite is an orthorhombic structure of aluminum
oxide hydroxide (γ-AlOOH), that is employed as precursor
for preparation of ceramic catalysts [25], membranes [26],
coatings [27], adsorbents [28], orthopedic or a dental mate-
rial [29]. It is notable that, boehmite nanoparticles (BNPs)
was prepared in green solvent (H2O) at room temperature
while not the necessity for inert atmosphere. Boehmite have
some attractive features such as: thermal, chemical and
mechanical stability, non-toxicity, not air or wetness sen-
sitive, large specific surface area and easily available and
eco-friendly [30].
In the coupling of nucleophilic aromatic substitution
with aryl halides in carbon–nitrogen and carbon–oxygen
coupling methods, palladium [4, 5], nickel [6], and copper
[7], catalysts have been used. Palladium has some disad-
vantages like high value and toxicity, which is hazardous to
the environment. To overcome these drawbacks, nowadays,
development of extremely active and reusable heterogeneous
palladium nanoparticles is high value [8, 9].
There are many methods in which homogeneous catalysts
such as CuO and CuI [10] are used and the limitations of
these methods are excess quantity of reactive substances and
therefore the problem of separating these catalysts from the
reaction environment [11, 12].
As such, one in all potential areas in which BNPs can be
utilized as an efficient solid support is in cross coupling reac-
tions such as C–N and C–O coupling have attracted much
attention due to their remarkable performance and capabil-
ity in the synthesis of pharmaceutical and natural products
[31–33]. Diaryl ethers have wide applications in polymer
industries and are useful ligands in metal-catalyzed organic
reactions [34]. It ought to be noted that many examples of
cross coupling reactions based on C–C [35], C–N [36], C–S
[36], and C–O [37] coupling have been reported in the lit-
erature. Historically, aryl amines and ethers were prepared
mostly by Ullmann-type coupling reactions in moderate
yields [38]. Previous ways have some disadvantages such
as use of organic solvents, High reaction temperature, long
periods of time, harsh conditions like neutral atmosphere,
using high catalyst loadings (50 mol %) and expensive bases
that chemists are trying to improve. Despite above promis-
ing advances, synthesis of cheap, efficient and recyclable
heterogeneous catalysts still has to be felt. Therefore, during
As a result, the employment of heterogeneous catalysts
has been thought-about to reduce the issues related to
homogenous catalysts and to boost the economic and envi-
ronmental aspects [13].
Numerous supports like polymers [14–16], MCM41 [4],
TiO2 NPs [17], SBA-15 [18], graphene oxide [19], Fe3O4
[20, 21], mesoporous and ionic liquids [22–24] have been
wieldy used to synthesize nanocatalyst containing palla-
dium. However, these supporters have some disadvantages
such as need high temperature for calcination, inert atmos-
phere and Lots of time and onerous conditions to synthesis.
Therefore, the development of new solid support for pal-
ladium is incredibly necessary. One of the most stable and
inexpensive solid support is boehmite.
Scheme 1 Synthesis of diaryl
ethers and aryl amines
1 3

Design of BNPs-TAPC Palladium Complex as a Reusable Heterogeneous Nanocatalyst for the…
this content, we have a tendency to introduce the boehmite
modified with 1,3,5-triazo-2,4,6-triphosphorine-2,2,4,4,6,6-
hexachloride (TAPC) containing 2-amino ethanol for palla-
dium (0)-catalyzed C–N and C–O cross-coupling reactions
of varied aryl halides with phenols and different amines in
high to excellent yields (Scheme 1).
2 Experimental Section
2.1 Materials and Methods
All products are characterized by comparison of their spec-
tral data and physical properties with those of authentic
samples. The purity determinations of the products and the
progress of the reactions were accomplished by TLC. Melt-
ing points were determined using a Stuart Scientific SMP2
Scheme 2 Synthesis steps of
the catalyst
1 3

K. Bahrami, M. Khodamorady
apparatus. The FT-IR spectra were recorded on pressed
KBr pellets using a Perkin-Elmer 683 spectrometer at room
temperature in the range between 4000 and 400 cm−1. The
NMR spectra were provided by Brucker Avance 300 and
400 MHz instruments in CDCl3 and DMSO in the presence
of tetramethylsilane as the internal standard and the cou-
pling constants (J values) are given in Hz. Mass spectra were
recorded with an Agilent Technologies 7890B instrument
at 70 eV electron impact ionization, in m/z (rel%). X-ray
powder diffraction (XRD) was performed on a PANalyti-
cal Company X’Pert Pro MPD diffractometer with Cu Ka
radiation [(λ=0.154 nm) radiation]. Transmission electron
microscopy (TEM) was performed with a EM10C (100 kV)
microscope (Zeiss, Germany). FE-SEM images were
recorded using a TESCAN, Model: MIRA3 scanning elec-
tron microscope (SEM) operating at an acceleration voltage
of 30.0 kV. Elemental compositions were determined with
an SC7620 energy-dispersive X-ray analysis (EDX) present-
ing a 133 eV resolution at 20 kV. Thermogravimetric ana-
lyis (TGA) was carried out using a STA PT-1000 Linseis
(Germany) in the temperature range of 25–800 °C at a heat-
ing rate of 10 °C min−1, under air atmosphere. Inductively
coupled plasma optical emission spectroscopy (ICP-OES)
was carried out on an Optima 7300D analyzer (PerkinElmer
America). All yields refer to isolated products after puri-
fication by thin layer chromatography/or recrystallization
by n-hexane. In addition, all of the products were known
compounds and they were characterized by 1H NMR, 13C
NMR spectroscopy and comparison of their melting points
with known compounds. The chemical composition of the
catalyst on the surface of the Boehmite was performed using
X-ray Photoelectron Spectroscopy (XPS), a Kratos Axis
Ultra-DLS spectrometer with an Al Kα as a source. The
data was analyzed by CasaXPS software.
2.2 Preparation of the Catalyst
BNPs@SiO2(CH2)3-TAPC-O-CH2CH2NH2-Pd(0) was
prepared by the route outlined in Scheme 2. A solution of
NaOH (3.25 g) in 25 mL distilled water was slowly added
to solutions of Al (NO3)3·9H2O (10 g) in 15 mL distilled
water by vigorous stirring for 30 min. The resulting white
mixture was subjected to mix in the ultrasonic bath for
3 h in 25 °C [30]. The resulted BNPs@SiO2 was filtered
and washed with distilled water and kept in the oven for
3 h at 200 °C. Then, (3 mL) (3-Chloropropyl)trimethoxysi-
lane (CPTMS) was added to BNPs@SiO2 (1.20 g) and the
mixture was dispersed in toluene (12 mL) and the resultant
solid was filtered, washed with ethanol and dried at 70 °C
to produce BNPs@SiO2(CH2)3-Cl. In the next step, the
TAPC (2 g) was added to BNPs@SiO2(CH2)3-Cl (1 g). The
mixture was sonicated for 20 min and stirred under reflux
in dichloromethane for 24 h to afford BNPs@SiO2(CH2)3-
TAPC. Then, mixture of the nanocatalyst modified with
TAPC (0.90 g) and 2-aminoethanol (2 mL) were exposed
to reflux in toluene for 24 h. After that, the resulted solid
was filtered washed with ethanol and dried at 70 °C to form
BNPs@SiO2(CH2)3-TAPC-OCH2CH2NH2. In the final
stage, BNPs@SiO2(CH2)3-TAPC-OCH2CH2NH2 (0.7 g)
was dispersed in 25 mL ethanol and then palladium chloride
0.2 g was added to the reaction mixture and reaction stirred
at room temperature for 10 h. The final product BNPs@
SiO2(CH2)3-TAPC-O-CH2CH2NH2-Pd(0) was filtered and
washed with ethanol and dried at room temperature.
2.3 General Procedure for the O‑arylation
and N‑arylation with Aryl Halides
A mixture of phenol or amine (1.0 mmol), aryl
iodide (1.5 mmol), KOH (2 mmol) and BNPs@
Fig. 1 a FT-IR spectra of the A: BNPs, B: BNPs-SiO2-TAPC-OCH2CH2NH2, C: BNPs-SiO2@(CH2)3TAPC-O-CH2CH2NH2-Pd(0), b TGA
curve of BNPs-SiO2@(CH2)3TAPC-O-CH2CH2NH2-Pd(0)
1 3

Design of BNPs-TAPC Palladium Complex as a Reusable Heterogeneous Nanocatalyst for the…
SiO2(CH2)3-TAPC-O-CH2CH2NH2-Pd(0) (0.05 g catalyst
equal 0.0725 mmol/g pd) in DMF (2 mL) was stirred at
100 °C. The reaction progress was monitored by TLC. After
the completion of the reaction, the catalyst was filtered,
washed with ethanol and dried. The reaction mixture was
extracted with ethyl acetate (3×5) and the organic layer was
dried over magnesium sulfate (MgSO4). Then pure products
were obtained from recrystallization in n-hexane.
presented in previous reports [39]. In IR spectrum strong
bonds at 480 and 720 cm−1 are related to vibrational fre-
quency of Al–O and bands at 1070, 1160 cm−1, can be
described as vibration of hydrogen bands OH…OH and
peaks at 1080 and 770 cm−1 related to Si–O–Si vibrational
frequency. It should be noted that the peaks for the con-
nection of phosphorus on boehmite with peaks related to
Al–O and Si–O overlaps in area 930–1250 cm−1. Finally,
the adsorption band in the region of 1637 cm−1 can be
attributed to the vibrational frequency of the nitrate impu-
rity [30]. It may also be seen from the TGA curve that
there are two weight losses between 150 and 700 °C.
The weight loss that occurred at 150 °C is related to the
organic solvent or water that is physically absorbed and
weight loss in the 200–600 °C range is due to the loss
of organic groups and the palladium complex attached to
BNPs. And eventually, the last weight loss which occurred
at 600–700 °C can be attributed to the transformation of
thermal crystal phase of BNPs (Fig. 1b).
3 Results and Discussion
3.1 Characterization
BNPs@SiO2(CH2)3-TAPC-O-CH2CH2NH2-Pd(0) was pre-
pared by the route outlined in Scheme 2. The structure of
nanocatalyst was confirmed by various techniques such as
FT-IR, TGA, TEM, XRD and EDX. The results obtained
from the IR spectra (Fig. 1a) are consistent with the results
To determine the crystalline structure of BNPs@SiO2,
and BNPs@SiO2(CH2)3-TAPC-O-CH2CH2NH2-Pd(0), XRD
was used over the diffraction angle (2Ɵ) of 5–80 °C (Fig. 2).
The XRD pattern of BNPs@SiO2, shows seven major peaks
at 14.58° (020), 29.33°, 30.11° (120), 40.46° (031), 47.93°
(131), 50.76° (051), 55.85° (151) and 65° (231), which
clearly confirms the orthorhombic structure of the boe-
hmite [40]. After adding tetraethyl orthosilicate (TEOS),
some couriers may be eliminated or peak intensity may be
reduced as seen in the spectrum. In the literature, after add-
ing TEOS the courier in the 14.58° nearly removed and other
couriers dropped or moved [41, 42] Also, in the XRD pattern
of BNPs@SiO2(CH2)3-TAPC-O-CH2CH2NH2-Pd(0), peaks
at 32.18° (136) and 56.48° (279) indicate the presence of
phosphorus on boehmite (a=18.8 Å, space group symmetry
I-, JCPDS PDF No. 025-0608) [40] and peaks at 2θ=28.5°
(111), 40.4° (200), 46.8° (220) and 68° (331) confirm that
Fig. 2 XRD patterns of a Boehmite b BNPs@SiO2, c BNPs@
SiO2(CH2)3-TAPC-O-(CH2)2NH2-Pd(0)
Fig. 3 a SEM image of the catalyst, b, c TEM images of BNPs@SiO2-(CH2)3TAPC-O-CH2CH2NH2-Pd(0)
1 3

K. Bahrami, M. Khodamorady
SiKα
20000
15000
10000
5000
0
As can be seen from the SEM image, the surface of BNPs@
SiO2(CH2)3-TAPC-O-CH2CH2NH2-Pd(0) is uniformly
coated, which confirms that the surface has been well-func-
tionalized and therefore the morphology of the particles is
spherical and the particle size is between 30 and 43 nm.
SEM images of catalyst are showed in Fig. 3a.
AlK
α
O Kα
N Kα
P Kα
The TEM image depicts that the organic components
attachment to BNPs has no particular effect on the mor-
phology and the shape of the particles is uniformly spherical
(Fig. 3b, c). Also, with appreciate to TEM, it could be visible
that palladium is deposited on BNPs and the average size of
palladium particles is between 25 and 40 nm.
α
PdL
α
C K
0
PdL
β
P K
β
keV
5
10
Another technique used to confirm the structure and study
of the existence of elements in BNPs was EDX and, as can
be seen in Fig. 4, the presence of palladium on the surface
of the catalyst has been confirmed.
Fig. 4 EDX of BNPs@SiO2-(CH2)3TAPC-O-CH2CH2NH2-Pd(0)
The XPS spectrum provides information about the ele-
ments and chemical environment surrounding them and their
oxidation processes. The presence of Al in boehmite is con-
firmed from the Al 2p signal with binding energy of 71.5 eV
(Fig. 5a, b). Figure 5c, d shows the survey XPS spectrum
Pd element exists in the form of Pd(0), not Pd(II) (space
group: Fm−3m, JCPDS Card No. 00-001-1201) [43].
SEM was accustomed verify the morphology and particle
size of BNPs@SiO2(CH2)3-TAPC-O-CH2CH2NH2-Pd(0).
Fig. 5 a XPS spectrum of BNPs, b expand of XPS spectrum of BNPs, c XPs of the the catalyst, d expand of XPS spectrum of the catalyst
1 3

Design of BNPs-TAPC Palladium Complex as a Reusable Heterogeneous Nanocatalyst for the…
of BNPs@SiO2(CH2)3-TAPC-O-CH2CH2NH2-Pd(0), which
depicts the existence of Pd, in addition to the elements of
boehmite support (Al, N, C, O, Cl). The high-resolution
palladium (Pd) 3d spectrum reveals the presence of mainly
metallic Pd (Pd0 with Pd 3d5/2 at 335.04 eV and Pd 3d3/2 at
340.31 eV) [44].
obtained (Table 1, entry 10). We conjointly examined the
impact of increasing the amount of catalyst, and that we
found a greater amount of BNPs@SiO2(CH2)3-TAPC-O-
CH2CH2NH2-Pd(0) does not have much effect on yield and
solely reduces the reaction time (Table 1, entries 11, 12).
However, by reducing the amount of the catalyst, the yield of
the product is reduced and also the reaction time is increased
(Table 1, entry 13). Within the next step, the effect of tem-
perature was investigated and by decreasing the temperature
to 70 °C and room temperature, the reaction time increased
and also the yield of product decreased (Table 1, entries
14, 15). Increasing the temperature to 120 °C did not have
an effect on the yield and reaction time (Table 1, entry 16).
This heterogeneous nanocatalyst is stable and shows the
smallest amount of palladium leaching, in line with the simi-
lar technique as within the previous report [9].
3.2 Catalytic Study
In order to study the catalytic effect of nanocatalyst, the
reaction between phenol and amines (1 mmol) with aryl
iodide (1.5 mmol) was selected as a model reaction. Then,
we have a tendency to turned our attention toward other
parameters that have an effect on the reaction time and yield,
such as solvent, base, the amount of catalyst and tempera-
ture. Next, varied solvents such as EtOH, CH3CN, Toluene,
H2O, CH2Cl2, EtOH: H2O (1:1) and DMF were studied in
the presence of 2 mmol KOH at 100 °C (Table 1, entries
1–7). As are often seen, the best results were obtained in
DMF (Table 1, entry 7). As part of our ongoing research,
the impact of varied inorganic bases such as Na2CO3 and
K2CO3 on yield and reaction time was investigated. A dra-
matic increase in yield was observed when the base source
was changed from K2CO3 or Na2CO3 to KOH (Table 1,
entries 7–9). Within the absence of base, no product was
With the optimized reaction conditions in hand, DMF as
a solvent KOH as base, and 0.05 mol% of the catalyst, we
investigated the catalytic effect of a nanocatalyst for the Ull-
man coupling reaction with a series of phenols and amines
with aryl halides. Worthy of note is that phenols with elec-
tron donating groups are much faster than those with electron
withdrawing groups phenols, because the nucleophilicity of
the corresponding phenoxides is reduced (Table 2, entries 8,
9). In general, most of aryl halides worked well to afford the
Table 1 Optimization of the reaction conditions
Entry
Solvent
Base
Catalyst (g)
Tem (°C)
Time (h)
Yield %
1
2
3
4
5
6
7
8
EtOH
CH3CN
Toluene
H2O
CH2Cl2
H2O: EtOH
DMF
DMF
DMF
DMF
DMF
KOH
KOH
KOH
KOH
KOH
KOH
KOH
Na2CO3
K2CO3
–
KOH
KOH
KOH
KOH
KOH
KOH
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.08
0.1
100
100
100
100
100
100
100
100
100
100
100
100
100
70
3.5
3
5.5
3
8
3
60
62
50
55
35
65
97
70
75
–
98
99
65
80
70
98
2
3
9
2.5
4
1.5
1.5
2.5
2
10
11
12
13
14
15
16
DMF
DMF
DMF
DMF
0.03
0.05
0.05
0.05
25
120
4
1
DMF
Reaction conditions: phenol or amine (1.0 mmol), aryl halide (1.5 mmol), catalyst (0.05 g equal 0.0725 mmol/g), base (2.0 mmol), solvent
(2.0 mL)
1 3

K. Bahrami, M. Khodamorady
Table 2 BNPs@SiO2(CH2)3-TAPC-O-CH2CH2NH2-Pd(0) catalyzed cross-coupling of aryl halides with phenols and amines
Entry
1
Phenol and amine
Aryl halides
Time (h)
2
Yield %
95
Mp [refs.]
Oil [37]
2
3
1.45
1.45
97
97
Oil [37]
Oil [37]
4
5
3
80
94
53 [37]
77 [45]
2.5
6
7
8
2.5
3
93
92
98
Oil [37]
69 [37]
76 [37]
1
9
1.5
97
108–110 [37]
10
11
12
13
14
15
16
17
18
19
2.5
2
90
92
97
92
87
90
50
82
92
92
144 [37]
47 [46]
1.5
5
96 [37]
53 [47]
5
135–136 [48]
88–90 [47]
88–90 [47]
135–136 [48]
95–97 [49]
Oil [50]
4.5
7
7
2.5
3
1 3

Design of BNPs-TAPC Palladium Complex as a Reusable Heterogeneous Nanocatalyst for the…
Table 2 (continued)
Reaction conditions: phenol or amine (1.0 mmol), aryl halide (1.5 mmol), catalyst (0.05 g equal 0.0725 mmol/g), base (2.0 mmol), solvent
(2.0 mL)
of the actual fact that some palladium is removed from the
catalyst surface in different steps.
SEM and FT-IR techniques were accustomed to confirm
and compare the structure and morphology of the nanocata-
lyst after the sixth load. To our great pleasure, the structure
of the nanocatalyst after the sixth load is totally like to the
structure of the fresh nanocatalyst (Fig. 7).
3.4 Catalyst Leaching Study
The amounts of palladium leaching in reaction mixture
was studied by checking the Pd loading amount before
Fig. 6 Reusability of the catalyst
and after recycling of the catalyst by ICP-OEIS technique.
Based on ICP-OEIS analysis, the amount of palladium in
fresh catalyst and the recycled catalyst after six times recy-
cling is 1.451 and 1.251 mmol/g, respectively.
corresponding products in high to excellent yields. To our
great pleasure, under optimized condition, 2-phenylethan-
1-ol well reacts with iodobenzene and 4-nitrochlorobenzene
(Table 2, entries 11, 12.). Additionally, amines with electron
donating and electron withdrawing groups with various aryl
halides such as 4-nitrochlorobenzene, bromobenzene and
iodobenzene gave the desired products in 80–92% yields
(Table 2, entries 13–15, 17–19).
In order to perform hot filtration experiment, toward
this point, the cross coupling reaction of iodobenzene with
phenol or amine were studied under optimized condition,
the biaryl ether was obtained after 30 min (in the half
time of the reaction) in 72% yield. Then, the catalyst was
removed from the reaction mixture by filtration and the
reaction mixture was allowed to run for another 30 min.
The yield of reaction in this stage was 74%. This experi-
ment confirmed that the leaching of catalyst is low.
The reaction rate of aliphatic amines with aryl halides
is higher than that of aromatic amines (Table 2, entries 18,
19). As a result, the reaction of aromatic amines with elec-
tron donating groups, are faster than amines with electron
withdrawing groups (Table 2, entry 15, 17). It ought to be
noted that, chlorobenzene is not very efficient in this reaction
conditions (Table 2, entries 4, 16). To our surprise, when
using 4-nitrochlorobenzene, the reaction rate is increased
and yields reach up to 90% (Table 2, entries 8, 9, 10 and 12).
4 Conclusion
In conclusion, an atom-economical and efficient procedure
has been developed for the O-arylation and N-arylation
via cross coupling reaction in the presence of BNPs@
SiO2(CH2)3-TAPC-O-CH2CH2NH2-Pd(0) as an efficient
heterogeneous nanocatalyst. The reaction worked well
with various substituted phenols and amines. In addition,
the heterogeneous catalyst will be simply recovered by
filtration and used again for many cycles with tiny loss
of activity. Therefore, this synthetic methodology will
be thought-about as a useful practical achievement in the
preparation of aryl amines and biaryl ethers. Some of the
features of the proposed method in this study are low cata-
lyst loading, high product yield, facile catalyst separation
and recovery, broad substrate scope. Further studies are
presently happening in our laboratory to understand other
applications of the catalyst in synthesis of various organic
compounds.
3.3 The Reusability of BNPs@SiO2(CH2)3‑TAPC‑O‑C
H2CH2NH2‑Pd(0)
The reusability and durability of heterogeneous catalysts are
important issues. In order to check the catalyst recyclability,
the reaction between phenol or amine was investigated by
iodobenzene under optimized conditions. Once the reaction
was completed the reaction mixture was cooled and so the
catalyst was separated from the reaction medium. In the next
step, the catalyst was washed with water and ethanol, dried
and used again in subsequent reactions. Figure 6 illustrates
the actual fact that the introduced catalyst has the ability to
use up to 6 times without significantly reducing its activity,
and after 7th time its activity is reduced, that is because
1 3

K. Bahrami, M. Khodamorady
Fig. 7 a SEM of the fresh catalyst b SEM of the catalyst after run 6 c FT-IR of the fresh catalyst and after run 6
13. Mora M, Jimenez-Sanchidrian C, Rafael Ruiz J (2012) Curr Org
Chem 16:1128–1150
Acknowledgements The authors gratefully appreciated the financial
support of this work by the research council of Razi University.
14. Choudhary H, Nishimura S, Ebitani K (2014) J Mater Chem A
2:18687–18696
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Affiliations
Kiumars Bahrami1,2 · Minoo Khodamorady1
2
* Kiumars Bahrami
Nanoscience and Nanotechnology Research Center (NNRC),
kbahrami2@hotmail.com
Razi University, Kermanshah 67149-67346, Iran
1
Department of Organic Chemistry, Faculty of Chemistry,
Razi University, Kermanshah 67149-67346, Iran
1 3