Palladium fabricated on boehmite as an organic-inorganic hybrid nanocatalyst for C-C cross coupling and homoselective cycloaddition reactions

Article abstract of DOI:10.1039/c9nj06129k

Herein, boehmite nanoparticles were prepared using an aqueous solution of NaOH and Al(NO₃)₃?9H₂O at room temperature. After modification of the boehmite nanoparticle (BNP) surface by 3-choloropropyltrimtoxysilane (CPTMS), adenine was anchored on the surface. Finally, a complex of palladium was fabricated on the BNP surface (Pd-adenine@boehmite). The obtained nanoparticles were identified by TGA, FT-IR, BET, EDS, WDX, SEM, XRD and AAS techniques. In continuation, the Pd-adenine@boehmite was employed as an efficient, reusable and organic-inorganic hybrid catalyst in the C-C cross coupling reactions without a phosphine ligand or an inert atmosphere. Moreover, the homoselective synthesis of tetrazoles was studied in the presence of Pd-adenine@boehmite as a heterogeneous and practical nanocatalyst which can be recovered and reused in the described organic reactions. Besides, organic products which were isolated in suitable TOF and TON numbers in the presence of Pd-adenine@boehmite as a catalyst revealed the practicality of this catalyst. The heterogeneous nature of this catalyst was confirmed by TEM, EDS, WDX, AAS, and FT-IR techniques and, then, compared to the fresh catalyst.

Full text of DOI:10.1039/c9nj06129k

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Palladium fabricated on boehmite as an organic-inorganic hybrid
nanocatalyst for the C-C cross coupling and homoselective
cycloaddition reactions
Received 00th January 20xx,
Accepted 00th January 20xx

Bahman Tahmasbi , Arash Ghorbani-Choghamarani, Parisa Moradi
DOI: 10.1039/x0xx00000x
www.rsc.org/
Herein, boehmite nanoparticles were prepared using aqueous solution of NaOH and
Al(NO ) .9H O at room temperature. After modification of boehmite nanoparticles (BNPs) surface
3 3 2
by 3-choloropropyltrimtoxysilane (CPTMS), adenine was anchored on its surface. Finally, a complex
of palladium was fabricated on the BNPs surface (Pd-adenine@boehmite). The obtained
nanoparticles were identified by TGA, FT-IR, BET, EDS, WDX, SEM, XRD and AAS techniques.
In continuation, the catalytic application of Pd-adenine@boehmite was employed as efficient,
reusable and organic-inorganic hybrid catalyst in the C-C cross coupling reactions without phosphine
ligand or inert atmosphere. Moreover, the homoselective synthesis of tetrazoles was studied in the
presence of Pd-adenine@boehmite as a heterogeneous and practical nanocatalyst which can be
recovered and reused in the described organic reactions. Besides, organic products which were
isolated in suitable TOF and TON numbers in the presence of Pd-adenine@boehmite as catalyst
revealed the practically of this catalyst. Heterogeneous nature of this catalyst was confirmed by TEM,
EDS, WDX, AAS, and FT-IR techniques and, then, compared to the fresh catalyst.
*
Address correspondence to B. Tahmasbi, Department of Chemistry, Ilam University, P.O. Box 69315516, Ilam, Iran;
Tel/Fax: +98 841 2227022; E-mail address: bah.tahmasbi@gmail.com
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expensive, and also moisture or air sensitivity of the previously
reported procedure. Additionally, instability and
The field of solid-state chemistry and nanoparticles have non‐recoverability can be regarded as the major disadvantages
1
Introduction
[29–31]
received intense attention in green chemistry, scientific of homogeneous catalyst and phosphine compounds
.
research and biological applications due to their unique Meanwhile, palladium catalyst without phosphine ligands is
properties such as high stability, high specific surface area, environmentally friendly and possesses more moisture- or air-
stability than phosphine ligands. Therefore, in order to keep
In this sense, it is worth mentioning that polymers , carbon pace with green chemistry principles, herein, we reported
[1,2]
non-toxicity and high environmentally friendly properties
.
[3]
[
4]
[5]
[6]
[7]
nanotubes , silica materials , MCM-41 , ionic liquids
,
palladium catalyst on BNPs as a phosphine free, reusable and
, magnetic highly stable nanocatalyst for the C-C bond forming.
, N-
Likewise, the synthesis of tetrazoles is an important
etc. have been reported in various procedure in medicinal or organic chemistry due to the fact that
[
8]
[9]
[10]
boehmite
nanoparticles
Heterocyclic carbenes
, zeolite
, graphene oxide
, microporous organic polymers
[1,11]
[12]
[13]
fields especially in chemistry and catalysis field. Among them, they have a wide range of biological compounds i.e. herbicidal,
boehmite has various applications i.e. optical material, vaccine analgesic, anti-hypertensive, anti-proliferative, antimicrobical,
adjuvants, flame retardant and reinforcing filler for plastics, antiviral, anxiety, anti-inflammatory, antibiotic, and anticancer
cosmetic products, coatings, catalysis support, composite agents [32–36]. In this regard, TAK-456, losartan, olmesartan
reinforcement material in ceramics, adsorbent, starting medoxomil, and valsartan are compounds with tetrazole ring
[
14,15]
material for synthesis of alumina etc.
nanoparticles are one of the polymorphs of Al-oxide hydroxide family drugs
γ‐AlOOH) which constructs double sheet structures formed studied and applied in the photographic industry, agriculture
. Boehmite which have biological activities like that of antihypertensive
[
37]
. Moreover, tetrazole derivatives have been
(
[16]
[38]
by only aluminum and oxygen . The surface of boehmite and explosives . Therefore, herein we reported palladium
nanoparticles which has high density of hydroxyl groups catalyst on boehmite nanoparticles as a practical and
makes the surface modification possible aiming at stabilizing heterogeneous catalyst for the homoselective synthesis of 5-
[17]
the catalysts . Therefore, boehmite nanoparticles have been substituted tetrazoles via [3+2] cycloaddition of NaN
synthesized by various methods and especially used as corresponding nitrile derivatives.
catalysis support for the fabrication of organocatalysts or metal
3
to the
[18,19]
particles
. Boehmite nanoparticle was usually synthesized 2 Results and discussion
(SO , NaAlO
. Herein, several
methods, i.e. solvothermal reaction [16], sol–gel [17], hydrolysis
by hydrolysis of aluminum salts such as Al
2
4
)
3
2
,
[20–22]
3 3 3
Al(NO ) , AlCl or aluminum alkoxide
2
.1 Catalyst preparation
[23]
[24]
[25]
Surface modification of boehmite nanoparticles by
CPTMS was performed according to the reported
of aluminum , coprecipitation , and hydrothermal have
been reported for the synthesis of BNPs. Stability, availability
and the environmentally friendly capabilities of BNPs are the
most notable advantages for boehmite in industrial and
[
39]
procedure
. Afterwards, the chloro groups were
replaced by adenine. Subsequently, the palladium catalyst
was stabilized on its surface. The procedure preparation of
this catalyst (Pd-adenine@boehmite) is outlined in
Scheme 1.
[26]
academic research
.
C-C bond forming as interest tools for the synthesis of bi-
aryls is commonly reported with palladium catalysts including
[27,28]
phosphine ligands
. Use of phosphine ligands led to toxic,
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N
HN
N
NH2
N
H
N
H
N
O
Cl
Si
N
Si
O
O
N
N
Si
O
H
N
O
o
N
Toluene, 90 C, 48 h
Cl
N
O
O
Si
HN
O
O
N
O
O
O
adenine@boehmite
CPTMS@boehmite
N
Pd
HN
N
N
N
H
O
O
Pd
Si
1
. Pd(OAc)2
o
EtOH, 80 C, 20 h
O
H
N
N
N
O
2
. NaBH4, 2 h
Pd
Si
O
HN
N
O
Pd-adenine@boehmite
Scheme 1. Screening procedure for the preparation of Pd-adenine@boehmite.
2
.2 Catalyst characterization
After the preparation of Pd-adenine@boehmite, the catalyst changed after modification and immobilization of the catalyst.
was identified by FT-IR, BET, WDX, EDS, SEM, XRD, TGA Besides, small increasing in size of the catalyst particles than
and AAS analyses. SEM images of boehmite nanoparticles, pervious steps is due to the coating of organic layers and
CPTMS@boehmite,
adenine@boehmite
and
Pd- palladium complex on the surface of modified boehmite
adenine@boehmite are shown in Figure 1 indicating that the nanoparticles. The very small particles of boehmite
catalyst has particle size in nanometer scale of diameter with nanoparticles (12-20 nm) provide a high surface area for
quasi-orthorhombic unit cell of particles. As shown in Figure catalyst loading. Therefore, immobilized catalyst on boehmite
1
, the shape and morphology of boehmite nanoparticle are not nanoparticles can play as semi-homogeneous catalyst.
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Figure 1. SEM images of (a) boehmite nanoparticles, (b) CPTMS@boehmite, (c) adenine@boehmite and (d) Pd-adenine@boehmite.
In order to indicate the elemental composition of the
catalyst, the EDS analysis of Pd-adenine@boehmite has been
performed (Figure 2). EDS diagram of this catalyst indicates
that this catalyst was formed from a combination of oxygen,
aluminum, carbon, silica, nitrogen, and as well as palladium
species. X-Ray Mapping (WDX analysis) of Pd-
adenine@boehmite confirmed a homogeneous distributions of
all elements (oxygen, aluminum, carbon, silica, nitrogen and
palladium) in the structure of Pd-adenine@boehmite (Figure
3
). Moreover, the exact amount of Pd which was loaded on
-3
-1
BNPs was calculated by AAS analysis (1.3 × 10 mol g ).
Figure 2. EDS diagram of Pd-adenine@boehmite.
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Figure 3. Elemental mapping of (a) aluminum, (b) oxygen, (c) silica, (d) carbon, (e) nitrogen and (f) palladium for Pd-adenine@boehmite.
In order to calculate the amount of organic groups, which
were fabricated on the surface of BNPs, the TGA analysis of
Pd-adenine@boehmite was used over the temperature range of
25–800 °C by heating rates at 10 °C/min and in the air
atmosphere (Figure 4). The small weight loss (about 6 %) at
low temperature is referred to solvents evaporation [35]. The
organic layers including CPTMS and adenine which were
stabilized on boehmite nanoparticles were decomposed at 200-
500 °C which is 25 W% of the catalyst. The final weight loss
which is less than 4 %W appears at high temperatures and can
[33]
be corresponded to thermal phase change of BNPs
.
Figure 4. TGA/DTA diagrams of Pd-adenine@boehmite.
The normal XRD pattern of Pd-adenine@boehmite is
shown in Figure5. The peaks of 2θ values were observed at
14.4° (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),
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64.04° (2 3 1), 65.56° (0 0 2), 68.09° (1 7 1), and 72.38° (2 5
1) in XRD pattern of Pd-adenine@boehmite which are related
to orthorhombic unit cell of the standard pattern of BNPs [19]
These results indicated that the modification of boehmite
nanoparticles did not lead to any transformation in the structure
of boehmite nanoparticles.
Adsorption / desorption isothe
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DOI: 10.1039/C9NJ06129K
r
m
1
1
50
00
.
Moreover, the normal XRD pattern of Pd-
adenine@boehmite indicate the four peaks of 2θ at 26.6 (111),
0
1
2
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4
5
6
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8
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0
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0
3
9.0º (200), 46.5º (220), and 67.4º (331) which are related to
[39]
valance state of Pd(0) in the catalyst
.
1600
0
0.5
p/p
1
0
1
1
1
400
200
000
800
ADS
DES
Figure 6. Nitrogen adsorption-desorption isotherms of Pd-
adenine@boehmite.
Table 1. Textural properties of Pd-adenine@boehmite
6
4
00
00
Pore diameter Pore volume
2
Entry
Sample
S
BET (m /g)
3
-1
(
nm)
(cm g )
0.22
[40]
[40]
1
2
boehmite nanoparticles 128.8 [8, 40]
Pd-adenine@boehmite 113.9
1.64
1.22
200
0
0.18
1
0
30
50
70
2
θ / degree
2
.3 Catalytic Study
Figure 5. XRD pattern of Pd-adenine@boehmite.
The catalytic application of Pd-adenine@boehmite has
been studied in the carbon-carbon coupling (Suzuki reaction)
and the homoselective synthesis of tetrazole derivatives.
The
N
2
adsorption-desorption isotherms of Pd-
adenine@boehmite are shown in Figure 6. Besides, the
obtained textural properties of Pd-adenine@boehmite from
BET technique are summarized in Table 1. As shown, this
catalyst displays a hysteresis loop of type IV whose catalytic amount of Pd-adenine@boehmite is outline in
characteristic of mesoporous materials is based on IUPAC Scheme 2. In order to obtain the best conditions, the coupling
classification. Based on the obtained results from the BET of C H B(OH) with iodobenzene has been selected. The effect
6 5 2
characterization, the specific surface area of Pd- of various parameters (such as amount of the catalyst, solvent,
adenine@boehmite is 62.3 m /g, which is lower than the base and temperature) was examined on yield and time of the
surface area of free boehmite nanoparticles (122.8 m /g)
The decrease in the specific surface area of the Pd- Table, the best results were observed in the presence of 5 mg
adenine@boehmite is related to the immobilization of organic of Pd-adenine@boehmite (0.65 mol%) using sodium carbonate
layers and palladium complex on boehmite nanoparticles
C-C coupling between aryl halides and NaBPh
4
,
C
6
H
5
B(OH) or 3,4-diF-C B(OH) in the presence of
2
6
H
3
2
2
2
[8]
.
selected reaction as illustrated in Table 2. As shown in this
[8]
.
(3 mmol) as base in water as solvent at 80 °C.
Moreover, BET analysis of this catalyst provided a lower pore
3
-1
diameter (1.64 nm) and lower pore volume (0.22 cm g ) in
comparison to boehmite nanoparticles indicating the
successful grafting of organic layers and palladium complex on
boehmite nanoparticles.
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Pd
HN
N
N
H
N
O
Pd
Si
O
X
+
B(OH)2
R
Pd-adenine@boehmite
R
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NaBPh4 or R'
R'
R'
o
Na CO , H O, 80 C
2
3
2
X= Cl, Br, I
R'= H or F
R'
Scheme 2. Suzuki C-C coupling reaction in the presence of Pd-adenine@boehmite
a
Table 2. Optimizing reaction conditions for the coupling of phenylboronic acid with iodobenzene in the presence of Pd-adenine@boehmite.
b
Entry
Catalyst (mg)
Solvent
Base
Temperature (ºC) Time (min) Yield (%)
c
1
2
3
4
5
6
7
8
9
-
H
H
H
H
2
2
2
2
O
O
O
O
Na
Na
Na
Na
Na
Na
Na
Na
2
2
2
2
2
2
2
2
CO
CO
CO
CO
CO
CO
CO
CO
3
3
3
3
3
3
3
3
80
80
80
80
80
Reflux
80
80
80
80
600
150
30
25
30
30
30
30
30
30
30
30
30
30
30
-
82
95
96
38
47
95
93
27
53
78
64
51
Trace
Trace
3
5
7
5
5
5
5
5
5
5
5
5
5
5
Dioxane
EtOH
DMSO
PEG
H
H
H
H
H
H
H
2
2
2
2
2
2
2
O
O
O
O
O
O
O
NaOEt
KOH
1
1
1
1
1
1
0
1
2
3
4
5
K
2
CO
3
80
80
60
40
Et
3
N
Na
Na
Na
2
2
2
CO
CO
CO
3
3
3
r.t.
a
c
b
Reaction conditions: phenylboronic acid (1 mmol),iodobenzene (1 mmol), solvent (1-2 mL) and base (3 mmol), Isolated yield,
No reaction.
The scope catalytic activity of Pd-adenine@boehmite was halides as PhI>PhBr>PhCl (Table 3, entries 1, 5, 6).
extended to differnt aryl halides including an electron-rich Moreover, aryl halides including an electron-donating
or electron-poor groups. All products were isolated in group are less reactive than aryl halides with an electron-
exellent yields and suitable TON values. TON values and withdrawing groups.
isolated yields of products in short times indicateed In continuation of this procedure, the coupling of NaBPh
indicate the practicaly and efficiency of Pd- (Table 3, entries 9, 10) or 3,4-difluorophenylboronic acid
adenine@boehmite in suzuki reaction. As accepted, the (Table 3, entry 8) with various aryl halides was studied in
4
coupling with C H B(OH) iodobenzene is faster than the presence of Pd-adenine@boehmite. As shown in Table
6 5 2
bromobenzene or chlorobenzene. As shown in Table 3, 3, the efficiency of Pd-adenine@boehmite and high TOF
order TOF values for iodobenzen, bromobenzen and values was observed for all products.
chlorobenzen were obtained as 146.2>79.1>54.1
respectively which clearly confirmed the reactivity of aryl
Table 3. Suzuki C-C coupling reaction catalyzed by Pd-adenine@boehmite.a
Time
Yield
(%)
TOF
(h )
Entry
Aryl halide
phenylating reagent
TON
b
-1
(min)
I
1
PhB(OH)
PhB(OH)
2
2
30
95
146.2
292.3
35.8
Br
2
3
240
75
93
96
143.1
147.7
Cl
Br
PhB(OH)
2
118.2
O N
2
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1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
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5
5
5
5
5
5
5
5
5
5
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ARTICLE
New Journal of Chemistry
I
View Article Online
DOI: 10.1039/C9NJ06129K
4
5
6
PhB(OH)
PhB(OH)
PhB(OH)
2
50
89
90
85
136.9
138.5
130.8
164.3
Me
Br
Cl
2
2
105
145
79.1
54.1
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Cl
7
PhB(OH)
2
60
91
140.0
140.0
O N
2
Br
8
9
3,4-diF-C
6
H
3
B(OH)
2
50
90
95
94
138.5
146.2
144.6
166.2
64.9
86.8
Br
Br
NaBPh
NaBPh
4
4
135
100
Me
NC
1
0
a
4 6 5 2 6 3 2
Reaction conditions: aryl halides (1 mmol), NaBPh (0.5 mmol) or C H B(OH) (1 mmol) or 3,4-diF-C H B(OH) (1 mmol), Pd-
b
adenine@boehmite (5 mg, containing 0.65 mol % of Pd), and sodium carbonate (0.318 g, 3 mmol) at 80 ºC in H
yield.
2
O(1-2 mL), Isolated
Additionally, the catalytic application of Pd-adenine@boehmite
was extended in the homoselective synthesis of tetrazoles as
outline in Scheme 3.
N
Pd
N
HN
N
H
N
O
Pd
Si
O
O
CN
Pd-adenine@boehmite
N
N
NaN3
+
N
N
o
R
R
PEG-400, 120 C
H
Scheme 3. Synthesis of tetrazoles in the presence of Pd-adenine@boehmite.
In order to obtain the best conditions, the effects of various solvent. Based on the summarized results in Table 4, the
parameters (such as the amount of the catalyst, amount of reaction cannot proceed without Pd-adenine@boehmite
sodium azide, solvent and temperature) were examined in (Table 4, entry 1) or room temperature (Table 4, entry 11).
the [3+2] cycloaddition of NaN with benzonitrile. The Moreover, when this reaction was examined using lower
3
obtained results are shown in Table 4. As shown, the amount of the catalyst (Table 4, entries 2-4) or at lower
acceptable results (time and yield of the reaction) were temperature (Table 4, entry 10), the product yields were
obtained in the presence of 35 mg of Pd- decreased.
adenine@boehmite (4.5 mol%) at 120 °C in PEG-400 as
8
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5
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8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
New Journal of Chemistry
ARTICLE
Table 4. Optimizing reaction conditions for the synthesis of 5‐substituted 1H‐tetrazole in the presence of Pd-adenine@boehmite.a
View Article Online
DOI: 10.1039/C9NJ06129K
Sodium azide
b
Entry
Catalyst (mg)
Solvent
Temp. (ºC)
Time (min) Yield (%)
(
mmol)
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.4
1
2
3
4
5
6
7
8
9
-
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
DMSO
120
120
120
120
120
120
120
Reflux
Reflux
100
24h
380
310
240
90
600
600
600
600
90
-c
10
15
20
35
35
35
35
35
35
35
35
80
88
91
95
62
45
84
41
46
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
DMF
H
2
O
EtOH
1
1
1
0
1
2
PEG-400
PEG-400
PEG-400
b
r.t
120
90
600
-
81
a
c
b
Reaction conditions: benzonitrile (1 mmol), NaN
No reaction
3
(1.4-1.5 mmol), solvent (1-2 mL) and temperature (25-120 °C), Isolated yield,
Using the optimized conditions, we next extended this due to quite regular geometric shape and very small
methodology for the other nitriles bearing electron- particle size based on SEM and TEM images. The
withdrawing and electron-donating groups which are homoselectivity of Pd-adenine@boehmite was studied in
attached on the aromatic ring of benzonitrile (Table 5). As the [3+2] cycloaddition of NaN with terephthalonitrile
shown, all products were obtained in great yields and TOF (Table 5, entry 6) which had two cyano functional groups
3
numbers.
with a same position in its structure. Interestingly, this
procedure showed a good homoselectivity in the synthesis
of tetrazoles and afforded the mono addition products in
the presence of Pd-adenine@boehmite (Scheme 4).
Homoselectivity is an interesting property of some organic
reactions which can be observed in the same functional
[41]
groups . Pd-adenine@boehmite is a selective catalyst
Table 5. Preparation of tetrazoles in the presence of Pd-adenine@boehmite.a
Entry
Nitrile
CN
Time (min)
Yield (%)b
TON
TOF (h-1)
1
90
95
21.1
14.1
CN
2
20
90
20
60
OH
CN
3
4
420
170
96
93
21.3
20.7
3.0
7.3
Cl
Cl
CN
CN
5
6
Me
20 h
240
85
92
18.9
20.4
0.9
5.1
O
CN
NC
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1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
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4
4
4
4
4
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ARTICLE
New Journal of Chemistry
CN
View Article Online
DOI: 10.1039/C9NJ06129K
7
8
100
370
89
88
19.8
19.6
11.9
Cl
CN
3.2
1.0
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
CN
9
21 h
15 h
91
90
20.2
20
O N
2
O N
CN
2
10
1.3
a
Reaction conditions: benzonitrile derivatives (1 mmol), NaN
3
(1.5 mmol), Pd-adenine@boehmite (4.5 mol% of Pd, 35 mg), at 120
b
ºC in PEG (1-2 mL), Isolated yield.
N N
NH
N
CN
N
N
Pd-adenine@boehmite
N
NaN3
NH
+
o
PEG-400, 120 C
CN
N
NC
00%
N
NH
N
1
0%
Scheme 4. Homoselectivity of [3+2] cycloaddition of NaN
3
with dicyano substituted derivatives in the presence of Pd-
adenine@boehmite
Based on the previous reports, a mechanism for the synthesis of
tetrazoles is outlined in Scheme 5 in the presence of Pd-
adenine@boehmite [
42]
.
N N
N
NH
Pd-adenine@boehmite
Pd(0)
Ph CN
Ph
NaN3
HCl
2
Na
N N N
N
N
N
Pd(0)
N
N
Na
Ph
Pd(0)
II
Ph
I
Scheme 5. A mechanism for the synthesis of 5-sustiated tetrazoles in the presence of Pd-adenine@boehmite.
1
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DOI: 10.1039/C9NJ06129K
New Journal of Chemistry
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
ARTICLE
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
2.4 Reusability of the Catalyst
The reusability of Pd-adenine@boehmite was studied in the
coupling of C B(OH) with iodobenzene. In this regard, in the
6
H
5
2
end of each reaction, the catalyst has been isolated by
centrifugation and washed by ethyl acetate. The isolated catalyst
was reused in the next reaction. Figure 7 indicates that Pd-
adenine@boehmite can be recycled up to 7 times.
Figure 8. FT-IR spectrums of Pd-adenine@boehmite (a) and
recovered Pd-adenine@boehmite (b).
The particle size and morphology of catalyst after reusing
was studied by TEM technique. The TEM images of the
catalyst after recycling are presented in Figure 9 in which the
morphology and size of the catalyst after recycling indicated a
good agreement with the fresh catalyst. Therefore, the
morphology and size of the catalyst are stable after recycling.
This figure indicated that the recovered catalyst is stable and
showed a regular geometric shape in cubic orthorhombic
structures with dimensions of 40-70 nm.
Figure 7. Recyclability of Pd-adenine@boehmite in the
coupling of iodobenzene with phenylboronic acid.
2
.5 Characterization of the recycled Catalyst
In order to indicate the stability of Pd-adenine@boehmite
after reusing, the recycled catalyst was characterized by
TEM, EDS, WDX, AAS, and FT-IR techniques and compared to
the fresh catalyst. FT-IR spectra of the recovered and fresh
catalyst are shown in Figure 8 in which there is not any changes
in FT-IR of the catalyst after reusing. These results are strong
evidences for the stability of Pd-adenine@boehmite after
recycling. Therefore, this catalyst can be recovered and recycled
without any change in its structure.
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2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
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New Journal of Chemistry
results were extended by X-Ray Mapping (WDXVie
a
w
n
A
a
r
l
t
y
ic
s
le
i
O
s)nli
of
ne
DOI: 10.1039/C9NJ06129K
Pd-adenine@boehmite after recycling (Figure 11). WDX
analysis of the reused catalyst confirmed a homogeneous
distributions of oxygen, aluminum, carbon, silica, nitrogen and
palladium.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Figure 9. TEM images of recovered Pd-adenine@boehmite.
The elemental composition of Pd-adenine@boehmite after
recycling was studied by EDS analysis (Figure 10). EDS
diagram of the recovered catalyst indicates that oxygen, Figure 10. EDS diagram of Pd-adenine@boehmite after
aluminum, carbon, silica, nitrogen, and as well as palladium
species which is agreement with the fresh catalyst. These
recycling.
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1
1
1
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1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
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ARTICLE
View Article Online
DOI: 10.1039/C9NJ06129K
a
b
e
c
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
d
f
Figure 11. Elemental mapping of (a) aluminum, (b) oxygen, (c) silica, (d) carbon, (e) nitrogen and (f) palladium for Pd-
adenine@boehmite after recycling.
2.7 Comparison of the Catalyst
2
.6 Leaching Study of the catalyst
In order to indicate the practically and accessibility of the Pd-
adenine@boehmite than the previously reported catalysts, the
obtained results from the coupling of phenylboronic with acid
iodobenzene in the presence of Pd-adenine@boehmite have been
compared to the reported results in the presence of the previously
reported catalysts (Table 6). In this comparison, various parameters
such as reaction times, reaction condition and yields were compared.
As shown in Table 6, the products were isolated with best yields when
Pd-adenine@boehmite was used as the catalyst. Moreover, Pd-
adenine@boehmite showed high effectivity than other catalysts in
terms of reaction time and isolated yield. Besides, some of the
previously reported methods employed ultrasonic sonication (Table 6,
entry 7) or microwave irradiation (Table 6, entries 6 and 7) to the out
coming Suzuki coupling reaction.
In order to confirm the stability and heterogeneous nature of Pd-
adenine@boehmite, the coupling of C B(OH) with iodobenzene in
6
H
5
2
the presence of this catalyst was repeated under optimal conditions
and, then, the catalyst was removed after 30 min without cooling.
Afterwards the palladium concentration was calculated in the
remained reaction solution by AAS technique which was found to be
-1
0.0000047 mmol mL . The very small amount of Pd proves that no
metal leaching occurred in the reaction medium. Therefore,
completion of the reaction is related to the heterogeneous palladium
species.
Table 6. Comparison results of Pd-adenine@boehmite with other catalysts for the coupling of iodobenzene with phenylboronic acid.
Time Yield (%)
min) [Reference]
Entry
1
Catalyst
Reaction conditions
(
K
2
CO
3
, 1,4-dioxane: H
ºC
2
O (1:1), 95
PANI-Pd
240
91 [43]
[
[
[
[
44]
45]
46]
47]
2
3
4
5
6
Pd(II)–NHC complex
NHC-Pd(II) complex
Pd NP
DMF, Cs
THF, Cs
O, KOH, 100 ºC
O, K CO , 100 ºC
PEG, Na CO , 80 °C
solvent-free, K CO , MW (400 W),
0 ºC
2
CO
3
, 100 ºC
24h
12h
12h
120
125
99
88
95
94
96
2
CO
3
, 80 ºC
H
2
CA/Pd(0)
H
2
2
3
[
48]
Pd(0)‐TBA@biochar
2
3
2
3
72 [28]
7
Pd nanocatalyst
5
5
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New Journal of Chemistry
H
2
O, K
2
CO
3
, MW, 60 ºC, ultrasonic
sonication
View Article Online
27]
[
8
9
Pd NPs@CMC/AG
30
75
DOI: 10.1039/C9NJ06129K
Pd-adenine@boehmite
2 2 3
H O, Na CO , 80 °C
90 95 [this work]
3.4. Selected spectral data
-nitro-1,1'-biphenyl: 1H NMR (400 MHz, CDCl
3
Experimental
4
3
H
): δ =
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
3
.1. Experimental procedure for the preparation of catalyst
The modified BNPs with CPTMS (CPTMS@boehmite)
8.35-8.33 (d, J= 8Hz, 2H), 7.79-7.77 (d, J= 8 Hz, 2H), 7.67-
13
7
.65 (d, J= 8Hz, 2H), 7.57-7.47 (m, 3H) ppm; C NMR (100
MHz, CDCl ): δ= 147.7, 147.1, 138.8, 129.2, 129.0, 127.9,
3
have been synthesized according to the recently reported
−1
1
1
5
27.4, 124.2 ppm. IR (KBr) cm : 3072, 3004, 1646, 1597,
[39]
method
. CPTMS@boehmite (1.0 g) was dispersed in
477, 1447, 1399, 1345, 1286, 1156, 1105, 835, 774, 740, 695,
32, 472.
toluene and mixed with 2.0 mmol of adenine. Then, the
obtained mixture was stirred for 48 hours at 90 °C in which the
terminal chloro groups on the modified boehmite surface were
instated with adenine. Afterwards, the reaction mixture was
cooled and, then, the prepared solid (adenine@boehmite) was
isolated by filtration, and washed with EtOH. Finally, in order
to synthesize the catalyst (Pd-adenine@boehmite), the
adenine@boehmite (1 g) was dispersed in EtOH for 20 min and
1
1-(4-(1H-tetrazol-5-yl)phenyl)ethanone: H NMR (400
MHz, DMSO): δ
H
= 8.21-8.19 (m, 2H), 8.18-8.16 (m, 2H), 2.66
3
(s, 3H) ppm; C NMR (100 MHz, CDCl ): δ= 197.9, 155.7,
3
−
1
138.9, 129.6, 128.8, 127.6, 27.4 ppm. IR (KBr) cm : 3417,
3348, 3082, 2922, 2858, 1732, 1679, 1573, 1497, 1435, 1367,
1269, 1155, 1126, 1058, 993, 961, 841, 751, 700, 615, 589,
mixed with 0.5 mmol of Pd(OAc)
mixture was stirred under reflux conditions for 20 hours. Then,
NaBH was injected to the reaction mixture and, then, the
2
. Finally, the obtained
5
20, 488, 460.
-(4-chlorophenyl)-1H-tetrazole: H NMR (400 MHz,
1
5
4
1
3
DMSO): δ
NMR (100 MHz, CDCl
H
= 8.09-8.05 (m, 2H), 7.73-7.70 (m, 2H) ppm;
): δ= 155.4, 136.4, 130.1, 129.2, 123.7
ppm. IR (KBr) cm : 3439, 3130, 3097, 2968, 2856, 2129,
C
stirring continued stirring for 2 hours.
3
−
1
1
1
731, 1647, 1609, 1486, 1435, 1402, 1272, 1155, 1126, 1092,
3.2 Experimental procedure for the Suzuki C-C bond forming
in the presence of Pd-adenine@boehmite
055, 990, 880, 834, 786, 742, 701, 556, 507, 465.
1
4
-(1H-tetrazol-5-yl)benzonitrile: H NMR (400 MHz,
aryl halide (1 mmol), 0.5 mmol of sodium tetraphenyl DMSO): δ = 8.22-8.19 (d, J= 12 Hz, 2H), 8.10-8.07 (d, J= 12
borate (NaBPh
H
1
3
4
)
or
) or 1 mmol of 3,4-diflorophenylboronic acid 129.3, 128.1, 118.7, 113.9 ppm. IR (KBr) cm : 3454, 3095,
B(OH) ), Pd-adenine@boehmite (5 mg, 2926, 2855, 2232, 1733, 1641, 1567, 1495, 1435, 1277, 1149,
1 mmol of phenylboronic acid Hz, 2H) ppm; C NMR (100 MHz, CDCl ): δ= 155.8, 133.8,
3
−
1
(C
6
H
5
B(OH)
2
(3,4-diF-C
6
H
3
2
containing 0.65 mol % of Pd), and sodium carbonate (0.318 g, 1123, 989, 847, 748, 700, 553, 474, 441.
1
3
mmol) were stirred at 80 ºC in H
2
O and the reaction proceeds
H
5-phenyl-1H-tetrazole: H NMR (400 MHz, DMSO): δ =
were controled by TLC. In the end of the reaction, the remained 8.05-8.01 (m, 2H), 7.62-7.60 (m, 1H), 7.59-7.57 (m, 2H) ppm;
catalyst was removed using simple filtration and washed by
ethyl acetate. The products were extracted from H O by ethyl 125.0 ppm. IR (KBr) cm : 3446, 3129, 3057, 2982, 2923,
acetate and, then, the organic phase was dried over sodium 2795, 1734, 1607, 1563, 1486, 1462, 1405, 1258, 1126, 1057,
sulfate (about 1.5 g). Finally, ethyl acetate was evaporated and 989, 958, 926, 786, 726, 572, 462.
biphenyls were remained in good to excellent yields.
13
3
C NMR (100 MHz, CDCl ): δ= 156.0, 131.5, 129.8, 127.4,
−1
2
4 Conclusions
3.3 Experimental route for the synthesis of tetrazoles in the
presence of Pd-adenine@boehmite
In summary, immobilization of Pd-complex on the surface
of BNPs (Pd-adenine@boehmite) was synthesized and
evidenced using TGA, BET, EDS, WDX, SEM, XRD and
AAS techniques. The catalytic application of Pd-
adenine@boehmite was studied in the Suzuki C-C cross
3
A mixture of NaN (0.0975 g, 1.5 mmol) and nitrile (1
mmol) was stirred in the presence of Pd-adenine@boehmite
(4.5 mol% of Pd, 35 mg) at 120 °C in PEG. The reaction
proceeds were controled by TLC. In the end of the reaction, the
remained catalyst was removed using filtration and washed by
ethyl acetate. The products were extracted from the mixture by
ethyl acetate and aqueous solution of hydrochloric acid (4 N).
The organic layer was dried over anhydrous sodium sulfate
3
coupling reactions and [3 + 2] cycloaddition of NaN with
nitriles toward the synthesis of tetrazoles. All organic products
were isolated in excellent yields and suitable TOF values
which showed good practically of this catalyst. This
methodology can be employed for other nitrile, phenylboronic
acid derivatives and aryl halides bearing Br, Cl, and I. Finally,
the recycled catalyst has been characterized by TEM, EDS,
WDX, AAS, and FT-IR techniques indicating a good
agreement with the fresh catalyst. Therefore this catalyst can
be reused without any change in its structure or content of the
loaded palladium.
(about 1.5 g). Then ethyl acetate was evaporated and, finally,
the products remained in excellent yields.
1
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New Journal of Chemistry
ARTICLE
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8. A. Maleki, A. Sarvary, RSC Adv. 2015, 5, 60938–60955.
View Article Online
9. A. Ghorbani-Choghamarani, B. Tahmasbi, R D. OH I.: E1 0. H. 1 0u d3 s9 o/ Cn ,9 AN .J H0 6e i1 d2 a9r Ki ,
Microporous Mesoporous Mater. 2019, 284, 366–377.
0. A. Ghorbani-Choghamarani, B. Tahmasbi, P.Moradi, RSC Adv ,2016,
6, 43205–43216.
Acknowledgements
Authors thank Ilam University and Iran National Science
Foundation (INSF) for financial support of this research
project.
4
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1. M. Safaiee, M. Moeinimehr, and M. A. Zolfigol, Polyhedron 2019, 170,
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38-150.
42. F. Abrishami, M. Ebrahimikia, F. Rafiee, Appl. Organomet. Chem.
2015, 29, 730–735.
3. H. A. Patel, A. L. Patel, A. V Bedekar, Appl. Organomet. Chem. 2015,
29, 1–6.
44. Q. Xu, W.-L. Duan, Z.-Y. Lei, Z.-B. Zhu, M. Shi, Tetrahedron 2005,
61, 11225–11229.
45. T. Chen, J. Gao, M. Shi, Tetrahedron 2006, 62, 6289–6294.
46. M. Nasrollahzadeh, S. M. Sajadi, M. Maham, J. Mol. Catal. A Chem.
2015, 396, 297–303.
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View Article Online
I: 10.1039/C9NJ06129K
Palladium fabricated on boehmite as an organic-inorganic hy
D
b
O
r
i
d
nanocatalyst for the C-C cross coupling and homoselective cycloaddition
reactions
Bahman Tahmasbi, Arash Ghorbani-Choghamarani, Parisa Moradi
0
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X
CN
R
R
Ar-B(OH)2
or NaBPh4
NaN3
R'
R'
N N
NH
N
Pd-adenine@boehmite
Pd NPs
=
R
R
Boehmite nanoparticles were synthesized via simple procedure in water without inert atmosphere using
commercially materials. Then an organometallic complex of palladium has been stabilized on its surface
and characterized by FT-IR, BET, SEM, EDS, WDX, TGA, XRD and AAS techniques. This catalyst
was applied as nanocatalyst for C-C cross coupling and homoselective synthesis of tetrazole derivatives.
Heterogeneous nature of this catalyst was confirmed by TEM, EDS, WDX, AAS, and FT-IR techniques
and compared to fresh catalyst.