Modification of boehmite nanoparticles with Adenine for the immobilization of Cu(II) as organic–inorganic hybrid nanocatalyst in organic reactions

Article abstract of DOI:10.1016/j.poly.2019.02.004

Boehmite nanoparticles are aluminum oxide hydroxide (γ‐AlOOH) particles, which has large specific surface area (>120 m² g^?1) and can be prepared using an inexpensive procedure in water. Herein, we present an economical, simple, and environmentally friendly route for the preparation of a copper catalyst on Adenine coated boehmite nanoparticles (Cu–Adenine@boehmite). This catalyst has been characterized by several techniques such as SEM, XRD, AAS, ICP and TGA analysis. Cu–Adenine@boehmite was applied as highly efficient and reusable nanocatalyst in carbon–carbon coupling reactions between various aryl halides and sodium tetraphenyl borate, phenylboronic acid, or 3,4-diflorophenylboronic acid under aerobic conditions, palladium-free and phosphine-free ligand. Also this catalyst was applied for the synthesis of polyhydroquinoline derivatives. In continuation, selective oxidation of sulfides to sulfoxides using hydrogen peroxide (H₂O₂) was studied in the presence of Cu–Adenine@boehmite as catalyst. The synthesis of sulfoxides using H₂O₂ in the presence of Cu–Adenine@boehmite does not generate waste and any byproducts. This catalyst was reused for several times in C–C coupling reaction without loss of its catalytic activity. Reused catalyst was characterized by SEM, XRD and ICP techniques. Heterogeneity and stability of Cu–Adenine@boehmite were studied by hot filtration test, poisoning test and ICP analysis.

Full text of DOI:10.1016/j.poly.2019.02.004

Accepted Manuscript
Modification of boehmite nanoparticles with Adenine for the immobilization of
Cu(II) as organic-inorganic hybrid nanocatalyst in organic reactions
Arash Ghorbani-Choghamarani, Parisa Moradi, Bahman Tahmasbi
PII:
S0277-5387(19)30097-X
https://doi.org/10.1016/j.poly.2019.02.004
POLY 13748
DOI:
Reference:
Polyhedron
To appear in:
Received Date:
Revised Date:
Accepted Date:
1 November 2018
25 January 2019
6 February 2019
Please cite this article as: A. Ghorbani-Choghamarani, P. Moradi, B. Tahmasbi, Modification of boehmite
nanoparticles with Adenine for the immobilization of Cu(II) as organic-inorganic hybrid nanocatalyst in organic
reactions, Polyhedron (2019), doi: https://doi.org/10.1016/j.poly.2019.02.004
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Modification of boehmite nanoparticles with Adenine for the immobilization
of Cu(II) as organic-inorganic hybrid nanocatalyst in organic reactions
Arash Ghorbani-Choghamarani, Parisa Moradi and Bahman Tahmasbi
Department of Chemistry, Faculty of Science, Ilam University, P.O. Box 69315516, Ilam, Iran
ABSTRACT
Boehmite nanoparticles are aluminum oxide hydroxide (γ‐AlOOH) particles, which has large
specific surface area (>120 m2g-1) and can be prepared using an inexpensive procedure in water.
Herein, we present an economical, simple, and environmentally friendly route for the preparation
of a copper catalyst on Adenine coated boehmite nanoparticles (Cu-Adenine@boehmite). This
catalyst has been characterized by several techniques such as SEM, XRD, AAS, ICP and TGA
analysis. Cu-Adenine@boehmite was applied as highly efficient and reusable nanocatalyst in
carbon-carbon coupling reactions between various aryl halides and sodium tetraphenyl borate,
phenylboronic acid, or 3,4-diflorophenylboronic acid under aerobic conditions, palladium-free
and phosphine-free ligand. Also this catalyst was applied for the synthesis of polyhydroquinoline
derivatives. In continuation, selective oxidation of sulfides to sulfoxides using hydrogen
peroxide (H2O2) was studied in the presence of Cu-Adenine@boehmite as catalyst. The synthesis
of sulfoxides using H2O2 in the presence of Cu-Adenine@boehmite does not generate waste and
any byproducts. This catalyst was reused for several times in C-C coupling reaction without loss
of its catalytic activity. Reused catalyst was characterized by SEM, XRD and ICP techniques.

Address correspondence to A. Ghorbani-Choghamarani, Department of Chemistry, Ilam University, P.O. Box 69315516, Ilam, Iran; Tel/Fax:
+98 843 2227022; E-mail address: arashghch58@yahoo.com or a.ghorbani@ilam.ac.ir
1

Heterogeneity and stability of Cu-Adenine@boehmite were studied by hot filtration test,
poisoning test and ICP analysis.
Keywords: Boehmite nanoparticles, Copper, Suzuki reaction, Polyhydroquinoline, Sulfoxide.
1. Introduction
Recently the nanomaterials widely attracted much attention, because they are as a precursor of
inorganic-organic hybrid materials [1-6]. Also they have excellent applications in catalytic
reactions, adsorption materials, optical and environmental problems, food processing, medical
industry, energy production and they have used in various fields of chemistry, physics,
engineering and science [7-10]. Boehmite (γ-AlOOH) is one of the polymorph phase of
aluminum oxihydroxide and inorganic lamellar compound. Boehmite is aluminum oxide
hydroxide that was formed by octahedral units of six oxygen atoms around the central aluminum
[10, 11]. Because, boehmite has only two elements (aluminum and oxygen), it can be used as a
high environmentally friendly and inexpensive material in different processes. Therefore, several
methods have been reported for the synthesis of boehmite nanoparticles such as hydrothermal
[12, 13], coprecipitation [14, 15], sol-gel [16] and hydrolysis of aluminum [17]. Among various
preparation procedures of boehmite nanoparticles, the hydrothermal method has several
advantages such as production in a one-pot process, green conditions and needs a low
temperature for preparation of nanoparticles [7, 18, 19]. The well-crystallized boehmite is easily
fabricated by a hydrothermal treatment using suspension of an aluminum salt (such as
Al(NO3)3.9H2O and aluminum chloride hexahydrate) or aluminum trihydroxide (such as bayerite
and gibbsite) in water [19-22]. Moreover, the morphology and size of boehmite nanoparticles
2

can be controlled in hydrothermal method, which make boehmite as useful material for various
applications in industrial point of view [21-24]. Thermal stability, non-toxicity, ease of surface
modification, mesoporous properties, high specific surface area (>120 m2g-1) of boehmite
nanoparticles are major advantages for its catalytic application [25-27]. Meanwhile, boehmite
nanoparticles have been rarely applied as support for the preparation of heterogeneous catalysts
[28-31]. Therefore herein we have reported a new procedure for the preparation of supported
copper (II) on Adenine coated boehmite nanoparticles (Cu-Adenine@boehmite), which
successfully applied as highly efficient and recoverable catalyst for the carbon-carbon cross
coupling reactions, synthesis of polyhydroquinoline derivatives and selective oxidation of
sulfides to sulfoxides.
Carbon-carbon coupling reactions are powerful tools for the preparation of advanced materials,
natural products, pharmaceuticals, agrochemicals, herbicides, biologically active compounds,
UV screens, polymers, hydrocarbons and liquid crystal materials [32-35]. Suzuki reaction is
usually reported with homogeneous or heterogeneous palladium catalysts [36-39]. The use of
palladium phosphine-based catalyst led to expensive, toxic, air and moisture sensitive procedure.
Also, use of phosphine ligands suffer from several drawbacks such as thermal instability and
non‐recoverability [40, 41]. Therefore, use of copper catalyst is environmentally friendly and
inexpensive rather than palladium catalysts. Additionally, copper catalyst is not moisture- or air-
sensitive, and have been synthesized and used without an inert atmosphere or phosphine ligands.
Therefore, with respect to green chemistry principles, we have reported immobilized Cu(II) on
modified boehmite nanoparticles as stable and reusable catalyst for the Suzuki C-C coupling
reaction.
3

The selective oxidation of sulfides to corresponding sulfoxides is an important transformation in
organic functional groups, because sulfoxides play an important role in organic synthesis,
enzymes activation, separation of radioactive or less common metals [42-44], and in medicinal
chemistry as antihypertensive, antibacterial, antifungal, anti-ulcer, anti-atherosclerotic agents,
cardiotonic agents and so on [42, 45, 46]. However, transformation of sulfides to sulfoxides have
been reported using both organic and inorganic reagents, which lead to toxic wastes byproducts
[47-49]. Therefore, to keep pace green chemistry principles, herein we have used hydrogen
peroxide as oxidant in the oxidation of sulfides in the presence of Cu-Adenine@boehmite as
catalyst. Because, use of H2O2 as oxidant for the transformation of sulfides to sulfoxides offers
several advantages such as cheapness, readily available, and environmentally friendly oxidant
with the water as only byproduct [50]. Also, multicomponent reactions has emerged as a
powerful tool for the synthesis of biological and organic compounds, which have several
advantages such as one-pot synthetic pathway, high atom economy and time saving without
isolation of any intermediates or generating any by-products [51-54]. Among different
heterocyclic compounds, polyhydroquinoline derivatives have a wide range of biological
activities such as antitumor, bronchodilator, vasodilator, antiatherosclerotic and antidiabetic
properties [50-58]. For example, polyhydroquinoline derivatives are a significant class of well-
known Ca2+ channel blockers and establish the skeletons of drug molecules utilized for the
treatment of hypertension and cardiovascular diseases [58, 59]. Therefore, the synthesis of
polyhydroquinoline derivatives is an area of remarkable attention in organic chemistry.
4

2. Experimental:
2.1. Preparation of catalyst
In the first step, boehmite nanoparticles were prepared and further modified by (3-chloropropyl)-
trimethoxysilane (CPTMS@boehmite) according to the new reported procedure [20]. In order to
modify boehmite nanoparticles with adenine, 1 g of CPTMS@boehmite was dispersed in toluene
and mixed with 2 mmol of adenine. Then, this mixture was stirred at 90 °C for 48 h. The
resulting solid (Adenine@boehmite) was separated using simple filtration, washed with ethanol
and dried at room temperature. In the final step, 1.0 g of Adenine@boehmite and 2 mmol of
Cu(NO3)2.9H2O were dispersed in ethanol and stirred for 20 hours under reflux conditions. The
solid product (Cu-Adenine@boehmite) was obtained by filtration, washed with ethanol and
water and dried at 50 °C.
2.2. General procedure for C-C coupling reaction through Suzuki reaction
1 mmol of aryl halide, 0.5 mmol of sodium tetraphenyl borate or 1 mmol of phenylboronic acid
or 1 mmol of 3,4-diflorophenylboronic acid, 1.5 mmol of sodium carbonate, and 20 mg of Cu-
Adenine@boehmite (containing 0.40 mol % of Cu) were stirred in water at 80 ºC and the
progress of the reaction was monitored by TLC. After completion of the reaction, the mixture
was cooled down to room temperature and catalyst was separated by simple filtration and
washed with ethyl acetate and the reaction mixture was extracted with water and ethyl acetate.
The organic layer was dried over Na2SO4 (1.5 g). Then the solvent was evaporated and pure
biphenyl derivatives were obtained in good to excellent yields.
2.3. General procedure for the synthesis of polyhydroquinoline derivatives
A mixture of aldehyde (1 mmol), dimedon (1 mmol), ethylacetoacetate (1 mmol), ammonium
acetate (1.3 mmol) and Cu-Adenine@boehmite (20 mg, 0.40 mol% of Cu) were stirred in
5

ethanol under reflux conditions and the progress of the reaction was monitored by TLC. After
completion of the reaction, catalyst was separated by simple filtration and washed with ethanol.
Then, the solvent was evaporated and all products was recrystallized in ethanol.
2.4. General procedure for the oxidation of sulfides to sulfoxides
0.008 g (0.17 mol %) of Cu-Adenine@boehmite was added to a solution of sulfide (1 mmol) and
0.4 mL of H2O2 (33%), the mixture was stirred under solvent free conditions at room
temperature for the specified time (Table 6) and the progress of the reaction was monitored by
TLC. After completion of the reaction, the catalyst was separated by simple filtration. The
product was extracted with water and ethyl acetate and dried over anhydrous Na2SO4 (1.5 g).
Then, the solvent was evaporated and pure products were obtained in high yields.
2.5. Selected spectral data
1
[1,1'-Biphenyl]-4-carbonitrile: H NMR (400 MHz, CDCl3): δH= 7.77-7.75 (d, J= 8 Hz, 2H),
7.73-7.71 (d, J= 8 Hz, 2H), 7.64-7.63 (d, J= 4 Hz, 2H), 7.55-7.51 (t, J= 8 Hz, 2H), 7.49-7.46 (t,
13
J= 8Hz, 1H) ppm; C NMR (400 MHz, CDCl3, ppm) δ = 145.6, 139.2, 132.6, 129.1, 128.7,
127.8, 127.3, 119.0, 110.9 ppm.
1
4-Nitro-1,1'-biphenyl: H NMR (400 MHz, CDCl3): δH= 8.36-8.32 (d, J= 8 Hz, 2H), 7.79-7.76
(d, J= 8 Hz, 2H), 7.68-7.66 (d, J= 8 Hz, 2H), 7.56-7.52 (t, J= 8 Hz, 2H), 7.51-7.47 (t, J= 8Hz,
1H) ppm; 13C NMR (400 MHz, CDCl3, ppm) δ = 147.6, 147.1, 138.8, 129.2, 128.9, 127.8, 127.4,
124.1 ppm.
1
3,4-Difluoro-4'-nitro-1,1'-biphenyl: H NMR (400 MHz, CDCl3): δH= 8.35-8.33 (d, J= 8 Hz,
2H), 7.73-7.71 (d, J= 8 Hz, 2H), 7.50-7.45 (m, 1H), 7.42-7.38 (m, 1H), 7.36-7.30 (m, 1H) ppm;
13C NMR (400 MHz, CDCl3, ppm) δ = 152.2, 149.5, 147.4, 145.3, 135.8, 127.4, 124.3, 123.6,
118.2, 116.5 ppm.
Ethyl
4-(3,4-dimethoxyphenyl)-7,7-dimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-
1
carboxylate: H NMR (400 MHz, CDCl3): δH= 6.96 (s, 1H), 6.83-6.81 (d, J= 8Hz, 1H), 6.74-
6.72 (d, J= 8Hz, 1H), 6.12 (s, 1H), 5.04 (s, 1H), 4.13-4.08 (q, J= 8 Hz, 2H), 3.86 (s, 3H), 3.83 (s,
3H), 2.41 (s, 3H), 2.38-2.29 (t, J= 16 Hz, 2H), 2.25-2.18 (dd, J= 16, 8 Hz, 2H), 1.27-1.23 (t, J= 8
13
Hz, 3H), 1.10 (s, 3H), 0.98 (s, 3H) ppm; C NMR (400 MHz, CDCl3, ppm) δ = 195.6, 167.5,
148.2, 147.9, 147.2, 143.2, 140.0, 119.8, 112.3, 111.9, 110.7, 106.2, 59.8, 55.8, 55.7, 50.8, 41.1,
35.9, 32.7, 29.5, 27.1, 19.5, 14.3 ppm.
6

Ethyl 4-(4-chlorophenyl)-7,7-dimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate:
1H NMR (400 MHz, CDCl3): δH= 7.28-7.26 (d, J= 8Hz, 2H), 7.20-7.18 (d, J= 8Hz, 2H), 7.03 (br,
1H), 5.05 (s, 1H), 4.12-4.07 (q, J= 8 Hz, 2H), 2.37 (s, 3H), 2.31-2.14 (m, 4H), 1.25-1.21 (t, J= 8
13
Hz, 3H), 1.08 (s, 3H), 0.94 (s, 3H) ppm; C NMR (400 MHz, CDCl3, ppm) δ = 195.8, 167.3,
149.3, 145.7, 144.1, 131.6, 129.4, 128.0, 111.5, 105.6, 59.9, 50.8, 40.8, 36.3, 32.7, 29.5, 27.1,
19.3, 14.3 ppm.
Ethyl4-(4-fluorophenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-
carboxylate: 1H NMR (400 MHz, CDCl3): δH= 7.31-7.27 (t, J= 8Hz, 2H), 6.92-6.88 (t, J= 8Hz,
2H), 6.27 (br, 1H), 5.06 (s, 1H), 4.11-4.06 (q, J= 8 Hz, 2H), 3.39 (s, 3H), 3.37-2.28 (t, J= 16 Hz,
13
2H), 2.24-2.15 (m, 2H), 1.24-1.20 (t, J= 8 Hz, 3H), 1.10 (s, 3H), 0.95 (s, 3H) ppm; C NMR
(400 MHz, CDCl3, ppm) δ = 195.6, 167.3, 162.5, 160.0, 148.2, 143.5, 142.9, 129.4, 114.7, 114.5,
112.1, 106.2, 59.9, 50.8, 41.0, 36.0, 32.7, 29.4, 27.1, 19.4, 14.2 ppm.
1
2-(Phenylsulfinyl)ethanol: H NMR (400 MHz, CDCl3): δH= 7.89-7.87 (d, J= 8 Hz, 1H), 7.61-
7.60 (d, J= 4 Hz, 2H), 7.48-7.47 (d, J= 4 Hz, 2H), 4.20 (br, 1H), 4.13-3.86 (m, 2H), 3.08-2.90
(m, 2H) ppm; 13C NMR (400 MHz, CDCl3, ppm) δ = 142.9, 131.2, 129.4, 123.9, 59.9, 55.9 ppm.
1
(Methylsulfinyl)benzene: H NMR (400 MHz, CDCl3): δH= 7.92-7.89 (d, J= 12 Hz, 1H), 7.62-
13
7.60 (m, 2H), 7.49-7.47 (m, 2H), 2.69 (s, 3H) ppm; C NMR (400 MHz, CDCl3, ppm) δ =
145.5, 131.1, 129.4, 123.5, 43.9 ppm.
3. Result and discussion
Initially, Cu-Adenine@boehmite was prepared based on Scheme 1 and characterized by
thermogravimetric analysis (TGA), scanning electron microscopy (SEM), X-ray diffraction
(XRD), atomic absorption spectroscopy (AAS), and inductively coupled plasma (ICP-OES)
techniques.
7

Scheme 1. Synthesis of Cu-Adenine@boehmite.
3.1. Catalyst characterizations
The particles size and morphology of Cu-Adenine@boehmite were studied by scanning electron
microscopies (SEM) technique. SEM image of this catalyst is shown in Figure 1. As shown, the
particles of catalyst were obtained with size of 60-90 nm of diameters. Also, the exact amount of
copper that is loaded on boehmite nanoparticles was found to be 0.20 × 10-3 mol g−1 based on
results of inductively coupled plasma (ICP). This result is good agreement with atomic
absorption spectroscopy (AAS) that is indicate 0.22 × 10-3 mol g−1 of copper in catalyst.
8

Figure 1. SEM image of Cu-Adenine@boehmite.
The XRD pattern of Cu-Adenine@boehmite is shown in Figure 2. As shown in Figure 2, the
peak positions of 2θ at 13.58, 28.49, 38.51, 45.89, 49.35, 51.51, 56.49, 60.65, 64.07, 65.19,
68.27, and 72.57 are in agreement with standard XRD pattern of boehmite nanoparticles and all
peaks strongly confirmed the crystallization of boehmite nanoparticles in orthorhombic unit cells
[3, 11].
400
350
300
250
200
150
100
50
10
20
30
40
50
60
70
80
2θ / degree
9

Figure 2. XRD pattern of Cu-Adenine@boehmite.
TGA/DTA diagrams of Cu-Adenine@boehmite are shown in Figure 3. The TGA curve of
catalyst shows the several steps of weight loss. The small mass loss in low temperatures (below
100 °C) about 7% is corresponded to the removal of adsorbed water, solvents and surface
hydroxyl groups [24-27]. Second weight loss (35 %) between 250-600 °C is related to
calcination of organic layers that are immobilized on boehmite nanoparticles. Final weight loss
(about 3%) in high temperatures that is happened above 600 °C, may be related to thermal
transformation of crystal phase of boehmite nanoparticles [34, 42]. On the basis of these results,
the well supporting of Adenine on the surface of boehmite nanoparticles was confirmed.
Figure 3. TGA/DTA diagrams of Cu-Adenine@boehmite.
10

3.2. Application of Cu-Adenine@boehmite in Suzuki reaction
Catalytic activity of Cu-Adenine@boehmite was studied in various organic reactions such as C-
C coupling reaction, synthesis of polyhydroquinoline derivatives and selective oxidation of
sulfides to sulfoxides. At first, C-C coupling reaction in the presence of Cu-Adenine@boehmite
has been studied (Scheme 2). In order to optimize the amount of catalyst in Suzuki reaction, the
reaction of iodobenzene with phenylboronic acid was investigated in the presence of different
amount of Cu-Adenine@boehmite. The best amount of catalyst was found to be 20 mg of Cu-
Adenine@boehmite (containing 0.40 mol% of Cu). In the next step, the C-C coupling reaction of
iodobenzene and phenylboronic acid in different solvents carried out in the presence of Cu-
Adenine@boehmite (20 mg). Based on the obtained results (Table 1), water showed a better
conversion in model reaction. Temperature and nature of base have been also studied and the
best results were obtained using 1.5 mmol of Na2CO3 at 80 °C. These results are summarized in
Table 1.
Scheme 2. Carbon-Carbon coupling reaction of aryl halides with phenylboronic acid, sodium tetraphenyl borate or
3,4-diF-C6H3B(OH)2 in the presence of Cu-Adenine@boehmite
11

Table 1. Optimization of Suzuki reaction conditions for coupling of iodobenzene with phenylboronic acid
in the presence of Cu-Adenine@boehmite.
Entry
Catalyst (mg)
Solvent
PEG
Base
Temperature (ºC) Time (min) Yield (%)a
1
2
15
20
25
20
20
20
20
20
20
20
20
20
20
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
NaOH
80
80
120
120
120
100
120
120
60
50
62
PEG
3
PEG
80
64
4
DMF
EtOH
Dioxane
H2O
80
90
5
reflux
80
24
6
27
7
80
98
8
DMSO
H2O
80
70
95
9
80
120
120
120
120
120
69
10
11
12
13
H2O
Et3N
80
40
H2O
NaOEt
Na2CO3
Na2CO3
80
Trace
Trace
H2O
50
b
H2O
r.t.
-
a Isolated yield, b No reaction.
Under the optimized reaction conditions, the scope of this procedure was explored with
various aryl halides and phenylboronic acid derivatives (Table 2). As shown in Table 2,
the coupling of phenylboronic acid with phenyl iodides performed in shorter reaction
times than phenyl bromides or phenyl chlorides. Aryl halides bearing an electron-
donating (Table 2, entries 8-12) or electron-withdrawing (Table 2, entries 4-7) groups
were converted to the corresponding biphenyles in high yields.
In order to extend the scope of our methodology, we next investigated the coupling of
various aryl halides with sodium tetraphenyl borate (Table 2, entries 11-14) and 3,4-diF-
C6H3B(OH)2 (Table 2, entries 15, 16). As expected, aryl iodides were more reactive than
12

aryl bromides. As shown in Table 2, high catalytic activity of Cu-Adenine@boehmite was
observed in C-C coupling reaction (Suzuki reaction). All products were obtained in high
TON and TOF values. In order to show the selectivity of this catalytic system, 1-bromo-
4-chorobenzene considered in coupling reaction with phenylboronic acid and sodium
tetraphenyl borate (Table 2, entries 5, 13). As shown in Scheme 3, chloro functional
group remained intact during the Suzuki reaction, and coupling of bromo functional group
was observed as only product. Also as shown in Table 2 (Entry 6), coupling of C-O was
not observed and pure biphenyl was obtained in 93% of yield. Therefore, this
experimental procedure is capable for coupling of various aryl halides including Cl, Br
and I in the presence of Cu-Adenine@boehmite as catalyst. The experimental procedure
is very simple, effective, and has ability to tolerate a variety of different electron-donor
and electron-withdrawing functional groups.
Table 2. Catalytic C-C coupling reaction of aryl halides with phenylboronic acid, sodium tetraphenyl borate
and 3,4-diF-C6H3B(OH)2 in the presence of Cu-Adenine@boehmite (0.40 mol%) in H2O at 80 °C.
phenylating
reagent
Time Yield
(min) (%)a
TOF Melting point Reported M.P.
Entry
Aryl halide
TON
(h-1)
245
87
(ºC)
65-67
64-67
64-67
110-112
69-72
[Ref.]
1
2
Iodobenzene
Bromobenzene
PhB(OH)2
PhB(OH)2
PhB(OH)2
PhB(OH)2
PhB(OH)2
PhB(OH)2
PhB(OH)2
PhB(OH)2
PhB(OH)2
PhB(OH)2
NaBPh4
60
150
190
45
98
87
92
93
90
86
87
93
96
95
89
245
217
230
232
225
215
217
232
240
237
222
64-66 [34]
64-66 [34]
64-66 [34]
110-113 [24]
69-71 [24]
3
Chlorobenzene
73
4
4-Bromonitrobenzene
4-Bromochlorobenzene
4-Chloronitrobenzene
4-Bromobenzonitrile
4-Bromophenol
310
50
5
270
90
6
143
174
70
111-114
84-87
110-113 [24]
86-88 [24]
157-160 [24]
42-44 [34]
42-44 [34]
42-44 [34]
7
75
8
200
100
90
158-161
42-44
9
4-Bromotoluene
4-Iodotoluene
144
158
148
10
11
41-43
4-Iodotoluene
90
42-43
13

12
13
14
Iodobenzene
NaBPh4
NaBPh4
NaBPh4
65
250
50
94
93
94
235
232
235
217
56
67-68
69-71
64-66 [34]
69-71 [24]
4-Bromochlorobenzene
4-Bromonitrobenzene
282
110-111
110-113 [24]
3,4-diF-
C6H3B(OH)2
3,4-diF-
15
Iodobenzene
75
91
90
227
225
182
135
39-42
39-41 [24]
16
4-Bromonitrobenzene
100
119-122
119-120 [24]
C6H3B(OH)2
aIsolated yield.
Scheme 3. Selectivity in C-C coupling in the presence of Cu-Adenine@boehmite.
3.3. Application of Cu-Adenine@boehmite in the synthesis of polyhydroquinolines
Also, catalytic activity of Cu-Adenine@boehmite has been studied for the synthesis of
polyhydroquinoline derivatives (Scheme 4). The condensation of benzaldehyde with dimedon,
ethyl acetoacetate, and ammonium acetate was selected as model reaction to found the best
conditions. Effect of various parameters on this reaction were studied and the results are
summarized in Table 3. The model reaction has been examined in the presence of different
amount of Cu-Adenine@boehmite. As shown in Table 3, low yield of product was obtained in
the absent of catalyst even long reaction time. The results in Tablte 3 indicate that 20 mg (0.40
mol%) of Cu-Adenine@boehmite is required for the synthesis of desired product. The less
14

amount of Cu-Adenine@boehmite gave a low yield, and the more amount of Cu-
Adenine@boehmite could not cause to increase the yield of the corresponding product. Also,
model reaction was studied in various solvents such as water, ethanol, ethyl acetate, acetonitrile
and PEG-400. As it can be seen, maximum yield (97%) of product was achieved in ethanol as
solvent. Finally, the effect of temperature was studied in model reaction (Table 3, entries 7-9).
The reaction not proceeded at room temperature even in long reaction time. But, the best results
were obtained at 80°C. Therefore, the reaction was kept at 80 °C.
Scheme 4. Synthesis of polyhydroquinoline derivatives in the presence of Cu-Adenine@boehmite.
Table 3. Optimization conditions for the synthesis of polyhydroquinolines via condensation of
benzaldehyde with dimedon, ethyl acetoacetate, and ammonium acetate in the presence of Cu-
Adenine@boehmite.
Entry
Catalyst (mg)
Solvent
EtOH
EtOH
EtOH
H2O
Temperature (ºC) Time (min) Yield (%)a
1
2
3
4
5
15
20
25
20
20
Reflux
Reflux
Reflux
80
75
75
69
97
98
33
71
70
100
75
PEG
80
15

6
7
8
9
20
20
20
20
Ethyl acetate
CH3CN
EtOH
Reflux
Reflux
60
100
100
80
52
64
70
48
EtOH
40
80
a Isolated yield
This optimized reaction conditions have been applied for the synthesis of various
polyhydroquinoline derivatives in the presence of Cu-Adenine@boehmite (Table 4). A wide
range of benzaldehydes including electron-donating and electron-withdrawing functional groups
were successfully converted to polyhydroquinoline derivatives, and all products were obtained in
good to excellent yields. Melting points of all products were found to be in good agreement with
reported melting point in the authentic literatures. High efficiency of Cu-Adenine@boehmite in
synthesis of polyhydroquinolines was confirmed by high TON and TOF values.
Table 4 Synthesis of polyhydroquinoline derivatives in the presence of Cu-Adenine@boehmite in ethanol
under reflux conditions.
TOF
(h-1)
682
564
119
138
194
267
112
136
141
227
Melting point
(ºC)
Reported M.P.
[Ref.]
Entry
Aldehyde
Time (min) Yield (%)a TON
1
2
4-Hydroxybenzaldehyde
3,4-Dimethoxybenzaldehyde
4-Chlorobenzaldehyde
4-Methoxybenzaldehyde
Benzaldehyde
20
25
91
94
95
97
97
89
90
91
94
91
227
235
237
242
242
222
225
227
235
227
227-230
201-204
234-236
254-256
202-205
226-228
176-178
183-185
252-254
173-174
228-230 [55]
200-202 [60]
233-235 [58]
258-260 [55]
203-204 [56]
228-230 [60]
175-176 [56]
185-187 [55]
253-255 [55]
176-178 [60]
3
120
105
75
4
5
6
3-Hydroxybenzaldehyde
3-Nitrobenzaldehyde
4-Fluorobenzaldehyde
4-Bromobenzaldehyde
4-Ethoxybenzaldehyde
50
7
120
100
100
60
8
9
10
aIsolated yield.
16

3.4. Application of Cu-Adenine@boehmite for the oxidation of sulfides
Also, catalytic activity of Cu-Adenine@boehmite was studied in the selective oxidation of
sulfides to sulfoxides (Scheme 5). Oxidation of methyl phenyl sulfide was selected as model
reaction to optimize the reaction conditions. In order to obtain suitable solvent and amount of
catalyst, model reaction was examined in the presence of different amount of Cu-
Adenine@boehmite and in different solvents (Table 5). As shown in Table 5, the best results
were obtained in the presence of 8 mg (0.17 mol%) of Cu-Adenine@boehmite when the reaction
was performed under solvent-free conditions at room temprature (Table 5, entry 2).
Scheme 5. Oxidation of sulfides to sulfoxides in the presence of Cu-Adenine@boehmite.
Table 5. Optimization of reaction conditions for the oxidation of methyl phenyl sulfide in the presence of
Cu-Adenine@boehmite at room temperature.
Entry
Catalyst (mg)
Solvent
Time (min)
Yield (%)a
1
2
3
6
8
solvent free
solvent free
solvent free
80
60
55
62
98
99
10
17

4
8
8
8
8
8
CH2Cl2
CH3CN
60
60
60
60
60
85
60
55
33
44
5
6
Ethyl acetate
Ethanol
7
8
H2O
a Isolated yield.
We have generalized the applicability of this method for the selective oxidation of a variety of
sulfides for the synthesis of sulfoxides (Table 6). Various aromatic, aliphatic and heterocyclic
sulfides were successfully evaluated and sulfoxides were obtained in good to excellent yields and
high TON and TOF values. Synthesis of sulfone as byproduct due to over oxidation was not
observed (Scheme 6). It was found that the aromatic sulfides reacted in longer times in
comparison with aliphatic ones. Also, other functional groups such as hydroxyl groups remained
intact during the oxidation of sulfides to sulfoxides (Scheme 6).
Table 6. Selective oxidation of sulfides to sulfoxides for the presence of Cu-Adenine@boehmite.
Time
(min)
TOF Melting point
Reported
Entry
Sulfide
Yield (%)a TON
(h-1)
(ºC)
M.P. [Ref.]
Methyl phenyl sulfide
2-Phenylthioethanol
Dipropylsulfane
1
2
3
4
5
6
7
60
10
10
5
98
95
96
98
90
89
95
576
559
567
576
529
523
559
576
29-32
30-32 [42]
Oil [20]
Oil [61]
Oil [62]
Oil [20]
61-64 [42]
Oil [20]
3352
3388
6917
1588
392
Oil
Oil
Tetrahydrothiophene
2-Methylthioethanol
Methyl(undecyl)sulfane
Dibutylsulfane
Oil
20
80
20
Oil
60-63
Oil
1676
a Isolated yield.
18

Scheme 6. Selective oxidation of sulfides to sulfoxides in the presence of Cu-Adenine@boehmite as catalyst.
3.5. Reusability Study
The recyclability of the catalysts is a great and important factor in catalytic studies. Therefore,
reusability of Cu-Adenine@boehmite as catalyst was considered in the coupling of iodobenzene
with phenylboronic acid under optimized reaction conditions (Figure 4). In the end of the
reaction, catalyst was isolated by centrifugation, washed with ethyl acetate and residual catalyst
was reused up to 8 times without lose of catalytic activity.
100
80
60
40
20
0
1
2
3
4
5
6
7
8
Run number
Fig 4. Recyclability of Cu-Adenine@boehmite in the coupling of iodobenzene (1 mmol) with PhB(OH)2 (1 mmol).
19

3.6. Characterization of recycled catalyst
In order to show the structure stability of Cu-Adenine@boehmite after recycling, recovered
catalyst was characterized by XRD technique. The XRD pattern of recovered catalyst was
compared to standard XRD pattern of boehmite nanoparticles. The XRD patterns of boehmite
nanoparticles and recovered Cu-Adenine@boehmite are shown in Figure 5. As it can be seen, the
XRD pattern of recovered catalyst showed a good agreement with standard XRD pattern of
boehmite nanoparticles. These results indicate that the crystalline structure of catalyst has not
changed after recycling. Therefore, these results are indicates that this catalyst can be reused for
next runs without any change in its structure.
Fig 5. The XRD pattern of boehmite nanoparticles (a) and Cu-Adenine@boehmite
after recycling (b).
The particle size of catalyst after recycling has been obtained by SEM technique. The SEM
image of recycled Cu-Adenine@boehmite is shown in Figure 6. As shown in figure 6, the size of
20

catalyst after recycling is as same as fresh catalyst, which is about 50-90 nm. As shown in Figure
6, the size and shape of recovered catalyst was shown a good similarly to fresh catalyst.
Fig 6. SEM image of Cu-Adenine@boehmite after recycling.
3.7. Leaching study of catalyst
Copper leaching of Cu-Adenine@boehmite was studied by ICP, poisoning test and hot filtration
test. Based on ICP-OES analysis, amount of copper in fresh and reused Cu-Adenine@boehmite
found to be 0.20 × 10-3 mol g−1 and 0.18 × 10-3 mol g−1, respectively, which indicated that metal
leaching of this catalyst is very low.
In order to study the heterogeneity of Cu-Adenine@boehmite, hot filtration experiment has been
performed in the coupling of iodobenzene with phenylboronic acid. In this study, in half‐time of
21

selected reaction, 56% of product was obtained. Then, this reaction was repeated and in half‐time
of reaction, catalyst was separated and the reaction was then permitted to continue without
catalyst for a further 60 min. In this stage, 59% of product was obtained. These experiments
confirm that leaching of copper didn’t not happened.
3.8. Poisoning test
Poisoning test is a powerful tool for homogeneity/heterogeneity nature of catalytic procedures.
Polyvinylpyridine and mercury poisoning tests were often used for extinguishing solution-phase
catalysis [63, 64]. In order to study of homogeneity/heterogeneity nature of Cu-
Adenine@boehmite, the Suzuki coupling reaction of iodobenzene with phenylboronic acid in the
presence of poly(vinyl pyridine) was performed under optimized condition. Therefore, a mixture
of iodobenzene (1.0 mmol), phenylboronic acid (1 mmol), Na2CO3 (1.5 mmol), water (3 ml),
0.005 g of poly(vinyl pyridine) and Cu-Adenine@boehmite (20 mg, 0.40 mol%) were stirred at
80 °C. In this experiment, considered reaction was completed and any change in conversion was
not observed, which proves that Cu-Adenine@boehmite has heterogeneous nature.
Poisoning test, ICP technique and hot filtration test were shown a good agreement for the
heterogeneity nature of Cu-Adenine@boehmite.
3.9. Comparison of the Catalyst
The efficiency of Cu-Adenine@boehmite as catalyst was considered by comparing these
obtained results with previously reported catalysts in the authentic literatures. Results for
synthesis of biphenyls from coupling reaction of aryl halide with phenylboronic acid in the
presence of Cu-Adenine@boehmite and previously reported catalysts are summarized in Table 7.
Nano-Cu-Adenine@boehmite catalyst has some merits in terms of high yields and shorter
22

reaction times, low reaction temperature, simple catalyst recovering, products purification, and
use of green solvent. Also, the TOF and TON numbers in the presence of Cu-
Adenine@boehmite are higher than other catalysts, which is confirmed the high efficiency of
this catalyst. Therefore, it can be found that Cu-Adenine@boehmite is an efficient catalyst and it
is useful in the organic reactions and synthesis of organic compounds. Additionally, Suzuki
reaction has usually been reported in the presence of palladium catalyst, which is more expensive
than copper catalyst. Also, several procedures used microwave irradiation (Table 7, entries 11-
15) or ultrasonic sonication (Table 7, entry 16) in Suzuki coupling reaction to decrease reaction
time or improvement of yield.
Table 7. Comparison of Cu-Adenine@boehmite in the coupling reaction of iodobenzene or 4-Iodotoluene with
phenylboronic acid with previously reported procedures.
Time
(min)
TOF Yield a (%)
(h-1) [Reference]
Entry
Catalyst (mol %)
Aryl halide
Reaction conditions
TON
1
2
K2CO3, 1,4-dioxane:
H2O (1:1), 95 ºC
PANI-Pd (2.2 mol%)
Iodobenzene
240
41
97
10
32
4
91 [65]
97 [66]
99 [67]
88 [68]
88 [69]
95 [70]
94 [71]
99 [72]
97 [73]
99 [74]
67 [75]
N,N'-bis(2-pyridinecarboxamide)-1,2-
benzene palladium complex (1 mol%)
Iodobenzene H2O, K2CO3, 100 ºC 180
Iodobenzene DMF, Cs2CO3, 100 ºC 24h
3
Pd(II)–NHC complex (1 mol%)
99
4
NHC-Pd(II) complex (1.0 mol%) Iodobenzene THF, Cs2CO3, 80 ºC
EtOH/H2O, K2CO3, 80
12h
24h
12h
88
7
5
Pd/Au NPs (4.0 mol%)
Iodobenzene
22
1
ºC
6
Pd NP (1.0 mol%)
Iodobenzene H2O, KOH, 100 ºC
95
4
7
CA/Pd(0) (0.5-2.0 mol%)
Iodobenzene H2O, K2CO3, 100 ºC 120
K2CO3, DMF: H2O
188
198
194
198
37.2
94
40
129
99
446
8
Polymer anchored Pd(II)
Schiff base complex (0.5 mol%)
Iodobenzene
300
(1:1), 80 ºC
9
Pd@SBA-15/ILDABCO (0.5 mol%) Iodobenzene K2CO3, H2O, 80 ºC
90
10
11
SBA-16-2 N-Pd(II) (0.5 mol%)
Iodobenzene EtOH, K2CO3, 60 ºC 120
solvent-free, K2CO3,
Pd NPs@APC (1.8 × 10-3 mol%) 4-Iodotoluene
5
MW (350 W)
23

12
13
14
15
16
solvent-free, Cs2CO3,
MW (400 W), 50 ºC
solvent-free, K2CO3,
MW (400 W), 50 ºC
solvent-free, K2CO3,
MW (400 W), 50 ºC
solvent-free, K2CO3,
MW (400 W), 50 ºC
H2O, K2CO3, MW, 60
ºC, ultrasonic sonication
AG-Pd (0.003 mol%)
CL-Gly-Pt (0.002 mol %)
Pd nanocatalyst (0.004)
4-Iodotoluene
4-Iodotoluene
4-Iodotoluene
4-Iodotoluene
4-Iodotoluene
6
7
28.3
30
283
257
225
150
150
85 [76]
60 [77]
72 [78]
75 [79]
75 [80]
97 [81]
5
18
Pd@chitosan/starch nanocomposite
(0.005 mol%)
6
15
Pd NPs@CMC/AG (1 mol%)
30
75
17 Pd(0)-Schif-base@MCM-41 (1.6 mol
%)
4-Iodotoluene PEG, K2CO3, 100 ºC 200
61
18
18 Cu-Adenine@boehmite (0.40 mol %) 4-Iodotoluene H2O, Na2CO3, 80 °C
95 [this
work]
98 [this
work]
237
158
90
60
19 Cu-Adenine@boehmite (0.40 mol %) Iodobenzene H2O, Na2CO3, 80 °C
245
245
4. Conclusion
In conclusion an efficient and reusable heterogeneous catalyst (Cu-Adenine@boehmite) was
synthesized and successfully applied for the C-C cross coupling reaction, synthesis of
polyhydroquinoline derivatives and selective oxidation of sulfides to sulfoxides. The present
methodology offers good turnover numbers (TON) and turnover frequency (TOF) in all
reactions. Also, all reaction were carried out in green conditions. Additionally, the Cu-
Adenine@boehmite is more economic and environment friendly because of its low Cu leaching.
Cu-Adenine@boehmite can be recovered and reused over than 8 times without any significant
loss of its activity. Also Cu-Adenine@boehmite is better in terms of facile synthesis of catalyst,
price, higher catalytic efficiency, heterogeneous nature, wide substrate scope, and green
conditions. Also, Suzuki reaction has usually been reported in the presence of palladium catalyst,
but in this work copper catalyst was employed for Suzuki reaction, which Cu catalyst is
nontoxic, more inexpensive, easy available and environmental friendly conditions compared with
Pd catalyst.
24

Acknowledgment
Authors thank Ilam University and Iran National Science Foundation (INSF) for financial
support of this research project.
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