Catalytic application of 1,3,5-triazine-pentaethylenehexamine polymer-supported palladium nanoparticles in the convenient reduction of nitroarenes with sodium borohydride or hydrazine

Article abstract of DOI:10.3906/kim-1702-8

The catalytic activity of 1,3,5-triazine-pentaethylenehexamine (TAPEHA) polymer-supported Pd nanoparticles was investigated in the reduction of nitro arenes to the corresponding amines by NaBH₄ or N₂H₄ .H₂ O. Optimized reaction conditions for both systems were successfully tested on 20 nitroarenes with different characteristics. Considerably high yields (80%-98% in NaBH₄ and 85%-98% in N₂H₄) were obtained in a short time and at ambient temperature. In addition to these methods being selective against other reducible functionalities such as -CN, -Br, -Cl, and -I, the catalyst can be recovered easily and reused more than ten times.

Full text of DOI:10.3906/kim-1702-8

Turk J Chem
2017) 41: 784 – 792
Turkish Journal of Chemistry
(
http://journals.tubitak.gov.tr/chem/
¨
˙
⃝
c TUBITAK
Research Article
doi:10.3906/kim-1702-8
Catalytic application of 1,3,5-triazine-pentaethylenehexamine polymer-supported
palladium nanoparticles in the convenient reduction of nitroarenes with sodium
borohydride or hydrazine
1
,∗
1
1
1
˙
¨
2
¨
˙
˘
˙
Hayriye GEN C¸ , Mustafa ZENGIN , Mustafa KU C¸ UKISLAMOGLU , Mustafa IMAMOGLU ,
1
¨
H u¨ seyin Ozkan TOPLAN , Mustafa ARSLAN
1
Department of Chemistry, Faculty of Arts and Sciences, Sakarya University, Serdivan, Sakarya, Turkey
Department of Metallurgical and Materials Engineering, Faculty of Engineering, Sakarya University,
2
Serdivan, Sakarya, Turkey
Received: 03.02.2017
•
Accepted/Published Online: 05.05.2017
•
Final Version: 10.11.2017
Abstract: The catalytic activity of 1,3,5-triazine-pentaethylenehexamine (TAPEHA) polymer-supported Pd nanoparti-
cles was investigated in the reduction of nitro arenes to the corresponding amines by NaBH or N .H O. Optimized
reaction conditions for both systems were successfully tested on 20 nitroarenes with different characteristics. Considerably
high yields (80%–98% in NaBH and 85%–98% in N ) were obtained in a short time and at ambient temperature.
4
2
H
4
2
4
2 4
H
In addition to these methods being selective against other reducible functionalities such as –CN, –Br, –Cl, and –I, the
catalyst can be recovered easily and reused more than ten times.
Key words: Heterogeneous catalysis, nitro reduction, Pd nanoparticles, reusable catalyst
1. Introduction
Primary amine compounds are important frameworks due to their excess properties that they present as
initial reactive or intermediates in some industrial branches like pigments, agrochemicals, pharmaceuticals, and
1
2
polymers. Hence, there are a wide variety of methods to obtain amine compounds in the literature. One of the
most preferred methods among them is the reduction of nitro groups to the corresponding amines.3 However,
current methods suffer from some drawbacks;4 many of them require high temperature/pressure, long reaction
time, and carcinogenic solvents; are toxic, expensive, and unstable with no reusable catalyst; and provide low
yields.5 In order to overcome these problems, researchers try to develop more economical, easily available,
and environmentally friendly methods for the synthesis of primary amines with high yield and minimum waste
products.6,7 One of the most popular methods in the last decades is the reduction of nitro groups by using
the combinations of a hydrogen source such as NaBH4 and N2 H4 with transition metals. Since the 1960s
many catalysts working very quickly and at high efficiency under moderate conditions have been developed and
considered practical in the reduction of nitro compounds.8 Today, transition metal-containing catalysts with
a hydrogen source are under development.9,10 However, many disadvantages such as high catalytic loading,
inability to reuse the catalyst, and high costs remain.11 Thus, developing environmentally friendly alternatives
is of great importance.
∗
Correspondence: hayriyegenc@sakarya.edu.tr
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GEN C¸ et al./Turk J Chem
Metallic nanoparticles that are used as heterogeneous catalysts offer particular advantages in terms of
selectivity, activity, stability, and energy efficiency.12 In spite of the fact that palladium-based catalysts have a
wide range of applications in both synthetic and industrial chemistry,13 the development of nanoscale palladium
particles and widespread applications in organic synthesis were carried out only during the last few decades.14
On the one hand, homogeneous palladium catalysts are generally preferred due to their high activity, but
recovery and reuse of the catalyst are impossible in this case.15 Furthermore, when it is considered palladium
is a precious metal and thus currently used palladium catalysts are really expensive and also sensitive to
the air,16 it is clear that stable and easily reusable palladium catalysts are urgently needed for sustainable
chemistry.17 In recent years, lots of studies were carried out for this purpose.18 To be able to produce
heterogeneous palladium catalysts, a large number of solid materials (such as carbon structures,19 polymers,20
and mesoporous silica21), micelles, microemulsions, surfactants, and ionic liquids (ILs) have been utilized as
supports for palladium.22 Nevertheless, the number of reusable palladium catalysts capable of reducing by green
solvent at room temperature is still limited.
In our previous works, we carried out hydrogenation of alkenes,23 hydrogenation of vegetable oils,24 and
nitro reduction25 with an automobile catalytic convertor. Here, palladium loaded 1,3,5-triazine-pentaethylenehe-
xamine (TAPEHA) polymer nanoparticle as a novel heterogeneous catalyst was used for reduction of aromatic
nitro compounds (Figure 1).
Figure 1. Reduction of aromatic nitro compounds with TAPEHA-Pd and NaBH
4 2 4 2
or N H .H O.
2. Results and discussion
The support material used in Pd-based catalysts should undoubtedly have a high palladium-adsorption capacity,
stability, and low resolution. TAPEHA demonstrated a good affinity toward palladium by virtue of having a high
density of amine and triazine functional groups. The Pd-adsorption capacity of this polymer was found to be
4
.18 mmol/g Pd(II) (444 mg/g) by column technique and this is one of the highest values in the literature.26,27
TAPEHA-Pd is also stable and has very low solubility in water and many organic solvents.
It is known that Pd(II) is reduced to Pd(0) in the presence of a hydride source like NaBH4 or N2 H4 .2
8−30
For this reason, Pd(II)-trapped TAPEHA has been reduced to Pd(0) state during the reduction experiment.
It can be clearly observed with color change in the polymer from yellow to black31 during the first second of
adding NaBH4 or N2 H4 .H2 O. As expected, nitro reduction has been carried out with Pd(0) catalyst in our
experiments. Thus, when recycled TAPEHA-PdNPs containing Pd(0) form are used in the next reaction, the
catalyst shows the same catalytic activity. TAPEHA-PdNPs can be recovered by filtration and used again in
another reduction reaction. It was reused ten times without any loss of activity. The amount of catalyst is
taken as 0.015 g for the reduction of 1 mmol nitro compound.
2.1. Optimum reaction conditions in NaBH4 mediated reductions
To determine the optimum reaction conditions in NaBH4 -mediated reductions, a series of experiments were
performed based on nitrobenzene (Table 1).
7
85

GEN C¸ et al./Turk J Chem
a
Table 1. Reduction of nitrobenzene in the presence of NaBH
4
under different reaction conditions .
Entry NaBH4 (mmol) EtOH/H2O (mL) Timeb Converted (%)
1
2
3
4
5
6
7
8
9
5.0
4.0
4.0
4.0
4.0
3.0
3.0
3.0
3.0
10/10
10/10
10/10
10/20
0/20
10/20
10/20
10/20
10/20
1.5 h
1 h
> 99
53
> 99
> 99
> 99
41
76
> 99
> 99
1.5 h
1.5 h
24 h
1.5 h
3 h
6 h
24 h
a
b
Reaction conditions: 1 mmol nitrobenzene, 0.015 g TAPEHA-Pd or TAPEHA-PdNPs, rt.
The reaction time was determined by TLC analysis.
Different ratios of EtOH/water were examined to find the best solvent mixture for the reduction. When
only water was used as the solvent, the reaction conversion was completed within 24 h. However, this method was
only applicable for liquid nitro compounds that are mixable in water such as nitrobenzene and 2-nitroanisole
and it is not suitable for solid nitroarenes. Using only an adequate amount of EtOH to solve compounds
shortened the reaction time. On the other hand, the excess of EtOH was not effective on the conversion ratio.
When 3 molar equivalents of NaBH4 were used the reaction was completed within 6 h. However, with 4 molar
equivalents of NaBH4 , the conversion can be completed within 1.5 h. Consequently, the optimum reaction
conditions for the reduction of nitrobenzene to aniline in NaBH4 -mediated reductions were 4 mmol of NaBH4
and 0.015 g of TAPEHA-PdNPs for a period of 1.5 h in 20 mL of a 1:1 mixture of EtOH/water.
2.2. Optimum reaction conditions in N2 H4 mediated reductions
N2 H4 -mediated reductions were also investigated to optimize the reaction conditions (Table 2). Effects of
different amounts of N2 H4 .H2 O in different solvent media like EtOH, EtOH/water mixture, tetrahydrofuran,
or diethyl ether were examined. When EtOH was used as the solvent, conversions were completed with 4 molar
equivalents of N2 H4 .H2 O in 20 min, 3 molar equivalents of N2 H4 .H2 O in 1 h, and 2 molar equivalents of
N2 H4 .H2 O in 3 h. Using 5 or more molar equivalents of N2 H4 .H2 O did not accelerate the reduction (20 min)
and 49% conversion ratio was detected with 1 molar equivalent of N2 H4 .H2 O in 3 h.
When THF was used, the reaction was completed in 45 min with 4 molar equivalents of N2 H4 .H2 O and
30 min with 5 molar equivalents of N2 H4 .H2 O. On the other hand, 8 molar equivalents of N2 H4 and diethyl
ether gave 75% yield in 30 min and 10 molar equivalents of N2 H4 .H2 O and diethyl ether gave quantitative
yield in 1 h. Hereby, the best reaction conditions for the reduction of nitrobenzene to aniline in N2 H4 .H2 O
mediated reductions were 4 mmol of N2 H4 .H2 O and 0.015 g of TAPEHA-PdNPs for a period of 20 min in 20
mL of EtOH or a 1:1 mixture of EtOH/water.
As shown in Table 3, optimized conditions were examined with 20 other aromatic nitro compounds with
both systems to make comparisons and determine the applicability of these methods. Isolated yields were
found to vary between 80% and 98% with NaBH4 and 85% and 98% with N2 H4 .H2 O. The highest yield of
786

GEN C¸ et al./Turk J Chem
a
2 4 2
Table 2. Reduction of nitrobenzene in the presence of N H .H O under different reaction conditions .
Entry N2H4.H2O (mmol) Solvent(s)
Timeb
3 h
3 h
Converted (%)
1
2
3
4
5
7
4
4
5
4
5
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
49
99
99
1 h
20 min > 99
20 min > 99
20 min > 99
EtOH/H2O 20 min > 99
THF
THF
Et2O
Et2O
45 min > 99
30 min > 99
30 min 75
1 h
> 99
a
b
Reaction conditions: 1 mmol nitrobenzene, 0.015 g TAPEHA-Pd or TAPEHA-PdNPs, rt.
The reaction time was determined by TLC analysis.
9
6
8% was obtained by reducing of 2-chloro-6-nitropyridine with NaBH4 (entry 17) and 4-nitrobenzonitrile and
-chloro-3-nitropyridin-2-amine (entries 16 and 18) with N2 H4 .H2 O, while relatively low yields were obtained
by reducing of 4-nitrophenol (entry 6) with NaBH4 (80%) and 2-nitroaniline (entry 7) with N2 H4 .H2 O (85%).
It is understood that nitroarenes with an electron-withdrawing group were reduced in higher yields than
for those containing an electron-donating group. At the same time, the presence of a group such as hydroxyl or
amine caused a lower yield because of slight dissolution of nitroarenes in water during the extraction process.
2.3. Pd leaching from TAPEHA after use as a catalyst
The Pd content of the TAPEHA before and after use was determined in order to investigate the leaching of
palladium from TAPEHA after use in the reduction reactions. The same level of Pd was found in the used
and nonused TAPEHA polymer. In summary Pd was not leached from TAPEHA and our process presents a
leach-free heterogeneous Pd system.
3. Conclusion
The results mentioned above demonstrate that aromatic nitro compounds are able to be reduced to correspond-
ing amine compounds by TAPEHA-PdNPs with a hydrogen source like NaBH4 or N2 H4 in high yields within
a short time and in mild conditions. Pd metal compounds that are normally air sensitive were made stable by
TAPEHA support polymer and additionally TAPEHA-PdNPs catalyst did not lose the property with reuse and
Pd was not leached. This system exhibited a selective catalyzed reduction with NaBH4 or N2 H4 in compounds
containing other reducible functionalities such as –CN, –Cl, –Br, and –I. Green solvents like EtOH and water
were used and nontoxic matters NaBO2 and N2 were obtained as byproducts. Consequently, selective, effective,
easy to use, environmentally friendly, and new catalyst systems have been developed.
4. Experimental
All the chemical substances used for reduction reactions were provided commercially (Merck, Sigma-Aldrich,
and Fluka).
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GEN C¸ et al./Turk J Chem
a,b
Table 3. Catalytic reduction of various nitroarenes using TAPEHA-Pd NPs.
c
d
Entry Reactant
nitrobenzene
Product
Aniline9
Yield (%) Yield (%)
92
90
86
88
81
80
84
85
81
83
92
93
84
93
93
96
98
94
93
90
87
88
86
85
87
88
88
90
90
89
96
96
98
97
98
95
94
4
4
2
3
4
2
4
3
1
1
1
4
2
3
4
2
6
5
2
-nitrotoluene
-nitroanisole
-nitroanisole
-nitrophenol
-nitrophenol
-nitroaniline
-nitroaniline
-nitroaniline
,3-dinitrobenzene
-bromo-3-nitrobenzene
-iodo-3-nitrobenzene
-methoxy-2-nitrophenol
-nitrobenzonitrile
-nitrobenzonitrile
-nitrobenzonitrile
-chloro-6-nitropyridine
4-toluidine9
4-methoxyaniline9
2-methoxyaniline9
3-aminophenol9
4-aminophenol9
2-phenylenediamine9
4-phenylenediamine9
3-phenylenediamine9
3-phenylenediamine9
3-bromoaniline32
3-iodoaniline33
2-amino-4-methoxyphenol34
2-aminobenzonitrile9
3-aminobenzonitrile35
4-aminobenzonitrile36
6-chloropyridin-2-amine37
-chloro-5-nitropyridin-2-amine 6-chloropyridine-2,5-diamine38 91
-nitroisoquinoline
5-aminoisoquinoline39
9h-fluoren-2-amine9
93
96
-nitro-9h-fluorene
a
Reaction conditions: 1 mmol nitroarene, 0.015 g TAPEHA-Pd or TAPEHA-Pd NPs, 4 mmol NaBH
4
2
, 20 mL EtOH/H O
(
1:1), at room temperature or 1 mmol nitroarene, 0.015 g TAPEHA-Pd or TAPEHA-Pd NPs, 4 mmol N
2 4 2
H .H O, 20
mL EtOH, at room temperature.
b
1
13
All products were characterized by H NMR and C NMR spectra and compared with authentic samples.
c
Isolated yield for NaBH
4
d
2 4 2
Isolated yield for N H .H O
4.1. Synthesis of 1,3,5-triazine-pentaethylenehexamine (TAPEHA) polymer
TAPEHA polymer was synthesized according to our earlier publication.26 In a three-necked round-bottom
flask, K2 CO3 (10 g, 72.36 mmol) was added to a solution of pentaethylenehexamine (35 g, 150.62 mmol)
in THF (50 mL) and the mixture was cooled with an ice bath. Cyanuric chloride (7.5 g, 40.76 mmol) and
pentaethylenehexamine (35 g, 150.62 mmol) in THF (50 mL) were slowly added from two separate dropping
funnels in two idle necks, while the mixture was constantly stirred. After being stirred for 24 h in an ice bath,
the THF was evaporated and the obtained cream color product was washed with deionized water and acetone
◦
three times, consecutively, and then dried in a vacuum oven for 24 h at 60 C (Figure 2).
Figure 2. Synthesis of TAPEHA.
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GEN C¸ et al./Turk J Chem
4.2. Preparation of Pd(II)-TAPEHA complex
In order to prepare Pd(II)-TAPEHA complex, 50 mg/L Pd(II) solution in 0.1 M HCl was passed through the
column (10 mm i.d., 150 mm length) loaded with TAPEHA particles (1 g) using a flow rate of 5 mL/min until
the Pd(II) concentration in the effluent reached 90% of its initial concentration. After this process, Pd(II)-
loaded TAPEHA was retrieved from the column and used for the reduction of nitro compounds. The amount
of Pd(II) loaded on TAPEHA was calculated to be 4.18 mmol/g (444 mg/g). Pd(II) ions can be uptaken by
TAPEHA via electrostatic attraction (Figure 3a) and/or complex formation (Figure 3b) mechanism.40,41
Figure 3. Proposed mechanism between Pd(II) ions and TAPEHA a) ion pair formation, b) complex formation.
4.3. General procedure for NaBH4 -mediated reduction of nitro compounds catalyzed by TAPEHA-
Pd
TAPEHA-Pd (0.015 g) was added to a solution of nitroarenes (1.0 mmol) in EtOH/water (1/1) (20 mL). After
NaBH4 (4.0 mmol) was slowly added to the mixture, the color of the reaction mixture turned gradually black in
a few minutes, resulting in the formation of palladium nanoparticles (TAPEHA-PdNPs).42 After being stirred
for 1.5 h at room temperature and atmospheric pressure, the catalyst was removed by filtering and the filtrate
was extracted with 3 × 30 mL of EtOAc. The combined organic layers were dried over MgSO4 and concentrated
in a vacuum.
4.4. General procedure for N2 H4 -mediated reduction of nitro compounds catalyzed by TAPEHA-
Pd
TAPEHA-Pd (0.015 g) was added to a solution of nitroarenes (1.0 mmol) in EtOH (20 mL). After N2 H4 .H2 O
(
4.0 mmol) was added the color of the catalyst was turned to black rapidly in the same way as reducing with
NaBH4 . This color change means formation of palladium nanoparticles43 TAPEHA-PdNPs as mentioned
above. After being stirred for 20 min at room temperature and atmospheric pressure, the catalyst was removed
by filtering and EtOH was removed under a vacuum.
4.5. The morphology and microstructure of TAPEHA-PdNPs
The morphology and microstructure of TAPEHA-PdNPs were examined by means of scanning electron mi-
croscopy, energy dispersive spectroscopy (SEM-EDS) (JEOL JSM-6060 LV Model), and high-resolution trans-
mission electron microscopy (HRTEM) (JEOL 2100 JEM Model). Phase analysis of dried and calcinated
powders alumina samples was performed via a Rigaku XRD instrument by using Cu Kα-radiation with a wave-
˚
length of 1.5418 A over a 2θ range of 10 ≤ 20 ≤ 90. The average crystallite sizes of powders are calculated using
Scherrer’s formula.4
4,45
The crystallite size calculated from the characteristic peak of Pd (about 2θ = 39.673
◦
◦
for and about 2θ = 40.341 , hkl values at 111) for Figures 4a and 4c is about 20 nm. The powders contain
mainly su-micrometer sized particles and close to spherical form (Figure 4b and 4d). Moreover, powders have
some particles size greater than 1 µm. These microparticles are aggregation of nano-sized primary particles.
High resolution transmission electron microscopy (HRTEM) observation also verified these results (Figure 5).
7
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GEN C¸ et al./Turk J Chem
Figure 4. a) XRD pattern of powders from NaBH
mediated reduction; c) XRD pattern of powders from N
-mediated reduction.
4
-mediated reduction; b) SEM micrograph of powders from NaBH
4
-
2
H
4
-mediated reduction; d) SEM micrograph of powders from
2 4
N H
Figure 5. HRTEM images of TAPEHA-Pd NPs.
4.6. Leaching of Pd from TAPEHA by use as a catalyst
First 4 mL of of aqua regia was added to the polymer for dissolution of the TAPEHA-PdNPs and then the
volatiles were evaporated to dryness. After this process was performed once more, the residue was dissolved
by 10 mL of 1 M HCl solution. The palladium level in the final solution was determined using flame atomic
absorption spectrometry.
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GEN C¸ et al./Turk J Chem
4.7. Reuse of the catalyst
After the reactions, the catalyst (TAPEHA-PdNPs) was filtered off and washed thoroughly with acetone, and
then dried in air for use in another reduction. The catalyst was able to be reused more than ten times without
any decrease in catalytic activity (Figure 6).
100
8
6
4
2
0
0
0
0
0
1
2
3
4
5
6
7
8
9
10
NaBH4
N H H O
2 4. 2
Figure 6. Reusability of TAPEHA-PdNPs for the reduction of nitrobenzene.
Acknowledgment
This work was supported by the research fund of Sakarya University.
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