Selectivity and activity in catalytic hydrogenation of azido groups over Pd nanoparticles on aluminum oxy-hydroxide

Article abstract of DOI:10.1039/c6nj01925k

Azidoarenes involving various functional groups were successfully reduced to aniline derivatives using commercially available aluminium oxy-hydroxide-supported palladium (Pd/AlO(OH)) nanoparticles (0.5 wt% Pd) in an aqueous medium with sodium borohydride as the hydrogen source. To develop the green process, water was utilized in conjunction with methanol. The results demonstrated that the halogen substituted azidoarenes were selectively converted to the corresponding aniline compounds without dehalogenation. In general, all of the reactions were completed within 10-30 min at room temperature with yields of over 99%. In order to optimize the reaction conditions, the parametric effects of the solvent type and the amount of the catalyst/NaBH₄ were examined. Consequently, for the first time, a novel, practical and environmentally friendly process was developed for the conversion of azidoarenes to aniline derivatives in the fluence of Pd/AlO(OH) nanoparticles.

Full text of DOI:10.1039/c6nj01925k

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DOI: 10.1039/C6NJ01925K
Journal Name
ARTICLE
Selectivity and activity in catalytic hydrogenation of azido groups
over Pd nanoparticles on aluminum oxy-hydroxide
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
b
Belgüzar Yasemin Kara , Benan Kılbaş* , Haydar Göksu*
DOI: 10.1039/x0xx00000x
Azido arenes involving various functional groups were successfully reduced to aniline derivatives using commercially
available aluminium oxy-hydroxide-supported palladium (Pd/AlO(OH)) nanoparticles (0.5 wt% Pd) in an aqueous medium
with sodium borohydride as the hydrogen source. To develop the green process, water was utilized in conjunction with
methanol. The results demonstrated that the halogen substituted azido arenes were selectively converted to
corresponding aniline compounds without dehalogenation. In general, all of the reactions were completed within 10-30
minute at room temperature with yields of over 99%. In order to optimize the reaction conditions, the parametric effects
www.rsc.org/
of the solvent type and the amount of the catalyst/NaBH were examined. Consequently, for the first time, a novel,
4
practical and environmentally friendly process was developed for the conversion of azido arenes to aniline derivatives in
the fluence of Pd/AlO(OH) nanoparticles.
hydrogenation processes have been developed that have many
Introduction
Aniline derivatives are important synthetic molecules due to their
reactive amino functionalities. They are extensively utilized as
chemical intermediates in the synthesis of drug molecules,
antioxidants and dye-sensitized solar cells (DSSCs).6 For example,
NSP-116 [4-(4-acetylpiperazin-1-yl)-2-(1H-imidazol-1-yl)] aniline has
been used to treat the photoreceptor degeneration causing vision
18,19
advantages such as recovery, reusability and stability.
Due to
20-25
their higher catalytic activity,
solid supported palladium
1-5
nanoparticles (NPs) have been extensively researched for use in
selective reduction processes. This study also utilized commercially
available Pd/AlO(OH) NPs in the hydrogenation of aryl azides.
Limited interest in these NPs as heterogeneous catalysts has been
shown in the literature. However, more recently, an exponential
growth has been observed in the number of publications dealing
,7
8
loss in the elderly. In addition, N-phenyl-1,4-phenylenediamine
9
(
NPPD) is recognized as a strong antioxidant and 4-(octyloxy)aniline
26
with the alkylation of ketones with alcohols, the reduction of
10
has been utilized as a starting material in the synthesis of DSSCs.
2
7
28
olefins and the dynamic kinetic resolution of primary amines.
Furthermore, Pd/AlO(OH) NPs were utilized for the effective
reduction of nitro compounds into primary amines for the first time
29
by the authors of the present study. This nanocatalyst is
preferable because it is more accessible, recoverable, and reusable
in addition to being more stable under different environmental
1
4
30
conditions, unlike commercial catalysts such as Fe
PdCl , Pd(OAc) .
2 2
3
O
4
,
FeCl
3
,
31
32
On the other hand, liquid hydrogen carriers like
glycerol, isopropyl alcohol and hydrazine and solid hydrogen
carriers such as sodium borohydride, dimethyl aminoborane,
magnesium hydride and ammonia borane have been frequently
used for the hydrogenation process. A distinct priority is given to
solid hydrogen sources because they are able to generate hydrogen
molecules without high temperatures. Therefore, for the catalytic
Various synthetic approaches have been employed for aniline
11
12
production, with the reduction process of the nitro, imine and
1
3,14
azide
groups being the easiest and most convenient method
15-17
among them.
Recently, using heterogeneous catalysts,
reactions, this study used NaBH
4 2
(10.8 wt% H ), which is stable,
3
3
safe, cheap, eco-friendly and water-soluble.
a.Department of Chemistry, Faculty of Sciences, Duzce University, 81620 Duzce,
Turkey. E-mail: benankilbas@duzce.edu.tr.
b
Kaynasli Vocational College, Düzce University, Düzce 81900, Turkey.
E-mail: haydargoksu@duzce.edu.tr; Fax: +90 380 5442812 Tel: +90 380 5442811
†
Electronic Supplementary Information (ESI) available: NMR spectra and spectral
data of aniline derivatives. See DOI: 10.1039/x0xx00000x
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DOI: 10.1039/C6NJ01925K
Fig. 1 (a) SEM image before the reaction; (b) SEM image after five uses; (c) EDX spectrum before the reaction; (d) EDX spectrum after five uses of Pd/AlO(OH)
NPs
in Table 1, the solvent system of 1.5 ml of water/methanol (v/v =
2
/1) was predominant in respect to the other solvents as it took the
Results and discussion
shortest time (15 min) (Table 1, entry 9). The effects of temperature
Herein, a novel process was developed for the one-pot selective and the amounts of sodium borohydride and the catalyst were also
hydrogenation of aryl azides to aniline derivatives in the presence tested. Experimental results indicated that the corresponding
of solid supported palladium NPs in an aqueous medium at
roomtemperature using sodium borohydride as the solid hydrogen Table 1 Optimization reactions for reduction of 1-azido-4-chlorobenzene a
source. The desired products, with absolute conversions and yields
of over 99%, were successfully obtained within 10-30 min.
The morphologies of Pd/AlO(OH) NPs both before the reaction
and after being reused five times were examined by SEM. The SEM
Catalyst
NaBH
(mmol)
4
Time
(min)
Yieldb
(%)
No
reaction
Trace
No
reaction
Trace
63
68
75
95
>99
images show the catalyst as a nanocrystalline Boehmite structure.
Under high magnification, the surface morphology of a nanocluster
can be clearly observed in Figure 1(a) and (b). Both images have an
irregular spread. The agglomeration of the catalyst surface was
observed after it was reused five times, corresponding to the image
in Figure 1(b). Carbon, aluminum and palladium are the elemental
components of the catalyst as seen in Figure 1(c) and (d). The
abundance of carbon is probably from the air. An XRD image of the
Pd/AlO(OH) NPs before the reaction is also exhibited in the ESI (†
Fig. S1 and S2). The diffraction peaks indicate that the face-
centered cubic (fcc) structure of the palladium was well established
on the surface of the AlO(OH), as mentioned in a previously
Entry
Solvent
(
mg)
1
2
3
CH
IPA
CH CN
Cl
2 2
25
0.5
120
120
120
25
0.5
3
25
0.5
4
5
6
7
8
9
EtOH
MeOH
25
25
25
40
25
25
25
25
0.5
0.5
0.5
0.75
0.5
0.5
0.25
0.5
120
45
45
60
20
15
45
25
H
H
2
O
2
O
H
2
O/CH
3
OH (1:1)
H
2
O/CH
O/CH
O/CH
3
OH (2:1)
1
0
H
H
2
3
OH (2:1)
OH (1:2)
65
92
No
reaction
65
11
2
2
3
34
published work.
1
2
H
O/CH
3
OH (2:1)
-
0.5
120
In the reduction processes, 1-azido-4-chlorobenzene was
utilized as a substrate in order to optimize the reaction medium.
The different solvent systems were examined for the hydrogenation
process, including dichloromethane, isopropyl alcohol, acetonitrile, aReaction conditions: 1-azido-4-chlorobenzene (0.25 mmol), Pd/AlO(OH)
ethanol, methanol, water and a methanol/water mixture. As shown NPs and room temperature. GC yield.
1
1
3
4
H
H
H
2
O/CH
O/CH
O/CH
3
OH (2:1)
3
OH (2:1)
3
OH (2:1)
10
15
20
0.5
0.5
0.5
30
30
30
2
2
72
87
15
b
2
| J. Name., 2012, 00, 1-3
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DOI: 10.1039/C6NJ01925K
Table 2 Pd/AlO(OH) NPs catalyzed reduction of various azido arenes
d
d
Entry
Substrate
Product
Yield (%) Time (min)
Entry
Substrate
Product
Yield (%) Time (min)
1
>99
15
8
>99
14
1
3
2
4
6
1
5
16
18
2
3
>99
>99
15
15
9
>99
>99
12
10
17
19
10
5
7
9
2
0
4
5
>99
>99
15
15
11
12
>99
>99
12
10
8
2
1
22
24
1
0
23
7
3
0
0
1
2
6
7
30
12
13
14
>99
>99
25
20
1
1
1
3
25
27
26
2
>99
14
2
8
a
Unless otherwise stated, substrate (0.25 mmol), NaBH
4
(0.5 mmol) and Pd/AlO(OH) NPs (25 mg, 0.12 mmol% Pd) was used with 1.5 ml of water/methanol
d
(v/v=2/1) at room temperature GC yield.
products were obtained at
a high yield without elevated reaction was not carried out under catalyst-free conditions (Table 1,
temperatures. As a consequence, the optimum reaction condition entry 12).
was firmly established as 0.25 mmol of substrate, 0.5 mmol of
Sodium borohydride provided a rapid reduction reaction as
hydrogen source and 25 mg of catalyst acting together in 1.5 ml of seen in Table 2. Even if the reaction is completed in a short time,
H O/CH OH mixture (2:1) at room temperature. The reduction the scale-up process can cause safety and quality issues due to the
2 3
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fast hydrolysis in water and the uncontrolled release of hydrogen after 30 min (Table 2, entry 6). Dehalogenation and azide reduction
View Article Online
DOI: 10.1039/C6NJ01925K
gas. In order to avoid this problem, alkaline reaction conditions (10- reactions compete with each other because the weaker C-I bond
4
0
2
0 wt% NaOH) were employed. As shown in the following reaction, reaction. Methyl substituted azidobenzenes have high reactivity in
when NaBH interacts with NaOH, a controlled release of hydrogen the reduction reaction due to the electron-donor ability of the
occurs. Thus, the reaction time is extended, but the risk is reduced methyl group. The o-, m- and p-methyl azidobenzenes (13, 15, 17)
4
35-38
to a minimum.
were easily reduced to corresponding aniline derivatives (14, 16,
8) within 12-14 min with quantitative yields (Table 2, entries 7-9).
1
The o-, m- and p-methoxy azidobenzenes (19, 21, 23) were
converted to corresponding aniline derivatives in a shorter time as
As expected, 1-azido-4-chlorobenzene (5) and 1-azido-4- in the case of methyl-substituted azidobenzenes (Table 2, entries
methylbenzene (17) were converted with high yields to 10-12). The reactivity of the m-methoxy azidobenzene (21) is quite
corresponding aniline derivatives over a longer time in the presence slow with respect to the other isomers. Moreover, 1-azido-2-
3
9
of 20 wt% sodium hydroxide solution (Table 3). On the other (trifluoromethyl)benzene
hand, the metaborate salt (NaBO ), which is a side product of the (trifluoromethyl)benzene (27) were also reduced to 2-
reduction process, can easily be removed from the reaction mixture (trifluoromethyl)aniline (26) and 4-(trifluoro methyl)aniline (28)
(25)
and
1-azido-4-
2
by rapid flash column chromatography.
with the yields being above 99% (Table 2, entries 13, 14). However,
the completion of the reduction process took longer than expected.
The plausible reasons for this include not only the electron-
withdrawing effect but also the sterical hindrance of the
trifluoromethyl group.
Table 3 The reduction of some azido compounds in NaOH mediuma
Leaching into the mixture is a common undesirable process in
catalytic systems. Reusability tests indicated there was no
significant amount of product distribution loss after the
corresponding catalyst was reused five times. Moreover, the ICP-
MS result showed that the palladium leaching into the reaction
mixture was only 1.2%, which in the reduction process was
negligible (Table 4).
b
Entry
1
Substrate
5
Product
Yield (%) Time (min)
96
97
35
28
6
2
Table 4 Reusing of Pd/AlO(OH) NPsa
1
7
18
1
st run
5th run
aConditions: substrate (0.25 mmol), NaBH
(0.5 mmol), catalyst (25 mg, 0.12
4
Entry
1
Substrate
Product
Yieldb
Yieldb
Time
min
Time
min
mmol% Pd), NaOH (20 wt%), 1.5 ml of water/methanol (v/v=2/1) and room
%
%
b
temperature. GC yield.
>99
>99
15
96
21
As illustrated in Table 2, all of the azido arenes were successfully
reduced to anilines within 10-30 min with quantitative yields via
hydrolysis of sodium borohydride with the contribution of solid
supported Pd NPs. Azidobenzene (1) was reduced to aniline (2)
with high yields within 15 min (Table 2, entry 1). Chlorine- and
2
15
95
18
bromine-substituted azido arenes (3, 5, 7, 9) were selectively aUnless otherwise stated, substrate (0.25 mmol), NaBH
4
(0.5 mmol ) and
Pd/AlO(OH) NPs (25 mg, 0.12 mmol% Pd) was used with 1.5 ml of
water/methanol (v/v=2/1) at room temperature. GC yield.
converted to corresponding halo aniline derivatives (4, 6, 8, 10)
with high yields in a short time (Table 2, entries 2-5). However, the
hydrogenation of 4-iodo azidobenzene (11) gave rise to both 4-
iodoaniline (12) and aniline (2), carefully determined by GC analysis,
can easily be broken by the catalyst-assisted hydrogenation
b
Table 5 Use of different commercially available catalysts for reduction of 1-azido-2-chlorobenzene (3) to 2-chloroaniline (4) a
b
Amount of
catalyst,
mg
Yield (%)
Time
TON
TOF
Entry
Catalyst
PdCl
2-
(min)
Aniline
55
(mol2-chloroaniline /molmetal(s)
(mol2-chloroaniline /molmetal(s)/hour
chloroaniline
1
2
1.77
60
45
11.2
11.2
2
3
4
Pd(OAc)
Pd/Cc
PdAlO(OH)d
2
2.24
10.6
25
60
60
15
78
82
22
18
-
19.5
20.5
19.5
20.5
>99
212.0
848.0
a
Reaction conditions, substrate (0.25 mmol), NaBH
4
(0.5 mmol) and catalyst (0.01 mmol) was used with 1.5 ml of water/methanol (v/v=2/1)
b
c
d
at room temperature. GC yield. 5 wt% Pd. 0.001 mmol of PdAlO(OH) NPs was used.
4
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A comparison of PdAlO (OH) NPs with other palladium-based received. Ultrasonic agitation was carried oDuOt Iu: 1s0in.1g03a9/LCa6bNoJr0g1e9r2a5tKe
commercially available catalysts was also conducted. The 1-azido-2- GmbH 100W (50 Hz) unit.
chlorobenzene (3) served as a substrate for the comparison test.
Under the same reaction conditions, 1-azido-2-chlorobenzene (3)
Characterization methods
Scanning electron microscopy (SEM) analysis was performed via a
JEOL SEM5800 device equipped with an EDX probe having an
accelerator voltage of 20 keV. The X-ray diffraction (XRD) was
conducted using a Panalytical Empyrean diffractometer with Ultima
was subjected to a transfer hydrogenation reaction to provide 2-
chloroaniline (4) in the presence of PdCl , Pd(OAc) , Pd/C and
PdAlO(OH) NPs by using sodium borohydride. The promising results
with TON/TOF values showed PdAlO(OH) NPs to have distinct
advantages, such as high yield and short time, for aniline formation
2
2
+
theta-theta high resolution goniometer and an X-ray generator
(
Cu K radiation, λ = 1.54056Å) operating at 45 kV and 40 mA. The
(
Table 5). Furthermore, it is more effective and more stable in the
paladium content after the reaction were determined by a Leeman
water component of the solvent system. On the other hand,
1
31
32
Lab inductively coupled plasma (ICP) spectrometer. The H NMR
2
PdCl ,
2
Pd(OAc) and Pd/C assisted reduction reactions are not
spectra were recorded on a Jeol ECS 400 MHz spectrometer.
selective, i.e., the chlorine group preserved its functionality when
only PdAlO(OH) was utilized.
General procedure for hydrogenation via sodium borohydride
Azidoarene (0.25 mmol) in 0.5 ml methanol was added to a
magnetically stirred aqueous suspension of Pd AlO(OH) NPs (1 ml/
2
4
5 mg catalyst) at room temperature. After NaBH (0.5 mmol) was
added to the reaction mixture, the vessel was closed. The reaction
continued while the mixture was vigorously stirred and monitored
by GC. Most of the reactions were completed over the time period
of 10-30 min. After the reaction, the catalyst was collected via
centrifugation at 6500 rpm and washed five times with ethanol and
water. The corresponding catalyst was then allowed to dry for
further use. The solvent was evaporated under vacuum and the
products were purified by rapid flash column chromatography. The
Scheme 1 Proposed mechanism for hydrogenation process.
1
yields of the reduced compounds were determined by H NMR with
3 3
CD OD or CDCl as the solvent, depending on the product
separated.
According to the proposed mechanism outlined in Scheme 1, free
hydrogen gas was released by the hydrolysis of sodium borohydride
with the contribution of the catalyst followed by hydrogen atom
transfer to the azide on the catalyst surface. The rearrangement of
the protons and subsequent elimination of nitrogen afforded
corresponding aniline derivatives.
Syntheses
1
Aniline (2).
.79-6.56 (m, 3H).
3
-chloro aniline (4). H NMR (400 MHz, CDCl ): δ 7.44 – 7.26 (m,
H NMR (400 MHz, CD OD): δ 7.14-6.94 (m, 2H),
3
6
1
1
2
H), 7.19 – 7.07 (m, 1H), 6.88 – 6.69 (m, 2H), 4.05 (s, 2H).
1
4-chloro aniline (6). H NMR (400 MHz, CD
3
OD): δ 7.13 –6.93
(
m, 2H), 6.77-6.58 (m, 2H).
Conclusions
1
2-Bromoaniline (8). H NMR (400 MHz, CDCl
3
): δ 7.55 (dd, J =
In summary, for the first time, the reduction of various azido arenes 8.0, 1.4 Hz, 1H), 7.22 (td, J = 8.0, 1.4 Hz, 1H), 6.80 (dd, J = 8.0, 1.4
to anilines with yields of over 99% was accomplished using Hz, 1H), 6.74 (td, J = 8.0, 1.5 Hz, 1H), 4.16 (s, 2H).
PdAlO(OH) nanoparticles as a heterogeneous catalyst. Sodium
borohydride was used as the hydrogen carrier in an aqueous (m, 2H), 6.71-6.44 (m, 2H).
medium at room temperature. Selective hydrogenation was
4-Iodoaniline (12). H NMR (400 MHz, CD OD): δ 7.31-7.28 (m,
observed where chlorine and bromine groups preserved their 2H), 6.52-6.48 (m, 2H).
functionality. The PdAlO(OH) nanoparticles exhibited excellent
2-Aminotoluene (14).
reusability performance without significant loss in product yield. (m, 2H), 6.80-6.63 (m, 2 H), 3.85 (s, 2H), 2.05 (s, 3H).
This reusability performance avoided tedious work-up procedures
3-Aminotoluene (16). H NMR (400 MHz, CD OD): δ 7.30-7.09
and revealed a practical, efficient and environmentally friendly (m, 1H), 6.81-6.73 (m, 2H), 6.67 (m, 1H), 2.30 (s, 3H).
4-Bromoaniline (10).
1
3
H NMR (400 MHz, CD OD): δ 7.21-7.02
1
3
1
3
H NMR (400 MHz, CD OD): δ 7.11-6.92
1
3
process.
1
3
4-Aminotoluene (18). H NMR (400 MHz, CDCl ): δ 7.00 (t, J =
8
2
.0 Hz, 2H), 6.63 (t, J = 6.4 Hz, 2H), 2.26 (s, 3H).
1
2-Methoxy aniline (20). H NMR (400 MHz, D
2
O) δ 6.85-6.77 (m,
Experimental
Materials
H), 6.77-6.68 (m, 2H), 3.85 (s, 3H).
1
3-Methoxy aniline (22). H NMR (400 MHz, CD
3
OD) δ 7.43-6.66
(
m, 1H), 6.25 (m, 3H), 3.69 (s, 3H).
Pd/AlO(OH) NPs, azidoarenes were obtained from Sigma-Aldrich.
NaBH
4
was also purchased from Sigma-Aldrich and used as
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1
26 M. S. Kwon, N. Kim, C. M. Park, J. S. Lee, K. Y. KanVgiewanArdticJle. POanlrinke,
4
-Methoxy aniline (24). H NMR (400 MHz, CD
H), 3.67 (s, 3H).
3
-(trifluoromethyl)aniline (26). H NMR (400 MHz, CD OD) δ
3
OD) δ 6.69 (m,
Org. Lett., 2005, 7, 1077-1079.
DOI: 10.1039/C6NJ01925K
4
2
7 F. Chang, H. Kim, B. Lee, S. Park and J. Park, Tetrahedron Lett.,
1
2
2010, 51, 4250-4252.
7
6
.35 (d, J = 7.9 Hz, 1H), 7.31-7.25 (m, 1H), 6.87 (d, J = 8.2 Hz, 1H),
.70 (t, J = 7.6 Hz, 1H).
-(trifluoromethyl)aniline (28). H NMR (400 MHz, CD
.31 (d, J = 8.5 Hz, 1H), 6.75 (d, J = 8.5 Hz, 1H).
2
8 M. J. Kim, W. H. Kim, K. Han, Y. K. Choi and J. Park, Org. Lett.,
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29 H. Goksu, New. J. Chem. 2015, 39, 8498-8504.
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3
3
3
3
1 S. C. Shim, K. N. Choi and Y. K. Yeo, Chem. Lett., 1986, 7, 1149-
Acknowledgements
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This research was supported by Duzce University Research Fund
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7
(
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3
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New Journal of Chemistry
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DOI: 10.1039/C6NJ01925K
Table of contents entry
Selectivity and activity in catalytic hydrogenation of azido groups over Pd nanoparticles
on aluminum oxy-hydroxide
a
a
b
Belgüzar Yasemin Kara , Benan Kılbaꢀ* , Haydar Göksu*
Practical and effective catalytic method has been developed for the reduction of aryl azides in
the presence of PdAlO(OH) nanoparticles and sodium borohydride.