Transfer hydrogenation of nitroarenes into anilines by palladium nanoparticles via dehydrogenation of dimethylamine borane complex

Article abstract of DOI:10.1039/c5ra14944d

This work reports a simple and highly efficient protocol for reduction of nitroarenes to corresponding amines via dehydrogenation of dimethylamine borane using palladium nanoparticle (Pd NPs) as a versatile heterogeneous catalyst. The facile approach for the synthesis of Pd NPs within 15 min in aqueous medium has been reported. The Pd NPs were well characterized using various analytical techniques such as XRD, FEG-SEM, TEM, EDAX and XPS. The developed catalytic system uses environmentally benign dimethylamine borane as a reducing agent which is highly stable, water soluble and nontoxic. The various amines were synthesized from nitroarenes in excellent yields within 10-60 min at room temperature. The catalyst was reused up to four successive cycles without significant loss in its catalytic activity.

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Transfer Hydrogenation of Nitroarenes into Anilines by Palladium
Nanoparticles via Dehydrogenation of Dimethylamine Borane
Complex
Received 00th January 20xx,
Accepted 00th January 20xx
Nilesh M. Patil, Manohar A. Bhosale, Bhalchandra M. Bhanage*
DOI: 10.1039/x0xx00000x
www.rsc.org/
This work report a simple and highly efficient protocol for reduction of nitroarenes to corresponding amines via
dehydrogenation of dimethylamine borane using palladium nanoparticle (Pd NPs) as a versatile heterogeneous catalyst.
The facile approach for the synthesis of Pd NPs within 15 min in aqueous medium has been reported. The Pd NPs were
well characterized using various analytical techniques such as XRD, FEG-SEM, TEM, EDAX and XPS. The developed catalytic
system uses environmentally benign dimethylamine borane as a reducing agent which is highly stable, water soluble and
nontoxic. The various amines were synthesized from nitroarenes in excellent yields within 10-60 min at room temperature.
The catalyst was reused up to four successive cycles without significant loss in its catalytic activity.
complexes for hydrogenation of various organic moieties with
DMAB as the reducing agent.16 However, in spite of their
potential utility, the above reports suffer from one or more
drawbacks such as use of phosphine ligands, longer reaction
time, harsh reaction conditions, difficulties in catalystꢀproduct
separation and complicated catalyst preparation procedure. So,
considering these drawbacks of homogenous system, the effort
was made to develop better heterogeneous recyclable catalytic
system for the dehydrogenation of DMAB.
Introduction
Hydrogen has been playing an important role as an alternative
power source for the transportation of fuel and fuel cell
vehicles.1 However, from safety point of view, it is very
difficult to control its storage and release limits.2 So, nowadays
various materials such as metalꢀorganic frameworks (MOF),3
metalꢀhydrides4 and organic materials5 have been tested for the
storage of hydrogen. Moreover, the aboveꢀmentioned materials
require high temperature, pressure and have problem with
storage capacity. Recently, ammoniaꢀborane class of family has
attracted great attention as a versatile material for chemical
hydrogen storage because of their low thermolysis temperature,
high stability, high water solubility and non toxicity.6 The
dehydrogenation of ammoniaꢀborane (NH3BH3, AB) and its
derivatives like methylamineꢀborane (CH3NH2BH3, MeAB)
and dimethylamineꢀborane (Me2NHBH3, DMAB) have found
wide potential applications in material science,7 polymer
Amine and their derivatives are important intermediates in
pharmaceuticals, agrochemicals, dyes, pigments, fine chemical
industries, biotechnology and material science.17 The catalytic
hydrogenation or transfer hydrogenation of nitro compounds is
one of the most useful methods for the synthesis of primary
amines. In this regard, Beller and coꢀworkers have developed
heterogeneous cobalt oxide and iron oxide based catalytic
system for the hydrogenation of nitroarenes using molecular
hydrogen.18 Nowadays, use of AB and DMAB as a reducing
agent has paying considerable attention due to its high
volume/mass hydrogen density, non toxicity and high stability
in water.19 In 2013, Stratakis and coꢀworkers reported Au NPs
catalyzed hydrogenation of nitroarenes using AB as reducing
agent.20 Later, Goksu et al. employed grapheneꢀsupported NiPd
and CoPd alloy catalytic system for reduction of nitroarenes
using AB as a hydrogen source.21 Subsequently, Yurderi et al.
have explored Ru(0) NPs stabilized by MOF for hydrogenation
of unsaturated hydrocarbons with dehydrogenation of DMAB.22
The nanoparticles have advantages over bulk materials such
as high surface area, which lead to increase in contact between
reactants, lower catalyst loading, reaction does not require any
ligand source, and low temperature.23 The palladium metal has
been extensively used for hydrogenation and transfer
hydrogenation reactions.24 In current research, the Pd NPs have
synthesis,8
transfer
hydrogenation9
and
tandem
dehydrogenationꢀhydrogenation reactions.10 In particularly, the
dehydrogenation of DMAB was studied using various
transitionꢀmetal catalysts such as palladium, ruthenium,
iridium,11 rhodium,12 rhenium,13 zirconium and titanium.14,15
Recently, Chirik’s reported homogeneous titanium precursor
complex
[(
η
5ꢀC5H3ꢀ1,3ꢀ(SiMe3)2)2Ti]2(ꢀ2
,
η1
,
η
1ꢀN2)
for
dehydrogenation of DMAB.14 It is noteworthy that, Williams
and coꢀworkers explored homogenous ruthenium and copper
Department of Chemistry, Institute of Chemical Technology, Matunga, Mumbai-
400019. India. E-mail: bm.bhanage@gmail.com, bm.bhanage@ictmumbai.edu.in;
Tel.: +91 2233612601; Fax: +91 2233611020.
Electronic Supplementary Information (ESI) available: [General reaction procedure
for synthesis of Pd NPs and transfer hydrogenation reaction, 1H NMR, 13C NMR and
GC-MS data of products]. See DOI: 10.1039/x0xx00000x
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been growing steadily due to their fascinating properties and The final product was washed several times with distilled water
activity. Hence, the Pd NPs have found several applications in followed by absolute ethanol and dried at 60 °C for 1 h in the
various fields such as lithiumꢀion batteries, electronics, oven.
biomedical sensing, surface enhanced Raman scattering,
hydrogen storage, magnetizations, water treatment and
heterogeneous catalyst.25ꢀ29 Literature study reveals that many
Methods of characterization
Xꢀray diffraction (XRD) patterns was recorded on a
methods have been developed for the synthesis of Pd NPs like Shimadzu XRDꢀ6100 using Cu Kα radiations = 1.5405 Å with
using solar energy,29 chemical reduction,30 by supercritical a scanning rate of 2° per min and 2 theta (θ) angle ranging from
31
CO2, sonochemical method,32 electrochemical method33 and 20o to 80o with current 30 mA and voltage 40 kV. The
biological method.34 Nagaraju and coꢀworkers demonstrated the morphology of prepared nanocatalyst was observed using field
synthesis of grapheneꢀpalladium nanocomposites using emission gunꢀscanning electron microscope (FEGꢀSEM)
hydrazine hydrate.35 Kalbasi and Mosaddegh reported Pdꢀ analysis on Tescan MIRA 3 model with operating voltage
poly(
N
ꢀvinylꢀ2ꢀpyrrolidone)/KITꢀ5
nanocomposite
using between 10.0 kV to 20.0 kV using secondary electron (SE)
hydrazine hydrate.36 Shen and coꢀworkers synthesized detector and transmission electron microscopy (TEM) using
poly(acrylic acid)ꢀPd(0) composites films using hydrazine Philips CMꢀ200, operating voltage at 200 kV. The energy
hydrate.37 However, these protocols have some drawbacks such dispersive Xꢀray spectrum (EDAX) was obtained using INCA
as use of hazards reagents, high temperature and long reaction xꢀact Oxford instrument (Model 51ꢀADD0007). The Xꢀray
time, use of specialized instruments and necessity of extra photoelectron spectrum (XPS) analysis of synthesized Pd NPs
additives. Hence, there is need for the development of simple, were recorded using PHI 5000 versa probe scanning ESCA
faster and convenient method for the synthesis of Pd NPs. Here, microprobe.
we have developed a simple and inexpensive method for the
synthesis of spherical Pd NPs via chemical reduction of PdCl2
using PEGꢀ6000 as a capping agent and hydrazine hydrate as a
Results and discussion
Catalyst characterization
reducing agent in aqueous medium within 15 min. Furthermore,
the transfer hydrogenation of nitroarenes into corresponding
amines using present Pd NPs via dehydrogenation of DMAB as
a hydrogen source was developed at room temperature (Scheme
1).
The synthesized Pd NPs were characterized using various
techniques. The phase identification of Pd NPs was carried out
using an Xꢀray diffractometer (Fig. 1), which show the
diffraction peaks at 2θ values of 40o, 47o, 68o, 82o and 87o
correspond to the (111), (200), (220), (311) and (222) phases
for Pd NPs. The obtained results from XRD are in good
agreement with JCPDS card 05ꢀ0681. The morphology of Pd
NPs was carried out using field emission gunꢀscanning electron
microscope (FEGꢀSEM). The low magnification (Fig. 2a) and
high magnification (Fig. 2b) FEGꢀSEM images display the size
and shape of the Pd NPs. It shows the formation of spherical Pd
NPs and the particles are in nano region.
Scheme 1 Transfer hydrogenation of nitroarenes via dehydrogenation of DMAB.
Experimental
Materials
The palladium chloride (PdCl2) was acquired from Parekh
Industries Ltd. Mumbai, India. Polyethylene glycol (PEGꢀ6000)
and hydrazine hydrate (100%) were procured from S. D. Fine
chemicals Pvt. Ltd. India. Dimethylamineꢀborane (Me2NHBH3)
was purchased from SigmaꢀAldrich. All chemicals were
procured from reputed firm and was used without further
purification.
Preparation of Pd NPs
In a round bottom flask, 20 mg of PdCl2 and 40 mg of PEGꢀ
6000 were dissolved in 5 mL distilled water and then heated at
80 °C for 5 min. After 5 min, the hydrazine hydrate (300 µL,
100%) was added drop wise into the above mixture and then
stirred for 10 min at 80 °C. After completion of reaction, the
color of the reaction mass changes reddish to black this
indicates the formation of Pd NPs. The catalyst was separated
by centrifugation of reaction mixture at 5000 rpm for 10 min.
Fig. 1 XRD pattern of Pd NPs.
2 | J. Name., 2012, 00, 1-3
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Table 1 Optimization of reaction conditions for transfer hydrogenation of
The TEM analysis was carried out by dispersing powder
sample in absolute ethanol and then sonicated for 10 min in
sonication bath. The drop of that slurry was deposited on
copper grid. The TEM images (Fig. 2c and 2d) for the Pd NPs
displays the formation of spherical NPs having size range 20
nm to 40 nm. PEGꢀ6000 acts as a capping agent in a reaction
which interact with Pd metal and helps to get shape and size
controlled morphology of nanoparticles. Fig. 3a displays the
EDAX spectrum of Pd NPs. It shows only the presence of Pd
peaks and no other impurities were observed. XPS analysis
describes elemental oxidation state of the metal from the
material. XPS spectrum shows the peak at 335.1 eV and 340.4
eV which corresponds to Pd 3d5/2 and Pd 3d3/2 respectively
(Fig. 3b). The XPS spectrum confirms that the Pd is in zero
Pd(0) state.
nitroarenesa
Catalyst
DMAB
Time
(min)
Entry
Catalyst
loading
(mol%)
Yield (%)b
(equiv.)
Effect of Catalyst loading
1
2
3
4
Pd NPs
Pd NPs
Pd NPs
-
2
4
6
-
3
3
3
3
10
10
10
10
40
82
99
00
Effect of hydrogen donor concentration
5
6
7
Pd NPs
Pd NPs
Pd NPs
6
6
6
2
1
-
10
10
10
79
37
00
Effect of time
8
9
Pd NPs
Pd NPs
6
6
3
3
5
45
99
15
a
Reaction conditions: Nitrobenzene (0.5 mmol), RT, 3 mL of water/methanol (v/v =
2/1). b Yield based on GC analysis.
nitrobenzene (Table 1, entries 1ꢀ3). It was found that the 6
mol% of Pd NPs catalyst furnished the corresponding aniline in
highest yield (Table 1, entry 3). However, when the reaction
was performed without catalyst, no product formation was
observed which shows the necessity of catalyst (Table 1, entry
4). Next, we have studied the effect of hydrogen donor
concentration and it was notice that yield of the product
decreases with decrease in concentration of DMAB (Table 1,
entries 5 and 6). Furthermore, it was observed that reaction
does not work in the absence of DMAB (Table 1, entry 7).
Fig. 2 (a, b) FEG-SEM images (c, d) TEM images of Pd NPs.
Scheme 2 Pd NPs catalyzed dehydrogenation of DMAB.
During the catalytic process, the hydrogen released from
DMAB is, immediately utilized for reduction of starting
material. However some hydrogen released by DMAB get
liberated to the atmosphere therefore 3 equivalents of DMAB is
required to catalyze the reaction. (Scheme 2).
Fig. 3 (a) EDAX spectrum (b) XPS spectrum of Pd 3d5/2 and 3d3/2 regions of Pd NPs.
Subsequently, we have also studied the effect of time and it
was found that 10 min is sufficient to get maximum yield of the
desired product (Table 1, entries 8 and 9). Thus, the best
optimized reaction parameter for tandem dehydrogenation of
DMAB and in situ transfer hydrogenation of nitroarenes were;
nitroarene (0.5 mmol), DMAB (1.5 mmol) and Pd NPs (6
mol%) for 10 min at room temperature (28ꢀ30 oC).
Study of optimization parameters for transfer hydrogenation of
nitroarenes
Initially, the various reaction parameters were optimized for
the synthesis of aniline from nitrobenzene using Pd NPs
catalyst via tandem dehydrogenation of DMAB along with in
situ reduction of nitrobenzene (Table 1). Firstly, we have
studied the effect of catalyst loading for the reduction of
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Table 2 Catalysts comparisons for transfer hydrogenation of nitroarenesa
We also carried out the caparison study of Pd NPs with
Pd/C for transfer hydrogenation of nitrobenzene to aniline. It
was observed that Pd NPs provides good yield with high TOF
than the Pd/C (Table 2, entries 1 and 2).
TOF
(min-1)
Catalyst
loading
(mol%)
DMAB
Time
(min)
Yield
(%)b
Entry
Catalyst
(equiv.)
With optimized conditions in hand, we investigate the
general applicability of present protocol for transfer
hydrogenation of various nitroarenes using DMAB. The several
aromatic nitro compounds were reduced to the respective
primary amines in excellent yields within 10ꢀ60 min at room
temperature (Table 3). Nitrobenzene was reduced into aniline
with a yield of >99% in 10 min. (Table 3, entry 1). Further, we
0.825
0.708
1
2
Pd NPs
6
6
3
3
10
10
99
85
(10%) Pd/C
a
Reaction conditions: Nitrobenzene (0.5 mmol), RT, 3 mL of water/methanol (v/v =
2/1). b Yield based on GC analysis.
Table 3 Pd NPs catalyzed transfer hydrogenation various nitroarenes via
dehydrogenation of DMABa
reduced different alkylꢀsubstituted nitrobenzene such as oꢁ, mꢁ
and pꢁnitrobenzenes to the respective amines in excellent yields
(Table 3, entries 2ꢀ4). We have also screened chloro and bromo
nitroarenes and observed the less yields of desired products
along with dehalogenated products. (Table 3, entries 5 and 6).
The Pd NPs catalyst was also active for the reduction of 2ꢀ
fluoro nitrobenzene to 2ꢀfluoro aniline in excellent yield
without affecting halogen group (Table 3, entry 7). Next, 2ꢀ
nitro benzyl alcohol and 2ꢀnitroaniline were also reduced giving
good yield of desired product (Table 3, entries 8 and 9).
Subsequently, we also check present protocol for reduction of
Time
(min)
Entry
Substrate
Product
Yield (%)b
1
99
10
2
3
99
88
15
15
mꢀnitro and pꢀnitro phenol and it was observed that reaction
provided good yield of the desired products within 10 min
(Table 3, entries 10 and 11). The 2ꢀnitroꢀ9Hꢀfluorene was
reduced giving corresponding product in moderate yield (Table
3, entry 12). Furthermore, we have also extended our protocol
for chemoselective reduction of 4ꢀmethylꢀ3ꢀnitrobenzonitrile,
2ꢀ(4ꢀnitrophenyl)acetonitrile and interestingly observed that
only selective reduction of nitro group into corresponding
amines without affecting the cyano group (Table 3, entries 13
and 14).
4
5
99
34
15
10
6
10
10
Catalyst recyclability study
7
8
9
99
99
90
20
20
30
In order to make our present catalytic system more
economically feasible, we have investigated recyclability of Pd
NPs for transfer hydrogenation of nitrobenzene to aniline. After
completion of reaction, Pd NPs catalyst was separated using
centrifugation at 5000 rpm. The catalyst was then washed
several times with water and absolute ethanol to remove the rest
of organic impurities and dried in oven and reused for next run.
The catalyst was efficiently recycled up to four successive
cycles without significant loss in its catalytic activity (Fig. 4).
The surface morphological study of fresh nanocatalyst and
recycled nanocatalyst was studied with FEGꢀSEM analysis
(Fig. 5). The FEG–SEM image (Fig. 5a) of fresh Pd
nanoparticles display the spherical and well dispersed
nanoparticles whereas, (Fig. 5b) display FEG–SEM analysis of
nanocatalyst after the fourth run. The detail study of recycled
catalyst reveals that recycled nanoparticles are more
aggregation and disturb the morphology than that of fresh
nanoparticles.
10
11
99
99
10
10
12
13
55
60
99
99
30
30
14
a
Reaction conditions: Nitroarenes (0.5 mmol), Pd NPs (6 mol%), (CH3)2NHBH3 (3
equiv.), RT, 3 mL of water/methanol (v/v = 2/1). b Yield based on GC analysis.
4 | J. Name., 2012, 00, 1-3
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distilled water and absolute ethanol. The separated catalyst was
dried in oven and reused for next reaction. The product was
extracted with DCM (3 × 10 mL) and dried over anhydrous
Na2SO4 and evaporated under vacuum to obtain the product. All
the obtained products are well known in literature and were
confirmed by GC (Perkin Elmer, Clarus 400) (BPꢀ10 GC
column, 30 m x 0.32 mm ID, film thickness 0.25 mm), GCMS
(Shimadzu GCꢀMS QP 2010), 1H NMR and 13C NMR
spectroscopy.
Characterisation data of products
1
2-amino-9H-fluorene. White solid, 52% yield. H NMR (400
MHz, CDCl3)
1H), 7.45 (d,
= 7.4 Hz, 1H), 6.87 (s, 1H), 6.70 (d,
2H); 13C NMR (101 MHz, CDCl3)
δ
7.62 (d,
J
= 7.6 Hz, 1H), 7.55 (d,
= 7.4 Hz, 1H), 7.17 (t,
= 8.0 Hz, 1H), 3.79 (s,
145.62, 145.21, 142.35,
J = 8.1 Hz,
J
= 7.4 Hz, 1H), 7.30 (t,
J
J
δ
J
Fig. 4 Recyclability study for Pd NPs.
142.07, 132.97,1 26.58, 125.04, 124.71, 120.61, 118.55,
113.96, 111.80, 36.79.
3-amino-4-methylbenzonitrile. Yellow solid, 96% yield, 1H
NMR (500 MHz, CDCl3)
= 7.7, 1.4 Hz, 1H), 6.90 (d,
(s, 3H); 13C NMR (126 MHz, CDCl3)
δ
7.11 (d,
= 1.4 Hz, 1H), 3.79 (s, 2H), 2.21
145.11, 131.01, 127.54,
J = 7.7 Hz, 1H), 6.98 (dd, J
J
δ
122.13, 119.39, 117.15, 110.40, 77.25, 77.00, 76.74, 17.65.
2-(4-aminophenyl)acetonitrile. Orange solid, 97% yield, 1H
NMR (400 MHz, CDCl3)
= 8.4 Hz, 2H), 3.70 (s, 2H), 3.60 (s, 2H); 13C NMR (101 MHz,
CDCl3) 146.18, 128.90, 119.28, 118.42, 115.44, 22.79.
δ 7.07 (d, J = 8.5 Hz, 2H), 6.65 (d, J
δ
Fig. 5 FEG-SEM images of (a) fresh Pd NPs (b) 4th recycled Pd NPs.
Acknowledgements
Author N. M. Patil thankful to University grand commission
(UGCꢀSAP), New Delhi and author M. B. Bhosale is grateful to
Council of Scientific and Industrial Research (CSIR), India for
providing fellowship. We are thankful to the Department of
Science and Technology (DST), India for financial support for
this work under Nano Mission Project No. SR/NM/NSꢀ
1097/2011.
Conclusions
In summary, we have developed simple, efficient and
greener catalytic system for tandem dehydrogenation of DMAB
along with in situ reduction of aromatic nitro compounds into
corresponding amines using Pd NPs as a heterogeneous
catalyst. The present catalytic system could be easily recycled
by simple centrifugation up to four successive cycles without
loss in its activity. The current protocol offers several
advantages such as 1) reuse of precious metal, 2) tandem
dehydrogenation and hydrogenation reaction, 3) ecoꢀfriendly
and nontoxic hydrogen source, 4) without using high pressure
reactor, 5) reaction can perform under ambient condition
providing excellent yield within short time and 6) wider
substrate applicability with chemoselectivity.
Notes and references
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The nitroarene (0.5 mmol) and Pd NPs catalyst (6 mol%)
were mixed in 3 mL of water/methanol mixture (v/v = 2/1) in a
schlenk tube at room temperature. Then, dimethylamineꢀborane
(3 equiv.) was added to the above reaction mixture and stirred
for 10 min. The progress of reaction was monitored by thin
layered chromatography (TLC) and gas chromatography (GC).
After completion of the reaction, the catalyst was separated by
centrifugation at 5000 rpm and washed several times with
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