Immobilized ruthenium metal-containing ionic liquid-catalyzed dehydrogenation of dimethylamine borane complex for the reduction of olefins and nitroarenes

Article abstract of DOI:10.1039/c6ra09785e

An efficient immobilized ruthenium metal containing ionic liquid (ImmRu-IL) catalyst has been developed for the transfer hydrogenation of olefins and nitroarenes. Various olefins and nitroarenes were reduced in excellent yields within 2-6 h at room temperature. This methodology uses eco-friendly dimethylamine borane as a reducing agent which is nontoxic, water soluble, highly stable and easy to handle. The reactions take place through tandem dehydrogenation and hydrogenation of dimethylamine borane complex in the presence of ImmRu-IL catalyst. The catalyst was reused in up to four consecutive cycles without any significance loss in its activity. The fresh and reused catalysts have been studied by XPS analysis.

Full text of DOI:10.1039/c6ra09785e

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Immobilized Ruthenium Metal-Containing Ionic Liquid-Catalyzed
Dehydrogenation of Dimethylamine Borane Complex for the
Reduction of Olefins and Nitroarenes
Received 00th January 20xx,
Accepted 00th January 20xx
a
b
a,
DOI: 10.1039/x0xx00000x
Nilesh M. Patil, Takehiko Sasaki and Bhalchandra M. Bhanage *
www.rsc.org/
An efficient immobilized ruthenium metal containing ionic liquid (ImmRu-IL) catalyst has been developed for the transfer
hydrogenation of olefins and nitroarenes. The various olefins and nitroarens were reduced in excellent yields within 2-6 h
at room temperature. This methodology uses eco-friendly dimethylamine borane as a reducing agent which is nontoxic,
water soluble, highly stable and easy to handle. The reactions take place through tandem dehydrogenation and
hydrogenation of dimethylamine borane complex in the presence of ImmRu-IL catalyst. The catalyst was reused up to four
consecutive cycles without any significance loss in its activity. The fresh and reused catalysts have been studied by XPS
analysis.
1
2
such as ruthenium, iridium and palladium. Berke and coꢀ
workers have reported homogenous Reꢀcatalyzed alkenes
hydrogenation using DMAB as a hydrogen source. Chirik’s
explored homogeneous system of titanium precursor complex
Introduction
1
3
Nowadays, dehydrogenation of ammoniaꢀborane (NH
3
2
BH
BH
3
3
,
,
AB) and its derivatives like methylamineꢀborane (CH
MeAB) and dimethylamineꢀborane (Me NHBH
been gaining great attention because of their high hydrogen
) storage capacity which could solve the problem of
3
NH
5
1
[(η ꢀC H ꢀ1,3ꢀ(SiMe ) ) Ti] (ꢀ2,η ,η1ꢀN ) for dehydrogenation
5 3 3 2 2 2 2
2
3
, DMAB) has
1
4
1
of DMAB. Of note, Williams and coꢀworkers have described
homogenous copper and ruthenium complexes for
dehydrogenation of DMAB and in situ reduction of various
(H
2
2
hydrogen economy. Several organic and inorganic materials
such as metalꢀorganic frameworks (MOF), organic materials
and metalꢀhydrides have been employed for the storage of
hydrogen. However, the uses of these materials are limited by
1
5
3
4
organic moieties. In spite of their potential utility of these
protocols, the use of homogeneous non recyclable catalytic
systems and expensive phosphine ligands, harsh reaction
conditions, longer reaction time and difficulty in catalystꢀ
product separation have limited the applicability of these
protocols. In additions to these limitations, it needs tedious
preparation of homogeneous catalytic systems. Therefore, there
is a need to develop a better costꢀeffective, heterogeneous, and
reusable catalytic system for the dehydrogenation of DMAB.
The transitionꢀmetal catalyzed hydrogenation or transfer
hydrogenation of olefinic bonds and the reduction of nitroarens
5
(i) the need of high pressure system (ii) the need high
temperature (iii) low storage H capacity and (iv) difficult to
handle. On the other hand, ammoniaꢀborane class of family has
great advantages compared to the above mentioned materials
because of their high H storage capacity, high stability and
2
nontoxicity. In addition, they are easy to handle and are highly
2
6
soluble in water at room temperature. Ammoniaꢀborane and its
7
analogs play vital role in polymer industry, material
1
6
8
9
are one of the most significant reactions in organic chemistry.
chemistry, tandem dehydrogenationꢀhydrogenation reactions
1
0
Hydrogenations of olefin bonds have been carried out in the
and transfer hydrogenation.
catalyzed transfer hydrogenations of unsaturated organic
moiety have been achieved by borane family. In particularly,
dehydrogenations of dimethylamineꢀborane (Me NHBH ,
3
DMAB) are known using various transitionꢀmetal catalysts
In recent decades, cobaltꢀ
1
7
18
presence of transition metals such as palladium, ruthenium,
1
9
20
1
1
rhodium
and iridium.
Beller and coꢀworkers have
documented heterogeneous iron and cobalt based catalytic
systems for the reduction of nitroarenes using molecular
2
2
1
hydrogen. Among the available reduction process, the transfer
hydrogenation is the most attractive process because it does not
a
Department of Chemistry, Institute of Chemical Technology, N. Parekh Marg, require high pressure reaction vessel (autoclave) or use of
Matunga,
bm.bhanage@ictmumbai.edu.in Tel.: +91 22 33612603; Fax: +91 22 33611020.
Department of Complexity Science and Engineering, Graduate School of Frontier
Mumbai-400019,
India.
*E-mail:
bm.bhanage@gmail.com;
flammable hydrogen gas. Nowadays, AB and DMAB have
been become popular reducing agent due its high hydrogen
b
2
2
Sciences, The University of Tokyo, 5-1-5, Kashiwanoha, Kashiwa, Chiba 277-8561, realizing capacity, highly soluble in water and nonꢀtoxicity.
Japan
.
NMR data of all products]. See DOI: 10.1039/x0xx00000x
1
Electronic Supplementary Information (ESI) available: [GC-MS, H NMR and
13
C
Yurderi et al. studied Ru(0) NPs catalyzed olefins reduction
2
3
using DMAB as hydrogen source. The bimetallic catalytic
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systems such as NiPd grapheneꢀsupported and CoPd alloy and was refluxed for 48 h under nitrogen atmosphere. After the
Au NPs for the reduction of nitroarenes using AB as hydrogen completion of reaction, material was filtered on glass filter and
2
4
source are also known.
Immobilization of metals on various supports is important ionic liquid. The obtained solid material is denoted as ImmꢀIL.
in heterogeneous catalysis as it could solve the problem of The 3.00 g of ImmꢀIL and 0.6721 g of RuCl •3H O were
catalyst recycling and product separation thereby making refluxed in 50 mL of acetonitrile for 24 h. Then solvent was
finally washed with hot dichloromethane to remove excess of
3
2
2
5
process greener and costꢀeffective. From this aspect, ecoꢀ removed using glass filter, followed by washing with acetone
friendly ionic liquids immobilized on solid materials have been several times. The obtained catalyst denoted as ImmRuꢀIL, was
use for many organic transformations. In continuation of our dried by evacuation at room temperature for 24h. The metal
interest in to develop efficient heterogeneous and loading of catalyst was 5.82 wt% as determined by XRF
environmentally benign protocols for the hydrogenation measurements (Scheme 2).
reactions, herein we explore a immobilized ruthenium metalꢀ
containing ionic liquid [ImmRuꢀIL] for the transfer
hydrogenation of olefins and nitroarenes using DMAB as
hydrogen source at room temperature (Scheme 1).
2
6
2
7
N
N
Cl
N
3
43 K
(OMe)3Si
N
+
(OMe) Si
Cl
+
3
48 h
1ꢀ Methylimidazole
OH
OH
Silica(Aerosil 300),
Toluene, reflux, 48 h
RuCl3 H2O
O
O
Cl
N
ImmRu-IL
SiO
Si
N
+
ACN,
Reflux, 24h
OMe
ImmꢀIL
Scheme 2 Preparation of ruthenium metal-ion-containing immobilized ionic liquid.
Scheme 1 Transfer hydrogenation of olefins and nitroarenes using ImmRu-IL.
Results and discussion
Experimental
Optimization study for transfer hydrogenation of styrene
The reaction conditions were optimized for the in situ
reduction of styrenes using ImmRuꢀIL catalyst via tandem
dehydrogenation of DMAB. For this purpose, styrene (0.5
mmol) was chosen as a model substrate in the presence of
ImmRuꢀIL as a catalyst (Table 1).
At the beginning, the reaction was carry out in the absence
of catalyst, the reaction did not proceed (Table 1, entry 1).
Next, we compared the activity of synthesized ImmRuꢀIL with
commercially available Ru/C (5%) and it was found that
ImmRuꢀIL catalyzed furnished excellent of yield of desired
product than Ru/C (Table 1, entries 2,3). It was found that the
Materials
3
ꢀtrimethoxysilylpropyl
Methylimidazole (99+%), dried redistilled 1ꢀmethylimidazole
99+%) and RuCl •3H O were purchased form Aldrich and all
chloride
(97+%),
Nꢀ
(
3
2
the dry solvents were obtained from WAKO commercially.
Aerosil 300 (300 m /g) was acquired from Japan Aerosil Co.
and calcined at 573 K for 1.5 h in air for 30 min in vacuum.
The catalyst loading was calculated by XRF measurements
using Philips PW2402 XRF spectrometer (Xꢀray source 40kV,
2
1
00 mA). The XPS of ImmRuꢀIL was measured using a
PHI5000 Versa Probe with monochromatic focused (100 ꢁm ×
00 ꢁm) Al Kα Xꢀray radiation (15 kV, 30 mA) and dual beam
2
.5 mol% of ImmRuꢀIL catalyst provided the corresponding
1
ethyl benzene in highest yield (Table 1, entries 3,4).Without
silica supported RuꢀIL also provided good yield of the desired
product (Table 1, entry 5). In the next set of experiments, we
screened various nonꢀpolar and polar solvents such as toluene,
water, THF, methanol and ethanol and it was observed that non
polar toluene gave excellent yield of desire product (Table 1,
entries 6ꢀ10). We have performed the model reaction in
absences of solvent and 96% yield of ethyl benzene was
observed (Table 1, entry 11). Thus, the optimized reaction
conditions for transfer hydrogenation of styrene are: styrene
neutralization using a combination of argon ion gun and
electron irradiation.
Catalyst Synthesis (ImmRu-IL)
In a dry flask 3ꢀtrimethoxysilylpropyl chloride (0.690 mol)
and
nitrogen condition and the resulting reaction mass refluxed for
8 h. After completion of reaction, the reaction mass was
Nꢀmethylimidazole (0.690 mol) were added under a
4
allowed to cool at room temperature and then washed with dry
ethyl acetate. The obtained residue (1ꢀmethylꢀ3ꢀ(3ꢀ
trimethoxysilylpropyl) imidazolium chloride) was dried at room
temperature under reduced pressure for 48 h and then stored at
(
0.5 mmol), DMAB (1 equiv.), and ImmRuꢀIL (3 mol%) and
toluene as a solvent at room temperature.
With optimized conditions in hand, we extend the
developed protocol for the transfer hydrogenation of various
olefins using DMAB. The several unsaturated compounds were
reduced to the saturated compounds in excellent yields within
253 K under dry nitrogen. 1ꢀmethylꢀ3ꢀ(3ꢀtrimethoxysilylpropyl)
imidazolium chloride (weight ratio 1:1) and Silica (Aerosil
2
3
00, surface area 300 m /g, calcined at 573 K for 1.5 h in air)
2
ꢀ6 h at room temperature (Table 2).
were dispersed in dry toluene and then the reaction mixture
2
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Table 1. Effect of reaction parameter on transfer hydrogenation of
a
7
8
6
6
85
84
styrene
Catalyst
b
Entry
Catalyst
loading
mol%)
Solvent
Yield(%)
(
O
O
Catalyst screening and Catalyst loading
9
6
6
6
80
90
88
1
2
3
4
5
No catalyst
Ru/C (5%)
ImmRu-IL
ImmRu-IL
Ru-IL
-
Toluene
Toluene
Toluene
Toluene
Toluene
00
42
99
59
98
HO
2.5
2.5
1
10
2.5
11
N
N
Effect of Solvent
a
Reaction conditions: olefins (0.5 mmol), ImmRu-IL (2.5 mol%), (CH
3
)
2
NHBH
3
6
7
8
9
ImmRu-IL
2.5
2.5
2.5
2.5
2.5
2.5
Toluene
Water
THF
99
30
45
64
69
96
b
(
1 equiv.), toluene (2 mL), RT, time (2-6 h). Yield based on GC and GC-MS analysis.
ImmRu-IL
ImmRu-IL
ImmRu-IL
ImmRu-IL
ImmRu-IL
Further, the present methodology was used for the transfer
hydrogenation of nitroarnes under the optimized conditions. A
series of nitro compounds could be reduced into corresponding
amines in excellent yields within 2ꢀ6 h. Interestingly, the
reactions works well even at room temperature without forming
any side products (Table 3).
Methanol
Ethanol
-
1
0
1
1
a
3 2 3
Reaction conditions: styrene (0.5 mmol), ImmRu-IL (2.5 mol%), (CH ) NHBH
b
(
1 equiv.), solvent (2 mL), RT, time (2 h). Yield based on GC and GC-MS analysis.
Table
nitroarenes
3
ImmRuꢀIL catalyzed transfer hydrogenation of various substitute
a
Styrene was reduced to ethyl benzene with a yield of >99%
in 2 h (Table 2, entry 1). Furthermore, Cyclohexene, aliphatic
ꢀDecene and 1ꢀHexene were providing good yields of the
desired saturated products (Table 2, entries 2ꢀ4). Next we also
check present protocol for hydrogenation of ꢀCH and ꢀamino
b
Yield. (%)
Entry Substrate
Product
Time (h)
1
1
NO2
p
3
p
2
99
styrene and it was found both substrates provided good yield of
the desired products (Table 2, entries 5,6). Allylbenzene and
substituted allylbenzene were easily reduced under optimized
conditions (Table 2, entries 7,8).The biomass derived Eugenol
was successfully reduced in corresponding product with
excellent yield (Table 2, entry 9). Furthermore, we have
extended our protocol for the reduction of bulky and
heterocyclic olefins and it was found that both substrate
provided excellent yield of the desired products (Table 2, entry
2
3
6
86
6
6
4
4
82
70
86
90
NO2
4
10,11).
I
a
Table 2 ImmRu-IL catalyzed transfer hydrogenation of various substitute Olefins
NO2
5
6
b
Entry Substrate
Product
Time (h)
Yield. (%)
1
2
99
7
8
4
5
92
86
2
2
99
NO2
3
4
1ꢀDecene
1ꢀHexene
NꢀDecane
NꢁHexane
2
2
96
99
MeO
5
6
4
6
82
86
9
2
96
H2N
2
H N
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in oven and reused for next reaction. The catalyst was recycled up to
four consecutive cycles without losing its activity.
NO2
1
0
1
2
6
97
85
HO
XPS study
st
XPS spectra were measured for the fresh ImmRuꢀIL, the 1
1
th
recycle, and the 4 recycle catalysts to indentified elemental
composition and valence states of the catalyst. Pollini reported
binding energy values for RuCl
3
at 285.40 eV ( 3d3/2
) and
2
8
1
2
3
6
6
80
84
2
81.0 eV(3d5/2), respectively. Therefore, the fresh catalyst
3
+
0
can be assigned as Ru state. Ru exhibits 284.20 eV for 3d3/2
and 279.01ꢀ280.20 eV for 3d5/2
recycle and the 4 recycle samples remain at Ru state with a
,
st
2
9
.
Main component of the 1
th
3+
1
0
slight component of reduced Ru state, corresponding to the
st
a
decrease in the intensity of Cl 2p signal for the 1 recycle and
Reaction conditions: nitroarenes (0.5 mmol), ImmRu-IL (2.5 mol%), (CH
3
)
2
NHBH
3
th
b
the 4 recycle samples (Figure 2).
(
3 equiv.) toluene (2 mL), RT, time (2-6 h). Yield based on GC and GC-MS analysis.
Nitrobenzene cleanly reduction into aniline with excellent
yield in 2 h (Table 3, entry 1). Next, the halogenꢀsubstituted
chloro, fluoro and iodo nitroarenes were studied and it was
found that in all the halogenated nitrobenzenes reduced very
easily into respective primary amines with good yield (Table 3,
2
entries 2ꢀ4). The ꢀNO groups with oꢀ, mꢀ and pꢀ methyl and pꢀ
methoxy nitrobenzene could also be reduced into related amine
successfully (Table 3, entries 5ꢀ8).The present catalytic system
also works well for nitro phenol reduction within 2 h (Table 3,
entries 9,10). The reduction of nitro benzyl alcohol and 2ꢀ
nitroaniline was employed providing products 2ꢀaminobenzyl
alcohol and
oꢀphenyldiamine in good yields (Table 3, entries
11,12). Furthermore, chemoselectively only nitro groups was
reduced when the 4ꢀNitrobenzonitrile was employed under the
optimized reaction conditions (Table 3, entry 13).
Recycle study
In an effort to make the present catalytic system more
economical and greener, we focused on reusability of ImmRuꢀ
IL catalyst for reduction reaction. As shown in Figure. 1
catalyst was recycled for standard reaction of styrene in the
presence of DMAB as a hydrogen donor. After completion of
reaction, ImmRuꢀIL catalyst was isolated by filtration method. region.
The filtrate catalyst was washed with toluene several times to
remove the rest of organic residue. The recovered catalyst dried
Fig. 2 (a) ImmRu-IL wide scan survey (b) XPS of Cl2p region (c) XPS of Ru3d
Table 4 Recent literature on catalytic transfer hydrogenation of various substitute
olefins and nitroarnes.
Sr.
No.
Recycle
study
T
( C)
t
Catalyst
H
2
Source
o
Ref.
(h)
[
Ru(pꢀ
Me
2
NHBH
3
1
ND
70
24
15
cymene)Cl ]
2 2
2
3
Cu(OTf)
Me
Me
2
2
NHBH
3
3
ND
ND
85
85
24
15
13
Re complex
Pd/KCCꢀ1ꢀ
NHBH
1ꢀ4
4
HCOOH
Me NHBH
Recycle
Recycle
100
40
6ꢀ24
16
16a
23
NH
2
RuNPs/ZIFꢀ
8
2
3
5
6
This
Work
ImmRu-IL
Me
2
NHBH
3
Recycle
RT
2-6
ND : Not demonstrated.
Fig. 1 Recyclability study of ImmRu-IL catalyst.
4
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1
3
(
t, J = 7.3 Hz, 3H). C NMR (126 MHz, CDCl
3
) δ 146.29, 143.49,
1
34.71, 120.96, 114.12, 111.05, 55.83, 37.77, 24.89, 13.82.
1
Conclusions
1-(tert-butyl)-4-ethylbenzene.Colorless liquid. H NMR (500 MHz,
CDCl
7.6 Hz, 2H), 1.32 (s, 9H), 1.25 (t, J = 7.6 Hz, 3H). C NMR (126
3
) δ 7.33 (d, J = 8.0 Hz, 2H), 7.16 (d, J = 7.8 Hz, 2H), 2.64 (q, J
In summary, we have developed a simple, environmentally
benign and recyclable catalytic system for transfer
hydrogenation of C=C bonds and nitro compounds by ImmRuꢀ
IL as a versatile heterogeneous catalyst. Various olefins and
nitroarenes were reduced via dehydrogenation of DMAB at
room temperature. The use of DMAB as hydrogen source
makes the developed methodology environmentally benign and
nontoxic. The ImmRuꢀIL catalyst was easily recovered by
filtration method and could be reused up to four consecutive
cycles without loss of its catalytic activity.
13
=
MHz, CDCl
3
) δ 148.33, 141.14, 127.48, 125.16, 34.32, 31.42, 28.25,
1
2
8
1
5.50.
1
-Ethylpyridine. Pale yellow liquid. H NMR (500 MHz, CDCl
.46 (d, J = 4.6 Hz, 1H), 7.53 (t, J = 7.6 Hz, 1H), 7.10 (d, J = 7.8 Hz,
H), 7.05 – 7.00 (m, 1H), 2.77 (q, J = 7.6 Hz, 2H), 1.25 (t, J = 7.6
3
) δ
13
Hz, 3H). C NMR (126 MHz, CDCl
21.97, 120.82, 31.31, 13.85.
3
) δ 163.40, 149.04, 136.31,
1
1
Aniline. Pale yellow liquid. H NMR (500 MHz, CDCl
3
) δ 7.22 (t, J
=
6.8 Hz, 2H), 6.86 – 6.79 (m, 1H), 6.73 (d, J = 7.8 Hz, 2H), 3.66 (s,
1
3
2
3
H). C NMR (126 MHz, CDCl ) δ 146.48, 129.35, 118.58, 115.19.
General procedure of ImmRu-IL catalyzed transfer hydrogenation
of olifins
1
2-Chloroaniline. Brown liquid. H NMR (500 MHz, CDCl ) δ 7.29
3
(
d, J = 8.0 Hz, 1H), 7.10 (t, J = 7.7 Hz, 1H), 6.77 (d, J = 8.0 Hz, 1H),
The olefins (0.5 mmol) and ImmRuꢀIL catalyst (2.5 mol%)
were mixed in 2 mL of toluene in a oven dried schlenk tube and
then DMAB (1 equiv.) was added. Then the reaction mixture
was stirred at room temperature for 2ꢀ6 h. The progress of
reaction was monitored by gas chromatography (GC) and
GGMS. All products are wellꢀknown in the 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) and
GCMS (Shimadzu GCꢀMS QP 2010) analysis.
13
6
1
2
–
6
.73 (t, J = 7.6 Hz, 1H), 4.07 (s, 2H). C NMR (126 MHz, CDCl ) δ
3
42.99, 129.45, 127.71, 119.29, 119.06, 115.97.
1
- Fluroaniline..Yellow liquid. H NMR (500 MHz, CDCl ) δ 7.06
3
7.00 (m, 1H), 6.98 (t, J = 7.7 Hz, 1H), 6.80 (t, J = 8.5 Hz, 1H),
13
.74 (dd, J = 12.9, 7.5 Hz, 1H), 3.76 (s, 2H). C NMR (126 MHz,
CDCl
3
) δ 152.72, 150.83, 134.63, 134.53, 124.53, 124.50, 118.68,
1
18.63, 117.05, 117.02, 115.33, 115.18.
1
4-Iodoaniline.Brown solid. H NMR (500 MHz, CDCl3) δ 7.41
13C
(
d, J = 7.9 Hz, 2H), 6.47 (d, J = 8.0 Hz, 2H), 3.24 (s, 2H).
NMR (126 MHz, CDCl ) δ 146.01, 137.89, 117.30, 79.40.
o-Toluidine. Brown liquid. H NMR (500 MHz, CDCl
7.4 Hz, 2H), 6.76 (t, J = 7.1 Hz, 1H), 6.71 (d, J = 7.7 Hz, 1H), 3.61
3
Characterisation data of products
1
3
) δ 7.10 (d, J
=
1
Ethyl benzene. Colorless liquid, H NMR (400 MHz, CDCl
3
) δ
13
(
s, 2H), 2.21 (s, 3H). C NMR (126 MHz, CDCl
3
) δ 144.58, 130.47,
7
1
1
.40 – 7.33 (m, 2H), 7.31 – 7.25 (m, 3H), 2.74 (q, J = 7.6 Hz, 2H), 126.99, 122.35, 118.65, 114.96, 17.39.
1
3
1
.33 (t, J = 7.6 Hz, 3H); C NMR (101 MHz, CDCl
3
) δ 144.28, m-Toluidine. Brown liquid. H NMR (500 MHz, CDCl
3
) δ 7.12 (t, J
=
7.6 Hz, 1H), 6.66 (d, J = 7.4 Hz, 1H), 6.55 (d, J = 9.6 Hz, 2H),
28.36, 127.91, 125.64, 28.96, 15.70.
13C
1
3.64 (s, 2H), 2.34 (s, 3H).
NMR (126 MHz, CDCl ) δ 146.46,
3
Cyclohexane. Colorless liquid. H NMR (400 MHz, CDCl
3
) δ 1.41
1
3
139.15, 129.22, 119.46, 115.98, 112.31, 21.51.
(s, 12 H); C NMR (101 MHz, CDCl
3
) 26.88.
1
p-Toluidine . White solid. H NMR (500 MHz, CDCl
3
) δ 6.97 (d, J
1
N-Decane. Colorless liquid. H NMR (400 MHz, CDCl
3
) δ 1.27 (d,
J = 15.0 Hz, 16H), 0.87 (t, J = 6.7 Hz, 6H); CNMR (101 MHz,
CDCl ) δ,31.91, 29.65, 29.35, 22.67, 14.04.
=
7.9 Hz, 2H), 6.62 (d, J = 7.9 Hz, 2H), 3.50 (s, 2H), 2.25 (s, 3H).
1
3
13
C NMR (126 MHz, CDCl
20.45.
p-Anisidine. Brown solid. H NMR (500 MHz, CDCl
8.6 Hz, 2H), 6.65 (d, J = 8.7 Hz, 2H), 3.74 (s, 3H), 3.23 (s, 2H). C
NMR (126 MHz, CDCl ) δ 152.78, 139.89, 116.41, 114.78, 55.73.
3
) δ 143.77, 129.74, 127.78, 115.24,
3
1
1
4-Ethyltoluene. Colorless liquid. H NMR (500 MHz, CDCl
3
) δ
) δ 6.75 (d, J
3
13
=
7
.11 (s, 4H), 2.63 (q, J = 7.6 Hz, 2H), 2.33 (s, 3H), 1.24 (t, J = 7.6
1
3
3
3
Hz, 3H). C NMR (126 MHz, CDCl ) δ 141.20, 134.98, 128.98,
1
m-Aminophenol. White solid. H NMR (500 MHz, DMSOꢀD
6
) δ
1
27.72, 28.43, 20.98, 15.79.
8
.79 (s, 1H), 6.73 (t, J = 7.9 Hz, 1H), 5.96 (s, 2H), 5.89 (d, J = 7.8
1
4-Ethylaniline. Yellow liquid. H NMR (500 MHz, CDCl ) δ 7.06
13
3
Hz, 1H), 4.84 (s, 2H). C NMR (126 MHz, DMSOꢀD
6
) δ 158.46,
(
=
d, J = 7.5 Hz, 2H), 6.68 (d, J = 7.9 Hz, 2H), 3.58 (s, 2H), 2.61 (q, J
1
50.25, 129.83, 105.80, 103.66, 101.34.
1
3
1
7.6 Hz, 2H), 1.26 (t, J = 7.6 Hz, 3H). C NMR (126 MHz, CDCl ) p-Aminophenol. Redish solid. H NMR (500 MHz, DMSOꢀD ) δ
3
6
1
3
δ 144.13, 134.45, 128.64, 115.33, 28.05, 16.05.
8.29 (s, 1H), 6.39 (dd, J = 29.8, 7.6 Hz, 4H), 4.37 (s, 2H). C NMR
(126 MHz, DMSOꢀD ) δ 148.59, 141.08, 115.93, 115.61.
1
Propylbenzene. Colorless liquid. H NMR (500 MHz, CDCl
3
) δ
6
1
2-Aminobenzylacohol. Brown solid. H NMR (500 MHz, CDCl
3
3) δ
7
.30 – 7.25 (m, 3H), 7.18 (d, J = 7.1 Hz, 2H), 2.58 (t, J = 7.6 Hz,
13
7.14 (t, J = 7.6 Hz, 1H), 7.07 (d, J = 7.4 Hz, 1H), 6.72 (dd, J = 13.5,
2
H), 1.69 – 1.60 (m, 2H), 0.94 (t, J = 7.3 Hz, 3H). C NMR (126
) δ 142.68, 128.44, 128.18, 125.56, 38.06, 24.58, 13.85.
13
7
.5 Hz, 2H), 4.66 (s, 2H). C NMR (126 MHz, CDCl ) δ 146.04,
3
MHz, CDCl
3
1
129.39, 129.19, 124.76, 118.14, 116.00, 64.41.
4-Propylanisole. Colorless liquid. H NMR (500 MHz, CDCl
3
) δ
1
o-Phenylenediamine. Gray solid. H NMR (500 MHz, CDCl
3
) δ
7
.12 (d, J = 7.3 Hz, 2H), 6.85 (d, J = 7.0 Hz, 2H), 3.81 (s, 3H), 2.55
1
3
13
3
6.75 – 6.69 (m, 4H), 3.24 (s, 4H). C NMR (126 MHz, CDCl ) δ
(
t, J = 7.6 Hz, 2H), 1.68 – 1.59 (m, 2H), 0.95 (t, J = 7.3 Hz, 3H). C
1
34.71, 120.27, 116.74.
3
NMR (126 MHz CDCl ) δ 157.60, 134.80, 29.31, 113.61, 55.23,
1
4-Aminobenzonitrile. White solid. H NMR (500 MHz, CDCl ) δ
3
3
7.15, 24.83, 13.80.
1
7.41 (d, J = 8.2 Hz, 2H), 6.64 (dd, J = 8.2, 0.4 Hz, 2H), 4.17 (s, 2H).
2-Methoxy-4-propylphenol. Colorless liquid. H NMR (500 MHz,
1
3
C NMR (126 MHz, CDCl
00.17.
3
) δ 150.35, 133.80, 120.13, 114.42,
CDCl
3
) δ 6.86 (d, J = 7.8 Hz, 1H), 6.70 (d, J = 8.8 Hz, 2H), 5.60 (s,
1
1H), 3.88 (s, 3H), 2.54 (t, J = 7.6 Hz, 2H), 1.69 – 1.59 (m, 2H), 0.96
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
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DOI: 10.1039/C6RA09785E
ARTICLE
Journal Name
Y.-Z. Chen, Z. U. Wang, Q. Xu and H.-L. Jiang, Chem.
Commun., 2015, 51, 10419-10422.
3 M. Yurderi, A. Bulut, M. Zahmakiran, M. Gulcan and S. Ozkar,
Appl. Catal. B-Environ., 2014, 160–161, 534–541.
4 (a) H. Goksu, S. F. Ho, O. Metin, K. Korkmaz, A. M. Garcia, M.
Acknowledgements
2
2
The author Nilesh. M. Patil is thankful to the University Grant
Commission (UGCꢀSAP), India for providing the Senior
Research Fellowship (SRF). XPS analysis was performed at the
Research Hub for Advanced Nano Characterization, the
University of Tokyo, supports by the Ministry of Education,
Culture, Sports, Science and Technology (MEXT), Japan. This
work has been supported by JSPS and DST under the Indiaꢀ
S. Gultekin and S. Sun, ACS Catal., 2014, 4, 1777-1782; (b) H.
Goksu, H. Can, K. Sendil, M. S. Gultekin and O. Metin, Appl.
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| J. Name., 2012, 00, 1-3
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DOI: 10.1039/C6RA09785E
Graphical Abstract
Immobilized Ruthenium Metal-Containing Ionic Liquid-Catalyzed
Dehydrogenation of Dimethylamine Borane Complex for the Reduction of
Olefins and Nitroarenes
a
b
a,
Nilesh M. Patil, Takehiko Sasaki and Bhalchandra M. Bhanage *
a
Department of Chemistry, Institute of Chemical Technology, N. Parekh Marg, Matunga,
Mumbai-400019, India.
*E-mail: bm.bhanage@gmail.com; bm.bhanage@ictmumbai.edu.in
Tel.: +91 22 33612603; Fax: +91 22 33611020.
b
Department of Complexity Science and Engineering, Graduate School of Frontier Sciences,
The University of Tokyo, 5-1-5, Kashiwanoha, Kashiwa, Chiba 277-8561, Japan.
An efficient immobilized ruthenium metal containing ionic liquid (ImmRu-IL) catalyst has been
developed for the transfer hydrogenation of olefins and nitroarenes. This methodology uses eco-
friendly dimethylamine borane as a reducing agent which is nontoxic, water soluble, highly
stable and easy to handle.