Amine modified mesoporous Al2O3@MCM-41: An efficient, synergetic and recyclable catalyst for the formylation of amines using carbon dioxide and DMAB under mild reaction conditions

Article abstract of DOI:10.1039/c5cy02277k

This work reports an amine modified meso Al₂O₃@MCM-41, particularly the ordered mesoporous silica, as a catalyst for the formylation of amines with carbon dioxide (CO₂) and with dimethylamine-borane (DMAB) as a green reducing source. This newly developed catalytic system represents a heterogeneous and environmentally benign protocol. Besides this, the catalyst could be reused for five consecutive cycles without any significant loss in its catalytic activity towards the synthesis of formamides. The amine modified meso Al₂O₃@MCM-41 catalysts were well characterized by high and low angle XRD, temperature programmed desorption (TPD), BET-surface area, TGA/DTA and FT-IR analysis techniques. The effect of various reaction parameters such as temperature, CO₂ pressure, time and the ratio of substrates to DMAB for the synthesis of formamides has been investigated. The developed protocol can be applicable for the synthesis of most important key intermediates like formoterol, orlistat, leucovarin and iguratimod in biologically active compounds.

Full text of DOI:10.1039/c5cy02277k

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Amine modified mesoporous Al O @MCM-41: An efficient,
2
3
synergetic and recyclable catalyst for the formylation of amines
using carbon dioxide and DMAB under solvent free and mild
reaction condition
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
a
b
b
a
a,
Deepak B. Nale, Dharitri Rath, K. M. Parida, Aravind Gajengi and Bhalchandra M. Bhanage *
www.rsc.org/
This work reports amine modified meso Al
2
O
3
@MCM-41 particularly the ordered mesoporous silica as the catalysts for the
) and dimethylamine-borane (DMAB) as a green reducing source. This new
formylation of amines with carbon dioxide (CO
2
developed catalytic system represents a heterogeneous and environmentally benign protocol. Besides this, catalyst could
be reused for five consecutive cycles without any significant loss in its catalytic activity towards the synthesis of
formamides. The catalysts amine modified meso Al
temperature programmed desorption (TPD), BET-surface area, TGA/DTA and FT-IR analysis techniques. Effect of various
reaction parameters such as temperature, CO pressure, time and the ratio of substrate to DMAB for the synthesis of
2 3
O @MCM-41 were well characterized by high and low angle XRD,
2
formamides has been investigated. The developed protocol can be applicable for the synthesis of most important key
intermediates like Formoterol, Orlistat, Leucovarin and Iguratimod in the biological active compounds.
also related higher long hydrocarbons, is one of the attractive
approaches. In which hydrogen gas is the cleanest and most
Introduction
2
In the last few decades, the application of carbon dioxide (CO ,
atom economical reductant, but due to harsh reaction
conditions (high reaction pressure and high temperature)
avoids broad application of the reducing agent. In this context,
a green house gas) in the synthesis of high-value-added
chemicals or fine chemicals is one of the immense importance
1
to the synthetic as well as an environmental chemistry. In
4
5
the use of boranes or hydrosilanes as reducing agents
facilitated the catalytic reduction of CO to the synthesis of
view of the fact that, CO
2
is an abundant, non-toxic,
2
inexpensive, non-flammable and therefore as a renewable C1
feedstock source in the regarding of “atom economy”, “green
chemistry” and “sustainable development”. However, due to
formamides under much milder reaction conditions. For that
another view is the synthesis of carbonyl containing chemicals
such as oxazolidinones, carbonates, formamides, derivatives of
the inherent thermodynamic and kinetic stability of CO
inertness), it is challenging to activate CO and achieve its
transformation especially under mild conditions. In this
2
various carbonyl compounds like, lactones, carbamates,
6
quinazoline-2,4(1H,3H)-diones, etc. through
(
2
a
catalytic
2
reaction, among all, the formation of formamides has
attracted much more attention because it plays an important
role in the industry.
respect, chemically reduction of CO
is really challenging.
2
into organic compounds
In order to reduce the emission of atmospheric CO
2
to protect
2
In the literature study, the reduction of CO is mainly achieved
an environment from the global warming and utilize the
carbon source, it is feasible to load amines on porous materials
forming new and efficient catalysts have been explored. The
by using silanes and molecular hydrogen. But, still there is a
need to develop highly desirable transition metal-free and
transfer hydrogenation protocol which could minimize the
number of waste streams and unit operations. Transfer
hydrogenation is a more practical and consistent method as a
production of hydrogen can be easily controlled in the reaction
2
catalytic reduction (by transfer hydrogenation) of CO to high
3
value-added chemical fuels, such as gasoline, alcohols and
a.
4 4 2 3 3
medium. Generally, NaBH , LiAlH , MgH , and NH BH have
Department of Chemistry, Institute of Chemical Technology, Matunga, Mumbai-
4
Department of Chemistry, Centre for Nano Science and Nano Technology,
Institute of Technical Education & Research, Siksha ‘O’ Anusandhan University,
Khandagiri, Bhubaneswar-751 030, India. Email:
7
00 019, India.
been widely used as hydrogen sources. Among these, eco-
friendly dimethylamine-borane (DMAB) is easily accessible,
non-toxic, non-flammable, highly stable, inexpensive, water-
b.
kulamaniparida@soauniversity.ac.in
Corresponding author: E-mail: bm.bhanage@ictmumbai.edu.in; Tel: +91 22
3612601; Fax: +91 22 33611020;
soluble and also has a high volume to mass hydrogen density
8
3.5 wt%). Thus, DMAB used as a green hydrogen source for
*
3
(
1
Electronic Supplementary Information (ESI) available: [Materials and methods, H, the synthesis of formamides.
C NMR of the products]. See DOI: 10.1039/x0xx00000x
1
3
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Formamide is one of the most versatile chemical and The industrial interest of alumina is highlighted by its intensive
important building blocks with widespread applications in the use as catalyst or as catalytic support materials for the
industry as solvents, raw materials, intermediates in various petroleum refinement and as automobile emission
1
5
synthetic processes, especially as a precursor to isocyanides controller. The use of alumina can be ascribed to both high
9
and formamidines. The formamide moiety have a functional thermal stability and moderate Lewis acidity as well as to the
group that serves a fundamental role in protein biosynthesis fact that it is a rather inexpensive material. γ-Al
and post-translational regulation steps and has a high commonly used as support for nanocrystals of MoS
biological activity in various pharmaceuticals drugs such as with Co or Ni for hydrodesulfurization (HDS) processes.
2
O
3
is
2
doped
1
6
1
0
Leucovarin, Formoterol, Orlistat and Iguratimod, etc.
Traditionally, formamides are commonly produced via the allowed increasing the catalytic behaviour of HDS catalysts.
formylation of amines. Instead of toxic CO source, we used CO Therefore, it is important to develop strategies to design
for the N-formylation reaction and hence CO is an attractive simple, reproducible and easy to scale-up procedures leading
and green alternative for the production of formamides.
However, most of the reported catalytic routes have some alumina by simple methods to be implemented in industrial
Recently, high surface area nanostructured alumina has
1
7
2
2
1
1
to high surface area, high pore volume and high pore size
1
8
drawbacks such as requiring metal catalysts, toxic organic processes. Since, the improvement of these materials
solvents, inert gas atmosphere, complicated reaction system, (recovery and recyclability) as compared with homogeneous
severe reaction conditions (i.e. high temperature and systems can lead to environmentally benign chemical
2 3
pressure) and difficulty in catalyst separation among others. methods. Therefore, amine modified meso Al O @MCM-41
Apart from this, narrow substrate scope, tedious work up have wide potential in designing the high performance and
procedures and problem in catalysts recovery which hinder the environmentally benign catalysts. Based on our research
6
b,c
commercial feasibility of these processes. Therefore, the interest in mesoporous materials,
development of a highly efficient, simple, recyclable, green modified mesoporous silica i.e. amine modified meso
catalytic system remains a challenge. Therefore, we look for a Al @MCM-41 catalyst, as solid base catalyst for
here we have reported
2
O
3
a
heterogeneous and recyclable catalyst which could efficiently formylation reaction. We envisaged that the existence of
catalyze the formylation reaction under milder reaction amino as a functional group of catalyst MCM-41 have a
conditions without the aid of phosphine ligands is focus of the immense potential to accelerate the rate of reaction in the
present work.
forward direction by transforming amine into corresponding
Recently, researchers have interest in MCM-41 grafted with bioactive formamide derivatives. In this present study, we
different amines which was reported to catalyze many organic have prepared mesoporous nano composites (amine modified
1
2
2 3
syntheses. Siliceous mesoporous materials in neat form are meso Al O @MCM-41) consisting of mesoporous silica and
lacking active sites on their surface. Hence their applications alumina followed by amine functionalization. The inorganic-
are restricted and their surface functionalization is required organic hybrid materials were well characterized and
essential according to their application. In order to utilize the demonstrated as a well-organized, efficient, stable, recyclable
unique properties of the mesoporous materials for specific and commercially feasible catalyst for the synthesis of
2
applications like catalysis, sorption, sensing, ion exchange etc., formamides from CO and amines by using DMAB as a
introduction of reactive organic functional groups is hydrogen source under solvent free and mild reaction
performed. The incorporation of organic components as part conditions (Scheme 1).
of the silicate walls or trapped within the channels to form
inorganic-organic hybrid materials remains the main issue. The
advantages of these materials arise from the fact that the
inorganic components can provide mechanical, thermal or
structural stability, while the organic features can readily be
modified for various specific applications.
Moreover, mesoporous materials with high textural properties
such as high surface area, wide pore volume and narrow pore
2
Scheme 1 Synthesis of formamide derivatives from amines, CO and DMAB.
diameter have been seen as an excellent support for many
1
3
catalytic applications.
Mesoporous materials, basically
mesoporous silica (MCM-41) and mesoporous alumina have Experimental section
been treated as an efficient catalyst and catalyst support for
Preparation and characterization of amine modified meso
Al @MCM-41 catalyst
Synthesis of mesoporous Al
Mesoporous Al (MA) was prepared using starch as
many catalyzed reactions due to high textural property,
mesoporosity, high thermal stability, strong covalent character
2
O
3
1
4
2 3
O
etc. Again, MCM-41 and mesoporous alumina with high
textural properties stabilized the metal and metal ions. That
means the metal and metal ions are bonded or anchored
properly in the mesoporous supports like MCM-41 and
mesoporous alumina which increases the catalytic activity of
the materials.
2 3
O
template. 20.2 g of starch was dissolved in 100 mL of deionized
water. Then 10.2 g of aluminium isopropoxide was added and
stirred vigorously for 30 min at room temperature. The pH of
the solution was maintained at 6 and then the solution was
2
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kept as it is for 5 h. After complete hydrolysis of aluminium
isopropoxide a high texture mesoporous Al . The mixture
was dried at 100 C in order to remove the volatile impurities.
2 3
O
°
The resultant solid was calcined at 600
removal of the template.
°C for 6 h for complete
General procedure for preparation of amine modified meso
Al @MCM-41 catalysts
2
O
3
Figure 1 XRD of APTES meso Al
A) 3.2 wt% APTES meso Al @MCM-41, B) 6.4 wt% APTES meso Al
2.8 wt% APTES meso Al @MCM-41, D) 16 wt% APTES meso Al
wt% APTES meso Al @MCM-41.
2
O
3
@MCM-41 (Low angle XRD inserted above).
@MCM-41, C)
@MCM-41, E) 20
2
O
3
2 3
O
1
2
O
3
2 3
O
2 3
O
2 3
The low angle XRD patterns for MCM-41, Al O @MCM-41
composite and 16 wt% of APTES modified composites are
shown in figure 1. All the samples showed a typical
mesoporous structure with three sharp peaks corresponding
Scheme
2 Schematic representation for synthesis of APTES modified meso-
Al @MCM-41.
2 3
O
(
100), (110) and (200) planes which indicate the long range
The material was synthesized by in situ method. 2.4 g of
Cetyltrimethylammonium bromide (CTAB) was dissolved in 200
mL of deionized water. 7 mL of 2 M NaOH solution was added
and the solution was stirred at 80 °C for 30 min. The pH is
ordering in the materials. After the modification with APTES,
the intensity of the peak is slightly reduced and peak position
is slightly shifted towards right but this material still remained
intact and shows the mesoporosity like MCM-41.
balanced at 12.4. To the above solution 0.95 g of meso Al
was added followed by 10 mL of tetra ethyl ortho silicate
TEOS) (Si/Al = 10). Different amounts of APTES (0.25 mL to
2 3
O
N adsorption-desorption study
2
(
1
.56 mL) were added to get different wt% of APTES modified The
meso Al
@MCM-41. A white precipitate was obtained after distribution of MCM-41, meso Al
stirring for 2 h at 80 °C.
wt% APTES Al @MCM-41 are shown in the figure S1(a-c)
N
2
adsorption-desorption isotherm and pore size
2
O
3
2
O
3
, Al @MCM-41 and 16
2 3
O
2 3
O
The above products were filtered hot, washed with water and and figure S2 respectively (See ESI). The textural properties
ethanol. The as synthesized material was treated with ethanol such as BET surface area, pore diameter and pore volume
and conc. HCl (100:1) at 80 °C for 6 h to remove the surfactant. derived from the N
The sample was filtered, washed with ethanol and dried at 60 included in Table S1 (See ESI). N
C. The synthesized materials were denoted as x wt% Amine IV isotherm which is defined by Brunauer et al. it indicated
modified meso Al
@MCM-41 (x = 3.2, 6.4, 12.8, 16.0 and that all the samples are mesoporous in nature. A steeper N
0.0 wt% respectively) (Scheme 2).
The amine modified meso Al
adsorption-desorption measurements are
2
sorption resulted typical type
2
2
0
°
2
O
3
2
2
adsorption step in the mid-relative pressure range of 0.1 to 0.8
@MCM-41 catalyst was well is indicative of relatively intra particle mesoporosity, which is
2
O
3
characterized by low angle XRD, temperature programmed shown in the figure S1 (See ESI). All the materials showed a
desorption (TPD), BET-surface area, FT-IR and TGA/DTA monomodal peak in the pore size distribution curves (See ESI,
analysis techniques.
Figure S2). The pore size of the parent meso Al
) XRD peaks are due to After APTES modification the pore size decreased up to 2-3
. The sharp peaks are assigned to nm.
the 220, 311, 222, 400, 511 and 440 reflection planes of γ- According to table S1 (See ESI), the BET surface area of parent
O is 7.8 nm.
2 3
The high angle (2θ = 10‒70°
2 3
mesoporous crystalline Al O
1
9
2
2
Al
influenced the material crystallinity. The 6.4 wt% APTES loaded respectively. The composite of the above two materials i.e.
Al
/MCM-41 shows the sharp peaks and then after the meso Al @MCM-41 showed an enhanced BET surface area
intensity of the peaks decreased gradually. This may be due to of 1045 m /g. The increase in specific surface area value is due
the multi layer of amine deposition on the surface of to substitution of Si by Al in the framework as well as
2 3
O
2 3
(JCPDS, 10-0425). The different wt% of APTES loading MCM-41 and meso Al O is 878 m /g and 213 m /g,
2
O
3
O
2 3
2
2 3
Al O
/MCM-41. As a result, the long range ordering and formation of nanocomposites. After modification with APTES,
crystallinity of the materials are affected.
the surface area of parent meso Al O @MCM-41 decreases
2 3
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further. This is due to the bonding of the organic amine with showed sharp peaks ranging from 400 °C to 800 °C. The peaks
the Si-OH and Al-OH groups in the framework which results in are due to both the physically and chemically adsorbed CO
surface coverage of the parent material. The pore volume data This indicates that the APTES modified materials contain
of the amine modified meso Al @MCM-41 also showed the strong basic sites required for the organic condensation
same trend as that of the surface area values. From all the reactions. The 16 wt% APTES modified meso Al @MCM-41
above surface analysis data, it is confirmed that the Al is showed the highest CO adsorption (1564 µmole/g) hence
modified into the framework of MCM-41 and APTES is expected to have highest basic sites.
2
.
2
O
3
2 3
O
2
O
3
2
modified onto the framework of meso Al
composite.
2 3
O @MCM-41
Thermo-gravimetric Analysis
The thermal gravimetric analysis (TGA) of Al O @MCM-41 and
2
3
FTIR Analysis
APTES modified meso Al
@MCM- figure S4 (See ESI). All the samples showed weight loss in three
1 composite, 3.2, 6.4, 12.8 and 16 wt% of APTES modified stages. First peak is below 120 °C, second is in the range 300-
meso Al @MCM-41 are shown in figure S3 (See ESI). FT-IR 400 °C and the third is a broad peak around 500 °C. The
spectroscopy analysis data confirms the presence of different highest weight loss is at 120 °C is for removal of physically
functional groups present in the synthesized materials. The adsorbed water molecules. Compared to parent Al @MCM-
2 3
O @MCM-41 samples are shown in
2 3 2 3
The FT-IR analysis results for meso Al O , meso Al O
4
2
O
3
2 3
O
-1
broad peaks present around 3500 cm in all the samples are 41, amine modified samples showed a higher rate of weight
due to adsorbed water by the molecules. Presence of H-O-H loss indicating the functionalization of APTES with
-1
bending vibrations is confirmed by the peak at 1630 cm in all Al
the materials. The amine modified samples showed the –NH break down of APTES-O-Al (in case of substituted Si-O bond by
bending vibrations at 1532 cm . This peak is absent in the Al-O bond) or APTES-O-Si linkage. The highest temperature
parent materials i.e. meso-Al and meso Al @MCM-41 peak (around 500 °C) is due to removal of surfactant from the
indicating the successful incorporation of amines in the materials.
2 3
O @MCM-41. The weight loss around 300-400 °C is due to
2
-1
2
O
3
2 3
O
-1
materials. In addition to that, peak at 750 cm indicates the N-
-
H bending vibrations in amine modified materials. The 960 cm Differential Thermal Analysis
1
peak is for Al-O-Si stretching vibrations which indicate the The differential thermal analysis curves for amine modified
successful modification of the parent MCM-41 frame work by meso Al O @MCM-41 is shown in figure S4 (See ESI). The DTA
2
3
Al
2
O
3
.
curves are complementing the TGA curves very well. They
showed three endothermic peaks correspond to the three
peaks in TGA pattern. The first peak (around 100 °C) is due to
removal of water. The second and third peaks (at 300-400 °C
and 500 °C) correspond to the removal of amine and
surfactant respectively.
CO
2
-TPD Analysis
General experimental procedure for synthesis of formamides from
2
amine, CO and DMAB
The experiments were carried out in a 100 mL high-pressure
reactor, in a typical reaction procedure; the catalyst (15 wt%
with respect to starting substrate) was introduced into a
reactor containing amine (1 mmol), DMAB (2 mmol), CO
pressure (2 MPa) at room temperature and then reactor
pressurized to 2.0 MPa of CO pressure and heated to a
2
2
specified temperature. After the completion of reaction, the
autoclave was cooled to room temperature and then the
2
excess CO was released slowly. The resultant reaction mixture
filtered off by simple filtration. The filtrate was then collected
in sample vial and the product was extracted for further
1
13
analysis which confirmed by GC, GC-MS, H and C NMR
spectroscopic techniques and also matched with those of
reported authentic data.
Figure 2 CO
2
-TPD of APTES modified meso Al
2 3
O @MCM-41 at different wt% of (a) 0 (b)
Results and discussion
3
.2 (c) 6.4 (d) 12.8 (e) 16.0 (f) 20.0
2 3
Catalytic activity of amine modified meso Al O @MCM-41
2 2 3
The CO TPD of all the amine modified meso Al O
@MCM-41 catalysts
are recorded and shown in figure 2. It is the property to We have developed an efficient methodology for the synthesis
measure the basic sites present in the sample. All the samples of formamides (2a
2ff) derivatives from various amines
‒
4
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(
1a‒
1ff) with CO
2
as a C1 source and DMAB as the green Thus, using amine modified meso Al
2
O
3
@MCM-41 (16 wt%) as
reductant by using amine modified meso Al
2 3
O @MCM-41 the choice of catalyst, we studied the effects of other reaction
under solvent free and mild reaction condition (Table 3, parameters such as temperature, time, pressure and DMAB
entries 1-32). We have prepared six types of thermally stable ratio, to estimate the scope and limitation of the present
and covalently linked amines loaded on the meso catalyst system.
2 3
Al O @MCM-41 catalysts by varying the amine loading such as
a
0, 3.2, 6.4, 12.8, 16.0 and 20.0 wt%, respectively (Table 1, Table 2 Effect of reaction parameters for the formylation of N-benzylmethylamine.
entries 1-7). Initially, the reaction was carried out in the
absence of catalyst and it was found that the desired product
was not afforded indicating that the amine modified meso
Al
desired product (Table 1, entry 1). On the other hand, we
noticed that 16 wt% amine modified meso Al @MCM-41
2 3
O @MCM-41 was only responsible for the formation of
1
:DMAB
Cat.
CO
2
Temp.
(°C)
Time
(h)
Yield of
2
O
3
Entry
b
(mmol)
(wt%)
(MPa)
2a (%)
catalyst is the best among all, to furnish the desired product
up to 99 % as an isolated yield of 2a (Table 1, entry 6).
Catalyst loading
Further, we have carefully performed the reactions in
1
2
3
1:2
1:2
1:2
20
15
10
2
2
2
100
100
100
6
6
6
99
99
90
presence of meso Al
2
O
3
and amine (APTES) without support as
and DMAB, it
catalysts to the formylation of amines with CO
2
was found that the formation of the desired product in lower
yield (Table 1, entries 8 and 9).
Effect of Temperature
4
5
6
1:2
1:2
1:2
15
15
15
2
2
2
120
80
6
6
6
99
79
51
a
Table 1 Catalyst screening for the formylation of N-benzylmethylamine.
Wt% of amine loaded on Al
MCM-41 catalyst
2
O
3
@
b
Entry
Yield (%)
60
Effect of Time
1
2
3
4
5
6
7
8
9
-
n.d.
10
62
70
89
99
99
12
25
7
8
9
1:2
1:2
1:2
15
15
15
2
2
2
100
100
100
10
8
99
99
81
0 (meso Al
2 3
O @MCM-41)
3.2
4
6.4
2
Effect of CO pressure
12.8
1
1
1
0
1
2
1:2
1:2
1:2
15
15
15
4
3
1
100
100
100
6
6
6
99
99
76
16.0
20.0
meso-Al
2 3
O
Effect of DMA-borane
APTES without support
a
13
14
1:4
1:0
15
15
2
2
100
100
6
6
99
Reaction conditions: N-benzylmethylamine (1 mmol), catalyst (15 wt% with
respect to starting substrate), CO pressure (2 MPa), DMAB (2 mmol),
2
n.d.
b
temperature (100 °C), time (6 h). Based on GC-GC/MS analysis. The yield is
quantified by using the external standard method using N-benzyl-N-
methylformamide as a reference compound. n.d. = not detected. APTES = (3-
Aminopropyl)triethoxysilane.
a
Reaction conditions: N-benzylmethylamine (mmol), catalyst (wt% with respect
to starting substrate), CO pressure (MPa), DMAB (mmol), temperature (°C), time
h). Based on GC-GC/MS analysis. The yield is quantified by using the external
2
b
(
standard method using N-benzyl-N-methylformamide as a reference compound.
n.d. = not detected.
In order to optimize the reaction parameters, the preliminary
studies were carried out by using amine modified meso Effect of temperature
Al @MCM-41 (16 wt%) as a choice of catalyst for the We have also performed the reactions to observe the effect of
synthesis of formamides from amines and CO as a best model temperature ranging from 60 °C to 120 °C was screened on the
2 3
O
2
reaction. Various reaction parameters such as catalyst yield of 2a (Table 2, entries 4-6). The experimental studies
screening, catalyst loading, temperature, pressure, time and revealed that 100 °C was the optimum temperature required
DMAB ratio were studied.
to reach the highest yield of 2a.
Effect of Catalyst Loading
Effect of Pressure and time
Next, the experiments were carried out by using different The effect on reaction time was studied and it was observed
catalytic concentrations of amine modified meso Al @MCM- that increasing the time from 4 h to 10 h, increase in yield of
1 (16 wt%) for the title reaction and the distinctive results the desired product was obtained (Table 2, entries 7-9). As the
was shown in Table 2 (Entries 1‒3). It was examined that the time increases, the yield of 2a was remains the same with
yield was an excellent and almost constant at 20 wt% and increasing the time from 6 to 10 h, indicating that the
5 wt% for this catalyst (Table 2, entries 1-2) On the other completion of the reaction in 6 h (Table 2, entries 2, 7, 8).
2 3
O
4
2a
1
hand, by decreasing the concentration of catalyst, decrease in Therefore, 6 h is optimum reaction time.
yield of the desired product was obtained (Table 2, entry 3).
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Next, the study of CO
2
pressure on the yield of 2a was
b
Entry Substrate
1
Product
Yield (%)
examined at 100 °C in 6 h shown in Table 2 (Entries 10-12). The
yield of 2a increased significantly with increasing the CO
99
2
pressure from 1 to 2 MPa, but above increasing the pressure
from 2 to 4 MPa, the yield was not so changed. Hence, the
optimum reaction pressure was achieved at 2 MPa.
2
3
95
Effect of Substrate to DMAB ratio
86
Besides this, we have also studied the effect of mole ratio of
amine to DMAB and it was shown that, without DMAB the
reaction did not offered the desired product (Table 2, entry
4
5
97
14). Subsequently, it was found that 1 mmol of amine and 2
mmol of DMAB was furnished the higher yield of the desired
product while further increasing the concentration to 4 mmol,
the yield remained constant at 6 h. Hence, the best optimized
reaction conditions for the desired product 2a are: N-
benzylmethylamine (1.0 mmol), catalyst amine modified meso
n.d.
Al
2
O
3
@MCM-41 (15 wt% with respect to starting substrate),
pressure (2 MPa), DMAB (2.0 mmol) at 100 °C for 6 h
6
7
45
CO
2
under solvent free condition.
Further, to examine the utility and generality of this approach,
we investigated the scope of the reactive 1° or 2° aliphatic as
84
98
well as aromatic amine substrates (1a
‒
1ff) were formylated to
2ff) in moderate to
the corresponding formamides (2a
‒
excellent yields under the optimized reaction conditions and
the results are shown in Table 3 (Entries 1-32). Interestingly,
for every 1° or 2° aliphatic as well as aromatic amines, solely
formylated product was obtained without any other by-
product.
8
9
2g
69
99
2
N-benzylmethylamine (1a) reacted with CO providing 99% as
1
1
0
1
an excellent yield of 2a under the optimized reaction
conditions (Table 3, entry 1). Dibenzylamine showed good
reactivity, providing 2b in a yield of 95% (Table 3, entry 2), and
interestingly, the sterically hindered tert-butyl group on
nitrogen atom of the N-benzyl-2-methylpropan-2-amine was
also easily converted into 2c with 86% yield (Table 3, entry 3).
Moreover, the developed catalyst could efficiently catalyze the
formylation of N-methylaniline, affording 2d in a good yield of
98
95
12
97% (Table 3, entry 4). It was observed that our system was
failed to give 2e due to electron withdrawing nitro group ortho
1
3
97
to the amino group (Table 3, entry 5). Some of the
11a,b
protocols
failed to convert from 1f to 2f product. But our
system likely proved to be a highly efficient for the synthesis of
diphenyl formamide in good yield of 45% (Table 3, entry 6).
The substrate of both the indole and indoline undergoes the
same product i.e. 2g with an excellent yield of the N-
formylation (Table 3, entries 7, 8). Whereas it was observed
that 1,2,3,4-tetrahydroquinoline also provided desired product
a good yield of 2h (Table 3, entry 9).
1
1
1
4
5
6
88
82
84
a
Table 3 Production of various formamide derivatives.
1
7
74
6
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1
8
98
90
and excellent yields of the cyclic formamides 2j
–p were
achieved (Table 3, entries 10-16). In case of the substrate 1p
,
the formylation occurred only at unhindered amine provided
with 84% yield of 2p. The experiments were also successful for
the N-formylation of secondary amines with longer dialkyl
1
9
chains seemed to be more favourable (1q-w), and providing
good to an excellent yield (65%-98%) of the corresponding
desired products (Table 3, entries 17-23).
2
2
0
1
87
89
Furthermore, we were also applying this developed system to
check the effectiveness of catalyst for the primary aliphatic
amines such as cyclohexyl amine and tert-butylamine and
provided the formamides 2x, 2y with 89%, 80% yields
respectively (Table 3, entries 24-25). Subsequently, we also
evaluated different from the above primary amines, the
formylation of aniline and its sterically hindered derivatives
2
2
2
2
2
2
3
4
5
6
91
65
89
80
91
(
1z
-
1ff) which only afforded to the mono formylated products
2ff with good to excellent
(Table 3, entries 26-32).
of the corresponding products 2z
-
1
1c,h
yield of 51%-91% than others
Therefore, the synthetic utility of this developed methodology
and the above results robustly demonstrated that the
formylation of 1° or 2° aliphatic as well as aromatic amines
from CO with DMAB under solvent free and mild reaction
2
conditions.
However, the recent studies reported that a reaction
forwarded through the hydroboration of carbon dioxide by a
Lewis base promotes intramolecular hydride delivery. It was
found that the amino group of the catalyst played synergistic
2
1,4h
role in catalyzing the formylation reactions.
2
7
75
Recyclability study
In order to craft the developed methodology, one of the most
important works for the heterogeneous catalysis is reusability
or consecutive recyclability. Hence the reusability of the amine
2
2
3
8
9
0
83
85
51
modified meso Al
studied for the synthesis of formamide derivatives from
amines and CO under the optimized reaction conditions
Figure 3).
O @MCM-41 (16 wt%) catalyst was also
2 3
2
(
3
3
1
2
69
81
Figure 3 Recyclability study of 16.0 wt% amine modified meso Al
2
O
3
@MCM-41 catalyst.
Reaction conditions: Substrate (1 mmol), Cat. 16 wt% amine modified meso
@MCM-41 (15 wt%), CO pressure (2 MPa), DMAB (2 mmol), temp. (100 °C), time
6 h).
a
a
Reaction conditions: Substrate (1 mmol), catalyst (15 wt%), DMAB (2 mmol),
b
Al
O
2 3
2
temperature (100 °C), time (6 h). Based on GC/GC-MS analysis. The yield is
(
quantified by using the external standard method using N-benzyl-N-
c
methylformamide. Isolated yield after column chromatography purification. n.d.
=
not detected.
After the completion of reaction, the product was separated
through simple filtration technique. The catalyst was washed
with distilled water and ethyl acetate, dried under vacuum and
then reused for successive runs. The catalyst was found to be
Similarly, cyclic aliphatic amine containing oxygen on its ring
1j) and other cyclic aliphatic amines (1k ) were also tested
(
–p
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effective up to five consecutive runs without any significant
loss in its catalytic activity and stability of the prepared
catalyst.
Zhang, Z. A. Li, M. Spasova, M. W. E. van den Berg, M. Farle,
Y. M. Wang, R. A. Fischer and M. Muhler, ChemCatChem,
2
010,
h) X. W. Zhou, J. Qu, F. Xu, J. P. Hu, J. S. Foord, Z. Y. Zeng, X.
L. Hong and S. C. E. Tsang, Chem. Commun., 2013, 49, 1747–
749.
2, 214–222; (g) D. Sperling, Energy, 2007, 28, 178–179;
(
1
Conclusions
4
(a) S. Chakraborty, J. Zhang, J. A. Krause, H. Guan, J. Am.
Chem. Soc., 2010, 132, 8872–8873; (b) S. Bontemps, L.
In conclusion, we have developed an efficient, green,
economical, phosphine-free and heterogeneous catalytic
methodology for the synthesis of formamides from amines and
Vendier, S. Sabo-Etienne, Angew. Chem. Int. Ed., 2012, 51,
671–1674; Angew. Chem., 2012, 124, 1703–1706; (c) M. A.
1
Courtemanche, M. A. Legare, L. Maron, F. G. Fontaine, J. Am.
Chem. Soc., 2013, 135, 9326–9329; (d) C. D. N. Gomes, E.
2 2 3
CO using amine modified meso Al O @MCM-41 as a catalyst
Blondiaux, P. Thuery, T. Cantat, Chem. Eur. J., 2014, 20
7
,
under solvent free and mild reaction conditions. After
completion of the reaction the catalyst was easily recovered
and again reused for five successive times without
considerable loss in its catalytic activity. This protocol was
highly efficient with respect to the various types of amines
098–7106; (e) T. Wang, D. W. Stephan, Chem. Eur. J. 2014,
, 3036–3039; (f) S. Bontemps and S. Sabo-Etienne, Angew.
2
0
Chem., Int. Ed., 2013, 52, 10253–10255. (g) S. Bontemps, L.
Vendier and S. Sabo-Etienne, J. Am. Chem. Soc., 2014, 136
,
4
2
419–4425. (h) R. Shintani and K. Nozaki, Organometallics,
013, 32, 2459–2462.
(1°/2° aliphatic as well as aromatic). The present catalytic
5
6
(a) F. J. Fernandez-Alvarez, A. M. Aitani, L. A. Oro, Catal. Sci.
Technol., 2014, , 611–624; (b) D. B. Nale and B. M. Bhanage,
reaction seems to be one of the ideal synthetic reactions.
4
Green Chem., 2015, 17, 2480–2486; (c) D. B. Nale and B. M.
Bhanage, Synlett, 2015, 26, 2835–2842.
(a) B. M. Bhanage, S. Fujita, Y. Ikushima and M. Arai, Appl.
Catal., A, 2001, 219, 259–266; (b) D. B. Nale, S. Rana, K. M.
Acknowledgements
The authors D. B. Nale thankful to the university grant
commission, India for providing financial support under UGC-
SAP-SRF program, Institute of Chemical Technology (ICT),
Mumbai, India.
Parida and B. M. Bhanage, Catal. Sci. Technol., 2014,
1608–1614; (c) D. B. Nale, S. Rana, K. M. Parida and B. M.
4,
Bhanage, Appl. Catal. A, 2014, 469, 340–349; (d) D. B. Nale,
S. D. Saigaonkar and B. M. Bhanage, J. CO Util., 2014, 8, 67–
2
7
Bhanage, Catal. Sci. Technol., 2012,
3; (e) R. A. Watile, K. M. Deshmukh, K. P. Dhake and B. M.
2, 1051–1055; (f) M.
Notes and references
Honda, A. Suzuki, B. Noorjahan, K. Fujimoto, K. Suzuki and K.
Tomishige, Chem. Commun., 2009, 4596–4598; (g) F. Shi, Y.
Q. Deng, T. L. SiMa, J. J. Peng, Y. L. Gu and B. T. Qiao, Angew.
Chem., Int. Ed., 2003, 42, 3257–3260; (h) M. Shi and K. M.
Nicholas, J. Am. Chem. Soc., 1997, 119, 5057–5058; (i) R.
Srivastava, M. D. Manju, D. Srinivas and P. Ratnasamy, Catal.
Lett., 2004, 97, 41–47; (j) J. S. Tian, J. Q. Wang, J. Y. Chen, J.
G. Fan, F. Cai and L. N. He, Appl. Catal., A, 2006, 301, 215–
221; (k) M. Yoshida, N. Hara and S. Okuyama, Chem.
Commun., 2000, 151–152; (l) K. Yamaguchi, Y. Wang, N.
Mizuno, Chem. Lett., 2012, 41, 633-635; (m) K. Yamaguchi, H.
Kobayashi, Y. Wang, T. Oishi, Y. Ogasawara and N. Mizuno,
1
(a) G. A. Olah, A. Goeppert, G. K. S. Prakash, Beyond Oil and
Gas: The Methanol Economy, Wiley-VCH, Weinheim,
Germany, 2006; (b) J. Louie, Curr. Org. Chem., 2005,
23; (c) M. Mori, Eur. J. Org. Chem., 2007, 4981–4993; (d) T.
Sakakura, J. C. Choi, H. Yasuda, Chem. Rev., 2007, 107, 2365–
9, 605–
6
2
2
2
387; (e) M. Aresta, A. Dibenedetto, Dalton Trans., 2007,
975–2992; (f) A. Correa, R. Martin, Angew. Chem. Int. Ed.,
009, 48, 6201–6204; Angew. Chem., 2009, 121, 6317–6320;
(
3
g) S. N. Riduan, Y. Zhang, Dalton Trans., 2010, 39, 3347–
357; (h) A. Behr, G. Henze, Green Chem., 2011, 13, 25–39;
(
i) K. Huang, C. L. Sun, Z. J. Shi, Chem. Soc. Rev., 2011, 40
,
435–2452; (j) X. B. Lu, D. J. Darensbourg, Chem. Soc. Rev.,
012, 41, 1462–1484; (k) W. Z. Zhang, X. B. Lu, Chin. J. Catal.,
012, 33, 745–756; (l) L. Zhang, Z. M. Hou, Chem. Sci., 2013,
, 3395–3403; (m) W. F. Xiong, C. R. Qi, H. T. He, O. Y. Lu, M.
2
2
2
4
Catal. Sci. Technol., 2013, 3, 318–327; (n) T. Kimura, H.
,
Sunaba, K. Kamata and N. Mizuno, Inorg. Chem., 2012, 51
13001–13008.
7
(a) H. Goksu, H. Can, K. Sendil, M. S. Gultekin and O. Metin,
Appl. Catal. A, 2014, 488, 176–182; (b) H. Goksu, S. F. Ho, O.
Metin, K. Korkmaz, A. M. Garcia, M. S. Gultekin and S. Sun,
Zhang, H. F. Jiang, Angew. Chem. Int. Ed., 2015, 54, 3084–
087; Angew. Chem., 2015, 127, 3127–3130.
(a) L. Yang, H. Wang, ChemSusChem, 2014,
W. Stephan, G. Erker, Chem. Sci., 2014, , 2625–2641; (c) L. J.
Hounjet, C. B. Caputo, D. W. Stephan, Angew. Chem. Int. Ed.,
012, 51, 4714–4717; Angew. Chem., 2012, 124, 4792–4795;
d) C. M. Mömming, E. Otten, G. Kehr, R. Fröhlich, S.
Grimme, D. W. Stephan, G. Erker, Angew. Chem. Int. Ed.,
009, 48, 6643–6646; Angew. Chem., 2009, 121, 6770–6773;
e) C. B. Caputo, K. Zhu, V. N. Vukotic, S. J. Loeb, D. W.
3
2
7
, 962–998; (b) D.
ACS Catal., 2014, 4, 1777–1782; (c) U. B. Demirci and P.
5
Miele, Phys. Chem. Chem. Phys., 2014, 16, 6872–6885; (d) H.
Goksu, New J. Chem., 2015, 39, 8498–8504; (e) Z. Li, F. Zhai,
Q. Wan, Z. Liu, J. Shan, P. Li, A. A. Volinsky and X. Qu, RSC
Adv., 2014, 4, 18989–18997; (f) H. Liu, X. Wang, Y. Liu, Z.
Dong, G. Cao, S. Li and M. Yan, J. Mater. Chem. A, 2013, 1,
12527–12535.
(a) T. D. Nixon, M. K. Whittlesey and J. M. J. Williams,
Tetrahedron Lett., 2011, 52, 6652–6654; (b) F. Sen and G.
Gokagac, J. Phys. Chem. C, 2007, 111, 1467–1473; (c) H.
Goksu, Y. Yıldız, B. Çelik, M. Yazici, B. Kilbas and F. Sen, Catal.
Sci. Technol. 2015, DOI: 10.1039/c5cy01462j.
2
(
2
(
8
9
Stephan, Angew. Chem. Int. Ed., 2013, 52, 960–963; Angew.
Chem., 2013, 125, 994–997; (f) A. H. Liu, B. Yu, L. N. He,
Greenhouse Gases: Sci. Technol., 2015,
(a) A. Behr and V. A. Brehme, J. Mol. Catal. A: Chem., 2002,
87, 69–80; (b) F. L. Liao, Y. Q. Huang, J. W. Ge, W. R. Zheng,
5, 17–26.
3
1
(a) J. Pouessel, O. Jacquet and T. Cantat, ChemCatChem,
2013, 5, 3552–3556; (b) K. Weissermel, H. J. Arpe, Industrial
K. Tedsree, P. Collier, X. L. Hong and S. C. Tsang, Angew.
Chem., Int. Ed., 2011, 50, 2162–2165; (c) I. Kasatkin, P. Kurr,
B. Kniep, A. Trunschke and R. Schlogl, Angew. Chem., Int. Ed.,
rd
Organic Chemistry, 3 ed., Translated by C. R. Lindley, Wiley-
VCH, Weinheim, 1997.
2
007, 46, 7324–7327; (d) F. C. Meunier, Angew. Chem., Int. 10 (a) M. Kozak, Microbiol. Rev., 1983, 47, 1–45; (b) J. R.
Wisniewski, A. Zougman, M. Mann, Nucleic Acids Res., 2008,
Ed., 2011, 50, 4053–4054; (e) G. A. Olah, Angew. Chem., Int.
Ed., 2005, 44, 2636–2639; (f) S. Schimpf, A. Rittermeier, X. N.
8
| J. Name., 2012, 00, 1-3
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Please do not adjust me ca rgin sl ogy
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36
Yoshida, S. Takano, Chem. Pharm. Bull., 2000, 48, 131–139.
1 (a) O. Jacquet, C. D. N. Gomes, M. Ephritikhine, T. Cantat, J.
Am. Chem. Soc., 2012, 134, 2934−2937; (b) C. D. N. Gomes,
O. Jacquet, C. Villiers, P. Thuery, M. Ephritikhine, T. Cantat,
Angew. Chem., Int. Ed., 2012, 51, 187−190; (c) X. J. Cui, Y.
1
Zhang, Y. Q. Deng, F. Shi, Chem. Commun., 2014, 50,
89−191; (d) J. L. Liu, C. K. Guo, Z. F. Zhang, T. Jiang, H. Z. Liu,
1
J. L. Song, H. L. Fan, B. X. Han, Chem. Commun. 2010, 46
,
5
770−5772; (e) P. Munshi, D. J. Heldebrant, E. P. McKoon, P.
A. Kelly, C. C. Tai, P. G. Jessop, Tetrahedron Lett., 2003, 44
,
2
6
725−2727; (f) S. Kumar, S. L. Jain, RSC Adv., 2014,
4277−64279; (g) K. Motokura, N. Takahashi, D. Kashiwame,
4,
S. Yamaguchi, A. Miyaji, T. Baba, Catal. Sci. Technol., 2013,
392−2396; (h) T. V. Q. Nguyen, W. J. Yoo and S. Kobayashi,
Angew. Chem., 2015, 127, 9341–9344.
3,
2
1
2 (a) K. M. Parida, D. Rath, J. Mol. Catal. A: Chem., 2009, 310
9
1
,
3−100; (b) J. N. Appaturi, F. Adam, Appl. Catal. B, 2013, 136-
37, 150−159; (c) S. Huh, J. W. Wiench, J. C. Yoo, M. Pruski,
V. S. Y. Lin, Chem. Mater. 2003, 15, 4247−4256; (d) S.
Udayakumar, M. K. Lee, H. L. Shim, D. W. Park, Appl. Catal. A,
2
009, 365, 88−95; (e) M. R. Mello, D. Phanon, G. Q. Silveira,
P. L. Llewellyn, C. M. Ronconi, Microporous Mesoporous
Mater., 2011, 143, 174−179; (f) M. Caplow, J. Am. Chem.
Soc., 1968, 24, 6795−6803; (g) P. V. Dankwerts, Chem. Eng.
Sci., 1979, 34, 443−446.
1
1
3 (a) Q. Liu, A. Wang, X. Wang, P. Gao, X. Wang and T. Zhang,
Microporous Mesoporous Mater., 2008, 111, 323–333; (b) I.
A. Lemus, Y. V. Gomez and L. A. Contreras, Int. J.
Electrochem. Sci., 2011,
Pradhan, J. Das and N. Sahu, Mater. Chem. Phys., 2009, 113
44–248.
6, 4176–4187; (c) K. M. Parida, A. C.
,
2
4 (a) N. Bejenaru, C. Lancelot, P. Blanchard, C. Lamonier, L.
Rouleau, E. Payen, F. Dumeignil and S. Royer, Chem. Mater.,
2
009, 21, 522–533; (b) K. M. Kolonia, D. E. Petrakis and A. K.
Ladavos, Phys. Chem. Chem. Phys, 2003, , 217–222; (c) A.
Sayari, D. Shee, N. Al-Yassir and Y. Yang, Top. Catal., 2010,
, 154–167; (d) T. A. Konovalova, Y. Gao, R. Schad and L. D.
5
53
Kispert, J. Phys. Chem. B, 2001, 105, 7459–7464.
1
5 (a) C. M. Alvarez, N. Zilkova, J. P. Pariente, J. Cejka, Catal.
Rev., 2008, 50, 222–286; (b) H. Liu, G. Lu, Y. Guo, Y. Wang, Y.
Guo, Catal. Commun. 2009, 10, 1324–1329.
1
1
6 R. Prins, V. H. de Beer, G. A. Somorjai, Catal. Rev. Sci. Eng.,
1
7 N. Bejenaru, C. Lancelot, P. Blanchart, C. Lamonier, L.
989, 31, 1–41.
Rouleau, E. Payen, R. S. Dumeignil, Chem. Mater., 2009, 21
22–533.
8 (a) A. Sayari, Y. Belmabkhout, J. Am. Chem. Soc., 2010, 132
,
5
1
,
6
1
312−6314; (b) S. Builes, L. F. Vega, J. Phys. Chem. C, 2012,
16, 3017−3024.
1
2
2
9 Q. Wu, F. Zhang, J. Yang, Q. Li, B. Tu, D. Zhao, Microporous
Mesoporous Mater., 2011, 143, 406−412.
0 S. Brunauer, L. S. Deming, E. Deming and E. Teller, J. Am.
Chem. Soc., 1940, 62, 1723−1732.
1 (a) E. J. Corey and J. O. Link, Tetrahedron Lett., 1989, 30,
275−6278; (b) E. J. Corey and R. K. Bakshi, Tetrahedron
6
Lett., 1990, 31, 611−614; (c) M. A. Courtemanche, M. A.
Legare, L. Maron and F. G. Fontaine, J. Am. Chem. Soc., 2014,
1
36, 10708−10717; (d) Z. Z. Yang, L. N. He, J. Gao, A. H. Liu, B.
Yu, Energy Environ. Sci., 2012,
5
, 6602−6639; (e) W. C. Chen,
J. S. Shen, T. Jurca, C. J. Peng, Y. H. Lin, Y. P. Wang, W. C.
Shih, G. P. A. Yap and T. G. Ong, Angew. Chem. Int. Ed., 2015,
54, 15207–15212.
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Graphical Abstract
Amine modified mesoporous Al O @MCM-41: An efficient, synergetic
2
3
and recyclable catalyst for the formylation of amines using carbon dioxide
and DMAB under solvent free and mild reaction condition
a
b
b
a
Deepak B. Nale, Dharitri Rath, K. M. Parida, Aravind Gajengi and Bhalchandra M.
Bhanage *
a,
a
Department of Chemistry, Institute of Chemical Technology, N. Parekh Marg, Matunga, Mumbai
4
00 019, India.
b
Department of Chemistry, Centre for Nano Science and Nano Technology, Institute of Technical
Education and Research, Siksha ‘O’ Anusandhan University, Khandagiri, Bhubaneswar- 751 030,
Odisha, India.
*
Corresponding author Tel.: + 91- 22 3361 1111/2222; Fax: +91- 22 3361 1020.
E-mail address: Prof. B. M. Bhanage: bm.bhanage@ictmumbai.edu.in and
Dr. K. M. Parida: paridakulamani@yahoo.com
2 3
A novel covalently linked amine modified meso Al O @MCM-41 catalysts were investigated
as a highly efficient, heterogeneous, environmental-friendly and sustainable mesoporous
catalytic system for the synthesis of formamides from 1°/2° aliphatic as well as aromatic
2
amines, CO and DMAB as a green reductant under solvent free and mild reaction conditions.