Palladium-catalyzed carbonylation of aryl halides: An efficient, heterogeneous and phosphine-free catalytic system for aminocarbonylation and alkoxycarbonylation employing Mo(CO)6 as a solid carbon monoxide source

Article abstract of DOI:10.1039/c6ra18679c

Immobilized palladium metal-containing magnetic nanoparticles (ImmPd(0)-MNPs) were synthesized and characterized as an immobilized, phosphine-free catalyst for carbonylation reactions, namely the alkoxycarbonylation and aminocarbonylation reactions. Various substituted aryl iodides tolerated the reaction conditions and a wide variety of alcohols and amines were used efficiently. The effects of the solvent, base, and temperature were studied in both the mentioned reactions. The developed catalytic system avoids the use of phosphine ligands and can be reused for up to eight consecutive cycles. The recycled catalyst was characterized by TEM and ICP analysis.

Full text of DOI:10.1039/c6ra18679c

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DOI: 10.1039/C6RA18679C
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ARTICLE
Palladium Catalysed Carbonylation of Aryl Halides: An Efficient,
Heterogeneous and Phosphine-Free Catalytic System for
Aminocarbonylation and Alkoxycarbonylation Employing Mo(CO)6
as a Solid Carbon Monoxide Source
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Abdol-Reza Hajipour,a,b Zeinab Tavangar-Rizia and Nasser Iranpoorc
www.rsc.org/
Immobilized palladium metal-containing magnetic nanoparticles core (ImmPd(0)-MNPs), has been synthesized and
characterized as an immobilized, phosphine-free catalyst for carbonylation reactions, containing alkoxycarbonylation and
aminocarbonylation reactions. Various substituted aryl iodides tolerated the reaction conditions and a wide variety of
alcohols and amines were used efficiently. The effects of solvent, base and temperature were studied in both reactions.
The developed catalytic system avoids the use of phosphine ligands and can be reused for up to eight consecutive cycles.
The recycled catalyst was characterized by TEM and ICP analysis.
allows a wide range of substrates, thus representing a great
advantage for the synthesis of substituted aromatic esters and
its derivatives.12-14 In this respect; various palladium-based
Introduction
Transition-metal catalyzed carbonylation reaction of aryl
halides in the presence of an appropriate nucleophile
represents a powerful strategy for the selective introduction of
important frameworks in natural products, pharmaceuticals,
agrochemicals, and functional materials.1-2 During the last
decades, considerable efforts have been performed to develop
transition-metal catalyzed carbonylation reaction for the
conversion of organic halides3-5 or organic pseudohalides6-7 to
carboxylic acid derivatives. Recently, Iranpoor et al. reported
nickel-catalyzed synthesis of thioesters, esters and amides
from aryl iodides in the presence of chromium hexacarbonyl.8
Among the different types of carbonylation reactions,
palladium-catalyzed carbonylations are reported more
frequently due to the exceptional power of palladium catalysts
in carbonylative couplings than the other metals.
Palladium catalyzed carbonylation of aryl halides with alcohols
and amines is accepted as an interesting and important
chemical transformation for the synthesis of aromatic esters
and amides9 which are important building blocks for various
pharmaceuticals and agrochemicals.10 Conventionally,
aromatic esters were synthesized via reaction of the carboxylic
acid with alcohols.11 Carbonylation of the aryl halides in the
presence of an alcohol is an attractive possible method that
catalytic
systems
have
been
investigated
for
alkoxycarbonylation reaction.15-19 Aromatic amides are also
important classes of carbonyl compounds in various natural
products and designed pharmaceutical molecules. Some
heterocyclic amides are potential CNS (central nervous
system)-active compounds.20 Aminocarbonylation is an
advantageous method for the direct one step synthesis of
aromatic amides via carbonylative coupling of aryl, heteroaryl,
or alkynyl halides with primary/secondary amines.
In 1974, Heck reported the first Pd-catalyzed
alkoxycarbonylation and aminocarbonylation of aryl halides
with carbon monoxide.21 After this report, some other Pd-
catalyzed carbonylation reactions were developed to obtain
carbonylative products from aryl halides in the presence of CO
10a, 17, 22
gas.
To avoid the use of carbon monoxide in these
a variety of sources such as Mo(CO)6,
reactions,
carbamoylstannes, and DMF have been used.23 Recently,
Iranpoor et al. reported the aminocarbonylation of aryl halides
in the presence of Mo(CO)6 as the carbonyl source,24 and also
25
26
DMF/POCl3
and DMF/WCl6
as a new combinatorial
carbonylation reagent system. Accordingly, performing
carbonylation reactions in which cheaper catalysts and CO
substituents can be used is of interest.
Literature reports reveal that a variety of palladium-based
homogeneous catalytic systems have been used for
alkoxycarbonylation and aminocarbonylation of aryl halides.17,
a.Pharmaceutical Research Laboratory, Department of Chemistry, Isfahan
University of Technlogy, Isfahan 84156, IR Iran. E-mail: haji@cc.iut.ac.ir;
Fax: +98 311 391 2350; Tel: +98 311 391 3262
27
b.Department of Neuroscience, University of Wisconsin, Medical School, 1300
University Avenue, Madison, 53706-1532 WI, USA
Although the homogeneous palladium catalysts offer high
selectivity and yields, high reaction rate, turnover numbers
(TON), the main drawback of homogeneous catalysis is
associated with recovery and recycling of the catalyst. In
c. Department of Chemistry, College of Sciences, Shiraz University, Shiraz 71454,
Iran.
†
Electronic
Supplementary
Information
(ESI)
available:
See
DOI: 10.1039/x0xx00000x
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addition, using an excess of N/P-containing ligand to avoid Fe3O4 onto the CS-Methionine support was cVoienwfiArrmticeledOnlbinye
catalyst deactivation, restrict the applicability of carbonylation comparison of the FT-IR spectra (Fig. 5) DoOf It:h10e.1C03S9-M/C6eRthA1io86n7in9Ce
procedures since its separation from the reaction products and before and after loading with Fe3O4. Thermal behavior of the
restoration is usually difficult.
catalyst was also investigated by a thermogravimetric analyzer
To get rid of these serious issues, heterogeneous Pd catalysis is (TGA) (Fig. 6). The magnetization curve of ImmPd(0)-MNPs
a promising option. Considering this, several groups have been represents the magnetic behavior of the catalyst (Fig. 7).
developed the carbonylation of aryl halides by using The TEM images of fresh and spent catalyst were shown in Fig.
immobilized palladium complexes on various supports such as 1 which indicates near spherical morphology of catalyst with
activated carbon,28 silica,10a, 29 MCM-41,30 organic polymer,22c, an average diameter of about 6-7 nm and well distribution.
31
SBA-15,32 ZIF-8,22b Fe3O4,22d and MOF-5.33 Recently Bhanage Field emission scanning electron microscopy (FE-SEM) image in
et al. demonstrated silica supported palladium-phosphine as a Fig. 2 illustrates spherical external morphologies of the
reusable
catalyst
for
alkoxycarbonylation
and catalyst. Moreover, to determine the Pd content on the
catalyst, the catalyst was treated with concentrated HCl to
aminocarbonylation of aryl and heteroaryl iodides.34
In the current study, we wish to report the synthesis of digest the Pd particles and then analyzed by ICP technique.
palladium nanoparticles immobilized on magnetic methionine The amount of palladium was detected to be 7.1 ppm (7.1
functionalized chitosan (ImmPd(0)-MNPs) as a new and highly mgL-1). Energy dispersive spectroscopy analysis of X-rays
efficient heterogeneous catalyst for alkoxycarbonylation and (EDAX) data for ImmPd(0)-MNPs catalyst is given in Fig. 3.
aminocarbonylation of aryl iodides.
Results and Discussions
Synthesis and characterization of the Immobilized palladium
metal-containing magnetic nanoparticles core (ImmPd(0)-MNPs)
As shown in Scheme 1, the catalyst was prepared in three
steps.
First, methionine-CS was prepared by the reaction between
methyl methioninate and chitosan in DMF. Then, it was
treated with Fe3O4 nanoparticles prepared by mixing of
FeCl3.6H2O and FeSO4 according to the reported procedure,35
to achieve Fe3O4–CS–methionine as a magnetic substrate.
Ultimately, palladium acetate has attached into this magnetic
support in ethanol to gain the ImmPd(0)-MNPs as the final
catalyst.
Fig. 1 TEM image of the ImmPd(0)-MNPs catalyst that indicate the
morphology of Pd nanoparticles on the magnetic chitosan support (a).
TEM image of the ImmPd(0)-MNPs catalyst after eight recycle (b)
Scheme 1 Synthesis of the Fe3O4–CS–methionine supported Pd(0)
catalyst.
The prepared catalyst was characterized with Transmission
Electron Microscopy (TEM); Field emission scanning electron
microscopy (FE-SEM); Powder X-ray Diffraction (XRD) and
Energy Dispersive X-ray spectroscopy (EDX). The attachment of
Fig.2 FE-SEM images of the ImmPd(0)-MNPs catalyst.
2 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C6RA18679C
Fig. 4 The XRD spectrum of the ImmPd(0)-MNPs catalyst.
Fig. 3 The SEM-EDX spectrum of the ImmPd(0)-MNPs catalyst.
chitosan, chitosan–methionine, Fe3O4 and the Fe3O4‒CS–
methionine substrate, describes that some absorption bands
The EDAX data shows the presence of the palladium on the
magnetic chitosan in the ImmPd(0)-MNPs catalyst. Moreover,
the EDX spectrum specified other elements, including S, O and
Fe, which are present in the Fe3O4‒CS‒methionine substrate.
The XRD spectrum (Fig. 4) provided more evidence for the
presence of palladium and iron in the catalyst. The XRD study
of ImmPd(0)-MNPs illustrates the presence of highly dispersed
palladium complexes in the structure of the modified-chitosan
support. According to Fig. 4, a sharp peak at 2θ=40° which is
linked to palladium, confirms the crystalline nature of the
palladium species. The peaks which are assigned as the (111),
(200), (220), (311) and (222), indicate the cubic phase of
palladium nanoparticles {JCPDS 01-087-0638}. As presented in
Fig. 3, 11 characteristic diffraction peaks *2θ = 30.1° (220),
35.5° (311), 43.1° (400), 47.2° (331), 53.5° (422), 57.0° (511),
62.6° (440), 75.1° (622), 82.0° (551), 86.8° (642) and 89.8°
(731)] can be clearly considered for Fe3O4 particles, which are
related to the cubic phase of Fe3O4 {JCPDS 01-075-0033}.
in Fe3O4
FT-IR spectrum of CS
–
CS
–
methionine exist in both chitosan and Fe3O4. The
methionine revealed a carbonyl group
–
absorption band, which confirms methionine, has been binded
into the chitosan after the reaction between chitosan and
methioninate.
appeared at around 3419 cm-1, assigned to the stretching
vibration of the OH group, the extension vibration of the N
group and inter-hydrogen bonds of polysaccharide in the
Fe3O4 CS
methionine spectrum.36, 37 In addition, the intensity
of the band at 1385 cm-1 increased in the spectrum of the CS
A characteristic strong and broad band
–
–H
–
–
–
methionine material due to the introduction of additional
amine groups.36 In the FT-IR spectrum, bands at 2925, 2354,
1632, 1394, 1064 and 566 cm-1 correspond to the bonds in
Fe3O4
the Fe
1632 cm-1 is representative of the (
–
–
CS
O stretching vibration of Fe3O4.38 An additional band at
CON ) carboxyl amid
–
methionine. The band at 566 cm−1 is attributed to
–
–
Comparison between the FT-IR spectra (Fig. 5) of pure group vibration of the methionine moiety.
Fig. 5 The FT-IR spectra of pure chitosan, CS–methionine, Fe3O4 and Fe3O4–CS–methionine substrate.
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Catalytic activities
Since supported palladium catalyst display high catalytic
activity in a wide range of industrially main processes and have
been widely studied for C-C coupling,40 thus after
characterizing the catalyst, we decided to explore the catalytic
properties of the ImmPd(0)-MNPs in the field of carbonylation
reactions.
Fig. 6 A typical TGA curves of the ImmPd(0)-MNPs catalyst.
The TGA analysis results (Fig. 6) show that two main weight
losses have been occurred. The one, which happened at
around 100 °C, was assigned to adsorbed adsorbed solvent
molecules and moisture.39 Another one, above 200 °C is
associated with the decomposition of polysaccharide chain. So,
the TGA analysis specifies the high thermal stability for the
catalyst.
Scheme 2 Palladium catalysed alkoxy and amino-carbonylation of aryl
iodides.
The magnetization curves of ImmPd(0)-MNPs and Fe3O4 Alkoxycarbonylation of aryl iodides catalysed by ImmPd(0)-MNPs
indicate the magnetic behavior of ImmPd(0)-MNPs (Fig. 7). The
To test the catalytic activity of the present catalyst, we
two samples represent zero coercivity and remanence on the
performed the reaction of iodobenzene (1a) with methanol
magnetization curve. The lack of a hysteresis loop displays the
(2a') as a model reaction to identify effective conditions for
magnetic property and the ability of the catalyst to be
promoting the Pd-carbonylation. The reaction was carried out
separated effeciently from the reaction mixture by an external
under various conditions (Table 1). Initially, the reaction was
magnetic force. In addition, the decrease in the magnetization
carried out under solvent-free conditions in the presence of
value of the catalyst in comparison with Fe3O4 offers that the
K2CO3 as the base. In this condition, the O-arylated product
surface of Fe3O4 is concealed by the attachment of chitosan
(4a") was gained in higher yield than carbonylated product
molecules through their bond formation via their hydroxyl
(3aa') (Table 1, entry 1). It was found that by employing water
functional groups. Even with this reduction in the saturation
as solvent, the corresponding ester product was obtained only
magnetization, the catalyst still can be separated simply from
in approximately 40% yield. The C-O coupling product (37%)
the solution by an external magnet.
and the formation of benzoic acid (15%) were observed as the
side products (Table 1, entry 2). Iodobenzene provided the
methyl benzoate as the major product with approximately 62%
yield in DMF with the formation of 21% O-arylated side-
product (Table 1, entry 3).
This result turned our attention to employ other reaction
conditions. Hence, the influence of base on the catalytic
performance of this system was investigated by employing a
series of bases in DMF. Comparison between various bases
utilized, showed that organic bases are more effective than
inorganic bases like K2CO3 and K3PO4. Due to the optimization
parameters, DMF and Bu3N were chosen as the most suitable
solvent and base. Under these conditions, the carbonylated
product was obtained in higher yield and the ether side-
product formation reduced to 6% (Table 1, entry 6). Therefore,
Fig. 7 The magnetization curves of ImmPd(0)-MNPs and Fe3O4.
we decided that the application of base was necessary for the
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reaction to complete. The temperature effect for the reaction The relative position of substituents had slight inflVuieewnAcreticolenOntlhinee
DOI: 10.1039/C6RA18679C
was also studied. No serious decrease in the yield of the coupling efficiency. As representative of sterically hindered
desired product was observed when the reaction temperature substrates, 2-iodotoluene resulted in lower yield than its p-
was decreased from 100 to 80 °C (Table 1, entry 7). As analogue (3fe', Scheme 3). Furthermore, this catalytic system
respects, in lower temperatures the carbonylated product was could be applied to the reaction of phenols with iodobenzene
achieved in lower yields; therefore, 80 °C was considered as an to give the corresponding esters in high yields (3ag', Scheme
optimum reaction temperature for further studies. The effect 3). The analogous less expensive aryl bromides or chlorides are
of catalyst loading was also examined. It was observed that the more attractive substrates; however the reaction often needs
yield of the product decreased in lower values of catalyst harsher reaction conditions. We have examined aryl bromides
(Table 1, entry 9). Similarly, by reducing the amount of alcohol, to synthesize the aryl esters under the optimized reaction
the yield of product decreased (Table 1, entry 10).
conditions but only trace amount of yield was obtained. Aryl
chloride did not react under the optimized reaction conditions.
Table 1 effect of different parameters on the alkoxycarbonylation of
iodobenzene (1a)a
R: -H, R’: Me10a
2a: 2 h, 90%
R: -H, R’: iso-butyl41a
2b: 2.5h, 83%
R: -H, R’: 2-
cyclohexylethyl41b
2c: 3 h, 85%
Entry Solvent Base
T/ °C
2a(%)
3a(%)
70
37
21
28
33
6
8
8
4
10
1b
2
—
K2CO3 100, Reflux 27
H2O
K2CO3 80, Reflux
K2CO3 100
KOH
43
62
60
57
90
90
42
58
72
R: -Me, R’: butyl41c
2d: 1.7 h, 90%
R: -OMe, R’: butyl41d
2e: 1.5 h, 91%
R: -Br, R’: butyl41c
2f: 3 h, 78%
3
4
5
6
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
100
K3PO4 100
Bu3N
Bu3N
Bu3N
Bu3N
Bu3N
100
80
60
80
80
7
R: -Me, R’: phenethyl41e
2g: 4 h, 75%
R: -Br, R’: phenethyl41e
2i: 3.5 h, 73%
R: -CN, R’: phenethyl41f
2h: 2.7 h, 81%
8
9c
10d
a
Reaction conditions: iodobenzene (0.5 mmol), methanol (0.75
mmol), base (1.5 mmol), catalyst (0.01 g, 0.14 mol%), Mo(CO)6 (0.5
mmol), solvent (4 mL), time (2 h). b excess amount of methanol was
used. c the amount of catalyst was 0.005 g (0.07 mol%). d 0.5 mmol of
methanol was used.
R: -H, R’: benzyl10a
2k: 4 h, 82%
R: -Me, R’: phenethyl41e
2j: 2.5 h, 90%
R: -H, R’: p-tolyl, m/z (%) =
212 10a
2l: 6.5 h, 80%
Scheme
3 ImmPd(0)-MNPs catalysed alkoxycarbonylation of aryl
iodides in DMF at 80 °C
In order to investigate the effect of substituent groups, a
variety of aryl iodides were tested in the reaction with
different alcohols and the desired aryl esters were obtained in
good to excellent yields. Scheme 3 clearly reveals that the
prepared catalyst is effective for the alkoxycarbonylation
reaction of aryl iodides.
With regard to the results shown in scheme 3, the
carbonylation reaction of aryl iodides bearing either electron-
donating or electron-withdrawing substituents, afforded the
corresponding cabonylative products in good to excellent
yields. Strong electron-donating groups such as methyl and
methoxy group on the phenyl ring of aryl iodides resulted in
slightly more yields than aryl iodides with electron-
withdrawing groups, such as CN and Br (Scheme 3). The
differences in the yield of the product of methyl, methoxy and
CN groups can be attributed to different efficiency of
separation.
Aminocarbonylation of aryl iodides catalysed by ImmPd(0)-MNPs
The
applicability
of
ImmPd(0)-MNPs
toward
aminocarbonylation reactions were evaluated using the
conditions previously employed for alkoxycarbonylation, that
is, ImmPd(0)-MNPs (0.14 mol%), Bu3N (1.5 mmol), 0.5 mmol of
amine, 4 mL of DMF at 80 °C in the presence of Mo(CO)6. First,
iodobenzene was subjected to aminocarbonylation reaction
with morpholine under these conditions. The results obtained
from the aminocarbonylation reaction indicates that these
conditions were not effective and only provided the
corresponding amide (6aa') in 60% yield (Table 2, entry 1).
Therefore, we changed the reaction conditions. Further
experiments demonstrated that toluene exhibits as the best
solvent (Table 2, entry 2).
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Table
2
Optimization of the reaction parameters for the
Catalyst reusability
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aminocarbonylation of iodobenzene (1a)a
The level of reusability is an important DpOoIi:n1t0.1c0o3n9c/Ce6rnRAin18g67th9Ce
use of heterogeneous catalyst. Easy catalyst separation and
recycling in sequential set operations can significantly increase
the efficiency of the reaction. We examined the reusability of
the present heterogeneous palladium catalyst in the
carbonylation of iodobenzene with methanol under optimized
reaction conditions. After completion of reaction, the catalyst
was separated by an external magnet, washed with water and
acetone (3 × 5 mL), and dried at room temperature to be used
in the next run. The recovered catalyst could be reused eight
times and no significant decrease was observed in the activity
of the ImmPd(0)-MNPs catalyst (Fig. 8); In order to investigate
that the observed catalytic activity is from the supported
Entry
Solvent
DMF
Base
Bu3N
Bu3N
K2CO3
Bu3N
T/ °C
80
4a(%)
60
1
2
3
Toluene
Toluene
Toluene
80
80
60
95
51
40
4
a
Reaction conditions: iodobenzene (0.5 mmol), morpholine (0.5
mmol), base (1.5 mmol), catalyst (0.01 g, 0.14 mol%), Mo(CO)6 (0.5
mmol), solvent (4 mL), time (1 h).
palladium nanoparticles on the Fe3O4–CS–methionine and not
from leached Pd in the solution; hot-filtration test was
performed in the carbonylation of iodobenzene. After
continuing the reaction for 1 h, the catalyst was removed by
an external magnet and the determined conversion was 60%.
The resulting filtrate was heated for further 6 h; it has been
found that after separation of the catalyst no conversion
happens in the filtrate part.
To determine this topic, TEM images and ICP analysis were
taken for the recycled catalyst to study the possible changes in
Pd particle morphology/size and Pd content on the catalyst
surface in comparison with fresh catalyst. As it is shown in Fig
1, the TEM image of the catalyst illustrates that the
morphology and size of the catalyst does not change
considerably after eight times of recycling. Additionally, the
ICP analysis data of the recovered catalyst after recycling eight
times indicates that during the reaction process only a small
amount of Pd nanoparticles (0.2 ppm) is lost. With regard to
these results, we concluded that high catalytic activity is
related to the ImmPd(0)-MNPs catalyst and not from the
leached palladium.
The best optimized reaction condition was then applied to a
various substituted aryl iodides using 0.14 mol% of catalyst
and Mo(CO)6 as a solid source of CO at 80 °C in toluene
(Scheme 4). Moreover, various amines were well tolerated to
give the desired amides in good to excellent yields. (Scheme
4). Both primary and secondary amines provided the desired
amide in high yield. It is significant that the amidation of aryl
iodides with benzylamine employing ImmPd(0)-MNPs was
performed successfully with no additional N-arylation side-
product under the optimal conditions.
Moreover, in the case of aromatic amines such as aniline, the
carbonylated product was formed in good yield (3af’, 3ag’,
Scheme 4).
R: -H, R’, R”: morpholin31b
4a: 1 h, 95%
R: Me, R’, R”:morpholin31b
R: -H, R’: -H, R”:
cyclohexyl31b
4c: 1 h, 93%
4b: 1.5 h, 90%
R: -H, R’: -H, R”: benzyl31b
4d: 1.7 h, 87%
R: -H, R’: Me, R”:
benzyl42a
4e: 2 h, 85%
R: Me, R’: -H, R”:
benzyl31b
4f: 1.8 h, 90%
R: Me, R’: -H, R”: benzyl23c
4g: 3 h, 78%
R: OMe, R’: -H, R”:
benzyl31b
4i: 2.2 h, 89%
R: CN, R’: -H, R”:
benzyl42b
4h: 2.5 h, 81%
Fig. 8 Catalyst reusability test of the ImmPd(0)-MNPs catalyst.
R: -H, R’: -H, R”:
phenyl31b
4k: 3.8 h, 80%
R: -H, R’: -H, R”: 4-
methoxybenzyl42c
4j: 2 h, 90%
R: Me, R’: -H, R”:
phenyl42d
4l: 4 h, 82%
Scheme
4 ImmPd(0)-MNPs catalysed aminocarbonylation of aryl
iodides in toluene at 80 °C
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mL), Mo(CO)6 (0.5 mmol, 0.123 g) in 4mL DMF, ImmPd(0)-
MNPs catalyst (0.01 g, 0.14 mol%) was added and stirred in 80
Experimental
Chemical, instrumentation and analysis
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DOI: 10.1039/C6RA18679C
°C for the time specified in Scheme 3. The reaction was
monitored by TLC or GC. After consumption of aryl iodide, the
mixture was cooled down to room temperature and the
catalyst was removed by an external magnet. Then, H2O (10.0
mL) was added to the remaining solution and the resulting
mixture was extracted with EtOAc (3 × 5 mL) and dried over
Na2SO4. The products were purified by column
chromatography (hexane/ethyl acetate) to achieve the desired
purity.
All chemical reagents were purchased from Merck and Aldrich
Chemical Companies and were used without further
purification. Chitosan was purchased from Acros Organics and
its molecular weight was 100000-300000. 1H-NMR and 13C-
NMR spectra were recorded on a Brucker (250 MHZ) Avance
DRX in pure CDCl3 solvent with tetramethylsilane (TMS) as
internal standards. FT-IR spectra were obtained as KBr pellets
on a JASCO 680- Plus spectrophotometer for characterization
of the ImmPd-MNPs catalyst. Magnetic measurement was
done by vibrating sample magnetometer (VSM) in 0.0001-50
emu. The transmission electron microscopy (TEM) using TEM
device (Zeiss–EM10C–80 KV) and field emission scanning
electron microscopy [MIRA3 TESCAN] were acquired for
characterization of the ImmPd-MNPs catalyst. The
thermogravimetry analysis (TGA) of the catalyst was studied
using a lab-made TGA instrument. The X-ray diffraction (XRD,
D8, Advance, Bruker, axs) was engaged for characterization of
the ImmPd-MNPs catalyst. The reaction monitoring was
accomplished by TLC or gas chromatography (GC) (BEIFIN 3420
gas chromatograph equipped with a Varian CP SIL 5CB column:
30 m, 0.32 mm, 0.25 mm). Column chromatography was
carried out on columns of silica gel 60 (70–230 mesh).
Spectral data for the selected esters
2-methylpropyl benzoate (2b). 1H-NMR (400 MHz, CDCl3) δ
(ppm): 8.03 (dd, 2H), 7.67-7.63 (m, 1H), 7.57-7.52 (m, 2H), 4.05
(d, J = 7.2, 2H), 1.81-1.88 (m, 1H), 0.87 (d, J = 7.6, 6H); 13C-NMR
(100 MHz, CDCl3) δ (ppm): 167.14, 131.77, 131.42, 129.48,
128.57, 68.15, 29.69, 21.04, 14.19
1
2-Cyclohexylethyl benzoate (2c). H-NMR (250 MHz, CDCl3) δ
(ppm): 8.06 (dd, J = 8.5, 1.5 Hz, 2H), 7.60–7.51 (m, 1H), 7.45–
7.40 (m, 2H), 4.35 (t, J = 6.7 Hz, 2H), 1.81–1.62 (m, 8H), 1.52–
1.40 (m, 2H), 1.27–1.20 (m, 1H), 1.03–0.90 (m, 2H); 13C-NMR
(62.9 MHz, CDCl3) δ (ppm): 166.5, 132.6, 130.4, 129.6, 128.2,
63.1, 35.9, 34.5, 33.1, 26.5, 26.2.
1
Phenethyl-2-methylbenzoate (2g). H-NMR (250 MHz CDCl3) δ
(ppm): 7.92 (d, J = 7.5 Hz, 1H), 7.44–7.26 (m, 8H), 4.55 (t, J =
7.1 Hz, 2H), 3.10 (t, J = 7.3 Hz, 2H), 2.60 (s, 3H); 13C-NMR (62.9
MHz, CDCl3) δ (ppm): 166.2, 145.5, 134.7, 132.5, 131.5, 131.4,
130.8, 130.0, 128.2, 127.2, 132.1, 67.1,36.2, 17.6; MW: 240.
Catalyst Preparation
Chitosan-Methionine (CS-Methionine) To a flask containing
methyl methioninate (10 mmol, 1.28 g) in DMF (20 mL)
chitosan (1 g) were added. The resulting mixture refluxed
under N2 atmosphere for 3 days. The mixture was allowed to
cool down to room temperature followed by separation to
obtain the methionine functionalized chitosan. Afterwards, the
product was collected and washed with methanol several
times to eliminate the impurities and dried.
1
2-Phenethyl-4-cyanobenzoate (2h). H-NMR (250 MHz, CDCl3)
δ
(ppm): 8.02 (d, J = 7.5 Hz, 2H), 7.64 (d, J = 7.5 Hz, 2H),
7.21–7.18 (m, 5H), 4.50 (t, J = 6.9 Hz, 2H), 3.00 (t, J = 6.9 Hz,
2H); 13C-NMR (62.9 MHz, CDCl3) δ (ppm): 164.6, 137.5, 134.1,
132.3, 130.0, 128.7, 128.5, 126.6, 118.0, 116.3, 66.1, 35.0
1
Fe3O4-Chitosan-Methionine
(Fe3O4-CS-Methionine)
Fe3O4
Benzyl benzoate (2k). H-NMR (250 MHz, CDCl3) δ (ppm): 7.98
nanoparticles were prepared by conventional co-precipitation
of iron(II) sulphate and iron(III) chloride according to a
reported procedure.35 After sonication, Fe3O4 nanoparticles
(2.1 g) were reacted with CS-methionine (0.7 g) in 2% wt acetic
acid solution. The resulting mixture was sonicated for 20 min
and then stirred for 30 min in room temperature. Then, the
product was collected and washed with ethanol and deionized
water several times. After drying in a vacuum oven at 70 °C
overnight, the Fe3O4-CS-Methionine catalyst was achieved as a
dark solid.
(dd, J = 8.0, 1.0 Hz, 2H), 7.45–7.35 (m, 1H), 7.33–7.23 (m, 7H),
5.25 (s, 2H); 13C-NMR (62.9 MHz, CDCl3) δ (ppm): 166.5, 135.8,
133.1, 130.0, 129.7, 128.5, 128.4, 128.2, 128.0, 66.5; m/z (%) =
212
1
p-Tolyl benzoate (2l). H-NMR (250 MHz, CDCl3) δ (ppm): 8.25
(d, J = 7.5 Hz, 2H), 7.65–7.62 (m, 1H), 7.56–7.50 (m, 2H), 7.26
(d, J = 7.5 Hz, 2H), 7.14 (d, J = 7.5 Hz, 2H), 2.39 (s, 3H); 13C NMR
(62.9 MHz, CDCl3) δ (ppm): 165.2, 148.8, 135.5, 133.6, 130.1,
129.9, 129.5, 128.6, 121.2, 21.0; m/z (%) = 212
General procedure for aminocarbonylation in the presence of the
ImmPd-MNPs catalyst
ImmPd(0)-MNPs (Fe3O4-CS-Methionine-Pd) To
a mixture of
magnetic methionine-functionalized chitosan (Fe3O4-CS-
Methionine) (0.5 g) in ethanol (20 mL), Pd(OAc)2 (0.05 g) was
added and stirred for 3 days in room temperature. Then, the
powder was filtered and washed with acetone multiple times.
The ImmPd-MNPs catalyst was attained as a black powder.
A mixture of aryl iodide (0.5 mmol), amine (0.5 mmol), Bu3N
(1.5 mmol, 0.35 mL), Mo(CO)6 (0.5 mmol, 0.123 g), and Pd-
catalyst (0.14 mol%, 0.01 g) was stirred in toluene (4.0 mL) at
80 °C in a round-bottom flask. TLC analysis was used to control
the completion of the reaction. After cooling, the catalyst was
removed by external magnet and the desired compound was
purified by chromatography on silica gel using n-hexane/EtOAc
(20/5) as the eluent to afford the corresponding amide in high
yield.
General procedure for alkoxycarbonylation in the presence of the
ImmPd-MNPs catalyst
In a typical experiment, to a flask containing a mixture of aryl
iodide (0.5 mmol), alcohol (0.75 mmol), Bu3N (1.5 mmol, 0.35
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Spectral data for the selected amides
supplies great potential toward additional appropriate
applications in other palladium transformations in the future.
View Article Online
DOI: 10.1039/C6RA18679C
N-Cyclohexylbenzamide (4b). 1H-NMR (250 MHz, CDCl3) δ
(ppm): 7.70 (dd, J = 7.5, 2.4 Hz, 2H), 7.40–7.30 (m, 3H), 6.00 (s,
1H), 3.95–3.85 (m, 1H), 1.97–1.90 (m, 2H), 1.73–1.54 (m, 2H),
1.38–1.12 (m, 6H); 13C-NMR (62.9 MHz, CDCl3) δ (ppm): 166.5,
135.0, 131.3, 128.5, 126.7, 48.5, 33.2, 25.6, 25.0; m/z (%) = 203
Acknowledgements
We gratefully acknowledge the funding support received for
this project from the Isfahan University of Technology (IUT), IR
Iran (A.R.H.) and Grant GM 33138 (A.E.R.) from the National
Institutes of Health, USA. Further financial support from the
Center of Excellence in Sensor and Green Chemistry Research
(IUT) is gratefully acknowledged.
1
N-Benzylbenzamide (4d). H NMR (250 MHz, CDCl3) δ (ppm):
7.73 (2H, d, J = 7.6 Hz), 7.24–7.43 (8H, m), 6.38 (1H, br s), 4.58
(2H, d, J = 5.6 Hz); 13C NMR (62.9 MHz, CDCl3) δ (ppm): 44.0,
127.1, 127.4, 127.8, 128.5, 128.7, 131.5, 134.4, 138.4, 167.6;
m/z (%) = 211
N-Benzyl-N-methylbenzamide (4e). bp: 213
bp: 212 °C/10 Torr); H NMR (250 MHz, CDCl3) δ (ppm): 7.09
7.40 (10H, m), 4.68 (1H, br s), 4.44 (1H, br s), 2.95 (1.5H, br s),
2.77 (1.5H, br s); IR (KBr disk) ν (cm-1) 3034, 2935, 2850, 1637,
1500, 1453, 1385, 1254, 1067, 700; m/z (%) = 226
–
215/10 Torr, (lit.
Notes and references
1
–
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N-Benzyl-2-methylbenzamide (4g). 1H NMR (250 MHz, CDCl3) δ
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with alcohols and amines in the presence of Mo(CO)6. Both
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Preparation and characterization of palladium nanoparticles
immobilized on magnetic methionine functionalized chitosan
View Article Online
DOI: 10.1039/C6RA18679C
as
a highly efficient, air stable and readily reusable
heterogeneous catalyst in carbonylation reactions
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