Double carbonylation of iodoarenes in the presence of a pyridinium SILP-Pd catalyst

Article abstract of DOI:10.1016/j.jorganchem.2020.121287

The efficiency of a palladium catalyst, immobilised on a supported ionic liquid phase (SILP) with adsorbed 1-butyl-4-methylpyridinium chloride, was investigated in aminocarbonylation reactions. Double carbonylation was found to be the main reaction using different iodoarenes and aliphatic amines as substrates. Application of aniline derivatives as nucleophiles led to the exclusive formation of substituted benzamides. The stabilisation effect of the adsorbed pyridinium ionic liquid was compared to that of imidazolium and phosphonium derivatives. It was proved that the pyridinium SILP-palladium catalyst could be reused in at least 10 cycles. Recyclability was tested in five successive runs for all of the substrates.

Full text of DOI:10.1016/j.jorganchem.2020.121287

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Double carbonylation of iodoarenes in the presence of a pyridinium SILP-Pd catalyst
Béla Urbán, Enikő Nagy, Petra Nagy, Máté Papp, Rita Skoda-Földes
PII:
S0022-328X(20)30189-3
DOI:
https://doi.org/10.1016/j.jorganchem.2020.121287
JOM 121287
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 30 March 2020
Accepted Date: 6 April 2020
Please cite this article as: Bé. Urbán, Enikő. Nagy, P. Nagy, Máé. Papp, R. Skoda-Földes, Double
carbonylation of iodoarenes in the presence of a pyridinium SILP-Pd catalyst, Journal of Organometallic
Chemistry (2020), doi: https://doi.org/10.1016/j.jorganchem.2020.121287.
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1
Double carbonylation of iodoarenes in the presence of a pyridinium SILP-Pd catalyst
Béla Urbán, Enikő Nagy, Petra Nagy, Máté Papp, Rita Skoda-Földes*
University of Veszprém, Institute of Chemistry, Department of Organic Chemistry , Egyetem
u. 10. (P.O.Box 158) H-8200 Veszprém, Hungary
Dedicated to the 65th birthday of Professor László Kollár, in recognition of his contribution
to coordination chemistry, homogeneous catalysis and carbonylation reactions
Abstract
The efficiency of a palladium catalyst, immobilised on a supported ionic liquid phase (SILP)
with adsorbed 1-butyl-4-methylpyridinium chloride, was investigated in aminocarbonylation
reactions. Double carbonylation was found to be the main reaction using different iodoarenes
and aliphatic amines as substrates. Application of aniline derivatives as nucleophiles led to
the exclusive formation of substituted benzamides. The stabilisation effect of the adsorbed
pyridinium ionic liquid was compared to that of imidazolium and phosphonium derivatives. It
was proved that the pyridinium SILP-palladium catalyst could be reused in at least 10 cycles.
Recyclability was tested in five successive runs for all of the substrates.
Keywords: aminocarbonylation; double carbonylation; heterogeneous catalysis,
immobilization; palladium.
* * Corresponding author. Tel.: +36-88-624719; fax: +36-88-624469; e-mail: skodane@almos.uni-pannon.hu.

2
1. Introduction
α-Ketoamides serve as important starting materials in synthetic organic chemistry [1] to
produce a great variety of heterocyclic compounds, such as indoles, [2] oxindoles [3],
dihydroisoquinolines [4], isatins [5] and imidazolidinones [6]. The α-ketoamide motif is
present in many natural and non-natural compounds bearing important biological effects, [7]
e. g. protease inhibitory activity [8] and as a result, antiviral- [9] and antitumor effect. [10]
Among the great variety of synthetic routes towards α-ketoamides, [7, 11] palladium-
catalysed double carbonylation of aryl halides represents a useful strategy mainly due to the
ready availability of starting materials with diverse structure and the good functional group
tolerance of the reaction. Competing aminocarbonylation, leading to carboxamides, can
usually be retarded by carrying out the reactions at lower temperature and higher pressure,
especially under homogeneous conditions. As an improvement, several heterogeneous
catalytic systems have been developed recently for carbonylation of aryl halides, [12] to
facilitate product separation and catalyst recycling and to make the methodology more
environmentally friendly. At the same time the application of immobilised catalysts for the
carbonylative synthesis of α-ketoamides is a much less explored field compared to other
carbonylation methodologies. Heterogeneous catalysts for double carbonylation were
obtained by the immobilisation of palladium-phosphine complexes on SBA-15 [13] or on an
organic polymer, [14] as well as by the addition of PPh3 to Pd/C [15] or to a polymer-
supported triazine based palladium complex. [16] In phosphine-free systems catalytically
active palladium species were deposited on silica-supported polytitazane [17], on covalent
triazine- [18] or metal organic frameworks [19] or on different polymers. [20] However, the
development of suitable catalysts is still a challenge, as efficiency is highly influenced not
only by the nature of the catalyst and the choice of carbonylation conditions, but also by the
structure of the reaction partners.

3
Stabilisation of palladium nanoparticles could also be achieved by the use of supported ionic
liquid phases (SILPs). [21-23] Catalysts with the best performance were obtained by the
deposition of palladium on SILPs with anchored dicationic moieties. [22,23] At the same
time, the preparation of these elaborate supports is cumbersome that might hinder their
application. Our previous studies have shown that even simple adsorption of an imidazolium
ionic liquid (IL) on silica can increase the efficiency of the Pd-silica system considerably. [21]
Although imidazolium salts are by far the most widely explored representatives of ionic
liquids, pyridinium derivatives are known to have some favourable properties, such as a better
stabilisation effect towards colloidal palladium. [24] In the present report it is shown that a
SILP-Pd catalyst, obtained by the simple adsorption of a mixture of a palladium precursor and
a pyridinium ionic liquid on silica, can be recycled efficiently in the double carbonylation
reaction of aryl iodides and secondary amines as well as in the aminocarbonylation of
iodobenzene and aniline derivatives. The stability of the catalysts obtained from SILPs with
different adsorbed ionic liquids is also compared.
2. Results and discussion
2.1. Preparation of SILP-Pd catalysts
The catalyst (CAT-1) was obtained by a wet impregnation method using a mixture of 1-butyl-
4-methylpyridinium chloride (IL-1, Figure 1) and the Pd-precursor, Pd2(dba)3.CHCl3.
In order to compare the stabilisation effect of the pyridinium IL (IL-1) with imidazolium-
(IL-2) and phosphonium salts (IL-3), catalysts supported on other SILPs (CAT-2 [22] and
CAT-3 [23]), as well as an IL-free version (CAT-4) were prepared (Table 1).

4
Me
Me
Br
N
N
P
Me
Bu
N
Cl
BF4
Bu
IL-2
IL-1
IL-3
Figure 1. Ionic liquids used for the preparation of SILP catalysts CAT-1 — CAT-3
Table 1. Supported palladium catalysts used during the carbonylation reactionsa
Catalyst
Ionic
liquid
IL-1
IL-2
IL-3
-
Pd-content [%]b
0.49
0.40
0.56
0.55
CAT-1
CAT-2
CAT-3
CAT-4
a: support: silica, Pd precursor: Pd2(dba)3.CHCl3; b: (mg Pd/mg catalyst)*100.
Figure 2. IR spectra of the fresh and spent catalyst CAT-1. (Spent catalyst: after two runs in
DMF, 30 bar, 100 °C, 3h.)

5
The presence of IL-1 on the surface of the silica support was proved by elemental analysis
and infrared spectroscopy. The IR spectrum of CAT-1 (Figure 2) reflects the presence of the
pyridinium salt. The signals at 2966, 2941 and 2879 cm-1 correspond to stretching vibrations
of alkyl C-H, while the absorption at 3059 cm-1 can be attributed to the presence of aromatic
C-H. The bands at 1645, 1522 and 1477 cm-1 can be assigned to the vibrations of the
pyridinium ring. [25]
2.2. Carbonylation of iodobenzene (1a) and morpholine (2a) in the presence of SILP-Pd
catalysts
First, the performance of CAT-1 was tested under different conditions in the model reaction
of iodobenzene (1a) and morpholine (2a) (Scheme 1). The reaction parameters were chosen
according to our previous observations in double carbonylation carried out with SILP
catalysts. [21-23]
I
O
O
H
N
O
O
[Pd]
N
N
N
+
+
CO
+
+
solvent
base
O
O
O
O
1a
2a
3aa
4aa
5a
Scheme 1. Aminocarbonylation of iodobenzene (1a) with morpholine (2a) as the nucleophile
α-Ketoamide 3aa was formed with good to excellent selectivity in all of the reactions (Table
2.). As it could be expected, some increase in the ratio of amide 4aa was observed at lower
pressures (entries 4, 8, 9), but selectivity for 3aa remained around 85% even in these cases.
The reaction was much slower in acetonitrile (entries 5-9) than in DMF (entries 1-4) or
toluene (entries 10,11) and good conversion could be achieved only in eight-hour long
reactions (entries 7-9).

6
Table 2. Aminocarbonylation of iodobenzene (1a) and morpholine (2a) in the presence of
CAT-1a
Entry
Solvent
Base
Pressure Reaction Conversion Ratio
of
[bar]
time [h] [%]b
products [%]b
3aa
100c
92c
93 c
85 c
100
93
4aa
0
1
DMF
DMF
DMF
DMF
Et3N
Et3N
Et3N
Et3N
30
30
30
5
0.5
1
21
98
100
91
15
41
97
96
95
30
100
2
8
3
3
7
4
3
15
0
5
acetonitrile Et3N
acetonitrile Et3N
acetonitrile Et3N
acetonitrile Et3N
acetonitrile Et3N
30
30
30
10
5
0.5
1.5
8
6
7
7
95
5
8
8
86
14
14
9
9
8
86
10
11
toluene
DBU
30
0.5
91
toluene
DBU
30
3
93
7
a: reaction conditions: 0.2 mmol 1a, 0.5 mmol 2a, 0.25 mmol base, catalyst (with 3.2 μmol
Pd-content) and 1 ml solvent, 100 °C; b: determined by GC; c: the presence of side product 5a
could not be detected in the reaction mixtures.
Next, the activity and recyclability of CAT-1 were compared with those of other
heterogeneous catalysts (CAT-2 — CAT-4) under different conditions. The use of all of the
catalysts resulted in the formation of α-ketoamide 3aa with good selectivity in the DMF/Et3N
solvent/base system at high pressure (Figures 3,4). The IL-free catalyst (CAT-4) showed a
similar performance to the SILP catalyst CAT-2 in the first runs, but a great loss of activity
was observed in the recycling experiments. A much lower decrease could be noticed when the
imidazolium catalyst (CAT-2) was recycled. Although iodobenzene (1a) was totally
consumed in all of the experiments carried out with CAT-3, the reuse of the catalyst led to a
considerable change in the selectivity. While the amide (4aa) content of the reaction mixture

7
dropped appreciably after the first run, a progressive increase in the amount of the side
product 5a, formed due to some decomposition of the solvent DMF, [26] could be detected.
The pyridinium-SILP catalyst CAT-1 exhibited the most stable performance and could be
reused efficiently in at least 10 cycles in eight-hour long reactions (Figure 4). It should be
mentioned that its selectivity towards the double carbonylation product 3aa was slightly
lower than that of CAT-2 due to the formation of side product 5a.
Figure 3. Recirculation experiments with CAT-1 — CAT-4. Reaction conditions: 0.2 mmol
1a, 0.5 mmol 2a, 0.25 mmol Et3N, 1 ml DMF, catalyst (Pd-content: CAT-1: 3.2 μmol, CAT-
2 and CAT-4: 3.6 μmol CAT-3: 2.8 μmol ), 100 °C, 30 bar, 3h. Yields are determined by
GC.

8
Figure 4. Recirculation experiments with CAT-1 — CAT-4 in eight-hour long reactions.
Reaction conditions: 0.2 mmol 1a, 0.5 mmol 2a, 0.25 mmol Et3N, 1 ml DMF, catalyst (Pd-
content: CAT-1: 3.2 μmol, CAT-2 and CAT-4: 3.6 μmol CAT-3: 2.8 μmol ), 100 °C, 30 bar,
8h. Yields are determined by GC.
An even greater difference in the stability of the pyridinium- (CAT-1) and imidazolium-type
(CAT-2) catalysts was observed when carbonylations were carried out at 5 bar CO pressure
(Figure 5). While CAT-1 showed an acceptable stability, CAT-2 lost its activity very quickly.
It should also be mentioned that although at 5 bar the α-ketoamide (3aa)/amide (4aa) ratio
was somewhat lower than at 30 bar CO pressure, the main product 3aa was still formed with
good selectivity in the presence of CAT-1. The influence of the reaction conditions applied in
the first run is well demonstrated by the fact that in eight-hour long reactions an increased
amount of side product 5a could be detected in the reaction mixtures from the second run on.
At lower pressures, the catalyst CAT-1 was less stable in acetonitrile than in DMF (Figure 6),
but at 30 bar it could be reused with only a small loss of activity. Moreover, it demonstrated a
remarkably better recyclability than CAT-2 under the same conditions.

9
Figure 5. Recirculation experiments with CAT-1 and CAT-2 at 5 bar CO pressure. Reaction
conditions: 0.2 mmol 1a, 0.5 mmol 2a, 0.25 mmol Et3N, 1 ml DMF, catalyst (Pd-content: 3.2
μmol), 100 °C, 5 bar. Yields are determined by GC.
In order to avoid dissolution of the ionic liquid film by the solvent, the applicability of the
toluene/DBU solvent/base system was also tested. In spite of the fact that these conditions
were proved to be suitable for double carbonylations carried out with SILPs decorated with
imidazolium-type dicationic moieties, [22] no formation of carbonylated products could be
observed with CAT-2 prepared from the SILP with adsorbed IL-2. On the contrary, good
conversions could be achieved in the presence of either CAT-1 or CAT-3 (Figure 7).
Unfortunately, reuse of CAT-1 led to a noticeable increase in the ratio of the amide product
4aa.

10
Figure 6. Recirculation experiments with CAT-1 and CAT-2 in acetonitrile. Reaction
conditions: 0.2 mmol 1a, 0.5 mmol 2a, 0.25 mmol Et3N, 1 ml acetonitrile, catalyst (Pd-
content: 3.2 μmol), 100 °C, 8h. Yields are determined by GC.
Figure 7. Recirculation experiments with CAT-1 and CAT-3 in toluene. Reaction conditions:
0.2 mmol 1a, 0.5 mmol 2a, 0.25 mmol DBU, 1 ml toluene, catalyst (Pd-content: 3.2 μmol),
100 °C, 3h. Yields are determined by GC.

11
2.3. Palladium leaching
Partial loss of immobilised palladium may have a decisive effect on the stability of
heterogeneous catalysts, so the next investigations were aimed at the determination of the
palladium content of the liquid phase of the reaction mixtures. Similarly to the results
obtained earlier with the catalyst on the imidazolum SILP CAT-2, [21] a considerable amount
of palladium leached into the reaction mixtures in the first experiments. However, in case of
CAT-2, the drop in the loss of palladium was observed already after the first run (from 23.7
% of the original load, to a total of 8.1% in the 5 successive runs). [21] Palladium leaching of
CAT-1 was smaller in the three-hour long reaction (Table 3, entry 3), but approximately the
same loss of palladium was measured in the recycling experiment (entry 4). The palladium-
content of the reaction mixture decreased noticeable only from the third run (entries 5, 6).
These observations are in good accordance with the differences in the dissolution of the two
1
different ionic liquids, IL-1 and IL-2. The H NMR investigations of the reaction mixtures
indicated that while in case of IL-1 almost the total amount of the adsorbed ionic liquid was
dissolved in the reaction mixture already in the first run, only circa half of IL-2 was removed
in the first cycle, and the other half was lost in the second one. That means that the initial loss
of palladium is mainly due to the increased solubility of palladium complexes/nanoparticles
in the ionic liquid/organic solvent mixture.
The absence of the bands corresponding to the alkyl-pyridinium moiety in the IR spectrum of
the spent catalyst (Figure 2) also supports the loss of the majority of the IL. (The signal at
1668 cm-1 can be attributed to some residual DMF that could not be completely removed after
the catalytic reaction.) These changes could also be followed by comparing the differences
between the composition of the fresh and spent catalyst. The decrease in the carbon content
from 18.8% to 7.73% indicated the loss of some organic moieties. The relatively high N

12
content (1.92%), can be attributed to residual DMF, and is in accordance with the IR results.
1H NMR investigations showed a similar behaviour in acetonitrile but the presence of IL-2
could not be detected in the reaction mixture obtained in toluene.
Examining the leaching data of experiments carried out with different reaction times in DMF
(Table 3, entries 1-3), an appreciable decrease in the palladium-content of the reaction
mixture could be detected in the three-hour long reaction (Table 3, entries 2 and 3). This
supports the assumption that after the completion of the reaction after one hour (see Table 2,
entry 2), a part of the leached palladium was redeposited on the support. So it can be
concluded that similarly to the reactions carried out with CAT-2, [21] a dissolution-
reprecipitation mechanism [27] may also operate here. While 5.1% of the original load of
palladium was lost in acetonitrile (entry 7), the metal content of the reaction mixture in
toluene was much lower (entry 8).
Table 3. Leaching of palladium during recirculation experiments for aminocarbonylation of
iodobenzene (1a) with morpholine (2a) in different solventsa
Entry
Solvent
DMF
Base
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
DBU
Reaction time [h] Pd-leaching [%]
1
2
3
4
5
6
7
8
0.5
6.4
11.7
8.8
10.4
3.2
<2
DMF
1
DMF
3
DMF
3 (2nd run)
3 (3rd run)
3 (4th run)
DMF
DMF
acetonitrile
8
3
5.1
<1
toluene
a: reaction conditions: 0.2 mmol 1a, 0.5 mmol 2a, 0.25 mmol base, catalyst CAT-1 (with 3.2
μmol Pd-content) in 1 ml solvent, 30 bar CO pressure, 100 °C; b: determined by ICP-AES.

13
To obtain information about the homogeneous or heterogeneous nature of the catalytic
reactions in the presence of CAT-1, hot filtration and mercury poising tests were also carried
out (Table 4). In a typical experiment the catalytic mixture was filtered after half an hour .
One half of the mixture was heated further under CO pressure and the other was treated
similarly but in the presence of mercury.
A considerable conversion of 1a was detected after the removal of the solid material using
either a fresh supply (entry 1) or a spent catalyst (entry 3) in DMF. This is in accordance with
the amount of leached palladium in the first two cycles. The reaction could be stopped almost
completely in the presence of mercury in case of the spent catalyst (entry 4) indicating that the
catalytically active species that have leached to the reaction mixture are mainly nanoparticles.
On the contrary, some further reaction of iodobenzene (1a) was observed in the filtrate of the
first reaction even when mercury was added. This can be due to an initial loss of palladium
complexes together with palladium nanoparticles in the first run experiment. In acetonitrile
(Table 4, entry 6) the complete lack of catalytic activity in the presence of mercury shows the
presence of nanoparticles only. According to the tests in toluene (entries 7, 8), both
complexes and nanoparticles contribute to the catalytic activity of the filtrate after a half an
hour long reaction.
In a summary of catalytic and leaching data, it can be stated that although the toluene/DBU
system was proved to be superior in terms of the dissolution of the ionic liquid as well as the
loss of the metal, a better selectivity towards α-ketoamide 3aa could be achieved in DMF or
acetonitrile. Comparing the latter solvents, better recyclability of the catalyst could be
achieved in DMF.

14
Table 4. Hot filtration and mercury poisoning tests in the aminocarbonylation of iodobenzene
(1a) with morpholine (2a) in different solventsa
Entry Solvent
Base
First stepb
Second stepc
Conv. of Ratio of
Hg
Conv. of
1a (%)d
Ratio of
3aa:4aad
95:5
1a (%)d
3aa:4aad
1
2
3e
4
5
6
7
8
DMF
DMF
Et3N
Et3N
21
100:0
-
57
+
-
31
98:2
18
41f
30
100:0
93:7
91:9
50
98:2
+
-
19
100:0
93:7
acetonitrile Et3N
55
+
-
41
93:7
toluene
DBU
50
92:8
+
35
91:9
a: reaction conditions: 0.2 mmol 1a, 0.5 mmol 2a, 0.25 mmol base, catalyst CAT-1 (with 3.2
b
c
μmol Pd-content), 1 ml solvent, 30 bar CO, 100 °C; : reaction time: 0.5h; : reaction time:
3h; d: determined by GC; e: recycled catalyst after a three hour-long first run; f: reaction time:
1.5h.
2.4. Carbonylation of other substrates in the presence of CAT-1
The efficiency of CAT-1 in the carbonylation of other substrates, aryl halides (1a-1f) and
aliphatic amines (2a-2f) (Schemes 2-5) as well as iodobenzene (1a) and aniline derivatives
(2g-2k) (Scheme 6), was also explored (Table 5). Because of the relatively high loss of
palladium in the first two cycles, the catalyst was used in five successive runs in each case to
prove recyclability. Good conversions could be achieved in most of the reactions with the
exception of the use of the sterically hindered amine 2d (entry 3). The α-ketoamides were the
main products in the reactions of secondary aliphatic amines 2a-c and 2e (entries 1, 2, 4, 11-

15
17). Poor selectivity was observed with 2-ethylpiperidine (2d) with the amide derivative 4ad
as the prevailing product (entry 3). It should be mentioned, that a similar difference between
the distribution of mono- and double carbonylated products was observed before in the
reactions of piperidine (2c) and 2-ethylpiperidine (2d) under homogeneous conditions. [28]
The application of N,N-diethylamine (2e) resulted in some change in the product distribution
towards the amide (4ae) when the catalyst was recycled (entry 4). In most of the reactions
with morpholine (2a) (entries 11-17) or pyrrolidine (2b) (entry 1) as the nucleophile, a slow
but noticeable increase in the amount of side product 5 could be detected in the consecutive
experiments. The imine derivative (6, Scheme 3 ) was the main product in the carbonylation
of the primary amine 2f, due to the reaction of ketoamide 1af with the excess of amine (entry
5).
O
O
R'
N
O
Me
N
R'
CAT-1
R'
+
+
CO
+
R
I
HN
+
R
N
R
R''
R
Me
Et3N
DMF
R''
R''
O
O
1x
2y
5x
3xy
4xy
a: R=Ph
b: R=4-MeO-C6H4
a: R'R''=(CH2)2-O-(CH2)2
b: R'R''=(CH2)4
c
:
R=3,4-Me2-C6H3
c
:
R'R''=(CH2)5
d: R=3-F-C6H4
e: R=4-Cl-C6H4
d: R'R''=CH(Et)-(CH2)4
e: R'=R''=Et
f:
R=1-naphthyl
Scheme 2. Carbonylation products formed from aryl iodides 1a-1f and secondary amines 2a-
2e
Scheme 3. Carbonylation of iodobenzene (1a) and n-butylamine (2f)

16
Table 5. Carbonylation of aryl iodides 1a-1i and amines 2a-2k in the presence of CAT-1a
entry
run 1
run 2
run 3
run 4
run 5
1
2
conv.
(%)b
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
conv.
(%)b
100
97
ratio of
conv.
(%)b
100
100
82
100
100
100
96
100
100
100
100
98
100
97
98
100
100
100
ratio of 3/4/5
conv.
(%)b
99
96
78
100
100
100
96
100
100
100
98
97
100
96
100
100
100
100
conv.
(%)b
98
100
72
ratio of
ratio of 3/4/5 b
ratio of 3/4/5 b
b
3/4/5 b
70/22/8
88/6/6
3/4/5 b
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
70/27/3
85/11/4
27/64/9
84/14/2
15/5/0c
0/100/0
0/100/0
0/100/0
0/100/0
0/100/0
91/9/0
70/17/13
88/6/6
57/26/17
88/6/6
57/26/18
87/6/7
1a 2b
1a 2c
1a 2d
1a 2e
1a 2f
1a 2g
1a 2h
1a 2i
1a 2j
1a 2k
1b 2a
1c 2a
1d 2a
1e 2a
1f 2a
1g 2a
1h 2a
1i 2a
88
43/55/2
83/14/3
10/12/2 c
0/100/0
0/100/0
0/100/0
0/100/0
0/100/0
87/5/8
45/52/3
81/17/2
7/16/1 c
0/100/0
0/100/0
0/100/0
0/100/0
0/100/0
84/5/11
82/6/12
78/9/13
72/14/11
68/24/6
79/8/10d
73/6/10e
(4f)/17(79g)/0
45/55/0
73/27/0
13/19/3 c
0/100/0
0/100/0
0/100/0
0/100/0
0/100/0
84/5/11
82/6/12
76/8/16
75/12/13
73/18/9
72/8/17d
75/6/9e
46/54/0
65/35/0
10/24/4 c
0/100/0
0/100/0
0/100/0
0/100/0
0/100/0
84/4/12
77/7/16
79/8/13
72/13/15
71/18/11
71/8/21
74/6/9e
100
100
100
90
100
100
97
100
100
100
98
100
100
100
100
95
100
100
90
96
100
98
92
91/7/2
96/4/0
86/7/7
100
100
96
81/9/10
76/14/8
74/22/4
79/10/7d
72/6/9e
69/27/4
68/32/0
66/21/1d
74/5/6e
99
100
100
100
18
(6f)/30(64g)/0
(5f)/19(76g)/0
(3f)/13(84g)/0
(3f)/9(88g)/0
a
b
: reaction conditions: 0.2 mmol 1, 0.5 mmol 2, 0.25 mmol Et3N, CAT-1 (3.2 μmol Pd, 1.6 mol%), 1 ml DMF, 100 °C, 30 bar, 8 h.
:
c
d
determined by GC. : main product: 6 (Scheme 2), formed in 85%, 86%, 86%, 75% and 72% yield in runs 1-5, respectively (GC). : side
products: 7g, 8g and 9g (Scheme 3), formed with a total yield of 12%, 4%, 3% and 3% (GC) in runs 1-4, respectively. e: side products: 7h, 8h
f
and 9h (Scheme 3), formed with a total yield of 15%, 13%, 11%, 10% and 11% (GC) in in runs 1-5, respectively. : in parenthesis: ratio of 4-
amino derivative 10, Scheme 4). g: in parenthesis: ratio of 4-amino derivative 11, Scheme 4).

17
A partial substitution of the bromo functionalities of bromo-iodobenzenes 1g and 1h was
observed (Scheme 4), especially in the first experiments (entries 16, 17). Unfortunately, no
conversion of bromobenzene, or activated bromobenzene derivatives, such as 4-nitro-
bromobenzene could be effected under similar conditions. Carbonylation of 4-nitro-
iodobenzene led to the 4-amino compounds (10 and 11, Scheme 5) as the main products
(entry 18).
O
O
O
O
O
CAT-1
I
N
N
CO
+
N
+
N
H
Et3N
DMF
O
O
O
Br
Br
Br
Br
3-Br: 1g
4-Br: 1h
2a
5g
5h
3ga
3ha
4ga
4ha
R
O
C
N
O
R,R'=
n,m
R'
9g:
9h:
7g:
7h:
8g:
8h:
n=1,m=2
n,m=1
n,m=2
Scheme 4. Carbonylation products of aryl iodides 1g and 1h
O
O
O
O
O
CAT-1
I
N
CO
+
N
+
N
+
N
H
Et3N
DMF
O2N
O
O
O
O2N
H2N
H2N
1i
2a
10
4ia
11
Scheme 5. Carbonylation products of 4-nitro-iodobenzene (1i)
Excellent recyclability together with a complete selectivity towards the amides 4ag-4ak were
achieved in the reactions of the aniline derivatives 2g-2k (Table 5, entries 6-10).

18
O
CAT-1
I
NH2
CO
N
+
R
H
Et3N, DMF
R
2y
4ay
1a
g: R=H
h
i
:
:
R=4-Bu
R=4-OMe
j: R=4-NO2
k
:
R=4-C(O)CH3
Scheme 6. Carbonylation of iodobenzene (1a) and aniline derivatives 2g-2k
O
O
O
O
O
N
N
N
N
O
O
O
O
3aa
3ab
82%
N
64%
3ae
3ac
78%
N
80%
N
O
O
O
O
O
O
O
O
N
F
O
O
O
O
Cl
H3C
H3CO
CH3
3ea
70%
3ca
3da
75%
70%
3ba
78%
O
O
O
O
O
O
N
Br
N
O
N
O
O
Br
68%a
O
3ha
3fa
54%
3ga
55%
Bu
OCH3
O
O
O
N
H
N
N
N
H
H
4ai
93%
4ah
86%
O
4ad
4ag
92%
35%
O
NO2
O
N
H
N
H
4ak
86%
4aj
84%
Figure 8. Yields of the main products after chromatographic separation of the combined
mixtures of runs 1-3. (Reaction conditions: 0.2 mmol 1a, 0.5 mmol 2a, 0.25 mmol Et3N, 1 ml
DMF, catalyst CAT-1 (Pd-content: 3.2 μmol), 100 °C, 30 bar, 8h. (a: Isolated from the
combined mixtures of runs 2-4)

19
The main products could be isolated by column chromatography in acceptable to good yields
(Figure 8).
3. Experimental
Reaction mixtures were analysed by gas chromatography (Hewlett Packard 5890) and GC-MS
(Hewlett Packard 5971A GC-MSD, HP-1 column). Conversions and selectivities of the
reactions were determined by GC.
The palladium-content of the catalysts and palladium leaching were determined by ICP-AES.
13
1H and C NMR spectra of the products were recorded in CDCl3 or DMSO-d6 on a Bruker
Avance 500 spectrometer at 500.15 MHz and 125.78 MHz, or on a Bruker Avance 400
spectrometer at 400.13 MHz and 100.62 MHz, respectively. Chemical shifts (δ) are reported
in ppm relative to CHCl3 (7.26 and 77.16 ppm for 1H and 13C, respectively). NMR spectra of
isolated products correspond well to those reported previously. [22] Other components were
characterised using GC-MS. IR spectra were made using a Thermo Nicolet Avatar 330 FT-IR
instrument. Samples were prepared as KBr pellets.
3.1.Preparation of supported catalysts
Catalysts CAT-2, [21] CAT-3 [22] and CAT-4 [21] were prepared as reported previously.
Preparation of CAT-1
200 mg 1-butyl-4-methylpyridinium chloride (IL-1) and 0.02 mmol (20.7 mg)
Pd2(dba)3.CHCl3 were dissolved in a mixture of 2 ml acetonitrile and 2 ml THF. The mixture
was stirred for 15 min at room temperature. Then 550 mg silica (Kieselgel 60 (0.040-0.063
mm), Merck, pre-treated by heating for 5 h at 250 °C) was added under stirring and the
resulting mixture was stirred for 24 h. The solvents were removed in vacuo and the catalyst
was dried at 40 °C in vacuo for 3 h and was stored under argon until use. Palladium content

20
of the catalyst: 0.49% (determined by ICP). Ionic liquid content: 1.33 mmol/ g modified silica
(determined from the weight increase after heating the material to constant weight at 150 °C
in vacuo, as well from the N-content of the solid material (elemental analysis: C: 18.8%; H:
2.84%; N: 1.90%).
3.2. Catalytic reactions
In a typical experiment the catalyst (containing 3.2 μmol Pd) was placed in a stainless steel
autoclave. The aryl iodide (0.2 mmol), amine (0.5 mmol), base (0.25 mmol) and solvent (1
ml) were transferred into it under an inert atmosphere. It was charged with carbon monoxide
(5 bar or 30 bar) and heated with stirring in an oil bath at 100 °C. After cooling to room
temperature the catalyst was removed by filtration and was reused without further
purification. The reaction mixture was analysed by gas chromatography.
After the evaporation of the solvent of the reaction mixture, the products were purified by
column chromatography (silica, eluent: ethyl acetate (3aa, 4ag), toluene:ethyl acetate = 3:2
(3ae, 3ba, 3ca, 3ea), toluene: ethyl acetate = 5:2 (4ah, 4ai, 4aj, 4ak), toluene: acetone = 4:1
(3ab, 3ac, 3da, 3fa, 3ga, 3ha, 4ad)).
3.3. Characterisation of the products
1
1-Morpholino-2-phenylethane-1,2-dione (3aa): H NMR (500.15 MHz, CDCl3): 7.95-7.99
(m, 2H), 7.63-7.69 (m, 1H), 7.50-7.55 (m, 2H), 3.78-3.82 (m, 4H), 3.65-3.67 (m, 2H), 3.37-
3.41 (m, 2H). 13C NMR (125.78 MHz, CDCl3): 191.3, 165.6, 135.1, 133.3, 129.8, 129.3,
66.9, 66.8, 46.4, 41.8..MS (m/z/rel.int.): 219 (M+)/6; 114/11; 105/100; 86/4; 77/54; 70/26;
51/22. Yield: 82%.
1-Phenyl-2-(pyrrolidin-1-yl)ethane-1,2-dione (3ab): 1H NMR (400.13 MHz, CDCl3): 7.97-
8.01 (m, 2H), 7.60-7.66 (m, 1H), 7.47-7.52 (m, 2H), 3.63-3.68 (m, 2H), 3.40-3.45 (m, 2H),

21
1.90-2.00 (m, 4H). 13C NMR (100.62 MHz, CDCl3): 191.7, 165.1, 134.7, 133.1, 130.0, 129.0,
46.8, 45.4, 26.1, 24.2. MS (m/z/rel.int.): 203(M+)/3; 202/6; 105/71; 98/100; 77/52; 70/31;
55/56. Yield: 82%. Yield: 64%.
1
1-Phenyl-2-(piperidin-1-yl)ethane-1,2-dione (3ac): H NMR (500.15 MHz, CDCl3): 7.89-
7.96 (m, 2H), 7.57-7.64 (m, 1H), 7.43-7.52 (m, 2H), 3.65-3.71 (m, 2H), 3.23-3.29 (m, 2H),
13
1.62-1.71 (m, 4H), 1.48-1.55 (m, 2H). C NMR (125.78 MHz, CDCl3): 192.0, 165.5, 134.7,
133.4, 129.6, 129.1, 47.1, 42.2, 26.3, 25.5, 24.4. MS (m/z/rel.int.): 217(M+)/5; 112/100;
105/54; 84/10; 77/33; 69/61. Yield: 80%.
1-Phenyl-2-(2-ethylpiperidin-1-yl)ethane-1,2-dione (3ad): MS (m/z/rel.int.): 245(M+)/2;
140/100; 105/60; 77/55; 55/45.
1
N,N-Diethyl-2-oxo-2-phenylacetamide (3ae): H NMR (500.15 MHz, CDCl3): 7.92-7.95
(m, 2H), .7.60-7.65 (m, 1H), 7.47-7.52 (m, 2H), 3.56 (q, J = 7.1 Hz, 2H), 3.24 (q, J = 7.1 Hz,
2H), 1.29 (t, J = 7.1 Hz, 3H), 1.15 (t, J = 7.1 Hz, 3H). 13C NMR (125.78 MHz, CDCl3):
191.7, 166.9, 134.7, 133.5, 129.8, 129.1, 42.2, 39.0, 14.2, 13.0. MS (m/z/rel.int.): 205(M+)/5;
105/61; 100/100; 77/42; 72/74; 51/21. Yield: 78%.
N-Butyl-2-oxo-2-phenylacetamide (3af): MS (m/z/rel.int.): 205(M+)/13; 105/100; 77/34;
57/29; 51/10; 41/10.
1-Morpholino-2-(4-methoxyphenyl)ethane-1,2-dione (3ba): 1H NMR (500.15 MHz,
CDCl3): 7.91-7.95 (m, 2H), 6.95-7.02 (m, 2H), 3.90 (s, 3H), 3.76-3.81 (m, 4H), 3.63-3.67 (m,
13
2H), 3.36-3.40 (m, 2H). C NMR (125.78 MHz, CDCl3): 190.0, 166.0, 165.2, 132.3, 126.4,
114.6, 67.0, 66.9, 55.8, 46.5, 41.7. MS (m/z/rel.int.): 249(M+)/3; 136/12; 135/100; 114/3;
107/11; 92/10; 77/14; 70/8; 64/5. Yield: 78%.
1
1-(3,4-Dimethylphenyl)-2-morpholinoethane-1,2-dione (3ca): H NMR (500.15 MHz,
CDCl3): 7.74 (brs, 1H), 7.69 (d, J=8.7Hz, 1H), 7.28 (d, J=8.7Hz, 1H), 3.76-3.83 (m, 4H),
3.62-3.67 (m, 2H), 3.35-3.39 (m, 2H), 2.35 (s, 3H), 2.33 (s, 3H). 13C NMR (125.78 MHz,

22
CDCl3): 191.3, 165.9, 145.2, 137.8, 131.1, 130.5, 130.4, 127.6, 66.8, 66.7, 46.3, 41.6, 20.4,
19.8. MS (m/z/rel.int.): 247(M+)/3; 133/100; 105/24; 79/9; 77/9; 70/9. Yield: 75%.
1
1-(3-Fluorophenyl)-2-morpholinoethane-1,2-dione (3da): H NMR (500.15 MHz, CDCl3):
7.72-7.75 (m, 1H), 7.67-7.63 (m, 1H), 7.48-7.52 (m, 1H), 7.32-7.37 (m, 1H), 3.75-3.81 (m,
4H), 3.63-3.67 (m, 2H) 3.35-3.40 (m, 2H). 13C NMR (125.78 MHz, CDCl3): 189.8 (d, J = 2.0
Hz), 164.9, 163.0 (d, J = 242.0 Hz), 135.3 (d, J = 6.0 Hz), 131.0 (d, J = 8.5 Hz), 125.9 (d, J =
3.6 Hz), 122.1 (d, J = 22.2 Hz), 116.1 (d, J = 22.5 Hz), 66.8 (2C), 46.4, 41.9. MS
(m/z/rel.int.): 237(M+)/9; 123/70; 114/100; 95/39; 86/12; 75/15; 70/77; 56/7; 45/6; 42/22.
Yield: 70%.
1
1-(4-Chlorophenyl)-2-morpholinoethane-1,2-dione (3ea): H NMR (500.15 MHz, CDCl3):
7.89-7.94 (m, 2H), 7.48.7.52 (m, 2H), 3.76-3.83 (m, 4H), 3.64-3.69 (m, 2H), 3.36.3.41 (m,
13
2H). C NMR (125.78 MHz, CDCl3): 189.8, 165.1, 141.8, 131.7, 131.2, 129.7, 66.9, 66.8,
46.5, 41.9.MS (m/z/rel.int.): 253(M+)/3; 141/33; 140/8; 139/100; 114/53; 113/9; 111/29;
86/14; 76/6; 75/22; 70/70; 56/8; 50/8; 42/29. Yield: 70%.
1
1-(Naphth-1-yl)-2-morpholinoethane-1,2-dione (3fa): H NMR (500.15 MHz, CDCl3):
9.24 (d, J = 8.6 Hz, 1H), 8.14 (d, J = 7.9 Hz, 1H), 8.04 (dd, J = 7.1, J = 0.9 Hz, 1H), 7.93 (d, J
= 7.9 Hz, 1H), 7.69-7.75(m, 1H), 7.55.7.63 (m, 2H), 3.82.3.85 (m, 4H), 3.65-3.70 (m, 2H),
3.42-3.47 (m, 2H). 13C NMR (125.78 MHz, CDCl3): 193.7, 166.2, 136.3, 134.6, 134.3, 131.1,
129.6, 128.9, 128.6, 127.3, 125.9, 124.7, 66.9 (2C), 46.6, 41.9. MS (m/z/rel.int.): 269(M+)/10;
156/12; 155/100; 128/6; 127/53; 126/8; 77/5; 70/10; 42/5. Yield: 54%.
1
1-(3-Bromophenyl)-2-morpholinoethane-1,2-dione (3ga): H NMR (500.15 MHz, CDCl3):
8.07-8.11 (m, 1H), 7.86-7.90 (m, 1H), 7.75-7.79 (m, 1H), 7.40 (td, J = 8.0 Hz, 1.9 Hz, 1H),
13
3.76-3.82 (m, 4H), 3.64-3.69 (m, 2H), 3.36-3.40 (m, 2H). C NMR (125.78 MHz, CDCl3):
189.6, 164.8, 137.8, 135.0, 132.5, 130.8, 128.5, 123.5, 66.9, 66.8, 46.4, 41.9.

23
MS(m/z/rel.int.): 299(M+)/5; 297(M+)/5; 185/28; 183/28; 157/11; 155/11; 114/100; 86/14;
76/15; 75/12; 70/63; 42/20. Yield: 55%.
1-(4-Bromophenyl)-2-morpholinoethane-1,2-dione (3ha): 1H NMR (500.15 MHz, CDCl3):
7.81-7.85 (m, 2H), 7.65-7.69 (m, 2H), 3.76-3.82 (m, 4H), 3.64-3.68 (m, 2H), 3.36-3.40 (m,
13
2H). C NMR (125.78 MHz, CDCl3): 190.0, 165.0, 132.7, 132.1, 131.2, 130.7, 66.9, 66.8,
46.5, 41.9. MS (m/z/rel.int.): 299(M+)/6; 297(M+)/6; 185/100; 183/100; 157/20; 155/20;
114/93; 86/31; 76/22; 75/19; 70/83; 42/27. Yield: 68%.
Morpholino(phenyl)methanone (4aa): MS (m/z/rel.int.): 191(M+)/11; 190/34; 176/9; 160/6;
105/100; 86/12; 77/68; 51/24.
Phenyl(pyrrolidin-1-yl)methanone (4ab): MS (m/z/rel.int.): 175 (M+)/44; 174/28; 146/28;
105/100; 77/57; 51/16.
Phenyl(piperidin-1-yl)methanone (4ac): MS (m/z/rel.int.): 189 (M+)/36; 188/100; 106/10;
105/98; 84/9; 77/56; 51/12.
1
Phenyl(2-ethylpiperidin-1-yl)methanone (4ad): H NMR (500.15 MHz, CDCl3): 7.35-7.42
(m, 5H), 4.52-4.92 (m, 1H), 3.42-3.83 (m, 1H), 2.74-3.33 (m, 1H), 1.44-1.88 (m, 8H), 0.66-
13
1.05 (m, 3H). C NMR (125.78 MHz, CDCl3): 170.8, 137.2, 129.1, 128.4, 126.5, 55.8/49.7,
43.2/37.2, 28.3, 26.0, 22.6, 19.1, 10.7. MS (m/z/rel.int.): 217(M+)/7; 188/38; 105/100; 77/43;
51/10. Yield: 35%.
N,N-Diethylbenzamide (4ae): MS (m/z/rel.int.): 177(M+)/13; 176/36; 105/100; 77/39; 51/11.
N-Butylbenzamide (4af): 177(M+)/7; 149/2; 105/100; 77/41; 72/48; 51/17.
1
N-Phenylbenzamide (4ag): H NMR (400.13 MHz, CDCl3): 7.86-7.90 (m, 2H), 7.78-7.86
(brs, 1H), 7.32-7.67 (m, 2H), 7.54-7.58 (m, 1H), 7.47-7.52 (m, 2H), 7.35-7.40 (m, 2H), 7.13-
7.19 (m, 1H). 13C NMR (100.62 MHz, CDCl3): 166.0, 138.1, 135.1, 132.0, 129.2, 129.0,
127.2, 124.8, 120.4. MS (m/z/rel.int.): 197(M+)/42; 105/100; 77/52; 51/14. Yield: 92%.

24
1
N-(4-Butylphenyl)benzamide (4ah): H NMR (500.15 MHz, CDCl3): 7.84-7.89 (m, 2H),
7.76-7.81 (brs, 1H), 7.52-7.56 (m, 3H), 7.45-7.52 (m, 2H), 7.16-7.20 (m, 2H), 2.60 (t, J = 7.6
13
Hz, 2H), 1.60 (qui, J=7.6 Hz, 2H), 1.35 (sext, J=7.6 Hz, 2H), 0.93 (t, J = 7.6 Hz, 3H). C
NMR (125.78 MHz, CDCl3): 165.8, 139.6, 135.7, 135.3, 131.9, 129.1, 129.0, 127.1, 120.4,
35.2, 33.8, 22.4, 14.1. MS (m/z/rel.int.): 253(M+)/57; 210/32; 105/100; 77/46; 51/5. Yield:
86%.
1
N-(4-Methoxyphenyl)benzamide (4ai): H NMR (500.15 MHz, CDCl3): 7.85 (d, J=6.6 Hz,
2H), 7.78-7.83 (brs, 1H), 7.51-7.57 (m, 3H), 7.47 (t, J=7.5 Hz, 2H), 6.90 (d, J=6.6 Hz, 2H),
3.81 (s, 3H). 13C NMR (125.78 MHz, CDCl3): 165.8, 156.8, 135.2, 131.8, 131.2, 128.9,
127.1, 122.3, 114.4, 55.7.MS (m/z/rel.int.): 227(M+)/51; 122/5; 105/100; 95/4; 77/38; 51/6.
Yield: 93%.
N-(4-Nitrophenyl)benzamide (4aj): 1H NMR (500.15 MHz, DMSO-d6): 10.80 (s, 1H), 8.25-
8.29 (m, 2H), 8.05-8.09 (m, 2H), 7.97-8.00 (m, 2H), 7.62-7.66 (m, 1H), 7.7.54-7.59 (m, 2H).
13C NMR (125.78 MHz, DMSO-d6): 166.2, 145.5, 142.5, 134.2, 132.1, 128.5, 127.9, 124.7,
119.8. MS (m/z/rel.int.): 242(M+)/7; 105/100; 77/51; 51/8. Yield: 84%.
1
N-(4-Acetylphenyl)benzamide (4ak): ): H NMR (500.15 MHz, CDCl3): 8.03-8.07 (brs,
1H), 7.97-8.01 (m, 2H), 7.87-7.90 (m, 2H), 7.75-7.79 (m, 2H), 7.56-7.60 (m, 1H), 7.49-7.53
(m, 2H), 2.60 (s, 3H). 13C NMR (125.78 MHz, CDCl3): 165.9, 142.5, 134.7, 133.3, 132.4,
130.0, 129.1, 127.2, 119.4, 26.6. MS (m/z/rel.int.): 239(M+)/25; 105/100; 77/39; 51/6; 43/35.
Yield: 86%.
Morpholino(4-methoxyphenyl)methanone (4ba): MS (m/z/rel.int.): 221(M+)/10; 220/16;
135/100; 107/8; 92/9; 77/15; 64/5; 56/3.
Morpholino(3,4-dimethylphenyl)methanone (4ca): MS (m/z/rel.int.): 219(M+)/11; 218/17;
133/100; 105/20; 79/11; 77/12.

25
Morpholino(3-fluorophenyl)methanone (4da): MS (m/z/rel.int.): 209(M+)/15; 208/28;
194/12; 178/5; 166/3; 123/100; 95/53; 86/24; 75/18; 56/41; 42/6.
Morpholino(4-chlorophenyl)methanone (4ea): MS(m/z/rel.int.): 227(M+)/3; 226/4;
225(M+)/10, 224/20;141/32; 140/8; 139/100; 113/13; 111/36; 86/23; 76/7; 75/29; 56/34;
44/29.
Morpholino(naphth-1-yl)methanone (4fa): MS (m/z/rel.int.): 241(M+)/38; 240/23; 156/23;
155/100; 127/81; 86/8; 77/8.
Morpholino(3-bromophenyl)methanone (4ga): MS(m/z/rel.int.): 271(M+)/26; 270/55;
269(M+)/26; 268/55; 256/16; 254/16; 185/92; 183/92; 157/42; 55/42; 104/14; 86/74; 77/12;
76/63; 75/42; 74/11; 72/16; 56/100; 55/11; 50/30; 42/24.
Morpholino(4-bromophenyl)methanone (4ha): MS (m/z/rel.int.): 271(M+)/17; 269(M+)/17;
268/42; 185/99; 183/100; 157/28; 155/22; 104/12; 86/41; 76/34; 75/26; 72/11; 56/54; 50/18;
42/12.
Morpholino(4-nitrophenyl)methanone (4ia): MS (m/z/rel.int.): 236(M+)/10; 235/14;
150/40; 86/37; 76/43; 56/100.
N,N-Dimethyl-2-oxo-2-phenylacetamide (5a): MS (m/z/rel.int.): 177(M+)/6; 105/100;
77/46; 72/54; 51/19.
N,N-Dimethyl-2-oxo-2-(4-methoxyphenyl)acetamide (5b): MS (m/z/rel. int.): 207(M+)/3;
137/100; 107/9; 92/9; 77615; 72/10
N,N-Dimethyl-2-oxo-2-(3,4-dimethylphenyl)acetamide (5c): MS (m/z/rel. int.): 205(M+)/3;
133/100; 105/26; 79/10; 77/11; 72/11.
N,N-Dimethyl-2-oxo-2-(3-fluorophenyl)acetamide (5d): MS (m/z/rel. int.): 195(M+)/8;
123/38; 95/25; 75/13; 72/100; 44/13.
N,N-Dimethyl-2-oxo-2-(4-chlorophenyl)acetamide (5e): MS (m/z/rel. int.): 213(M+)/2;
211(M+)/7; 141/13; 139/41; 113/6; 111/19; 75/15; 72/100.

26
N,N-Dimethyl-2-oxo-2-(naphth-1-yl)acetamide (5f): MS (m/z/rel. int.): 227 (M+)/9;
155/100; 127/66; 101/5; 77/8; 72/20.
N,N-Dimethyl-2-oxo-2-(3-bromophenyl)acetamide (5g): MS (m/z/rel. int.): 257(M+)/4;
255(M+)/4; 185/48; 183/50; 157/13; 155/13; 76/20; 75/19; 72/100; 50/15.
N,N-Dimethyl-2-oxo-2-(4-bromophenyl)acetamide (5h): MS (m/z/rel. int.): 257(M+)/4;
255(M+)/4; 185/19; 183/20; 157/9; 155/8; 76/13; 75/11; 72/100; 44/7.
N-Butyl-benzoylformamide N’-butylimine (6): MS (m/z/rel.int.): 260(M+)/3; 217/18;
160/3; 130/4; 117/3; 104/100; 77/9; 57/8; 41/10.
1,3-Phenylenebis(morpholinomethanone) (7g): MS (m/z/rel.int.): 304(M+)/26; 303/18;
219/16; 218/100; 189/11; 160/10; 133/33; 114/10; 105/12; 104/27; 86/86; 77/11; 76/37;
70/18; 56/42; 42/15.
1,4-Phenylenebis(morpholinomethanone) (7h): MS (m/z/rel.int.): 304(M+)/6; 191/11;
190/100; 91/5; 77/6.
1-(3-Morpholinocarbonyl)phenyl-2-morpholinoethane-1,2-dione (8g): MS (m/z/rel.int.):
332(M+)/22; 304/14; 218/100; 133/35; 114/86; 104/24; 86/12; 76/27; 70/67; 56/16; 42/25.
1-(4-Morpholinocarbonyl)phenyl-2-morpholinoethane-1,2-dione (8h): MS (m/z/rel.int.):
332(M+)/8; 304/10; 219/13; 218/100; 208/7; 114/31; 104/17; 76/9; 70/26; 56/6; 42/10.
1,3-Phenylenebis(2-morpholinoethane-1,2-dione) (9g): MS (m/z/rel.int.): 360(M+)/14;
246/100; 133/12; 114/96; 104/17; 78/13; 76/20; 70/84; 45/11; 42/32.
1,4-Phenylenebis(2-morpholinoethane-1,2-dione) (9h): MS (m/z/rel.int.): 360(M+)/16;
332/12; 247/14; 246/100; 218/8; 114/98; 104/21; 76/12; 70/71; 45/5; 42/22.
1-Morpholino-2-(4-aminophenyl)ethane-1,2-dione (10): MS (m/z/rel.int.): 234(M+)/3;
120/100; 92/17; 70/6; 65/16.
4-Aminophenyl(morpholino)methanone (11): MS (m/z/rel.int.): 206(M+)/13; 205/9; 121/8;
120/100; 93/2; 92/18; 91/2; 66/2; 65/17; 64/2; 56/2; 39/5.

27
4. Conclusions
A supported ionic liquid phase with adsorbed pyridinium ionic liquid was proved to exert
efficient stabilising effect toward the immobilised palladium catalyst. Detailed investigations
revealed that in spite of the loss of the majority of the ionic liquid in the first two cycles, the
catalyst can be used effectively in at least 10 consecutive runs. The importance of the choice
of the ionic liquid was demonstrated by the comparison of the catalytic performance of
pyridinium- (CAT-1) and imidazolium (CAT-2) SILP-Pd catalysts. Although very similar
leaching data could be measured for the two catalysts, the former showed higher activity and
better recyclability. The heterogeneous catalyst CAT-1 could be reused during the
carbonylation of a wide scope of substrates, but the structure of the reaction partners has a
decisive effect both on the recyclability of the catalyst and the selectivity of the carbonylation
reaction.
Acknowledgments
This work was supported by the GINOP-2.3.2-15-2016-00049 grant
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
References
[1]
A. Muthukumar, S. Sangeetha, G. Sekar, Org. Biomol. Chem. 16 (2018) 7068–7083.

28
[2]
(a) Y.X. Jia, D. Katayev, E. P. Kündig, Chem. Commun. 46 (2010) 130–132. (b) A.
Muthukumar, G. N. Rao, G. Sekar, Org. Biomol. Chem. 17 (2019) 3921-3933.
[3] J. X. Hu, H. Wu, C. Y. Li, W. J. Sheng, Y. X. Jia, J. R. Gao, Chem. Eur. J. 17 (2011)
5234–5237.
[4]
[5]
H. Masui, N. Ishizawa, S. Fuse, T. Takahashi Tetrahedron 71 (2015) 6354–6360.
S. R. Laursen, M. T. Jensen, A. T. Lindhardt, M. F. Jacobsen, T. Skrydstrup, Eur. J.
Org. Chem. (2016) 1881–1885.
[6]
[7]
[8]
[9]
Z. Zhu, X. Lv, J. E. Anesini, D. Seidel, Org. Lett. 19 (2017) 6424−6427.
C. De Risi, G. P. Pollini, V. Zanirato, Chem. Rev. 116 (2016) 3241−3305.
L. Kaysser, Nat. Prod. Rep. 36 (2019) 1654−1686.
(a) C. Steuer, C. Gege, W. Fischl, K. H. Heinonen, R. Bartenschlager, C. D. Klein,
Bioorg. Med. Chem. 19 (2011) 4067–4074. (b) K. O. Chang, Y. Kim, S. Lovell, A. D.
Rathnayake, W. C. Groutas, Viruses 11 (2019) 197.
[10] S. Pacifico, V. Ferretti, V. Albanese, A. Fantinati, E. Gallerani, F. Nicoli, R. Gavioli,
F. Zamberlan, D. Preti, M. Marastoni, ACS Med. Chem. Lett. 10 (2019) 1086−1092.
[11] D. Kumar, S. R. Vemula, G. R. Cook, ACS Catal. 6 (2016) 4920−4945.
[12] B. Urbán, M. Papp, R. Skoda-Földes, Curr. Green Chem. 6 (2019) 78−95.
[13] M. Genelot, N. Villandier, A. Bendjeriou, P. Jaithong, L. Djakovitch, V. Dufaud,
Catal. Sci. Technol. 2 (2012) 1886−1893.
[14] J. Balogh, Á. Kuik, L. Ürge, F. Darvas, J. Bakos, R. Skoda-Földes, J. Mol. Catal. A
302 (2009) 76–79.
[15]
L. Liu, S. Zheng, W. Sun, C. Xia, Chin. J. Chem. 27 (2009) 623−627.
[16] S. S. Islam, R. A. Molla, S. Ta, N. Yasmin, D. Das, S. M. Islam, J. Organomet. Chem.
882 (2019) 18−25.
[17] Y. Yan, H. Zuo, Z. Jin, 1997. React. Funct. Polym. 32 (1997) 1−24.

29
[18] Z. Wang, C. Liu, Y. Huang, Y. Hu, B. Zhang, Chem.l Commun. 52 (2016)
2960−2963.
[19] V. M. Solano, G. G. Miera, V. Pascanu, A. K. Inge, B. Martín-Matute, ChemCatChem
10 (2017) 1−7.
[20] (a) R. A. Molla, M. A. Iqubal, K. Ghosh, A. S. Roy, Kamaluddin, S. M. Islam, RSC
Adv. 4 (2014) 48177−48190. (b) B. Chen, F. Li, Z. Huang, T. Lua, G. Yuan, 2014. Appl.
Catal. A 481 (2014) 54–63. (c) S. S. Islam, S. Riyajuddin, R. A. Molla, N. Yasmin, K Ghosh,
S. M. Islam, New J. Chem. 44, (2020) 1979−1987. /
[21] M. Papp, R. Skoda-Földes, J. Mol. Catal. A 378 (2013) 193−199.
[22] M. Papp, P. Szabó, D. Srankó, G. Sáfrán, L. Kollár, R. Skoda-Földes, RSC Adv. 7
(2017) 44587−44597.
[23] B. Urbán, P. Szabó, D. Srankó, G. Sáfrán, L. Kollár, R. Skoda-Földes, Mol. Catal. 445
(2018) 195–205.
[24] W. Wojtków, A. M. Trzeciak, R. Choukroun, J. L. Pellegatta, J. Mol. Catal. A. 224
(2004) 81–86.
[25] (a) D. Cook, Can. J. Chem. 39 (1961) 2009-2024. (b) C. Pichon, P. Mialane, J.
Marrot, C. Binet, A. Vimont, A. Travert, J. C. Lavalley, Phys. Chem. Chem. Phys. 13 (2011)
322–327.
[26] M. Papp, B. Urbán, E. Drotár and R. Skoda-Földes, Green Proc. Synth. 4 (2015) 103–
115.
[27] R. G. Heidenreich, J. G. E. Krauter, J. Pietsch, K. Köhler, J. Mol. Catal. A 182–183
(2002) 499-509.
[28] Z. Szarka, R. Skoda-Földes, Á. Kuik, Z. Berente, L. Kollár, Synthesis (2003) 545–
550.