Ionic liquids containing anionic selenium species: Applications for the oxidative carbonylation of aniline

Article abstract of DOI:10.1002/1521-3773(20021115)41:22<4300::AID-ANIE4300>3.0.CO;2-V

Highly active catalysts for the carbonylation of a variety of substrate materials have been prepared in the form of selenium-containing ionic liquids. Products from the reactions of [KSeO₂(OCH₃)] and 1-alkyl-3-methylimidazolium chlorides (see scheme) exhibit surprisingly high activity for the oxidative carbonylation of aniline, even at temperatures as low as 40 °C.

Full text of DOI:10.1002/1521-3773(20021115)41:22<4300::AID-ANIE4300>3.0.CO;2-V

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CCDC-185168 (1) and CCDC-185167 (2) contains the supplementary
crystallographic data for this paper. These data can be obtained free of
charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cam-
bridge Crystallographic Data Centre, 12, Union Road, Cambridge
CB21EZ, UK; fax: (þ 44)1223-336-033; or deposit@ccdc.cam.ac.uk).
Ionic Liquids Containing Anionic Selenium
Species: Applications for the Oxidative
Carbonylation of Aniline**
Hoon Sik Kim,* Yong Jin Kim, Hyunjoo Lee,
Kun You Park, Chongmok Lee, and
Chong Shik Chin
Received: May 14, 2002
Revised: August 26, 2002 [Z19300]
Non-phosgene processes for the synthesis of carbamates
and/or substituted ureas have attracted increasing interest in
recent years, particularly in the area of green chemistry
because of the environmental concern regarding the use of
highly toxic phosgene.[1] Of the various non-phosgene proc-
esses, one approach involves the catalytic oxidative carbon-
ylation of an amine in the presence of an appropriate catalyst
or catalytic system.[2]
In previous reports, we have demonstrated that alkali
metal-containing selenium compounds, obtained from the
reaction of SeO2 and M2CO3 (M ¼ alkali metal) in methanol,
are effective catalysts for the oxidative carbonylation of
aniline to produce phenyl carbamate and diphenylurea.[3] The
major disadvantage of using these selenium compounds is the
difficulty in separating the product and the catalyst from the
reaction mixture, which arises from the coproduction of
insoluble diphenylurea and soluble alkyl phenyl carbamate,
with high conversion of aniline. A further disadvantage is the
formation of small quantities of unknown, highly volatile,
malodorous, and possibly toxic selenium species at relatively
high reaction temperatures.
Recently, there have been a considerable number of papers
regarding ionic liquids and their use in immobilizing volatile,
precious, and/or toxic homogeneous catalysts, thereby im-
proving the stability and facilitating the recovery of the
catalyst.[4]
In this context, the alkali metal-containing selenium com-
pound [KSeO2(OCH3)] can be reacted with 1-alkyl-3-meth-
ylimidazolium chlorides to prepare new imidazolium-based
ionic liquids containing anionic selenium species. The ionic
liquids are found to show surprisingly high activity for the
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[*] Dr. H. S. Kim
CFC Alternatives Research Center
KIST
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39-1, Hawolgokdong, Seongbukgu, Seoul 136-791 (Korea)
Fax : (þ 82)2-958-5859
E-mail: khs@kist.re.kr
H. Lee, K. Y. Park
[15] Y. Laligant, M. Leblanc, J. Pannetier, G. Fÿrey, J. Phys. C 1986, 19,
1081 1095.
Korea Institute of Science and Technology
Seoul (Korea)
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Chem. 1989, 78, 66 77.
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Samouel, G. Fÿrey, J. Solid State Chem. 1992, 101, 296 308.
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[21] G. M. Sheldrick, SHELXTL-PLUS Program for Crystal Structure
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many).
Prof. C. Lee
Department of Chemistry
Ewha Womans University
Seoul (Korea)
Y. J. Kim, Prof. C. S. Chin
Department of Chemistry
Sogang University
Seoul (Korea)
[**] This work was supported by the Ministry of Science and Technology.
We thank to Prof. Myoung Soo Lah for the X-ray crystallographic
analysis at Hanyang University.
Supporting information for this article is available on the WWW under
http://www.angewandte.org or from the author.
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carbonylation of aniline, even at temperatures as low as 408C.
Furthermore, malodorous selenium species are not formed
when the immobilized selenium compound is used as a
catalyst for carbonylation.
1,3-dimethylimidazolium), respectively. Although the melting
points of 2a, 3a, and 4a were not precisely established, they
were all liquids at -108C.
We now report, for the first time, the synthesis and
reactivity of a series of new, room-temperature ionic liquids
consisting of imidazolium cations (1-R-3-methylimidazolium,
R ¼ CH3, C2H5, n-C4H9) and selenium-containing anions
[SeO2(OR’)]À (R’ ¼ CH3, CH2CH3, CH2CF3, C6H5), which
are highly active, easily recyclable, and air and moisture
stable.
The reaction of SeO2 with 0.5 equiv of K2CO3 in methanol
for 1 h at room temperature, followed by the addition of THF
into the resulting solution produced [KSeO2(OCH3)] (1) as an
extremely hygroscopic white precipitate [Eq. (1)], which was
characterized by elemental analysis and H NMR spectros-
copy.
Interestingly, reactions of 3a with various alcohols pro-
duced a series of new selenium-containing ionic liquids, as
shown in Equation (2).
1
½emimꢀ½SeO2ðOCH3Þꢀ þ ROH ! ½emimꢀ½SeO2ðORÞꢀ þ CH3OH
ð2Þ
ð3 b : R ¼ CH3CH2; 3 c : R ¼ CF3CH2; 3 d : R ¼ PhÞ
2 SeO2 þ K2CO3 þ 2 CH3OH ! 2 KSeO2ðOCH3Þ þ H2O þ CO2
ð1Þ
The viscosity and conductivity of 2a, [bmim]-
[SeO2(OCH2CF3)] (2c), and (bmim)BF4 were measured.
Ionic liquid 2c surprisingly exhibits lower viscosity (15 cP)
and higher conductivity (4.33 mScmÀ1) than both 2a (viscos-
ity: 6055 cP, conductivity: 0.14 mScmÀ1) and (bmim)BF4
(viscosity: 233 cP, conductivity: 1.73 mScmÀ1).[6] These results
demonstrate that the physical properties of the ionic liquids
could be significantly altered by replacing the alkoxide group
in the anionic moiety.
The ambiguous spectroscopic data of 1 led us to carry out a
single-crystal X-ray diffraction study to elucidate its structure,
which revealed that 1 was, indeed, potassium methyl selenite,
[KSeO2(OCH3)], in which the methoxy group is bonded to
the selenium center (Figure 1).[5]
The activities of various ionic liquids consisting of imida-
zolium cations and selenium-based anions were evaluated as
catalysts for the oxidative carbonylation of aniline, and
compared with the activities of 1 and 5% Pd/C KI (a catalyst
for the Asahi process).[7]
The results in Table 1 show that the activities of the ionic-
liquid catalysts 2a, 3a c, and 4 are significantly higher than
those of 1 and 5% Pd/C KI at 408C. The reason for the
enhanced activities of ionic liquid-immobilized selenium
catalysts cannot be fully explained at the moment, but it is
likely that the imidazolium cation plays an important role in
the catalytic process by electronically communicating with the
anionic selenium species. This is partially supported by
Figure 1. Single-crystal X-ray structure of 1. Selected bond lengths [ä] and
angles [8]: Se¥¥¥K 3.7364(9), Se-O1 1.6590(19), Se-O2 1.6579(19), Se-O3
1.8460(19), O3-C 1.438(4); O2-Se-O1 106.27(10), O2-Se-O3 95.31(9), O1-
Se-O3 101.44(10), C-O3-Se 112.74(16).
Table 1. Activities of various catalysts for the oxidative carbonylation reactions of aromatic amines.[a]
To immobilize the selenite anion
within an imidazolium-based ionic
liquid, (bmim)Cl (bmim ¼ 1-n-butyl-
3-methylimidazolium) and 1 were
reacted in methanol at room temper-
ature for 6 h. Filtration of KCl and
subsequent removal of methanol un-
der reduced pressure afforded an air-
stable yellow liquid, which was char-
acterized as [bmim][SeO2(OCH3)]
(2a) b y1H NMR spectroscopy, ele-
mental analysis, and mass spectrom-
etry. Similarly, [emim][SeO2(OCH3)]
(3a) and [dmim][SeO2(OCH3)] (4a)
were prepared by reacting 1 with
(emim)Cl (emim ¼ 1-ethyl-3-methyl-
imidazolium) and (dmim)Cl (dmim ¼
[c]
Amine
Catalyst
T [8C]
Conversion [%]
Selectivity [%][b]
TOF [hÀ1
]
PhNH2
PhNH2
PhNH2
PhNH2
PhNH2
PhNH2
PhNH2
PhNH2
PhNH2
o-Tolu[f]
p-Tolu
1
2a
3a
4a
3b
3c
40
40
40
40
40
40
40
60
120
60
60
60
60
5.1
100
100
100
100
100
100
100
98.9
99.3
100
100
100
100
18
93
97
96
95
99
26
177
3680
51
173
149
168
51.3
53.6
52.6
52.4
54.5
7.2
97.4
36.8
28.0
95.2
81.8
92.4
Pd/C KI[d]
3a
3a[e]
3a
3a
3a
3a
MDA[g]
PhCH2NH2
[a] amine (40 mmol), catalyst (0.11 mmol), methanol (25 mL), P ¼ 1.36 MPa (O2/CO, 20:80 v/v), t ¼ 2 h.
[b] N,N’-diphenylurea for aniline; (CH3C6H4NH)2CO for toluidine, (NH2C6H4CH2C6H4NH)2CO for
MDA; (C6H5CH2NH)2CO for PhCH2NH2. [c] TOF ¼ (moles of aniline consumed/moles of catalyst)hÀ1
.
[d] 5% Pd/C (234 mg, 0.11 mmol Pd), KI (90 mg, 0.55 mmol). [e] t ¼ 1 h, aniline (160 mmol), 3a
(0.016 mmol). [f] Tolu ¼ toluidine. [g] MDA ¼ 4,4’-methylenedianiline.
Angew. Chem. Int. Ed. 2002, 41, No. 22
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comparing the cyclic voltammograms (CVs) of [dmim]-
[SeO2(OCH3)], (dmim)Cl, and [KSeO2(OCH3)] (Figure 2),
where the reversibility of the oxidation wave of [dmim]-
[SeO2(OCH3)] at þ 0.3 V (versus Ag/AgCl) is pronounced,
while such a reversible wave is not observed in the CVs of 1
and (dmim)Cl.
Figure 3. 1H NMR spectra: a) 3a in [d4]methanol; b) after the carbon-
ylation reaction with 2 equiv of PhNH2 at 1008C and 1.0 MPa of O2/CO
(20:80 v/v) for 2 h.
Table 2. Catalyst recycling studies with 3a.[a]
Cycle
Conversion [%]
Selectivity [%][b]
TOF [hÀ1
]
1
2
3
4
5
97.0
96.8
95.3
94.2
93.9
99.1
99.4
99.0
98.9
99.3
176
176
173
171
170
Figure 2. Cyclic voltammograms of 0.12m solutions of 4a (–– ), (dmim)Cl
(––), and 1 (
) in CH3OH at a platinum disk with a Ag/AgCl reference
electrode at a scan rate of 0.05 VsÀ1
.
[a] aniline (40 mmol), 3a (0.11 mmol), methanol (25 mL), P ¼ 1.36 MPa
(O2/CO 20:80 v/v), t ¼ 2 h. [b ]N,N’-diphenylurea.
Compound 3a was also found to be a highly active catalyst
for the carbonylation of other substrates including toluidines
(both ortho and para), benzylamine, and 4,4-methylenediani-
line. Interestingly, p-toluidine shows much higher conversion
than o-toluidine, possibly as a result of the steric hindrance of
As a consequence of the possible toxicity of the selenium-
based ionic liquids, the level of selenium contamination in the
isolated urea was measured using induced coupled plasma
(ICP) analysis. When 3a was used as the catalyst for the
carbonylation of aniline, the isolated diphenylurea was found
to contain 45.4 ppm of selenium, which was significantly
reduced to 2.5 ppm after additional washing with methanol
(2 î 10 mL). After this treatment, the isolated diphenylurea
was found not to have an unpleasant odor. This was in contrast
to similar experiments using 1 as the catalyst, in which the
isolated urea did exhibit a strong, unpleasant odor even after
additional washing with methanol (2 î 10 mL), and showed
higher levels of selenium contamination (54.3 ppm after
filtration and 13.2 ppm after additional washing).
There are many advantages to selenium-containing ionic-
liquid catalyst systems. In addition to the improved catalytic
performance and the absence of species responsible for
potentially foul odors, they are recyclable without losing their
initial activity. Furthermore, they are air stable and highly
soluble in various organic solvents including CH2Cl2, CHCl3,
and CH3CN. Spectroscopic and electrochemical investigations
to elucidate the mechanism for the oxidative carbonylation of
amines are now in progress.
À
the methyl group next to the NH2 group. Only one amino
group in 1,4-methylenedianiline is carbonylated to give
(NH2C6H4CH2C6H4NH)2CO under the reaction conditions.
The catalytic activity of 3a for the carbonylation of aniline
increases with increasing temperature, resulting in a high
turnover frequency (TOF) of 3680 hÀ1 at 1208C. It should be
mentioned that TOFs for the selenium-based catalyst systems
reported by other groups are usually lower than 100 hÀ1.[8]
During the oxidative carbonylation of aniline, 3a is likely to
react with aniline to form an intermediate species, [emim][-
SeO2(NHC6H5)], which in turn reacts with CO to give
1
[emim][SeO2(CONHC6H5)]. The in situ H NMR spectrum
of the reaction mixture in [d4]methanol clearly demonstrates
the transformation of 3a into two other selenium species that
contain the imidazolium cation (see Figure 3); there is no
evidence that selenium species without imidazolium cations
are present.
To investigate the possibility of recycling these novel
catalyst systems, experiments have been conducted with
aniline and 3a at 608 and 1.4 MPa of O2/CO (20:80 v/v) for
2 h, at which time the reaction mixture was filtered off to
remove diphenylurea and the solution containing the ionic
liquid was reused for further carbonylation reactions with a
fresh charge of consumed aniline and methanol. As can be
seen in Table 2, 3a retains most of its original activity even
after five cycles, which indicates that 3a is, indeed, a
recyclable catalyst.
Experimental Section
The imidazolium salts (bmim)Cl, (emim)Cl, and (dmim)Cl were prepared
according to the literature procedure.[9] Aniline, o-toluidine, p-toluidine,
benzylamine, and 4,4’-methylenedianiline were purchased from Aldrich
Chemical Co. and used as received.
1: A solution of SeO2 (3.3 g, 30 mmol) in methanol (30 mL) was treated
with K2CO3 (2.0 g, 15 mmol) in a 100-mL 2-neck flask at room temperature
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for 1 h. As soon as K2CO3 was added, CO2 started to evolve. Addition of
THF into the resulting colorless solution produced a white solid (yield
92%). Elemental analysis calcd (%) for CH3KSe: C 6.6, H 1.7, K 21.5, Se
43.6; found: C 6.8, H 1.8, K 21.4, Se 42.7; 1H NMR (300 MHz, [D4]meth-
anol, 258C): d ¼ 3.35 (s).
Single crystals of 1 suitable for X-ray diffraction studies were grown inside
a dry-box (under argon). Compound 1 (0.5 g) was dissolved in methanol
(3 mL) in a vial which was contained within a larger vial charged with
approximately 2 mL of diethyl ether. The diethyl ether was allowed to
slowly diffuse into the methanol solution by maintaining the vials at room
temperature for several days.
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176, 264 266; b) H. S. Kim, Y. J. Kim, H. Lee, S. D. Lee, C. S. Chin, J.
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Ellis, T. Welton, Chem. Commun. 2001, 1862 1863; d) J. E. L. Dullius,
P. A. Z. Suarez, S. Einloft, R. F. de Souza, J. Dupont, Organometallics
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Commun. 1999, 1043 1044.
[5] X-ray single-crystal diffraction data for 1 was collected on a Siemens
SMART CCD diffractometer. Crystal data for 1: monoclinic, space
group P21/c, a ¼ 10.2502(16), b ¼ 7.3115(12), c ¼ 6.4330(10) ä, b ¼
103.012(2)8, V¼ 469.74(13) ä3, Z ¼ 2, 1calcd ¼ 2.561 gcmÀ1, m(MoKa) ¼
8.746 mmÀ1, R1 ¼ 0.0332, wR2 ¼ 0.0886, (I > 2sI); R1 ¼ 0.0340, wR2 ¼
0.0893 (all data). CCDC-185119 contains the supplementary crystallo-
graphic data for this paper. These data can be obtained free of charge
via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge
Crystallographic Data Centre, 12, Union Road, Cambridge CB21EZ,
UK; fax: (þ 44)1223-336-033; or deposit@ccdc.cam.ac.uk).
[6] R. Hagiwara, Y. Ito, J. Fluorine Chem. 2000, 105, 221 227.
[7] S. Fukuoka, M. Chono, M. Kohno, J. Chem. Soc. Chem. Commun.
1984, 399 400.
[8] a) S. A. Aky¸z, A. B. Dempster, R. L. Morehouse, N. Zengin, J. Chem.
Soc. Chem. Commun. 1972, 307 308; b) N. Sonoda, T. Yasuhara, K.
Kondo, T. Ikeda, S. Tsutsumi, J. Am. Chem. Soc. 1971, 93, 6344; c) K.
Kondo, N. Sonoda, K. Yoshida, M. Koishi, S. Tsutsumi, Chem. Lett.
1972, 401 404; d) J. G. Zajacek, J. J. McCoy, K. E. Fuger, USP
3956360 1976.
2a: A solution of (bmim)Cl (3.1 g, 18 mmol) in methanol (30 mL) was
treated with 1.1 equiv of 1 (3.6 g, 19.8 mmol) in methanol (30 mL) at room
temperature. After stirring for 6 h, the solution was filtered to remove KCl
and the solvent was evaporated under reduced pressure to give a yellow
liquid. The resulting liquid was further purified by adding CH2Cl2 and
filtering to remove excess 1 and KCl, followed by drying under high
vacuum for 12 h (yield 85%). Elemental analysis calcd (%) for C9H18N2Se:
C 38.45, H 6.41, N 9.97, Se 28.09; found: C 38.18, H 6.30, N 9.60, Se 28.10;
1H NMR (300 MHz, CDCl3, 258C): d ¼ 0.91 (t, 3J(H,H) ¼ 7.5 Hz, 3H; CH3),
1.34 (m, 2H; CH2), 1.83 (m, 2H; CH2), 3.45 (s, 3H; OCH3), 4.06 (s, 3H;
NCH3), 4.27 (t, 3J(H,H) ¼ 7.2 Hz, 2H; NCH2), 7.23 (d, 3J(H,H) ¼ 1.5 Hz,
1H; C3H3N2), 7.33 (d, 3J(H,H) ¼ 1.5 Hz, 1H; C3H3N2), 10.58 ppm (s, 1H;
C3H3N2); LC-MS (CH3OH): positive ion: 139 [bmim]þ; negative ion: 143
[SeO2(OCH3)]À.
3a and 4a were prepared in a similar manner to that of 2a, by replacing
(bmim)Cl with (emim)Cl and (dmim)Cl, respectively.
3a: Yield 86%; elemental analysis calcd (%) for C7H14N2Se: C 33.21, H
5.54, N 11.07, Se 31.20; found: C 32.90, H 5.50, N 11.50, Se 29.70; 1H NMR
3
(300 MHz, CDCl3, 258C): d ¼ 1.51 (t, J(H,H) ¼ 7.8 Hz, 3H; CH3), 3.47 (s,
3H; OCH3), 4.04 (s, 3H; NCH3), 4.35 (q, 3J(H,H) ¼ 7.5 Hz, 2H; NCH2), 7.28
(s, 1H; C3H3N2), 7.30 (s, 1H; C3H3N2), 10.88 ppm (s, 1H; C3H3N2). LC-MS
(CH3OH): Positive ion: 111 [emim]þ; Negative ion: 143 [SeO2(OCH3)]À.
[9] a) M. Hasan, I. V. Kozhevnikov, M. R. H. Siddiqui, A. Steiner, N.
Winterton, Inorg. Chem. 1999, 38, 5637 5641; b) J. S. Wilkes, J. A.
Levisky, R. A. Wilson, C. L. Hussey, Inorg. Chem. 1982, 21, 1263
1264.
[10] See the Supporting Information for the 1H NMR data of the trans-
formation reactions of 3a into 3b, 3c, and 3d.
4a: Yield 87%; elemental analysis calcd (%) for C6H12N2Se: C 30.14, H
5.02, N 11.72, Se 33.03; found: C 30.00, H 5.00, N 11.90, Se 32.10; 1H NMR
(300 MHz, CDCl3, 258C): d ¼ 3.45 (s, 3H; OCH3), 3.98 (s, 6H; 2(NCH3)),
7.31 (s, 2H; C3H3N2), 10.83 ppm (s, 1H; C3H3N2). LC-MS (CH3OH):
Positive ion: 97 [dmim]þ; Negative ion: 143 [SeO2(OCH3)]À.
Transformation reactions of 3a to give 3b and 3c:[10] A solution of 3a (0.1 g,
0.4 mmol) in CH3CH2OH (3 mL) or CF3CH2OH (3 mL) was stirred at
room temperature for 6 h, followed by removal of the solvent under high
vacuum for 12 h to give a yellow liquid (yield 99%).
Transformation of 3a to give 3d:[10] A solution of 3a (0.1 g, 0.4 mmol) in
CH2Cl2 (3 mL) was treated with 1.3 equiv of PhOH (0.05 g, 0.52 mmol) at
room temperature for 6 h. The subsequent removal of the solvent and
excess PhOH under high vacuum for 12 h gave a yellow liquid (yield 99%).
Spatially Directed Protein Adsorption by Using
a Novel, Nanoscale Surface Template**
Catalysis reaction: All of the carbonylation reactions were conducted in a
100-mL Parr reactor with a magnetic drive stirrer and an electrical heater.
The reactor was charged with an aromatic amine, methanol, an appropriate
catalyst and toluene (1 mL) as an internal standard. The reactor was
pressurized with a gaseous mixture of O2 and CO (20:80 v/v), and then
heated to a specified temperature. The pressure was maintained at 1.4 MPa
throughout the reaction using a reservoir tank equipped with a high-
pressure regulator and a pressure transducer. After the reaction was
completed, the reactor was cooled to room temperature and the reaction
mixture was filtered off to remove the solid diaryl urea. The resulting
solution and the isolated urea were analyzed by GC, HPLC, and GC-MS.
Patricia Moraille and Antonella Badia*
Phase-separated, ultrathin organic films can serve as sur-
face templates for the selective and patterned deposition of
6]
macromolecules on the submicron scale.[1 Deposition is
generally directed by chemical differences in the domains or
domain edges generated by phase separation. We demon-
strate herein that a chemically homogeneous surface exhibit-
ing solid/fluid-phase coexistence can also be used as an
Recycling experiment: The 100-mL reactor was charged with aniline
(40 mmol), methanol (25 mL), 3a, and toluene (1 mL) as the internal
standard, and then reacted at 608C for 2 h under pressure of 1.4 MPa of O2/
CO (20:80 v/v). When the reaction was completed, diphenylurea was
removed by filtration and the solution that contained the ionic liquid was
reused for further carbonylation reactions with a fresh charge of consumed
aniline.
[*] Prof. A. Badia, P. Moraille
Department of Chemistry, Universitÿ de Montrÿal
C.P. 6128, succursale Centre-ville, Montrÿal, QC H3C 3J7 (Canada)
Fax : (þ 1)514-343-7586
E-mail: antonella.badia@umontreal.ca
[**] This work was supported by the NSERC (Canada), the FCAR
(Quÿbec), the CFI (Canada), and the Universitÿ de Montrÿal. A.B. is
a Cottrell Scholar of the Research Corporation. P.M. gratefully
acknowledges salary support from VRQ-NanoQuÿbec.
Received: June 20, 2002
Revised: August 1, 2002 [Z19573]
[1] a) A. M. Tafesh, J. Weiguny, Chem. Rev. 1996, 96, 2035 2052; b) J. D.
Gargulak, W. L. Gladfelter, Organometallics 1994, 13, 698 705; c) I.
Supporting information for this article is available on the WWW under
http://www.angewandte.org or from the author.
Angew. Chem. Int. Ed. 2002, 41, No. 22
¹ 2002 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
0044-8249/02/4122-4303 $ 20.00+.50/0
4303