Tunable aryl alkyl ionic liquids (TAAILs): The next generation of ionic liquids

Article abstract of DOI:10.1002/anie.200903399

The combination of aromatic and aliphatic substituents at the imidazolium ring leads to a new generation of imidazolium-based ionic liquids (TAAILs: tunable aryl alkyl ionic liquids; see charge distribution of the methoxyphenyl methyl derivative). Electro

Full text of DOI:10.1002/anie.200903399

Communications
DOI: 10.1002/anie.200903399
Ionic Liquids
Tunable Aryl Alkyl Ionic Liquids (TAAILs): The Next Generation of
Ionic Liquids**
Sebastian Ahrens, Anke Peritz, and Thomas Strassner*
During the last 15 years ionic liquids have been shown to be
very promising “green” solvents with several advantages
compared to traditional organic solvents.[1] Most notably,
their nonvolatility, high thermal stability, and extraordinary
solvent properties make them important solvents for the
chemical industry.[2] Ionic liquids (ILs) are salts which contain
only organic cations and organic or inorganic anions, resulting
in a melting point below 1008C or even at room temperature
(RTILs, room-temperature ionic liquids). Organic cations
such as imidazolium, pyridinium, ammonium, and phospho-
nium ions can be combined with a variety of anions, for
example, halides, PF6À, BF4À, or (CF3SO2)2NÀ, which leads to
a large number of possible combinations. Therefore, many of
their physicochemical properties have previously been tuned
by changing the anion or the substitution on the quaternary
nitrogen or phosphorous center, but to date only alkyl
substituents were used to modify the properties of the
resulting ionic liquids.[3] The last generation, the task-specific
ionic liquids,[4] still suffers from the disadvantage that the
currently known motives really do not allow for a wide range
of modifications to tune the properties of the ionic liquids.
Only in the field of liquid crystal research has a publication
recently reported the beneficial effect of aryl and biphenyl
groups on the mesomorphic properties of ionic liquid
crystals.[5]
ents as well as of their position at the aromatic ring. The new
cations can be combined with many previously used anions;
this study compares the effects of BrÀ, PF6À, BF4À, and
(CF3SO2)2NÀ.[6]
We study imidazolium-based compounds as precursors for
the synthesis of N-heterocyclic carbene (NHC) metal com-
plexes;[7] NHCs are a very prominent class of ligands in
homogeneous catalysis.[8] They are generally more stable than
phosphane ligands and have been described as predominantly
s donors with negligible p character. But for substituted
aromatic systems we found a large substituent effect on the
chemical shifts of the imidazolium core in the corresponding
NMR spectra and started to investigate the contribution of
electron-withdrawing and -donating substituents.[9] We also
realized that current imidazolium-based ionic liquids usually
carry alkyl groups on the two nitrogen atoms, which do not
allow electronic communication between the + I substituents
and the core. Nowadays, changes are mainly restricted to the
anionic part of the ILs. Introduction of a real electronic
variation by (+/À) M effects would be a large step forward
towards the development of new tunable ILs.
Owing to the aromatic rings and the possibility to
introduce electronic and steric effects through substituents
at the ring (Scheme 1, R1) we have additional possibilities to
Imidazolium salts are currently the most prominent class
of ionic liquids, usually carrying sp3-hybridized carbon atoms
as substituents at both nitrogen atoms of the heterocycle. As
described herein, the combination of sp3 alkyl and sp2 aryl
substituents at those nitrogen atoms of the imidazolium core,
however, allows a far greater variation of the ionic liquid
characteristics than imagined compared to the current
systems. For the first time not only s-based but also
p-system-based electronic effects can be used to tune the
properties. We observed a strong influence of the type
(electron-withdrawing vs. donating) and number of substitu-
Scheme 1. Two-step synthesis of aryl alkyl ionic liquids (TAAILs).
[*] A. Peritz, Prof. Dr. T. Strassner
Technische Universitꢀt Dresden, Physikalische Organische Chemie
01062 Dresden (Germany)
Fax: (+49)351-463-39679
tune the system. Tunable aryl alkyl ionic liquids (TAAILs) are
not restricted to van der Waals interactions; they also allow
p–p interactions, which will be important for applications in
the separation of compounds as well as for the stabilization of
catalytically active metals. TAAILs can be synthesized by a
two-step, atom-economical synthesis. First an aniline deriva-
tive, glyoxal, formaldehyde, and an ammonia source are
converted into an aryl imidazole in a one-pot synthesis;[10]
subsequent nucleophilic substitution leads to the imidazolium
salt (Scheme 1).[11]
E-mail: thomas.strassner@chemie.tu-dresden.de
Dr. S. Ahrens
BASF SE, Ludwigshafen, M301, 67056 Ludwigshafen (Germany)
[**] Funding by the DFG (Priority Program 1191, “ionic liquids”) is
gratefully acknowledged. S.A. thanks the Konrad-Adenauer-Stiftung
for their support.
Supporting information for this article, including details of the
syntheses and characterization of all compounds and details of the
quantum chemical calculations, is available on the WWW under
http://dx.doi.org/10.1002/anie.200903399.
A range of aniline derivatives with a variety of different
substituents R1 and even systems with multiple substituents
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Chemie
R1, electron-withdrawing as well as -donating, are commer-
cially available. The synthesis shown in Scheme 1 is only one
of several possible ways to construct the imidazole core; many
others are known.[12]
Introducing functional groups in the alkyl part of ionic
liquids to form TSILs was the major improvement of the last
generation of ionic liquids. The alkyl part of the new
generation TAAILs (Scheme 1, R2) can be functionalized in
a similar way, as we could show for different functional groups
such as OH, COOH, and SO3H (Scheme 2). Details are given
in the Supporting Information.
(Figure 1, ), and that not all combinations fulfill the general
ionic liquid criterion of a melting point below 1008C.
However, starting with a chain length of more than five
carbon atoms, the BF4À, PF6À, and (CF3SO2)2NÀ salts fulfill
this criterion, and most of the (CF3SO2)2NÀ salts are even
RTILs.
^
The decomposition temperatures mainly depend on the
anion, and are for some of the TAAILs they are significantly
higher than for most currently known dialkyl imidazolium-
based ionic liquids. It is interesting to note that mesityl alkyl
imidazolium salts with the (CF3SO2)2NÀ counterion decom-
pose at about 4408C, independent of the length of the alkyl
chain. According to thermogravimetric analysis (TGA, see
the Supporting Information), the TAAILs contain only small
amounts of water after the workup. Concerning the misci-
bility with other solvents and their solubility in other polar or
nonpolar solvents, the properties strongly depend on the
individual system (substituents, chain lengths, counterion).
The general concept is not restricted to imidazolium
compounds, and we see similar behavior in the case of
benzimidazolium- as well as 1,2,3- and 1,2,4-triazolium-based
ionic liquids, which will be reported in the near future.[15]
We could obtain solid-state structures of some of the
TAAILs with higher melting points, and all compounds have
been characterized by 1H and 13C NMR spectroscopy as well
as by elemental analysis; some were also characterized by
differential scanning calorimetry (DSC) and TGA measure-
ments. The NMR spectra do not show a large dependence on
the counterion or chain length. Comparing the chemical shifts
in the NMR spectra of the imidazolium and phenyl rings of
mesityl bromide TAAILs, we observed only very small
differences (0.1–0.2 ppm) for different lengths of the alkyl
chain (1–14 carbon atoms). Examples are the 13C signal of the
C1 carbon atom of the mesityl substituent next to the
imidazolium nitrogen, observed at (131.2 Æ 0.1) ppm, or the
imidazolium NCN carbon atom at (137.1 Æ 0.2) ppm. Typical
signals in the 1H NMR spectrum (in [D6]DMSO) are those of
the hydrogen atoms at the aromatic ring, observed at (7.19 Æ
0.02) ppm, and the hydrogen atom at the C2 position of the
imidazolium ring at (9.50 Æ 0.05) ppm, which indicate that the
length of the alkyl chain has almost no electronic influence on
the imidazolium core. But it does show a strong influence on
the melting points of the new TAAILs!
Scheme 2. Example of the introduction of functional groups.
Our new TAAILs are superior to the currently known
systems in many respects. For example, their surprising
behavior allows us to pinpoint the desired melting point.
The new cations can be combined with many anions known to
À
[13]
À
[13]
À
[14]
date (BF4
,
PF6
,
N(SO2CF3)2
,
halides, …), and by
blocking the 2-position of the imidazolium core the stability
of the ionic liquid might be additionally improved. Figure 1
shows a comparison of the melting points in dependence on
the chain length of the linear aliphatic substituents for four
different counterions. The aromatic part in this example is the
2,4,6-trimethylphenyl (mesityl) group. It is interesting to note
that the melting point difference resulting from an anion
exchange (e.g. BrÀ vs. (CF3SO2)2NÀ, R2 = 1-propyl) can be as
big as 1608C, whereas for the known dialkyl systems such as
1-(1-butyl)-3-methylimidazolium (bmim), the reported differ-
ence for the same anion exchange is only 758C.[2]
It becomes quite obvious that especially the bromide salts
show an almost linear dependency of the melting point on the
aliphatic chain length from one to eight carbon atoms
Not only the variation of the chain length and of the
counterions leads to strong effects. It was also interesting to
evaluate the electronic influence of a substituent in the para-
position of the aromatic ring. We therefore synthesized
substituted imidazoles with various aromatic substituents
with para-R1 groups, which was possible in good yields. Owing
to the large number of possible combinations, we restricted
the comparison to one short (1-propyl), two medium (1-hexyl,
1-heptyl), and one long alkyl chain (1-tetradecyl). The results
clearly show an influence of electron-withdrawing and
-donating substituents on the melting points. Electron-with-
drawing groups (NO2, halogens) tend to lead to higher
melting points than electron-donating (Me, OMe, OEt)
substituents in the para-position of the phenyl ring at the
imidazole. After exchanging the bromide counterion for a
non-coordinating anion, similar trends can be observed as
Figure 1. Dependence of the melting point [8C] of 1-alkyl-3-(2,4,6-
trimethylphenyl)-imidazolium salts on the counterion XÀ (X=(Br, BF4,
PF6, (CF3SO2)2N)) and on the alkyl chain length (C1–C8, C11, C14).
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Communications
described above for the mesityl system. The melting points
has been done for the third generation of ILs, the TSILs. We
can combine these new cations with all anions and can
therefore optimize the properties of our TAAILs for different
applications.
drop in a way similar to that shown in Figure 1.[9]
By means of high-level density functional theory calcu-
lations[16] (B3LYP/6-311 + G(d,p)), we further compared the
charge distribution in the cationic part of the well-known
dialkyl ionic liquids to the new generation of ionic liquids
(TAAILs). The chain length on the alkyl side was kept
constant (CH3) while we compared 4-methoxyphenyl,
4-nitrophenyl, 4-bromophenyl, 4-chlorophenyl, and phenyl
to a methyl (mmim) and a 1-butyl substituent (bmim). The
charge distribution is given in Table 1. All systems carry a
Received: June 23, 2009
Published online: September 16, 2009
Keywords: imidazolium salts · ionic liquids · substituent effects ·
.
TAAILs
[1] Ionic Liquids in Synthesis (Eds.: P. Wasserscheid, T. Welton)
2008, Wiley-VCH, Weinheim.
Table 1: Comparison of the charge distribution between mmim, bmim,
[2] N. V. Plechkova, K. R. Seddon, Chem. Soc. Rev. 2008, 37, 123.
[3] R. Giernoth, Top. Curr. Chem. 2007, 276, 1.
and different TAAILs.
[4] J. H. Davis, Jr., P. Wasserscheid in Ionic Liquids in Synthesis
(Eds.: P. Wasserscheid, T. Welton), 2008, Wiley-VCH, Wein-
heim, p. 45.
N1
C2
N3
C4
C5
[5] P. H. J. Kouwer, T. M. Swager, J. Am. Chem. Soc. 2007, 129,
14042.
[6] S. Ahrens, T. Strassner, WO2009/095012, 2009.
[7] M. A. Taige, A. Zeller, S. Ahrens, S. Goutal, E. Herdtweck, T.
Strassner, J. Organomet. Chem. 2007, 692, 1519.
[8] T. Strassner, Top. Organomet. Chem. 2007, 22, 125.
[9] T. Strassner, S. Ahrens, unpublished results.
[10] The aniline (0.1 mol) is dissolved in MeOH (50 mL) and
aqueous glyoxal (0.1 mol) is added. The mixture is stirred at
room temperature (2–30 h) until a yellow precipitate forms. The
suspension is diluted with MeOH (400 mL), and NH4Cl
(0.2 mol) and formaldehyde solution (37%, 0.21 mol) are
added. After addition of H3PO4 (14 mL, 85%), the solution is
heated at reflux for 5–9 h. The majority of the solvent (ca. 85%)
is removed, and ice water and KOH solution are used to adjust
the pH value to pH 9. The product is extracted with CH2Cl2, the
combined organic layers are dried over MgSO4, and the solvent
is removed in vacuo. The product is subsequently purified by
distillation or recrystallization.
R1 =
CH3
C4H9
C6H5
C6H4Cl
C6H4Br
C6H4NO2
C6H4OCH3
À0.046
0.179 À0.046
0.106
0.106
À0.013 À0.079 À0.110 À0.077 À0.118
0.017
0.017
0.019
0.005
0.012
0.058
0.080
0.076
0.106
0.098
0.337
0.291
0.368
0.332
0.381
0.202
0.204
0.219
0.224
0.262
0.084
0.090
0.083
0.093
0.056
positive charge, but the charge distribution is quite different.
For the previously known dialkyl cations such as 1,3-
dimethylimidazolium (mmim) or 1,3-butylmethylimidazo-
lium (bmim), the positive charge is mostly located on the
alkyl groups, while the new TAAILs carry most of the charge
(ca. 70%) at the imidazolium core (Figure 2).
[11] A tube is filled with 1-N-substituted imidazole (1.0 equiv)
dissolved in THF (10 mL) and haloalkane (1.1 equiv) and then
sealed. The reaction mixture is heated to 80–1108C in the sealed
tube for 8–10 h. Filtration furnishes the solid precipitate, which is
washed several times with THF and dried in vacuo.
[12] T. Eicher, S. Hauptmann, H. Suschitzky, The Chemistry of
Heterocycles, Wiley-VCH, Weinheim, 2003.
[13] Imidazolium bromide salt (1.0 equiv) is dissolved in H2O(or
H2O/MeOH) before NH4BF4 (or NH4PF6; 1.1 equiv) is added.
After a short time, two phases separate. The ionic liquid is
separated from the aqueous phase by extraction with CH2Cl2.
The combined organic phases are dried over MgSO4 and filtered,
and the solvent is removed in vacuo.
Figure 2. Different charge distributions in standard ILs and TAAILs.
The numbers represent energy per charge in units of Hartree per
elemental charge.
[14] Imidazolium bromide salt (1.0 equiv) is dissolved in H2O or
H2O/MeOH before Li+(CF3SO2)2NÀ (1.1 equiv) is added. After
a short time two phases separate. The ionic liquid is separated
from the aqueous phase by extraction with CH2Cl2. The
combined organic phases were dried over MgSO4 and filtered,
and the solvent is removed in vacuo.
Our concept of combining aromatic and aliphatic sub-
stituents at the imidazolium core leads to a new generation of
ionic liquids, TAAILs, an interesting class with promising
properties. Electronic interaction between the aromatic
substituent and the imidazolium core together with a great
variety of possible substitution patterns on the aromatic ring
allows us to tune these new ionic liquids far better than is
currently possible by inductive interactions. It is also possible
to modify the alkyl part of the TAAILs in the same way as it
[15] D. Meyer, T. Strassner, unpublished results.
[16] All calculations were performed with Gaussian03 using the
density functional/Hartree–Fock hybrid model Becke3LYP and
the split valence triple-z (TZ) basis set 6-311 + + G(d,p). No
symmetry or internal coordinate constraints were applied during
optimizations. Details and references are given in the Supporting
Information.
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