Pyridine-bridged benzimidazolium salts: Synthesis, aggregation, and application as phase-transfer catalysts

Article abstract of DOI:10.1002/anie.200801628

(Chemical Equation Presented) Simply structured benzimidazolium salts efficiently gelate a variety of polar organic solvents. π-Stacking, hydrogen bonding, and van der Waals interactions are responsible for the self-assembly process. A packing model is deduced from the single crystal structure of gelator 1. Fiber aggregates of benzimidazolium salts in acetonitrile are efficient phase-transfer catalysts (PTCs) for N-alkylation.

Full text of DOI:10.1002/anie.200801628

Angewandte
Chemie
DOI: 10.1002/anie.200801628
Phase Transfer Catalysis
Pyridine-Bridged Benzimidazolium Salts: Synthesis, Aggregation, and
Application as Phase-Transfer Catalysts**
Tao Tu,* Wilfried Assenmacher, Herwig Peterlik, Gregor Schnakenburg, and Karl Heinz Dötz*
The benzimidazole skeleton is found in a variety of natural
products.[1] Dimethylbenzimidazole, for example, is a key
component in vitamin B12 and its derivatives. Besides its
prominent role in pharmaceutical chemistry, the benzimida-
zole moiety also serves as a basis for ionic liquids[2] and as
precursor for N-heterocyclic carbenes (NHCs).[3,4] Herein we
show that benzimidazolium salts provide a novel structural
motive for efficient, readily accessible, and easy-to-handle
low-molecular-mass gelators (LMMGs) which are also suited
as phase transfer catalysts (PTCs).
Owing to the physical properties of their gels, LMMGs
and their potential applications have become a rapidly
expanding interdisciplinary field of research. Hydrogen
Scheme 1. Pyridine-bridged bisbenzimidazolium and bisimidazolium
salts.
bonding, p-stacking, van der Waals, and dipole interactions
are considered as the major physical and chemical interac-
tions responsible for the formation of a three-dimensional
network capable of the uptake and immobilization of
solvents.[5,6] The majority of LMMGs that have been reported
are based on cholesterol, amino acid, and carbohydrate
skeletons having a multifunctional structure. A rational
correlation of molecular structure and gelation ability in a
given solvent still remains a challenge. Our interest in
LMMGs derives from functional organometallics,[7] and we
present benzimidazolium salts of type 1 (Scheme 1) as a
simple structural motif.
The synthesis of bisbenzimidazolium salts 1 by reaction of
2,6-dibromopyridine[3] and N1-alkylated benzimidazoles[3] is
troublesome and hampered by low yields, even under micro-
wave conditions. In contrast, amination of 2,6-difluoropyr-
idine with two equivalents of benzimidazole followed by N-
alkylation with alkyl bromides or iodides in a sealed tube
affords the bisbenzimidazolium salts 1a–e in almost quanti-
tative yields.[7a,8]
The gelation abilities of bisbenzimidazolium halides 1
were studied by heating them to reflux in a variety of protic
and aprotic polar organic solvents, followed by cooling of the
resulting solutions to room temperature. In general, bisben-
zimidazolium salts 1a–d form thermoreversible turbid gels
within a few minutes in most polar solvents, such as acetic
acid, acetonitrile, or various alcohols. For the shorter alkyl
analogue 1e, however, no gelation was observed under the
same conditions. Gelation experiments with 2 wt% 1a–d
(wt/v; equal to 1.97 ” 10À2 m for 1b) in a selection of solvents
are summarized in Table 1. Bisbenzimidazolium salts 1a–d
Table 1: Gelation behavior of bisbenzimidazolium salts 1a–d in selected
[*] Dr. T. Tu, Prof. Dr. K. H. Dötz
KekulØ Institute of Organic Chemistry and Biochemistry, University
of Bonn
solvents.[a]
Solvent
1a
1b 1c 1d
Solvent
1a
1b
1c
1d
Gerhard-Domagk-Strasse 1, 53121, Bonn (Germany)
Fax: (+49)228-73-5813
E-mail: tao.tu@uni-bonn.de
doetz@uni-bonn.de
Homepage: http://www.chemie.uni-bonn.de/oc/ak_do/
Glycerol
(CH2OH)2
MeOH
EtOH
nPrOH
iPrOH
G
G
C
PG
S
G
WG
G
G
G
G
G
G
G
G
G
G
G
S
G
G
G
G
G
G
G
S
tBuOH
MeCN
AcOH
WG I[b]
I[b]
G
G
PG
PG
I
G
WG
I
I
I
I
S
G
PG
G
P
G
G
G
G
WG Dioxane
G
G
G
G
THF
DCE
Acetone
DMSO
Dr. W. Assenmacher, G. Schnakenburg
Institute of Inorganic Chemistry,
University of Bonn (Germany)
P
I
WG PG
WG WG
nBuOH
iBuOH
P
PG
S
Prof. Dr. H. Peterlik
Faculty of Physics, University of Vienna
Boltzmanngasse 5, 1090 Vienna (Austria)
[a] Gelator concentration 2 wt%; C: crystal, G: gel, I: insoluble, PG:
partial gel, P: precipitate, S: soluble, WG: weak gel. DCE=1,2-dichloro-
ethane. [b] At 1 wt% (upper limit of solubility), a weak gel is formed.
[**] T.T. thanks the Alexander von Humboldt Foundation for a research
fellowship. We thank Prof. Dr. W. Mader for technical assistance
(TEM). Financial support from the DFG (SFB 624 “Templates”) is
gratefully acknowledged.
most efficiently gelate a wide structural variety of alcohols;
firm gels were obtained from glycerol, 1,2-ethanediol, iso-
propanol, isobutanol, and also in acetonitrile. The gelation
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/anie.200801628.
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ability decreases with the length of the alkyl chains. Whereas
are circa 200 nm wide and 1–2 mm long is observed in the
partial gel 1b/DMSO. All these morphologies indicate that
the gels are formed by a parallel columnar packing self-
assembly.
The gel–sol phase-transition temperatures (Tg) of gels in
selected solvents were determined by the dropping ball
method.[9] The stability of the gel network increases with the
concentration and the length of the N-alkyl chain of the
gelator, as established for the series 1b/nBuOH, 1c/nBuOH,
and 1d/nBuOH of gels, with concentrations varying from
0.5 to 5.0 wt% (Figure 2). At 3 wt%, Tg for gels 1d/MeCN,
iodides 1c and 1d bearing C12 and C8 alkyl groups are soluble
in methanol, their C16 analogue 1b induces gelation. This
phenomenon, which is also observed with other polar
solvents, such as acetic acid, dioxane, and THF, may suggest
that van der Waals interactions between the alkyl chains of
gelator and solvent molecules are crucial for the self-assembly
process required for gelation. In contrast to iodide 1b, the
gelation ability of bromide 1a in C1–C4 alcohols decreases
with the alkyl chain length of the solvent used; from
methanol, a needle-shaped crystal could even be grown.
This observation indicates a significant influence of the
counter-anion on the gelation.
The morphologies of selected typical three-dimensional
networks of xerogels obtained from 1a–d in iBuOH are
presented in Figure 1. For 1a, circa 250–500 nm wide and
Figure 2. Correlation of gel–sol transition temperatures (Tg) for gels
1b–d/nBuOH with gelator concentration.
1c/MeCN, 1a/MeCN, and 1b/MeCN increase in the order of
488C, 548C, 588C, and 788C; a similar trend was observed
with gels 1a–d with iBuOH, 1,2-ethanediol, and glycerol,[8]
which further supports the superior aggregation potential of
the counterion iodide in 1b over bromide in 1a.
Bisbenzimidazolium bromide 1a is a rare example[10] of an
efficient gelator which, despite having two long alkyl chains,
could be characterized by single crystal X-ray crystallography
(Figure 3). Analysis of a needle-type crystal grown from
methanol reveals a network of a parallel array of columns
(Figure 3d) which are held together by van der Waals
interactions between the alkyl chains (H···H distances of
2.75–2.99 Š).[8] Hydrogen bonding and p stacking are the
major interactions within these columns (fibers). Br···H
distances of 2.6–3.4 Š indicate inter-and intramolecular
hydrogen bonds between the molecules within the same
layer.[8] Adjacent layers are connected by two different types
of p stacking to form a unit: p–p interactions between both
the pyridine rings (3.43 Š, Figure 3a) and between the phenyl
rings of benzimidazole moieties (3.45 Š, Figure 3b) keep two
layers together to form the structural unit of the column.
These units are assembled by two strong hydrogen-bonding
interactions (2.75 Š each, Figure 3c) between a bromide
counterion and a hydrogen atom of the phenyl ring, and
between another bromide ion and an NCH2 hydrogen atom.
These principal interactions, along with additional ionic
interactions between the BrÀ and N+ centers, with the
shortest distance being 3.55 Š (Figure 3a), may explain the
efficient gelation ability of LMMGs 1.
Figure 1. Selected transmission electron microscopy (TEM) images of
gels formed with bisbenzimidazolium salts 1a–d in iBuOH (3 wt%):
Gel from a) 1a, b) 1b, c) 1c, and d) 1d.
several micrometer long straight fibers are observed (Fig-
ure 1a). Similar morphologies are also found in the gels 1c–d/
iBuOH (Figure 1c–d). Gel 1b/iBuOH (Figure 1b) has twisted
thin and long fibers (ca. 200 nm wide and several micrometers
long) which are also observed in the gels obtained from 1b
with MeOH, EtOH, nPrOH, iPrOH, and nBuOH. Film-type
morphologies are found in all the gels of 1a–d formed with
glycerol and 1,2-ethanediol.[8] Thinner and thicker straight
fibers (ca. 200–400 nm wide and several micrometers long)
are observed with gels 1a/MeCN, 1b/DCE and 1b/THF.[8]
A
looser network consisting of thicker fibers (ca. 2 mm wide) is
encountered in gels 1a/EtOH, 1d/EtOH, 1d/MeCN, and gels
1a–d/AcOH.[8] Morphologies of gels 1b/acetone and 1b/
dioxane are similar, and have a densely structured film-type
network.[8] A rod-like gel network consisting of fibers which
Shorter N-alkyl chains, such as in 1e, suppress the ability
to form gels. Instead, growth of single crystals having the
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Figure 4. Temperature-dependent 1H NMR spectra (aromatic and
NCH2 alkyl region) of a 2 wt% 1b/CD3OD gel.
to 8.94 ppm over a temperature range of 40 K). This effect is
reversible and suggests reduced aromatic p–p interactions
between gelator molecules upon warming. To evaluate the
role of the annulated benzo moiety in salts 1, we included
their homologous imidazolium halides 2 in our gelation study.
However, no gel formation could be observed in any of the
selected solvents under similar testing conditions, even if the
gelator concentration was increased to > 5 wt%. This result
clearly demonstrates the efficiency of p stacking resulting
from the benzo substitution pattern of bisbenzimidazolium
halides 1.
The structures and the dimensions of the gel network of
1a–c/nBuOH have been studied by small-angle X-ray scatter-
ing (SAXS).[5,11] The SAXS patterns confirm that the
crystalline columnar structure of 1a is preserved in the gels,
giving a characteristic distance within the columns of 3.65 nm
for 1a/nBuOH, 2.80 nm for 1b/nBuOH, and 2.37 nm for 1c/
nBuOH, as derived from the intense peaks at 2q = 2.42, 2.65,
and 3.158, respectively (Figure 5). The distance between the
Figure 3. Structure of 1a (crystal grown from methanol): a) p interac-
tion between the pyridine rings from two adjacent layers, b) p inter-
action between phenyl groups of the two adjacent layers, c) hydrogen-
bonding interactions connecting adjacent layers, d) part of the colum-
nar structure of the truncated 2”2”2 array of unit cells (view along b
axis).
composition 1e·0.61CHCl3 and characterized by a similar
parallel array of columns is favored.[8] The layers in the
column are held together by p stacking (3.42 Š) between the
phenyl rings, and by hydrogen bonding (2.99 Š). There are no
obvious van der Waals interactions between the columns;
instead, hydrogen bonds (3.12–3.15 Š) are responsible for the
interactions of n-butyl groups with solvent guests.
The contribution of p stacking to the gelation process was
evaluated by temperature-dependent 1H NMR studies and by
comparison of homologous bisbenzimidazolium (1) and
bisimidazolium (2) salts.[7a] Broad NMR signals for the
aromatic hydrogen atoms observed for gel 1b (2 wt% in
CD3OD) at 298 K indicate extensive aggregation (Figure 4).
Upon warming to 338 K by 10 K steps, the broad signals
characteristic of the heteroaromatic protons and the NCH2
atoms at 298 K steadily sharpen and are shifted downfield
(e.g. the g proton of the pyridine ring is shifted from 8.60 ppm
Figure 5. X-ray scattering patterns of gels of 5 wt% 1a/nBuOH, 1b/
nBuOH, and 1c/nBuOH gels (after subtraction of background from
the solvent). In the inset, the curves are amplified and vertically shifted
for clarity.
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columns in the crystal of 1a (4.15 nm, Figure 3d) is slightly
leads to a partial degradation of the gel network into gel
fibers, which remain visible during the reaction. Because of
their insolubility, they can be recovered after filtration and
reused as a catalyst after regelation with acetonitrile. The
procedure has been extended to the synthesis of benzotriazole
and imidazol analogues 3b,c (Table 2, entries 5–7), affording
slightly lower yields. Dialkylation of m-dibromoxylene gave
3d in a 90% yield (Table 2, entry 8); similar results were
obtained with o-and p-dibromoxylene.[8]
These results indicate that the gel fibers obtained from
benzimidazolium salts 1a,b are quite efficient in phase-
transfer N-alkylations. We propose that the fibers formed
after partial degradation of the gel may increase the specific
surface area of the catalytic centers. In addition, long N-alkyl
chains force the pincer core towards the organic solvent/water
interface. The multiple catalytic centers in the fiber aggre-
gates, evident in Figure 3c, may explain the efficiency of the
catalyst.
larger than that found for gel 1a/nBuOH. This indicates that
alcohols with longer alkyl chains improve the linkage of
gelator molecules, strengthening the van der Waals interac-
tions between the columns, which results in gel formation
(Table 1). The SAXS study reveals a significant counterion
effect which, in comparison to bromide salt 1a, results in a
more efficient gelation by the iodide homologue 1b. A
repeating distance of 3.65 nm observed for gel 1a/nBuOH is
reduced to 2.8 nm for gel 1b/nBuOH which, moreover, is
characterized by a more complex aggregation pattern, as
indicated by additional peaks in the range of larger scattering
angles (Figure 5, insert).
Although metallogels[12] formed by LMMGs have been
applied as catalysts in the oxidization of benzylic alcohol[13]
and in a double Michael addition reaction,[7a] no example of a
metal-free catalysis in a gel has been reported so far. We
turned our attention to phase-transfer catalysts (PTC),[14] and
in particular to 2,6-bis[(benz)imidazolylmethyl]pyridines 3a–
d, which are key precursors of NHC complexes[15] and cationic
cyclophanes.[16] Recently, quaternary ammonium salts and
pyridinophanes have been applied as PTCs to the synthesis of
3a,c under standard conditions (25% aqueous NaOH solu-
tion and MeCN at room temperature) resulting in low yields
(up to 30% for 3c) after longer reaction times (> 12 h).[16a] We
have found that gels 1a,b/MeCN significantly accelerate these
phase-transfer reactions (Table 2).
In conclusion, simply structured benzimidazolium halides
1a–d present a novel type of LMMGs, which not only
efficiently gelate a variety of polar protic and aprotic solvents
even in concentrations as low as 0.5 wt%, but are also well-
suited as PTCs for N-alkylation, as demonstrated for (benz)-
imidazole and benzotriazole. A packing model derived from
single-crystal X-ray diffraction of gelator 1a suggests that
p stacking between the (hetero)aromatic rings, hydrogen
bonding, and van der Waals interactions between the alkyl
chains are responsible for the self-assembly in the gelation
process. This hypothesis was confirmed by both X-ray
Table 2: Phase-transfer catalyzed N-alkylation of benzimidazole, benzo-
triazole and imidazole.
1
analysis, SAXS, and temperature-dependent H NMR stud-
ies, and by a comparison of the aggregation behavior of
homologous imidazolium and benzimidazolium salts. The role
as metal-free catalysts extends the scope of benzimidazolium
salts beyond their application as ionic solvents and carbene
precursors.
Entry
Catalyst
Time [h][a]
Product
Yield [%][b]
1
2
3
4
5
6
7
8
1a (1b)[c]
–
50
50
3
5
3
6
5
3
3a
3a
3a
3a
3b
3c
3c
3d
60 (61)
60
89
92
59
67
63
90
gel 1b/MeCN (5 wt%)
gel 1a/MeCN (5 wt%)
gel 1b/MeCN (5 wt%)
gel 1a/MeCN (5 wt%)
gel 1b/MeCN (5 wt%)
gel 1b/MeCN (5 wt%)
Experimental Section
Synthesis of benzimidazolium halides (1): A mixture of 2,6-bis(ben-
zimidazol-1-yl)pyridine[8] (622 mg, 2 mmol) and haloalkane RX
(4 mmol) was stirred neat at 1608C for 30 h. After cooling, the
mixture was dissolved in CHCl3 (50 mL), and then Et2O (250 mL) was
added. The crude product was purified by reprecipitation from
CHCl3/Et2O to give a yellow solid 1 in almost quantitative yield,
which was shown to be pure by NMR spectroscopy. For 1a: 1H NMR
[a] Determined by GC-MS and TLC. [b] Yield of isolated product.
[c] Saturated solution of 1a or 1b in MeCN (10 mL).
([D6]DMSO 500 MHz, 358 K): d = 10.25 (s, 2H), 8.17 (t, J = 8.0 Hz,
,
1H), 7.87 (dt, J = 8.3 and 1.0 Hz, 2H), 7.85 (d, J = 8.0 Hz, 2H), 7.68
(dt, J = 8.3 and 1.0 Hz, 2H), 7.25 (ddd, J = 8.0, 7.5, and 1.0 Hz, 2H),
7.19 (ddd, J = 8.0, 7.5, and 1.0 Hz, 2H), 4.14 (t, J = 7.5 Hz, 4H), 1.54
(quintet, J = 7.5 Hz, 4H), 0.92 (quintet, J = 7.8 Hz, 4H), 0.83 (quintet,
J = 7.5 Hz, 4H), 0.65–0.79 (m, 44H), 0.30 ppm (t, J = 7.0 Hz, 6H).
13C NMR ([D6]DMSO, 125 MHz, 298 K): d = 147.23, 145.44, 143.53,
132.65, 130.58, 128.88, 128.36, 119.19, 116.47, 115.15, 48.57, 32.04,
29.78, 29.72, 29.63, 29.40, 29.37, 29.31, 26.73, 22.78, 14.55 ppm. HRMS
(MALDI, DCTB): m/z = 840.5536 [MÀBr]+ (found), 840.5513
(calcd). Elemental analysis (%) calcd for C51H79Br2N5·H2O
(940.0297): C 65.16, H 8.69, N 7.45; found: C 65.38, H 8.39, N 7.49.
Owing to the low solubility of the bisbenzimidazolium
salts in acetonitrile, saturated solutions of 1a,b do not
accelerate the formation of 3a relative to a blank test (50 h/
RT; Table 2, entries 1 and 2). When, however, gel 1b/MeCN
was applied as a PTC, the reaction was completed within
three hours, with an 89% yield of isolated product (Table 2,
entry 3). Replacing iodide with bromide slows down the
reaction (Table 2, entry 4), indicating a counterion effect.
Stirring is required for the phase-transfer catalysis, which
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Analytical data for 1b–e are compiled in the Supporting Informa-
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Received: April 7, 2008
Published online: August 7, 2008
Keywords: aggregation · benzimidazolium salts · gels ·
.
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phase-transfer catalysis · self-assembly
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ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
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