Cyanobiphenyl versus alkoxybiphenyl: Which mesogenic unit governs the mesomorphic properties of guanidinium ionic liquid crystals?

Article abstract of DOI:10.1071/CH14376

A series of phenylguanidinium salts 3·X, which are linked via an alkoxy spacer either to a 4-decyloxy- or 4-cyano-substituted biphenyl mesogen, was prepared and the mesomorphism studied. A decyloxybiphenyl core and a spacer of at least C6 chain length were required for mesophase formation. Replacement of the chloride counterion by other anions like bromide or tetrafluoroborate improved the thermal stability of the mesophase. A comparison of substitution pattern (meta v. para) on the phenyl ring revealed decreased melting and clearing points for the bent cationic head group. All guanidinium ionic liquid crystals 3 displayed only smectic A (SmA) phases. A packing model is assumed where the molecules in a bilayer stack over each other in opposite direction with interdigitated terminal decyloxy groups and spacers. CSIRO 2014.

Full text of DOI:10.1071/CH14376

RESEARCH FRONT
CSIRO PUBLISHING
Aust. J. Chem. 2014, 67, 1088–1099
Full Paper
http://dx.doi.org/10.1071/CH14376
Cyanobiphenyl versus Alkoxybiphenyl: Which
Mesogenic Unit Governs the Mesomorphic Properties
of Guanidinium Ionic Liquid Crystals?
A
A
A
Johannes Christian Haenle, Manuel M. Neidhardt, Stuart Beardsworth,
A
A
A B
,
Jochen Kirres, Angelika Baro, and Sabine Laschat
A
Institut fur Organische Chemie, Universitat Stuttgart, Pfaffenwaldring 55,
¨
¨
D-70569 Stuttgart, Germany.
B
Corresponding author. Email: sabine.laschat@oc.uni-stuttgart.de
.
A series of phenylguanidinium salts 3 X, which are linked via an alkoxy spacer either to a 4-decyloxy- or 4-cyano-
substituted biphenyl mesogen, was prepared and the mesomorphism studied. A decyloxybiphenyl core and a spacer of at
least C6 chain length were required for mesophase formation. Replacement of the chloride counterion by other anions
like bromide or tetrafluoroborate improved the thermal stability of the mesophase. A comparison of substitution pattern
(meta v. para) on the phenyl ring revealed decreased melting and clearing points for the bent cationic head group. All
guanidinium ionic liquid crystals 3 displayed only smectic A (SmA) phases. A packing model is assumed where the
molecules in a bilayer stack over each other in opposite direction with interdigitated terminal decyloxy groups and spacers.
Manuscript received: 28 March 2014.
Manuscript accepted: 11 June 2014.
Published online: 30 June 2014.
Introduction
For the structurally related pyridinium salt 2a, SmE and
SmA phases were also observed, whereas the corresponding
4-decyloxybiphenyl derivative 2b displayed a SmC instead of a
SmA phase.[60] In contrast, cyanobiphenyl pyridinium bromide
2c formed only a SmA phase.
Based on these results, we envisaged a class of ILC
derivatives 3, in which the pyridinium was replaced with a
guanidinium-substituted phenol under maintenance of the cen-
tral 4-cyano- or 4-decyloxybiphenyl mesogen (Chart 1). Study-
ing the mesomorphism of m- and p-3, we were interested to see
whether the mesogenic unit, the spacer lengths, or the substitu-
tion pattern of the head group controls the mesomorphic
properties with a focus on the formation of SmC mesophases.
The results towards this goal are reported below.
Guanidine derivatives and guanidinium ions have attracted
researchers from various fields over the last decade.[1–5] With
high thermal stability, the ease of charge delocalization and
coordination properties as well as the possibility to attach up to
six different substituents on the guanidine moiety has driven
research activities in diverse directions, resulting in their use as
superbases,[6,7] ligands for coordination complexes,[8–11] orga-
nocatalysts,[12–16] stimuli-responsive materials,[17] hydro-
gels,[18] anion exchange polymer electrolytes for fuel cells,[19]
and biologically active compounds[20–29] for drug development.
Furthermore, guanidinium salts have also entered the field of
ionic liquid crystals (ILCs)[30–45] as an alternative cationic head
group to the imidazolium-derived ILCs, which have dominated
this research area so far.[46]
ILCs provide an ideal combination of the physical properties
of ionic liquids,[47–50] and thermotropic liquid crystals[51] giving
access to novel materials with fluid-like viscosity, anisotropic
properties such as birefringence, wide thermal and electrochemi-
cal stability as well as 1D ionic and electronic conductivity.[42–45]
The formation of stable mesophases in ILCs is caused by
nanosegregation of subunits of different polarity such as lipo-
philic side chains and polar aryl moieties with cationic (and/or
anionic) head groups.[52–54] In addition, the presence of rod-
shaped (calamitic) or disk-shaped (discotic) mesogens connected
to the cationic head group may further contribute to mesophase
stabilization and the preference of a certain mesophase type, as
was recently shown for cyanobiphenyl- and triphenylene-
imidazolium ILCs.[55–58] Imidazolium salt derivatives 1a,b with
a calamitic p-alkoxybiphenyl mesogen displayed two smectic
(SmE and SmA) phases regardless of spacer length (Chart 1).[59]
Results and Discussion
Synthesis of Guanidinium ILCs
The synthesis commenced with a Williamson etherification of
acetamide 4 with 1,10-dibromodecane to yield bromide m-5 in
58 % yield (Scheme 1). Subsequent Williamson etherification of
bromides m-5 and p-5[61] with 40-decyloxy- (6a) or 40-cyano-1-
hydroxybiphenyl (6b) provided the tethered compounds 7a,b
without any problems in 59–87 % yield. However, with excep-
tion of m-7a, attempted hydrolysis of the acetamide turned out
to be problematic. Under various conditions either no conver-
sion or decomposition was observed (see Supplementary
Material for details).
Therefore, N-Boc-protected hydroxyanilines 8 were used
instead (Scheme 2). In a similar fashion compounds 8 were
submitted to two sequential Williamson etherifications via
Journal compilation Ó CSIRO 2014
www.publish.csiro.au/journals/ajc

Alkoxybiphenyl-Guanidinium ILCs
1089
N
from ,7.5 to 12.0 ppm in the following order: PF6 , BF4 ,
OTf , I , SCN , Br ECl (Fig. 1).
ꢀ
ꢀ
O(CH2)n
R
N
N
ꢁ
Br
Br
This correlation between the anion and the N–H proton shift
indicates the presence of contact between the ion pairs that
also led to small chemical shifts of the aromatic protons of
the phenylguanidinium moiety (Fig. 1, grey). To estimate the
1
O(CH2)n
ꢁ
R
1
2
effect of concentration on the N–H signal, H NMR measure-
.
Compd
R
n
phase
ments of m-3b Cl with concentrations varying from 0.83 to
2.50 mg mLꢀ1 were carried out. The N–H signal shift of 0.1 ppm
turned out to be negligible with respect to the strong dependence
of the NH signal on the anion (see Supplementary Material for
details). This effect rather might be due to either the interaction
of the anion with the anisotropic cone of the aryl ring than due
to the conjugation between the guanidinium cation and the aryl
ring. Previous DFT calculations of several guanidinium salts
revealed no or only very little conjugation, i.e. the guanidinium
moiety behaves like an isolated cation.[39] In agreement with
these studies, the N–H signal shifted upfield with increasing
anion radii[64,65] with an almost linear correlation (Fig. 2).
OC3H7
OC3H7
8
g 29
g 38
SmE 138 SmA 156
SmE 154 SmA 180
l
l
1a
1b
2a
2b
2c
12
OC3H7
10
10
6
SmE 150 SmA 183
Cr 136 SmC 165
l
l
l
OC10H21
CN
g
17 SmA
65
Me2N
NH
ꢁ
NMe2
R
R
O(CH2)nO
ꢀ
X
p-3
Mesomorphic Properties of Guanidinium ILCs
ꢀ
X
O(CH2)nO
The mesomorphic properties of guanidinium salts 3 were stud-
ied by differential scanning calorimetry (DSC), polarizing
optical microscopy (POM), and X-ray diffraction (XRD).
The results of DSC investigations are summarised in Table 1.
Whereas both cyanobiphenyl guanidinium chlorides p- and
ꢁ
NMe2
m-3
HN
NMe2
R ꢂ OC10H21, CN
.
.
Chart 1.
m-3b Cl as well as m-3e Cl with a butyl spacer were non-
mesomorphic (entries 2, 3, and 9), the other chlorides revealed
mesophases and some crystal-to-crystal transitions. ILCs
OH
Br
Br
O
O
10
Br(CH2)10Br
.
.
10
m-3c Cl and m-3d Cl with spacer lengths , C10 showed mono-
tropic phase behaviour, forming small SmA phases upon first
cooling (entries 5, 7). As recently reported,[35] bending of the
K2CO3, MeCN
NHAc
100ꢃC, 17 h
NHAc
NHAc
m-5 (58 %)
p-5
4
.
cationic core by meta-substitution (m-3a Cl) decreased melting
and clearing points compared with the para-substituted ana-
.
logue p-3a Cl. Their mesophase widths ranged from 16 to 23 K
(entries 1, 8).
Upon successive heating and cooling cycles, however, melt-
.
ing and clearing points of the guanidinium chloride m-3a Cl
were shifted to lower temperatures after each cycle, indicating
OH
R
R
6,7
a
b
6a or 6b
OC10H21
CN
K2CO3, MeOH, 85ꢃC (for 6b)
or 110ꢃC (for 6a), 17–60 h
O
O
NHAc
O
O
10
10
.
thermal decomposition (Fig. 3a). Para-substituted 3a Cl
behaved similarly. Replacement of chloride by other anions
NHAc
m-7a (83 %)
m-7b (87 %)
p-7a (81 %)
p-7b (59 %)
.
giving m-3a X not only led to lower clearing temperatures as
.
compared with m-3a Cl, but also decomposition was suppressed
R
R
and clearing transitions stayed constant at the same temperature
(Fig. 3b), as recently reported for guanidinium phenylalkoxy-
Scheme 1.
benzoates.[37] Guanidinium salts m-3a X (X ¼ Br, BF4) formed
.
bromides 9 giving the tethered compounds p-10a,b and
m-10b–e in 78–88 % yield. N-Boc-deprotection to derivatives
p-11a,b and m-11b–e was achieved very cleanly with methane
sulfonic acid in CHCl3. Derivative m-11a was obtained in 94 %
yield by acidic hydrolysis[62] of acetamide m-7a. The aniline
derivatives 11 were finally treated with chloro-N,N,N0,N0-
tetramethylformamidinium chloride[63] and either NEt3 or
NaHCO3. Workup strictly required an inert gas atmosphere to
.
provide the neat target guanidinium salts 3 Cl in 70–98 % yield.
To further study the anion effect, decyloxybiphenyl guanidi-
.
nium chloride m-3a Cl was submitted to salt metathesis with
NaBr, KI, NaOTf, NaBF4, KPF6, KOAc, and KSCN yielding the
reproducible enantiotropic mesophases (Table 1, entries 10, 14).
.
.
In contrast, m-3a I and m-3a SCN showed only monotropic
.
phase behaviour (entries 12, 18) and salts m-3a X (X ¼ OTf,
OAc, PF6) were non-mesogenic.
Under POM, the liquid crystalline guanidinium salts 3
exhibited strong tendencies for a homeotropic alignment, which
could be distinguished from the isotropic phase by shearing
textures. It should be noted that a homeotropic alignment is a
typical feature of SmA phases.[45] As exemplarily shown for
.
guanidinium chlorides 3a, focal-conic textures (m-3a Cl) and
.
Maltese crosses (p-3a Cl) were observed, indicating the pres-
ence of SmA mesophases (Fig. 4).
XRD experiments (wide-angle X-ray scattering (WAXS)
and small-angle X-ray scattering (SAXS)) of both decyloxy-
.
biphenyl guanidinium chlorides p- and m-3a Cl supported the
assignment of phase geometry. For example, at 1308C the
.
corresponding guanidinium ILCs m-3a X (Scheme 2).
Anion Effect in Guanidinium ILCs
Comparison of the 1H NMR spectra of phenylguanidinium salts
.
m-3a X revealed a significant downfield shift of the N–H signal
.
chloride m-3a Cl exhibited a typical smectic diffraction pattern

1090
J. C. Haenle et al.
Cl
ꢀ
R
OH
Cl
O
O
O
O
10
ꢁ
ꢁ
NMe2
10
NMe2
Me2N
6a or 6b
R1
N
H
NMe2
ꢀ
method A or B
K2CO3, MeCN
90ꢃC, 14–23 h
.
p-3a,b Cl (70–91 %)
Cl
p-10a,b R1 ꢂ NHBoc
p-11a,b R1 ꢂ NH2
R
R
10,11,3a R ꢂ OC10H21
b R ꢂ CN
(ii)
Cl
H
N
ꢀ
NHBoc
3ꢅ
2
R1
NMe2
Cl
O
O
10
O
O
3
ꢁ
1
4ꢅ
ꢁ 6b
2ꢅ
1ꢅ
10
NMe2
Me2N
K2CO3, MeCN
90ꢃC, 14 h
ꢁ
NMe2
ꢀ
method B
1ꢄ
Cl
OX
8 X ꢂ H
9 X ꢂ (CH2)nBr
.
m-3b Cl (85 %)
2ꢄ
m-10b R1 ꢂ NHBoc
m-11b R1 ꢂ NH2
4ꢄ
NC
NC
3ꢄ
(ii)
(i)
Cl
H
N
ꢀ
Cl
R1
ꢁ
O
O
NMe2
O
O
n
n
Me2N
NMe2
ꢁ 6a
ꢁ
NMe2
K2CO3, MeCN
90ꢃC, 20 h
method A
ꢀ
Cl
.
m-3a,c–e Cl (79–98 %)
C
10H21
O
m-10c–e R1 ꢂ NHBoc
m-11c–e R1 ꢂ NH2
C10H21
O
(ii)
MX, MeCN, 100ꢃC, 10 min
10,11,3
a
c
d
e
9
a b
c
d
n ꢂ 10 8
6
4
.
n ꢂ 10 8
6
4
m-3a X
HCl/H2O
m-11a R1 ꢂ NH2 (94 %)
ꢀ
ꢂ Br, l, OTf, BF4, PF6, OAc, SCN
m-7a
X
Scheme 2. Synthesis of guanidinium ionic liquid crystals 3 from precursors 9. (i) 8, Br(CH2)nBr, K2CO3, 708C (for p-8), 1008C (for m-8), 16–21 h;
(ii) methane sulfonic acid, CHCl3, r.t., 20–27 h or 2 h (for p- and m-10b). Method A: NEt3, KOH; method B: NaHCO3. Numbering for NMR assignment.
m-3a·X
13
Xꢂ
NH
12
11
10
9
Br
PF6
BF4
OTf
I
Cl
I
BF4
PF6
8
7
SCN
Br
170
190
210
230
250
270
Anion radius [pm]
Fig. 2. Correlation of the chemical shift of the N–H proton with the
.
corresponding anion radii for guanidinium salts m-3a X (in CDCl3).
Cl
and indication by POM textures, all mesophases of liquid
crystalline guanidinium salts 3 were assigned to the SmA phase
as well.
12
11
10
9
8
7
δ [ppm]
In order to obtain a greater understanding of the formed
SmA phase, temperature-dependent SAXS measurements were
carried out in the mesophases of para- and meta-substituted
Fig. 1. Anion-dependent chemical shift of the N–H proton and protons of
the phenyl moiety (grey) in 1H NMR spectra (in CDCl3) of decyloxybi-
.
phenyl guanidinium salts m-3a X.
.
guanidinium chlorides 3a Cl. Based on these measurements,
with a sharp (10) reflection in the small-angle region together
with a diffuse halo which is generated by the fluidity of the
alkoxy chains (Fig. 5, black line). By measuring this sample in
a magnetic field, an oriented sample could be obtained. Radial
integration of the (10) reflection with the software Datasqueeze
and the halo led to an angle of 908 between these two signals.
This is a very strong indicator for the presence of a SmA phase.
Upon further cooling to 1288C (Fig. 5, grey line) a much
sharper diffraction peak at wide angles in the region of the halo is
visible indicating crystallization. Due to structural similarities
layer spacings were determined through Gaussian fitting of
the (10) signal (software QtiPlot) and Bragg’s equation. To
get good comparability of the layer spacing LXRD, all calcula-
tions were extrapolated from a reduced temperature (Tred ¼ 0.95
Tiso).[66] The experimental values of p-3a Cl (LXRD ¼ 5119 pm)
.
.
and m-3a Cl (LXRD ¼ 5162 pm) can be compared with the
calculated all-trans lengths Lcal ¼ 4330 pm and Lcal ¼ 4070 pm,
respectively (Chem3D 13.0). Regarding Lcal , LXRD , 2Lcal
and the electrostatic repulsion between the ionic head groups,
a proposed interdigitation of the terminal decyloxy chain with

Alkoxybiphenyl-Guanidinium ILCs
1091
(a)
(b)
Table 1. Phase transition temperatures (T ) and enthalpies (DH) of
.
guanidinium ionic liquid crystals 3 X upon first heating
Phase transitions and enthalpies were determined by DSC. Heating/cooling
rate: 5 K minꢀ1. Cr, crystalline; SmA, smectic A; I, isotropic; þ, observed;
ꢀ, not observed
Entry Compd
CrA
T [8C]
(DH [kJ molꢀ1])
SmA
T [8C]
(DH [kJ molꢀ1])
I
.
1
p-3a Cl
þ
þ
þ
þ
þ
þ
þ
þ
þ
þ
þ
þ
þ
þ
þ
þ
þ
þ
144 (19.0)
135 (37.1)
184 (63.2)
150 (58.3)
129 (52.7)
154 (60.7)
131 (39.6)
133 (8.6)
þ
ꢀ
ꢀ
ꢀ
þ
ꢀ
þ
þ
ꢀ
þ
ꢀ
þ
ꢀ
þ
ꢀ
ꢀ
ꢀ
þ
167 (6.8)
þ
þ
þ
þ
þ
þ
þ
þ
þ
þ
þ
þ
þ
þ
þ
þ
þ
þ
.
2
p-3b Cl
.
3
m-3e Cl
.
m-3d Cl
4
5
141 (3.4)B
Fig. 4. Polarizing optical microscopy image of (a) Maltese crosses of
.
.
m-3c Cl
6
.
p-3a Cl at 1578C; (b) focal-conic textures of m-3a Cl at 1358C upon cooling
(magnification ꢁ 200; cooling rate: 5 K minꢀ1).
7
136 (7.5)B
149 (13.5)
.
8
m-3a Cl
.
9
m-3b Cl
149 (47.0)
123 (6.2)
.
10
11
12
13
14
15
16
17
18
m-3a Br
128 (8.4)
127 (3.4)B
135 (4.0)
128ꢃC
130ꢃC
.
m-3a I
124 (16.9)
124 (14.8)
117 (28.5)
129 (15.2)
127 (27.5)
87 (91.4)
.
m-3a OTf
.
m-3a BF4
.
m-3a PF6
.
m-3a OAc
(10)
.
m-3a SCN
125 (28.7)
124 (18.6)
127 (4.4)B
halo
18
AFor further crystal-to-crystal transitions, see Experimental.
BUpon first cooling.
2
6
10
14
22
2θ [degree]
.
Fig. 5. X-Ray diffraction profile of m-3a Cl at 1308C (black line) illustrat-
ing a SmA mesophase, and at 1288C (grey line) indicating crystallization.
Inset: wide-angle X-ray scattering (WAXS)diffraction pattern of an oriented
(a)
1stC
2nd
.
sample of m-3a Cl at 1308C.
C
3rdC
1stH
ꢀ
ꢁ
ꢀ
ꢁ
Cr1
Cr2
Cr3
SmA
2
ndH
ꢁ
ꢀ
ꢀ
ꢁ
3rdH
LXRD
100
110
120
130
140
150
Temperature [ꢃC]
(b)
phenyl moiety
ꢁ
H
N
NMe2
biphenyl moiety
ꢁ
1stC
ndC
NMe2
ꢀ
ꢀ
Cl
2
3rdC
Fig. 6. Model of the proposed bilayer structure of the guanidinium
.
chlorides 3a Cl.
Cr1
Cr2
SmA
1stH
2
ndH
the alkoxy spacer between the biphenyl and the head group
within a bilayer structure is in good agreement with the experi-
mental values (Fig. 6).
3rdH
105
115
125
135
Conclusions
Temperature [ꢃC]
We successfully prepared a class of ILCs 3 consisting of a bent or
linear phenylguanidinium moiety tethered via an alkoxy spacer
to a biphenyl mesogen starting from N-Boc-protected hydroxy-
anilines 8. All mesomorphic representatives self-assembled
Fig. 3. Comparison of differential scanning calorimetry curves of decyl-
.
.
oxybiphenyl guanidinium ionic liquid crystals m-3a Cl (a) and m-3a Br (b).
C ¼ cooling, H ¼ heating, Crx ¼ crystalline, SmA ¼ smectic A.

1092
J. C. Haenle et al.
into smectic A (SmA) mesophases, as was indicated by POM
and further confirmed by XRD. Prerequisites for mesophase
formation are a tether length of at least C6 and the
4-alkoxybiphenyl unit. The symmetry of the head group did
not affect the mesophase properties but melting and clearing
points. The molecules seem to form a bilayer structure with
interdigitation of the terminal decyloxy substituent and the alk-
colourless solid, mp 578C. nmax/cmꢀ1 3370, 2982, 2941, 2920,
2854, 1703, 1602, 1587, 1521, 1474, 1438, 1392, 1364, 1329,
1286, 1236, 1193, 1168, 1152, 1087, 1053, 1039, 1017, 987,
971, 881, 846, 832, 797, 771, 758, 737, 716, 680. dH (500 MHz,
CDCl3) 1.26–1.47 (m, 12H, 6 ꢁ CH2), 1.51 (s, 9H, C(CH3)3),
1.71–1.79 (m, 2H, BrCH2CH2), 1.81–1.89 (m, 2H, OCH2CH2),
3.41 (t, J 6.9, 2H, BrCH2), 3.94 (t, J 6.5, 2H, OCH2), 6.44 (s, 1H,
NH), 6.55–6.81 (m, 2H, 4-H, 6-H), 7.08–7.17 (m, 2H, 2-H, 5-H).
dC (126 MHz, CDCl3) 26.0, 28.2, 28.3, 28.7, 29.3, 29.4, 32.8,
34.1, 67.9, 80.5, 104.7, 109.3, 110.5, 129.6, 139.5, 152.6, 159.9.
m/z (ESI) 450 [M þ Na]þ, 428 [M þ H]þ, 393, 372, 348, 311,
292. m/z (HRMS ESI) 450.1608. C21H34BrNNaOþ3 [M þ Na]þ
requires 450.1614. Anal. Calc. for C21H34BrNO3: C 58.88,
H 8.00, N 3.27. Found: C 59.18, H 8.02, N 3.19 %.
.
oxy spacer. Most surprisingly, ILCs 3b Cl with 4-cyanobiphenyl
unit were not liquid crystalline at all. Regardless of the symmetry
of the phenylguanidinium head group the molecular architecture
of ILCs 3 strongly favours SmA phases while neither SmE nor
SmC phases could be detected in contrast to structural analogues
1 and 2. Thus, further studies are necessary to elucidate the
parameters that favour SmC over SmA mesophases in ILCs. This
current work contributes to the understanding of structure–
property relationships in ILCs which are required for applica-
tions such as electrolytes in dye-sensitized solar cells.[67–69]
tert-Butyl 3-[(8-Bromooctyl)oxy]
phenylcarbamate (m-9c)
After heating for 40 h at 1008C, CH2Cl2 (50 mL) was added,
the precipitate was filtered off, washed with CH2Cl2 (50 mL)
and EtOAc (50 mL), silica was added to the filtrate, the solvent
removed under reduced pressure, and the residue purified by
chromatography (silica; 40 : 1 - 10 : 1 hexanes/EtOAc) to
Experimental
Materials
All reagents were used as purchased from the suppliers. Silica 60
(40–63 mm) was purchased from Fluka. Solvents were dried
following known methods, hexanes and EtOAc were distilled
before use.
afford m-9c (1.81 g, 45 %) as a colourless solid, mp 638C. nmax
/
cmꢀ1 3005, 2978, 2931, 2854, 1758, 1730, 1702, 1605, 1524,
1495, 1474, 1423, 1392, 1367, 1334, 1286, 1267, 1231, 1192,
1154, 1092, 1051, 1026, 992, 874, 851, 767, 723, 688, 646, 557,
528. dH (300 MHz, CDCl3) 1.29–1.49 (m, 8H, 4 ꢁ CH2), 1.51
(s, 9H, C(CH3)3), 1.71–1.91 (m, 4H, OCH2CH2, BrCH2CH2),
3.41 (t, J 6.8, 2H, BrCH2), 3.94 (t, J 6.5, 2H, OCH2), 6.46 (s, J
8.0, 1H, NH), 6.54–6.82 (m, 2H, 4-H, 6-H), 7.09–7.18 (m, 2H,
2-H, 5-H). dC (75 MHz, CDCl3) 26.0, 27.7, 28.1, 28.3, 28.7, 29.2,
32.8, 34.0, 67.9, 80.5, 104.7, 109.3, 110.5, 129.6, 139.6, 152.6,
159.8. m/z (ESI) 422 [M þ Na]þ, 402 [M þ H]þ, 368, 332, 301,
266, 227. m/z (HRMS ESI) 422.1289. C19H30BrNNaOþ3 [M þ
Na]þ requires 422.1301. Anal. Calc. for C19H30BrNO3: C 57.00,
H 7.55, N 3.50. Found: C 57.00, H 7.56, N 3.41 %.
General Procedure for the Williamson Etherification
with 1,v-Dibromoalkanes[70]
The respective 1,v-dibromoalkane (20.2 mmol) was added
to a solution of the appropriate p- or m-8 (3.36 mmol) and
K2CO3 (10.7 mmol) in MeCN (30 mL), and the reaction
mixture heated at reflux for the given time. Workup is given for
the respective product.
tert-Butyl 4-[(10-Bromodecyl)oxy]
phenylcarbamate (p-9a)
After heating for 21 h at 708C, the precipitate was filtered off
and washed with EtOAc (50 mL), silica was added to the filtrate,
the solvent removed under reduced pressure, and the residue
purified by chromatography (silica; 10 : 1 hexanes/EtOAc)
to afford p-9a (1.56 g, 76 %) as a colourless solid. mp 1108C.
tert-Butyl 3-[(6-Bromohexyl)oxy]
phenylcarbamate (m-9d)
After heating for 40 h at 1008C, CH2Cl2 (50 mL) was added,
the precipitate was filtered off, washed with CH2Cl2 (50 mL)
and EtOAc (50 mL), silica was added to the filtrate, the solvent
removed under reduced pressure, and the residue purified
by chromatography (silica; 60 : 1 - 12 : 1, hexanes/EtOAc) to
n
max/cmꢀ1 3358, 3008, 2988, 2938, 2921, 2902, 2869, 2851,
1692, 1618, 1596, 1521, 1434, 1443, 1414, 1390, 1366, 1316,
1296, 1249, 1228, 1156, 1115, 1057, 1040, 1017, 941, 924, 906,
889, 835, 806, 772, 761, 739, 722, 641, 624, 592, 562, 517.
dH (500 MHz, CDCl3) 1.26–1.47 (m, 12H, 6 ꢁ CH2), 1.50
(s, 9H, C(CH3)3), 1.71–1.78 (m, 2H, BrCH2CH2), 1.81–1.89
(m, 2H, OCH2CH2), 3.40 (t, J 6.9, 2H, BrCH2), 3.91 (t, J 6.6, 2H,
OCH2), 6.35 (s, 1H, NH), 6.82 (d, J 8.9, 2H, 3-H), 7.22–2.26
(m, 2H, 2-H). dC (126 MHz, CDCl3) 26.0, 28.2, 28.4, 28.7, 29.3,
29.4, 32.8, 34.1, 68.3, 80.2, 114.9, 120.5, 131.2, 153.2, 155.2.
m/z (ESI) 450 [M þ Naþ], 396, 372, 227. m/z (HRMS ESI)
450.1591. C21H34BrNNaOþ3 [M þ Na]þ requires 450.1614.
Anal. Calc. for C21H34BrNO3: C 58.88, H 8.00, N 3.27. Found:
C 58.90, H 8.01, 3.23 %.
afford m-9d (1.82 g, 49 %) as a colourless solid, mp 898C. nmax
/
cmꢀ1 3338, 3005, 2978, 2936, 2859, 1729, 1699, 1604, 1537,
1523, 1494, 1474, 1442, 1423, 1392, 1367, 1286, 1267, 1231,
1192, 1153, 1092, 1050, 1027, 990, 943, 872, 849, 767, 733, 688,
645, 597, 560. dH (300 MHz, CDCl3) 1.42–1.50 (m, 4H, 2 ꢁ
CH2), 1.51 (s, 9H, C(CH3)3), 1.72–1.94 (m, 4H, OCH2CH2,
BrCH2CH2), 3.38–3.45 (m, 2H, BrCH2), 3.95 (t, J 6.4, 2H,
OCH2), 6.46 (s, 1H, NH), 6.54–6.81 (m, 2H, 4-H, 6-H), 7.10–
7.19 (m, 2H, 2-H, 5-H). dC (75 MHz, CDCl3) 25.3, 27.9, 28.3,
29.1, 32.7, 33.8, 67.7, 80.5, 104.7, 109.3, 110.5, 129.6, 139.6,
152.6, 159.8. m/z (ESI) 394 [M þ Na]þ, 338, 316, 266, 248, 154.
m/z (HRMS ESI) 394.0999. C17H26BrNNaOþ3 [M þ Na]þ
requires 394.0988. Anal. Calc. for C17H26BrNO3: C 54.84, H
7.04, N 3.76. Found: C 54.59, H 6.95, N 3.50 %.
tert-Butyl 3-[(10-Bromodecyl)oxy]
phenylcarbamate (m-9a)
After heating for 16 h at 1008C, CH2Cl2 (30 mL) was added,
the precipitate was filtered off, washed with CH2Cl2 (80 mL)
and EtOAc (50 mL), the filtrate was concentrated under reduced
pressure, and the residue purified by chromatography (silica;
40 : 1 - 8 : 1 hexanes/EtOAc) to afford m-9a (3.33 g, 55 %) as a
tert-Butyl 3-[(4-Bromobutyl)oxy]
phenylcarbamate (m-9e)
After heating for 40 h at 1008C, CH2Cl2 (50 mL) was added,
the precipitate was filtered off, washed with CH2Cl2 (50 mL)

Alkoxybiphenyl-Guanidinium ILCs
1093
and EtOAc (50 mL), silica was added to the filtrate, the solvent
removed under reduced pressure, and the residue purified
by chromatography (silica; 60 : 1 - 40 : 1 hexanes/EtOAc)
to afford m-9e (1.97 g, 54 %) as a colourless solid, mp 748C.
7.22–7.25 (m, 2H, 2-H), 7.49–7.57 (m, 2H, 20-H), 7.60–7.73
(m, 4H, 200-H, 300-H). dC (75 MHz, CDCl3) 26.0, 28.4, 29.2, 29.3,
29.4, 29.5, 68.2, 68.3, 80.2, 110.0, 114.9, 115.1, 119.1, 120.6,
127.1, 128.3, 131.3, 132.6, 145.3, 153.2, 155.2, 159.8. m/z (ESI)
565 [M þ Naþ] 543 [M þ Hþ], 509, 487, 443, 393, 298. m/z
(HRMS ESI) 565.3024. C34H42N2NaOþ4 [M þ Naþ] requires
565.3037. Anal. Calc. for C34H42N2O4: C 75.25, H 7.80, N 5.16.
Found: C 74.32, H 7.69, N 5.01 %.
n
max/cmꢀ1 2978, 2930, 2872, 1729, 1698, 1604, 1523, 1494,
1474, 1442, 1422, 1392, 1367, 1286, 1232, 1191, 1151, 1092,
1049, 1028, 990, 965, 823, 850, 768, 726, 688, 651, 598, 559.
dH (300 MHz, CDCl3) 1.51 (s, 9H, C(CH3)3), 1.86–2.12 (m, 4H,
OCH2CH2, BrCH2CH2), 3.49 (m, 2H, BrCH2), 3.99 (t, J 5.9, 2H,
OCH2), 6.47 (s, 1H, NH), 6.53–6.82 (m, 2H, 4-H, 6-H), 7.11–
7.27 (m, 2H, 2-H, 5-H). dC (75 MHz, CDCl3) 27.9, 28.3, 29.5,
33.5, 66.8, 80.6, 104.7, 109.2, 110.7, 129.6, 139.6, 152.6, 159.6.
m/z (ESI) 368 [M þ Na]þ, 332, 310, 288, 266, 249, 173, 137. m/z
(HRMS ESI) 366.0686. C15H22BrNNaOþ3 [M þ Na]þ requires
366.0675. Anal. Calc. for C15H22BrNO3: C 52.34, H 6.44,
N 4.07. Found: C 52.00, H 6.32, N 3.90 %.
tert-Butyl 3-({10-[(40-Cyano-1,10-biphenyl-4-yl)oxy]
decyl}oxy)phenylcarbamate (m-10b)
Reaction time 14 h. Filtration at 08C, suspension (sonifica-
tion), filtration, washing with H2O (3 ꢁ 10 mL) and MeCN
(2 mL), and drying afforded m-10b (1.13 g, 86 %) as a colourless
solid, mp 1228C. nmax/cmꢀ1 3327, 3139, 3036, 2983, 2945,
2922, 2852, 2224, 1690, 1604, 1583, 1536, 1493, 1467, 1438,
1393, 1369, 1315, 1285, 1243, 1196, 1179, 1154, 1116, 1093,
1054, 1031, 999, 946, 868, 848, 821, 806, 783, 770, 718, 694,
616, 647, 593, 562, 531. dH (500 MHz, CDCl3) 1.28–1.50
(m, 12H, 6 ꢁ CH2), 1.51 (s, 9H, C(CH3)3), 1.71–1.85 (m, 4H,
2 ꢁ OCH2CH2), 3.91–4.03 (m, 4H, 2 ꢁ OCH2), 6.45 (s, 1H,
NH), 6.54–6.80 (m, 2H, 4-H, 6-H), 6.97–7.01 (m, 2H, 30-H),
7.10–7.13 (m, 1H, 2-H), 7.13–7.17 (m, 1H, 5-H), 7.50–7.53
(m, 2H, 20-H), 7.61–7.65(m, 2H, 200-H), 7.66–7.70(m, 2H, 300-H).
dC (126 MHz, CDCl3) 26.0, 28.3, 29.2, 29.3, 29.5, 67.9, 68.2,
80.5, 104.7, 109.3, 110.0, 110.5, 115.1, 119.1, 127.1, 128.3,
129.6, 131.2, 132.6, 139.6, 145.3, 152.6, 159.8, 159.9. m/z (ESI)
565 [M þ Na]þ. m/z (HRMS ESI) 565.3024. C34H42N2NaOþ4
[M þ Na]þ requires 565.3037. Anal. Calc. for C34H42N2O4:
C 75.25, H 7.80, N 5.16. Found: C 75.30, H 7.82, N 5.09 %.
General Procedure for the Williamson Etherification
with Biphenyl-4-ols 6 Analogous to Das et al.[71]
Biphenyl-4-ol 6a or 6b (1.54 mmol), the respective bromide 9
(1.40 mmol), and K2CO3 (4.90 mmol) were suspended in MeCN
(40 mL) and the reaction mixture heated at 908C for the given
time. The precipitate was filtered off and washed with MeCN
(50 mL) (for 10c–e) before suspension in CHCl3 (50 mL). The
remaining solid was filtered off, washed, and dried under vac-
uum. In the case of 10b, H2O (50 mL) was added, the solid fil-
tered off, washed, and recrystallized (EtOAc) (p-10b) or dried
under vacuum (m-10b).
tert-Butyl 4-[(10-{[40-(Decyloxy)-1,10-biphenyl-4-yl]
oxy}decyl)oxy]phenylcarbamate (p-10a)
Reaction time 23 h. Washing with CHCl3 (3 ꢁ 10 mL) and
drying afforded p-10a (766 mg, 90 %) as a colourless solid, mp
1438C. nmax/cmꢀ1 3333, 3041, 2937, 2920, 2873, 2851, 1696,
1607, 1595, 1569, 1536, 1521, 1500, 1474, 1462, 1445, 1414,
1392, 1366, 1329, 1314, 1295, 1273, 1245, 1232, 1174, 1110,
1060, 1045, 1032, 1012, 981, 952, 936, 908, 824, 800, 774,
759, 742, 719, 646, 595, 545. dH (500 MHz, CDCl3) 0.88 (t, J
7.0, 3H, CH2CH3), 1.23–1.49 (m, 26H, 13 ꢁ CH2), 1.50 (s, 9H,
C(CH3)3), 1.72–1.84 (m, 6H, 3 ꢁ OCH2CH2), 3.87–4.00 (m, 6H,
3 ꢁ OCH2), 6.32 (s, 1H, NH), 6.80–6.85 (m, 2H, 3-H), 6.91–
6.96 (m, 4H, 30-H, 300-H), 7.21–7.27 (m, 2H, 2-H), 7.43–7.48 (m,
4H, 20-H, 200-H). dC (126 MHz, CDCl3) 14.1, 22.7, 26.0, 26.1,
28.4, 29.3, 29.4, 29.5, 29.6, 31.9, 68.1, 68.1, 68.3, 114.7, 114.9,
120.5, 127.6, 131.2, 133.3, 153.2, 155.3, 158. m/z (ESI) 696
[M þ Na]þ, 673 [M]þ, 579, 443, 350. m/z (HRMS ESI)
696.4591. C43H63NNaOþ5 [M þ Na]þ requires 696.4598. Anal.
Calc. for C43H63NO5: C 76.74, H 9.42, N 2.05. Found: C 76.63,
H 9.42, N 2.08 %.
tert-Butyl 3-[(8-{[40-(Decyloxy)-1,10-biphenyl-4-yl]
oxy}octyl)oxy]phenylcarbamate (m-10c)
Reaction time 20 h. Washing with CHCl3 (3 ꢁ 10 mL) and
drying afforded m-10c (701 mg, 87 %) as a colourless solid,
mp 1078C. nmax/cmꢀ1 3360, 3041, 2979, 2957, 2935, 2919,
2874, 2852, 1737, 1702, 1608, 1527, 1501, 1475, 1441, 1423,
1393, 1367, 1328, 1273, 1250, 1226, 1197, 1177, 1156, 1068,
1037, 1013, 992, 936, 911, 884, 844, 824, 808, 772, 760, 734,
723, 685, 644, 627, 596, 573, 552. dH (300 MHz, CDCl3) 0.88
(t, J 6.7, 3H, CH2CH3), 1.24–1.49 (m, 22H, 11 ꢁ CH2), 1.51
(s, 9H, C(CH3)3), 1.71–1.86 (m, 6H, 3 ꢁ OCH2CH2), 3.91–4.01
(m, 6H, 3 ꢁ OCH2), 6.44 (s, 1H, NH), 6.54–6.82 (m, 2H, 4-H,
6-H), 6.90–6.98 (m, 4H, 30-H, 300-H), 7.08–7.11 (m, 1H, 2-H),
7.12–7.18 (m, 1H, 5-H), 7.40–7.50 (m, 4H, 20-H, 200-H).
dC (75 MHz, CDCl3) 14.1, 22.7, 26.0, 26.1, 28.3, 29.3, 29.4,
29.6, 31.9, 67.9, 68.0, 68.1, 80.5, 104.7, 109.4, 110.5, 114.7,
127.7, 129.6, 133.3, 139.5, 152.6, 158.2, 159.9. m/z (ESI) 668
[M þ Na]þ, 590, 546, 465, 393, 327. m/z (HRMS ESI) 668.4266.
C41H59NNaOþ5 [M þ Na]þ requires 668.4285. Anal. Calc.
for C41H59NO5: C 76.24, H 9.21, N 2.17. Found: C 76.02,
H 9.23, N 2.07 %.
tert-Butyl 4-({10-[(40-Cyano-1,10-biphenyl-4-yl)oxy]
decyl}oxy)phenylcarbamate (p-10b)
Reaction time 14 h. The solid washed with H2O (3 ꢁ 10 mL)
and 9 : 1 H2O/MeCN (10 mL); recrystallization afforded p-10b
(600 mg, 78 %) as a colourless solid, mp 1608C. nmax/cmꢀ1
3362, 3073, 3042, 3014, 2990, 2974, 2945, 2924, 2906, 2855,
2224, 1690, 1599, 1578, 1520, 1493, 1473, 1413, 1392, 1368,
1318, 1289, 1268, 1251), 1230), 1180, 1157, 1117, 1075, 1054,
1027, 1012, 989, 934, 903, 855, 836, 821, 806, 773, 748, 735,
721, 660, 636, 622, 560. dH (300 MHz, CDCl3) 1.26–1.48
(m, 12H, 6 ꢁ CH2), 1.50 (s, 9H, C(CH3)3), 1.69–1.88 (m, 4H,
2 ꢁ OCH2CH2), 3.87–4.04 (m, 4H, 2 ꢁ OCH2), 6.34 (s, 1H,
NH), 6.79–6.86 (m, 2H, 3-H), 6.95–7.02 (m, 2H, 30-H),
tert-Butyl 3-[(6-{[40-(Decyloxy)-1,10-biphenyl-4-yl]
oxy}hexyl)oxy]phenylcarbamate (m-10d)
Reaction time 20 h. Washing with CHCl3 (3 ꢁ 10 mL) and
drying afforded m-10d (854 mg, 87 %) as a colourless solid, mp
1218C. nmax/cmꢀ1 3360, 3038, 2980, 2956, 2938, 2922, 2910,
2872, 2848, 1734, 1702, 1689, 1605, 1528, 1499, 1473, 1442,
1427, 1392, 1366, 1326, 1287, 1271, 1245, 1197, 1176, 1156,
1069, 1051, 1033, 1018, 996, 983, 936, 883, 844, 823, 804, 773,
759, 734, 682, 646, 592, 547. dH (300 MHz, CDCl3) 0.88 (t, J

1094
J. C. Haenle et al.
6.7, 3H, CH2CH3), 1.23–1.49 (m, 18H, 9 ꢁ CH2), 1.51 (s, 9H,
C(CH3)3), 1.73–1.88 (m, 6H, 3 ꢁ OCH2CH2), 3.93–4.03 (m, 6H,
3 ꢁ OCH2), 6.44 (s, 1H, NH), 6.55–6.82 (m, 2H, 4-H, 6-H),
6.90–6.98 (m, 4H, 30-H, 300-H), 7.09–7.12 (m, 1H, 2-H),
7.12–7.19 (m, 1H, 5-H), 7.42–7.50 (m, 4H, 20-H, 200-H).
dC (75 MHz, CDCl3) 14.1, 22.7, 25.9, 26.1, 28.3, 29.3, 29.4,
29.6, 31.9, 67.8, 67.9, 68.1, 80.5, 104.7, 109.4, 110.5, 114.7,
127.7, 129.6, 133.3, 133.4, 139.6, 152.6, 158.2, 158.2, 159.8.
m/z (ESI) 640 [M þ Na]þ, 612 [M þ H]þ, 481. m/z (HRMS ESI)
640.3958. C39H55NNaOþ5 [M þ Na]þ requires 640.3972. Anal.
Calc. for C39H55NO5: C 75.81, H 8.97, N 2.27. Found: C 75.99,
H 9.03, N 2.09 %.
326 (1), 287 (3), 216 (2), 186 (14), 157 (1), 109 (13), 83 (2), 55
(2). m/z (HRMS EI) 573.4196. C38H56NOþ3 [M þ H]þ requires
573.4182. Anal. Calc. for C38H55NO3: C 79.53, H 9.66, N 2.44.
Found: C 78.16, H 9.52, N 2.32 %.
40-{[10-(4-Aminophenoxy)decyl]oxy}-1,10-
biphenyl-4-carbonitrile (p-11b)
Reaction time 2 h. Chromatography (3 : 1 - 1 : 1 hexanes/
EtOAc) afforded p-11b (253 mg, 58 %) as a colourless solid,
mp 1458C. nmax/cmꢀ1 3375, 2935, 2919, 2851, 2225, 1630,
1601, 1580, 1511, 1493, 1474, 1462, 1494, 1293, 1269, 1254,
1233, 1182, 1120, 1047, 1025, 1012, 981, 817, 799, 770, 746,
717, 662, 621. dH (500 MHz, CDCl3) 1.28–1.51 (m, 12H, 6 ꢁ
CH2), 1.70–1.85 (m, 4H, 2 ꢁ OCH2CH2), 3.41 (s, 2H, NH2),
3.85–4.04 (m, 4H, 2 ꢁ OCH2), 6.61–6.76 (m, 4H, 2-H, 3-H),
6.97–7.01 (m, 2H, 30-H), 7.50–7.54 (m, 2H, 20-H), 7.62–7.70 (m,
4H, 200-H, 300-H). dC (126 MHz, CDCl3) 26.0, 26.1, 29.2, 29.3,
29.4, 29.5, 68.2, 68.7, 110.0, 115.1, 115.6, 116.4, 119.1, 127.1,
128.3, 131.2, 132.6, 139.8, 145.3, 152.3, 159.8. m/z (ESI) 465
[M þ Na]þ, 443 [M þ H]þ, 393. m/z (HRMS ESI) 443.2699.
C29H35N2Oþ2 [M þ H]þ requires 443.2693. Anal. Calc. for
C29H34N2O2: C 78.70, H 7.74, N 6.33. Found: C 78.45, H
7.82, N 6.14 %.
tert-Butyl 3-[(4-{[40-(Decyloxy)-1,10-biphenyl-4-yl]
oxy}butyl)oxy]phenylcarbamate (m-10e)
Reaction time 20 h. Washing with CHCl3 (3 ꢁ 10 mL) and
drying afforded m-10e (987 mg, 88 %) as a colourless solid,
mp 1408C. nmax/cmꢀ1 3337, 3039, 2956, 2920, 2873, 2851,
1702, 1606, 1535, 1501, 1475, 1442, 1426, 1390, 1366, 1324,
1289, 1271, 1234, 1194, 1175, 1159, 1072, 1048, 1032, 1012,
995, 956, 890, 847, 814, 779, 759, 724, 688, 644, 595, 540. dH
(300 MHz, CDCl3) 0.88 (t, J 6.7, 3H, CH2CH3), 1.22–1.48
(m, 14H, 7 ꢁ CH2), 1.51 (s, 9H, C(CH3)3), 1.73–2.01 (m, 6H,
3 ꢁ OCH2CH2), 3.93–4.09 (m, 6H, 3 ꢁ OCH2), 6.45 (s, 1H,
NH), 6.56–6.82 (m, 2H, 4-H, 6-H), 6.90–6.98 (m, 4H, 30-H,
300-H), 7.12–7.13 (m, 1H, 2-H), 7.13–7.19 (m, 1H, 5-H), 7.41–
7.49 (m, 4H, 20-H, 200-H). dC (75 MHz, CDCl3) 14.1, 22.7, 26.0,
26.1, 28.4, 29.3, 29.4, 29.6, 31.9, 67.4, 67.6, 68.1, 80.5, 104.8,
109.3, 110.6, 114.8, 127.7, 127.7, 129.6, 133.3, 133.5, 139.6,
152.6, 158.1, 158.3, 159.7. m/z (ESI) 612 [M þ Na]þ, 578, 556,
481. m/z (HRMS ESI) 612.3644. C37H51NNaOþ5 [M þ Na]þ
requires 612.3659. Anal. Calc. for C37H51NO5: C 75.35, H 8.72,
N 2.37. Found: C 75.65, H 8.79, N 2.20 %.
40-{[10-(3-Aminophenoxy)decyl]oxy}-1,10-
biphenyl-4-carbonitrile (m-11b)
Reaction time 2 h. Chromatography (70 : 13 : 1 hexanes/
EtOAc/MeCN) afforded m-11b (623 g, 94 %) as a colourless
solid, mp 1078C. nmax/cmꢀ1 3457, 3370, 2934, 2918, 2851,
2224, 1627, 1600, 1580, 1525, 1494, 1473, 1462, 1395, 1337,
1290, 1269, 1252, 1216, 1182, 1160, 1116, 1182, 1045, 1025,
1012, 985, 953, 822, 772, 759, 717, 691, 662. dH (500 MHz,
CDCl3) 1.29–1.51 (m, 12H, 6 ꢁ CH2), 1.71–1.84 (m, 4H, 2 ꢁ
OCH2CH2), 3.63 (s, 2H, NH2), 3.85–4.02 (m, 4H, 2 ꢁ OCH2),
6.23–6.25 (m, 1H, 2-H), 6.26–6.33 (m, 2H, 4-H, 6-H), 6.96–7.01
(m, 2H, 30-H), 7.02–7.06 (m, 1H, 5-H), 7.49–7.55 (m, 2H, 20-H),
7.61–7.65 (m, 2H, 200-H), 7.66–7.71 (m, 2H, 300-H). dC
(126 MHz, CDCl3) 26.0, 29.2, 29.3, 29.4, 29.5, 67.7, 68.2,
101.7, 104.6, 107.7, 110.0, 115.1, 119.1, 127.1, 128.3, 130.0,
131.2, 132.6, 145.3, 147.7, 159.8, 160.3. m/z (ESI) 465 [M þ
Na]þ, 443 [M þ H]þ, 393, 339, 279, 246, 228. m/z (HRMS ESI)
443.2699. C29H35N2Oþ2 [M þ H]þ requires 443.2693. Anal.
Calc. for C29H34N2O2: C 78.70, H 7.74, N 6.33. Found: C
78.95, H 7.83, N 6.24 %.
General Procedure for the Deprotection
of Boc-Protected Derivatives 10
A solution of the respective 10 (985 mmol) in CHCl3 (30 mL)
was stirred with methane sulfonic acid (3.25 mmol) at room
temperature for the given time. After neutralization with K2CO3
or NaHCO3 (9.85 mmol) in H2O (20 mL), the phases were
separated, and the aqueous layer was extracted with CHCl3
(4 ꢁ 75 mL). The combined organic layers were concentrated
under reduced pressure and the remaining solid was dried under
vacuum. With exception of p-11a, all other products 11 were
further purified by column chromatography (silica).
3-[(8-{[40-(Decyloxy)-1,10-biphenyl-4-yl]oxy}octyl)
oxy]aniline (m-11c)
4-[(10-{[40-(Decyloxy)-1,10-biphenyl-4-yl]oxy}decyl)
oxy]aniline (p-11a)
Reaction time 20 h. Chromatography (800 : 55 : 20, hexanes/
EtOAc/NEt3 - 100 : 3, EtOAc/NEt3) afforded m-11c (485 g,
86 %) as a colourless solid, mp 1578C. nmax/cmꢀ1 3438, 3402,
3207, 3069, 3040, 2955, 2933, 2918, 2873, 2850, 1630, 1598,
1566, 1497, 1470, 1442, 1390, 1329, 1318, 1289, 1272, 1247,
1196, 1177, 1157, 1136, 1119, 1049, 1031, 1014, 996, 985, 962,
907, 823, 808, 770, 740, 720, 688, 645, 592, 552. dH (500 MHz,
CDCl3) 0.88 (t, J 6.9, 3H, CH3), 1.21–1.51 (m, 22H, 11 ꢁ CH2),
1.71–1.84 (m, 6H, 3 ꢁ OCH2CH2), 3.63 (s, 2H, NH2), 3.91 (t, J
6.5, 2H, C3-OCH2), 3.96–4.00 (m, 4H, 2 ꢁ biphenyl-OCH2),
6.23–6.25 (m, 1H, 2-H), 6.26–6.33 (m, 2H, 4-H, 6-H), 6.92–6.96
(m, 4H, 30-H, 300-H), 7.02–7.06 (m, 1H, 5-H), 7.43–7.48 (m, 4H,
20-H, 200-H). dC (126 MHz, CDCl3) 14.1, 22.7, 26.0, 26.1, 29.3,
29.4, 29.6, 31.9, 67.7, 68.0, 68.1, 101.7, 104.6, 107.7, 114.7,
127.7, 130.1, 133.3, 133.3, 147.7, 158.2, 158.2, 160.3. m/z (ESI)
Reaction time 27 h. Extraction with hot CHCl3 (4 ꢁ 75 mL)
afforded p-11a (664 mg, 92 %) as a colourless solid, mp 1498C.
n
max/cmꢀ1 3575, 3379, 3318, 3041, 2957, 2935, 2918, 2874,
2850, 1605, 1569, 1515, 1499, 1473, 1462, 1393, 1329, 1298,
1273, 1248, 1177, 1128, 1124, 1096, 1047, 1032, 1010, 994,
979, 930, 824, 808, 798, 736, 719, 644, 593, 556, 519, 507.
dH (500 MHz, DMSO, 1008C) 0.86 (t, J 6.8, 3H, CH3), 1.20–1.47
(m, 26H, 13 ꢁ CH2), 1.59–1.75 (m, 6H, 3 ꢁ OCH2CH2), 3.81
(t, J 6.5, 2H, C4-OCH2), 3.99 (t, J 6.5, 4H, 2 ꢁ biphenyl-OCH2),
4.23 (s, 2H, NH2), 6.49–6.65 (m, 4H, 2-H, 3-H), 6.91–6.97 (m,
4H, 30-H, 300-H), 7.43–7.49 (m, 4H, 20-H, 200-H). dC (126 MHz,
DMSO, 1008C) 12.0, 21.3, 24.9, 27.9, 28.0, 28.1, 28.2, 28.3,
28.4, 30.6, 67.5, 68.2, 114.6, 114.8, 115.4, 126.6, 132.1, 141.6,
150.1, 157.5. m/z (EI) (%) 573 (100) [M þ H]þ, 466 (5), 433 (1),

Alkoxybiphenyl-Guanidinium ILCs
1095
546 [M þ H]þ, 512, 490, 393, 381. Anal. Calc. for C36H51NO3:
(m, 4H, 30-H, 300-H), 7.41–7.51 (m, 4H, 20-H, 200-H). dC
(126 MHz, DMSO) 13.6, 21.9, 25.5, 25.6, 28.6, 28.7, 28.9,
31.2, 67.6, 68.1, 101.2, 103.2, 107.3, 115.3, 127.2, 129.4,
132.8, 149.7, 158.1, 160.1. m/z (ESI) 612 [M þ K]þ, 596 [M þ
Na]þ, 574 [M þ H]þ, 490, 441, 393, 371, 327. m/z (HRMS ESI)
574.4241. C38H56NOþ3 [M þ H]þ requires 574.4255. Anal.
Calc. for C38H55NO3: C 79.53, H 9.66, N 2.44. Found: C
79.48, H 9.61, N 2.40 %.
C 79.22, H 9.42, N 2.57. Found: C 78.27, H 8.77, N 2.71 %.
3-[(6-{[40-(Decyloxy)-1,10-biphenyl-4-yl]oxy}hexyl)
oxy]aniline (m-11d)
Reaction time 20 h. Chromatography (300 : 10 - 0 : 1
hexanes/EtOAc) afforded m-11d (550 mg, 78 %) as a colourless
solid, mp 1428C. nmax/cmꢀ1 3425, 3344, 3068, 3040, 2958,
2938, 2919, 2874, 2850, 1630, 1600, 1567, 1497, 1473, 1462,
1395, 1329, 1316, 1293, 1271, 1248, 1200, 1177, 1158, 1138,
1121, 1072, 1032, 1013, 993, 951, 889, 824, 805, 776, 756, 740,
728, 718, 690, 645, 587, 550. dH (500 MHz, CDCl3) 0.88 (t, J
6.9, 3H, CH3), 1.24–1.58 (m, 18H, 9 ꢁ CH2), 1.75–1.86 (m, 6H,
3 ꢁ OCH2CH2), 3.62 (s, 2H, NH2), 3.90–4.02 (m, 6H, 3 ꢁ
OCH2), 6.23–6.25 (m, 1H, 2-H), 6.26–6.33 (m, 2H, 4-H, 6-H),
6.92–6.96 (m, 4H, 30-H, 300-H), 7.02–7.07 (m, 1H, 5-H), 7.43–
7.48 (m, 4H, 20-H, 200-H). dC (126 MHz, CDCl3) 14.1, 22.7, 26.0,
26.1, 29.3, 29.4, 29.6, 31.9, 67.7, 68.0, 68.1, 101.7, 104.6, 107.7,
114.7, 127.7, 130.1, 133.3, 133.3, 147.7, 158.2, 158.2, 160.3. m/z
(ESI) 518 [M þ H]þ, 393. m/z (HRMS ESI) 518.36. C34H48NOþ3
[M þ H]þ requires 518.36. Anal. Calc. for C34H47NO3: C 78.87,
H 9.15, N 2.71. Found: C 78.77, H 9.06, N 2.60 %.
General Procedure for the Linkage of the Guanidinium
Head Group Analogous to Butschies et al.[39]
A solution of chloro-N,N,N0,N0-tetramethylformamidinium
chloride (502 mmol) in CH2Cl2 was added dropwise to a stirred
suspension or solution of the respective 11 (418 mmol) in dry
THF (20 mL) followed by addition of NEt3 (1.88 mmol)
(method A) or NaHCO3 (method B) and the reaction mixture
stirred for the given time at room temperature. After addition of
an excess of H2O and stirring for 15 min, purification with HCl-
treated silica was carried out. Organic byproducts were sepa-
rated by elution with EtOAc and the product eluted with
CH2Cl2/MeOH. The eluate was filtered to remove trace amounts
of silica, and the filtrate concentrated under reduced pressure. In
the case of NEt3 (method A), the remaining colourless solid was
dissolved or suspended in MeOH (10 mL) and a solution of
KOH (5.44 mmol) in MeOH (5 mL) added and the mixture
stirred for 15 min. The solvent was removed under reduced
pressure and the residue dried under high vacuum. Under N2
atmosphere, the solid was then dissolved or suspended in Et2O
and HCl in Et2O added until pH 1. After stirring for 15 min, all
volatile materials were removed under vacuum.
3-[(4-{[40-(Decyloxy)-1,10-biphenyl-4-yl]oxy}butyl)
oxy]aniline (m-11e)
Reaction time 24 h. Chromatography (1 : 1 hexanes/EtOAc,
then 10 : 1 CH2Cl2/MeOH) afforded m-11e (688 mg, 86 %) as a
colourless solid, mp 1598C. nmax/cmꢀ1 3434, 3402, 3308, 3210,
3070, 3040, 2956, 2934, 2918, 2873, 2850, 1630, 1601, 1567,
1497, 1470, 1442, 1390, 1329, 1317, 1290, 1272, 1247, 1196,
1177, 1158, 1136, 1120, 1049, 1031, 1014, 996, 985, 962, 907,
823, 807, 771, 741, 720, 688, 645, 614, 592, 531. dH (500 MHz,
CDCl3) 0.88 (t, J 6.9, 3H, CH3), 1.23–1.50 (m, 14H, 7 ꢁ CH2),
1.75–2.00 (m, 6H, 3 ꢁ OCH2CH2), 3.60 (s, 2H, NH2), 3.96–4.08
(m, 6H, 3 ꢁ OCH2), 6.22–6.24 (m, 1H, 2-H), 6.26–6.33 (m, 2H,
4-H, 6-H), 6.91–6.96 (m, 4H, 30-H, 300-H), 7.01–7.06 (m, 1H,
5-H), 7.42–7.48 (m, 4H, 20-H, 200-H). dC (126 MHz, CDCl3) 14.1,
22.7, 26.1, 26.2, 29.3, 29.4, 29.4, 29.6, 29.6, 31.9, 67.4, 67.7,
68.2, 101.9, 104.8, 108.0, 114.9, 127.7, 127.7, 130.1, 133.4,
133.6, 147.8, 158.2, 158.4, 160.3. m/z (ESI) 490 [M þ H]þ, 459,
319, 290, 262, 222. m/z (HRMS ESI) 490.3316. C32H44NO3þ
[M þ H]þ requires 490.3316. Anal. Calc. for C32H43NO3:
C 78.49, H 8.85, N 2.86. Found: C 78.33, H 8.79, N 2.78 %.
N00-{4-[(10-{[40-(Decyloxy)-1,10-biphenyl-4-yl]oxy}
decyl)oxy]phenyl}-N,N,N’,N’-tetramethyl
.
Guanidinium Chloride (p-3a Cl)
Method A: reaction time 3 days. Chromatography with 20 : 1
.
CH2Cl2/MeOH afforded p-3a Cl (270 mg, 91 %) as a colourless
solid. nmax/cmꢀ1 2935, 2917, 2849, 2360, 1631, 1607, 1562,
1516, 1500, 1474, 1397, 1327, 1274, 1247, 1177, 1166, 1111,
1068, 1034, 1011, 914, 825, 808, 728, 594, 565. dH (500 MHz,
CDCl3) 0.88 (t, J 7.0, 3H, CH3), 1.19–1.51 (m, 26H, 13 ꢁ CH2),
1.71–1.83 (m, 6H, 3 ꢁ OCH2CH2), 2.90 (m, 12H, N(CH3)2),
3.90–4.01 (m, 6H, 3 ꢁ OCH2), 6.83–6.88 (m, 2H, 3-H), 6.91–
6.96 (m, 4H, 30-H, 300-H), 7.06–7.11 (m, 2H, 2-H), 7.43–7.47 (m,
4H, 20-H, 200-H), 11.94 (s, 1H, NH). dC (126 MHz, CDCl3) 14.1,
22.7, 26.0, 26.1, 29.2, 29.3, 29.4, 29.5, 29.6, 31.9, 40.6, 68.1,
68.1, 68.3, 114.7, 115.5, 122.3, 127.6, 130.6, 133.3, 133.3,
156.8, 158.2, 158.2, 158.8. m/z (ESI) 673 [M]þ. m/z (HRMS
ESI) 672.5082. C43H66N3Oþ3 [M]þ requires 672.5099. Anal.
Calc. for C43H66ClN3O3: C 72.90, H 9.39, N 5.93. Found: C
69.73, H 9.09, N 5.30 %. DSC: Cr1 119 (15.6 kJ molꢀ1), Cr2 144
(19.0 kJ molꢀ1), SmA 167 (6.8 kJ molꢀ1), I.
3-[(10-{[40-(Decyloxy)-1,10-biphenyl-4-yl]oxy}decyl)
oxy]aniline (m-11a) Analogous to Lee et al.[62]
Aqueous HCl (37 %, 2.8 mL) was added to a suspension of
m-7a (567 mg, 921 mmol) in EtOH (30 mL), and the reaction
mixture heated for 2.5 days at 1008C. After cooling to room
temperature, an aqueous solution of NaHCO3 (20 mL) was
carefully added (gas formation!) until a pH of 8–9. The suspen-
sion was filtered off, the solid washed with H2O (20 mL) and
dried under vacuum to afford m-11a (496 mg, 94 %) as a
colourless solid, mp 1388C. nmax/cmꢀ1 3069, 3041, 2957,
2936, 2919, 2875, 2850, 1625, 1602, 1567, 1500, 1474, 1461,
1394, 1330, 1315, 1292, 1273, 1248, 1196, 1177, 1159, 1138,
1122, 1082, 1047, 1032, 1010, 994, 980, 950, 913, 890, 824, 808,
798, 777, 759, 718, 689, 645, 594, 520. dH (500 MHz, DMSO)
0.85 (t, J 6.8, 3H, CH3), 1.21–1.48 (m, 26H, 13 ꢁ CH2), 1.63–
1.78 (m, 6H, 3 ꢁ OCH2CH2), 3.86 (t, J 6.4, 2H, C3-OCH2), 3.99
(t, J 6.4, 4H, 2 ꢁ biphenyl-OCH2), 4.59 (br s, 2H, NH2), 6.06–
6.21 (m, 3H, 2-H, 4-H, 6-H), 6.83–6.89 (m, 1H, 5-H), 6.91–7.00
N00-[4-({10-[(40-Cyano-1,10-biphenyl-4-yl)oxy]decyl}
oxy)phenyl]-N,N,N’,N’-tetramethyl Guanidinium
.
Chloride (p-3b Cl)
Method B: reaction time 2 days. Chromatography with 10 : 1
.
CH2Cl2/MeOH afforded p-3b Cl (185 mg, 70 %) as a colourless
solid, mp 1858C. nmax/cmꢀ1 3038, 3005, 2942, 2920, 2850,
2803, 2771, 2222, 1620, 1596, 1564, 1510, 1493, 1471, 1453,
1426, 1414, 1399, 1323, 1290, 1267, 1239, 1228, 1204, 1178,
1170, 1153, 1113, 1067, 1040, 1012, 982, 959, 911, 855, 825,
799, 746, 721, 687, 661, 635, 608, 565, 551. dH (300 MHz,

1096
J. C. Haenle et al.
CDCl3) 1.27–1.53 (m, 12H, 6 ꢁ CH2), 1.70–1.88 (m, 4H, 2 ꢁ
OCH2CH2), 2.86 (s, 12H, N(CH3)2), 3.85–4.05 (m, 4H, 2 ꢁ
OCH2), 6.86 (m, 2H, 3-H), 6.96–7.02 (m, 2H, 30-H), 7.06–7.15
(m, 2H, 2-H), 7.49–7.56 (m, 2H, 20-H), 7.62–7.72 (m, 4H, 200-H,
300-H), 11.94 (s, 1H, NH). dC (75 MHz, CDCl3) 26.0, 29.2, 29.4,
29.5, 40.6, 68.2, 68.3, 110.0, 115.1, 115.5, 119.1, 122.3, 127.1,
128.3, 130.6, 131.2, 132.6, 145.3, 156.8, 158.8, 159.8. m/z (ESI)
541 [M]þ. m/z (HRMS ESI) 541.3530. C34H45N4Oþ2 [M]þ
requires 541.3537. Anal. Calc. for C34H45ClN4O2: C 70.75, H
7.86, N 9.71. Found: C 70.08, H 7.86, N 9.66 %. DSC: Cr 135
(37.1 kJ molꢀ1) I.
a colourless solid. nmax/cmꢀ1 2934, 2918, 2851, 1629, 1606,
1563, 1499, 1417, 1431, 1399, 1327, 1314, 1272, 1247, 1226,
1177, 1159, 1066, 1036, 1014, 994, 905, 825, 807, 725, 649,
595, 564. dH (500 MHz, CDCl3) 0.88 (t, J 7.0, 3H, CH3),
1.23–1.53 (m, 22H, 11 ꢁ CH2), 1.73–1.84 (m, 6H, 3 ꢁ
OCH2CH2), 3.01 (s, 12H, N(CH3)2), 3.94–4.01 (m, 6H, 3 ꢁ
OCH2), 6.55–6.60 (m, 1H, 4-H), 6.66–6.70 (m, 1H, 6-H), 6.86–
6.90 (m, 1H, 2-H), 6.91–6.96 (m, 4H, 30-H, 300-H), 7.18–7.23
(m, 1H, 5-H), 7.43–7.48 (m, 4H, 20-H, 200-H), 12.12 (s, 1H,
NH). dC (126 MHz, CDCl3) 14.1, 22.7, 26.0, 26.1, 29.2, 29.3,
29.4, 29.6, 31.9, 40.7, 68.1, 68.1, 68.2, 107.2, 111.7, 112.2,
114.7, 127.7, 130.2, 133.3, 139.0, 158.2, 158.8, 160.3. m/z
(ESI) 644 [M]þ. m/z (HRMS ESI) 644.4779. C41H62N3O3þ
[M]þ requires 644.4786. Anal. Calc. for C41H62ClN3O3: C
72.38, H 9.18, N 6.18. Found: C 71.55, H 8.81, N 5.98 %.
DSC: Cr [131 (39.6 kJ molꢀ1) SmA 136 (7.5 kJ molꢀ1)] 154
(60.7 kJ molꢀ1) I.
N00-{3-[(10-{[40-(Decyloxy)-1,10-biphenyl-4-yl]oxy}
decyl)oxy]phenyl}-N,N,N’,N’-tetramethyl
.
Guanidinium Chloride (m-3a Cl)
Method A: reaction time 3 days. Chromatography with 10 : 1
.
CH2Cl2/MeOH afforded m-3a Cl (440 mg, 97 %) as
a
colourless solid. nmax/cmꢀ1 2936, 2918, 2849, 1630, 1605,
1562, 1556, 1501, 1473, 1463, 1431 8, 1395, 1329, 1315,
1273, 1249, 1226, 1179, 1159, 1067, 1033, 1011, 995, 951,
906, 848, 824, 808, 917, 690, 641, 621, 594, 573. dH (500 MHz,
CDCl3) 0.88 (t, J 6.9, 3H, CH3), 1.22–1.51 (m, 26H, 13 ꢁ CH2),
1.72–1.84 (m, 6H, 3 ꢁ OCH2CH2), 3.01 (s, 12H, N(CH3)2),
3.93–4.01 (m, 6H, 3 ꢁ OCH2), 6.55–6.60 (m, 1H, 4-H), 6.66–
6.71 (m, 1H, 6-H), 6.85–6.89 (m, 1H, 2-H), 6.92–6.97 (m, 4H,
30-H, 300-H), 7.18–7.23 (m, 1H, 5-H), 7.43–7.49 (m, 4H, 20-H,
200-H), 12.07 (s, 1H, NH). dC (126 MHz, CDCl3) 14.1, 22.7, 26.0,
26.1, 29.2, 29.3, 29.4, 29.5, 29.6, 31.9, 40.7, 68.1, 68.2, 107.2,
111.7, 112.2, 114.7, 127.6, 130.2, 133.3, 139.0, 158.2, 158.7,
160.3. m/z (ESI) 673 [M]þ. m/z (HRMS ESI) 672.5078.
C43H66N3Oþ3 [M]þ requires 672.5099. Anal. Calc. for
C43H66ClN3O3: C 72.90, H 9.39, N 5.93. Found: C 69.54, H
9.29, N 5.23 %. DSC: Cr1 112 (14.7kJ molꢀ1), Cr2 125 (5.7 kJ
molꢀ1), Cr3 133 (8.6 kJ molꢀ1), SmA 149 (13.5 kJmolꢀ1), I.
N00-{3-[(6-{[40-(Decyloxy)-1,10-biphenyl-4-yl]oxy}
hexyl)oxy]phenyl}-N,N,N’,N’-tetramethyl
.
Guanidinium Chloride (m-3d Cl)
Method A: reaction time 5 h. Chromatography with 20 : 1
.
CH2Cl2/MeOH afforded m-3d Cl (139 mg, 79 %) as a colour-
less solid. nmax/cmꢀ1 2924, 2853, 1624, 1606, 1563, 1498,
1470, 1431, 1400, 1314, 1289, 1269, 1241, 1174, 1158, 1065,
1036, 1013, 905, 824, 806, 723, 687, 641, 595, 519.
d
H (500 MHz, CDCl3) 0.88 (t, J 6.9, 3H, CH3), 1.23–1.58 (m,
18H, 9 ꢁ CH2), 1.76–1.87 (m, 6H, 3 ꢁ OCH2CH2), 3.01 (s,
12H, N(CH3)2), 3.94–4.02 (m, 6H, 3 ꢁ OCH2), 6.55–6.60 (m,
1H, 4-H), 6.67–6.71 (m, 1H, 6-H), 6.87–6.91 (m, 1H, 2-H),
6.92–6.96 (m, 4H, 30-H, 300-H), 7.19–7.23 (m, 1H, 5-H), 7.43–
7.48 (m, 4H, 20-H, 200-H), 12.11 (s, 1H, NH). dC (126 MHz,
CDCl3) 14.1, 22.7, 25.9, 26.1, 29.1, 29.2, 29.3, 29.4, 29.6, 31.9,
40.7, 67.9, 68.1, 68.1, 107.2, 111.7, 112.2, 114.8, 127.7, 127.7,
130.2, 133.3, 133.4, 139.0, 158.2, 158.2, 158.7, 160.3. m/z
(ESI) 616 [M]þ. m/z (HRMS ESI) 616.4459. C39H58N3O3þ
[M]þ requires 616.4473. Anal. Calc. for C39H58ClN3O3: C
71.81, H 8.96, N 6.44. Found: C 72.19, H 9.10, N 5.97 %.
DSC: Cr [129 (52.7 kJ molꢀ1) SmA 141 (3.4 kJ molꢀ1)] 150
(58.3 kJ molꢀ1) I.
N00-[3-({10-[(40-Cyano-1,10-biphenyl-4-yl)oxy]decyl}
oxy)phenyl]-N,N,N’,N’-tetramethyl Guanidinium
.
Chloride (m-3b Cl)
Method B: reaction time 38 h. Chromatography with 10 : 1
.
CH2Cl2/MeOH afforded m-3b Cl (225 mg, 85 %) as a colourless
solid. nmax/cmꢀ1 3193, 3054, 3032, 2941, 2923, 2852, 2778,
2220, 1630, 1597, 1560, 1521, 1492, 1471, 1449, 1425, 1414,
1396, 1330, 1313, 1296, 1266, 1249, 1228, 1178, 1116, 1085,
1067, 1047, 1025, 1013, 998, 950, 904, 870, 854, 824, 780, 756,
723, 691, 660, 630, 606, 590, 565. dH (500 MHz, CDCl3) 1.28–
1.52 (m, 12H, 6 ꢁ CH2), 1.72–1.85 (m, 4H, 2 ꢁ OCH2CH2),
3.02 (s, 12H, N(CH3)2), 3.94–4.03 (m, 4H, 2 ꢁ OCH2), 6.51–
6.56 (m, 1H, 4-H), 6.66–6.70 (m, 1H, 6-H), 6.89–6.95 (m, 1H,
2-H), 6.98–7.03 (m, 2H, 30-H), 7.18–7.23 (m, 1H, 5-H), 7.50–
7.54 (m, 2H, 20-H), 7.62–7.66 (m, 2H, 200-H), 7.66–7.71 (m, 2H,
300-H), 12.04 (s, 1H, NH). dC (126 MHz, CDCl3) 26.0, 29.2, 29.3,
29.4, 29.5, 40.7, 68.2, 68.2, 107.2, 110.0, 111.7, 112.1, 115.1,
119.2, 127.1, 128.3, 130.2, 131.2, 132.6, 139.1, 145.3, 158.7,
159.8, 160.4. m/z (ESI) 541 [M]þ. m/z (HRMS ESI) 541.3534.
C34H45N4Oþ2 [M]þ requires 541.3537. Anal. Calc. for
C34H45ClN4O2: C 70.75, H 7.86, N 9.71. Found: C 70.70, H
7.86, N 9.76 %. DSC: Cr 149 (47.0 kJ molꢀ1) I.
N00-{3-[(4-{[40-(Decyloxy)-1,10-biphenyl-4-yl]oxy}butyl)
oxy]phenyl}-N,N,N’,N’-tetramethyl Guanidinium
.
Chloride (m-3e Cl)
Method A: reaction time 22 h. Chromatography with 200 : 15
.
CH2Cl2/MeOH afforded m-3e Cl (113 mg, 80 %) as a colourless
solid, mp 1508C. nmax/cmꢀ1 2956, 2934, 2919, 2850, 1629,
1605, 1563, 1499, 1470, 1431, 1400, 1315, 1272, 1246, 1226,
1177, 1159, 1067, 1050, 1035, 1014, 907, 826, 806, 729, 688,
646, 593. dH (300 MHz, CDCl3) 0.88 (t, J 6.6, 3H, CH3), 1.20–
1.51 (m, 14H, 7 ꢁ CH2), 1.73–2.04 (m, 6H, 3 ꢁ OCH2CH2),
3.02 (s, 12H, N(CH3)2), 3.95–4.12 (m, 6H, 3 ꢁ OCH2), 6.55–
6.63 (m, 1H, 4-H), 6.67–6.73 (m, 1H, 6-H), 6.88–6.91 (m, 1H,
2-H), 6.91–6.98 (m, 4H, 30-H, 300-H), 7.17–7.25 (m, 1H, 5-H),
7.42–7.50 (m, 4H, 20-H, 200-H), 12.13 (s, 1H, NH). dC (126 MHz,
CDCl3) 14.1, 22.7, 25.9, 26.1, 29.3, 29.4, 29.6, 31.9, 40.7, 67.5,
67.8, 68.1, 107.2, 111.7, 112.3, 114.8, 127.6, 127.7, 130.3,
133.3, 133.5, 139.1, 158.1, 158.3, 158.7, 160.2. m/z (ESI) 588
[M]þ. m/z (HRMS ESI) 588.4152. C37H54N3Oþ3 [M]þ requires
588.4160. Anal. Calc. for C37H54ClN3O3: C 71.18, H 8.72,
N 6.73. Found: C 71.17, H 8.59, N 6.59 %. DSC: Cr 184
(63.2 kJ molꢀ1) I.
N00-{3-[(8-{[40-(Decyloxy)-1,10-biphenyl-4-yl]oxy}octyl)
oxy]phenyl}-N,N,N’,N’-tetramethyl Guanidinium
.
Chloride (m-3c Cl)
Method A: reaction time 1.5 h. Chromatography with
.
400 : 15 CH2Cl2/MeOH afforded m-3c Cl (211 mg, 98 %) as

Alkoxybiphenyl-Guanidinium ILCs
1097
General Procedure for the Salt Metathesis Analogous
to Butschies et al.[39]
2-H), 6.68–6.72 (m, 1H, 6-H), 6.91–6.96 (m, 4H, 30-H, 300-H),
7.19–7.24 (m, 1H, 5-H), 7.43–7.48 (m, 4H, 20-H, 200-H), 9.33
(s, 1H, NH). dC (126 MHz, CDCl3) 14.1, 22.7, 26.0, 26.1,
29.2, 29.3, 29.4, 29.5, 29.6, 31.9, 40.4, 68.1, 68.1, 68.3, 106.7,
111.9, 111.9, 114.7, 120.6, 127.6, 130.6, 133.3, 133.3, 138.5,
158.2, 158.2, 158.7, 160.5. m/z (ESI) C43H66N3Oþ3 673 [M]þ.
m/z (HRMS ESI) 672.5079. C43H66N3Oþ3 [M]þ requires
672.5099. m/z (ESI) CF3O3Sꢀ 149 [M]ꢀ. m/z (HRMS ESI)
148.9519. CF3O3Sꢀ [M]ꢀ requires 148.9526. Anal. Calc. for
C44H66F3N3O6S: C 64.29, H 8.09, N 5.11. Found: C 64.63,
H 8.12, N 4.87 %. DSC: Cr1 105 (16.5 kJ molꢀ1), Cr2 117
(28.5 kJ molꢀ1), I.
.
Chloride m-3a Cl (30 mmol) was suspended with the respective
salt (44 mmol) in MeCN (5 mL) and the reaction mixture heated
for 10 min at reflux. The solvent was removed under reduced
pressure, the residue taken up in CH2Cl2 and filtered. The filtrate
was concentrated under reduced pressure and the product dried
under vacuum.
N00-{3-[(10-{[40-(Decyloxy)-1,10-biphenyl-4-yl]oxy}
decyl)oxy]phenyl}-N,N,N’,N’-tetramethyl
.
Guanidinium Bromide (m-3a Br)
Yield 22 mg (quant.) of a colourless solid. nmax/cmꢀ1 2960,
2919, 2851, 1625, 1606, 1563, 1499, 1470, 1431, 1399, 1314,
1272, 1248, 1227, 1177, 1159, 1066, 1034, 1011, 995, 905, 846,
824, 807, 730, 688, 648, 595, 556. dH (500 MHz, CDCl3) 0.88
(t, J 7.0, 3H, CH3), 1.23–1.50 (m, 26H, 13 ꢁ CH2), 1.72–1.83
(m, 6H, 3 ꢁ OCH2CH2), 3.02 (s, 12H, N(CH3)2), 3.94–4.00
(m, 6H, 3 ꢁ OCH2), 6.54–6.61 (m, 1H, 4-H), 6.67–6.71
(m, 1H, 6-H), 6.84–6.88 (m, 1H, 2-H), 6.92–6.97 (m, 4H, 30-H,
300-H), 7.18–7.23 (m, 1H, 5-H), 7.42–7.49 (m, 4H, 20-H, 200-H),
11.96 (s, 1H, NH). dC (126 MHz, CDCl3) 14.1, 22.7, 26.0, 26.1,
29.2, 29.3, 29.4, 29.5, 29.6, 31.9, 40.7, 68.1, 68.3, 107.2, 111.7,
112.2, 114.7, 127.6, 130.2, 133.3, 139.0, 158.2, 158.7, 160.3.
m/z (ESI) 673 [M]þ. m/z (HRMS ESI) 672.5090. C43H66N3O3þ
[M]þ requires 672.5099. Anal. Calc. for C43H66BrN3O3: C
68.60, H 8.84, N 5.58. Found: C 69.48, H 9.34, N 4.94 %.
DSC: Cr1 111 (17.9 kJ molꢀ1), Cr2 123 (6.2 kJ molꢀ1), SmA
128 (8.4kJ molꢀ1), I.
N00-{3-[(10-{[40-(Decyloxy)-1,10-biphenyl-4-yl]oxy}
decyl)oxy]phenyl}-N,N,N’,N’-tetramethyl
.
Guanidinium Tetrafluoroborate (m-3a BF4)
Yield: 23 g (96 %) of a colourless solid. nmax/cmꢀ1 2934,
2918, 2851, 2252, 1630, 1607, 1536, 1500, 1473, 1434, 1399,
1273, 1249, 1228, 1177, 1161, 1068, 1034, 1011, 995, 904, 824,
808, 725, 689, 649, 594, 549. dH (500 MHz, CDCl3) 0.88 (t, J
6.9, 3H, CH3), 1.21–1.49 (m, 26H, 13 ꢁ CH2), 1.72–1.83
(m, 6H, 3 ꢁ OCH2CH2), 2.98 (s, 12H, N(CH3)2), 3.92–4.01
(m, 6H, 3 ꢁ OCH2), 6.46–6.51 (m, 1H, 4-H), 6.59–6.63 (m,
1H, 2-H), 6.68–6.73 (m, 1H, 6-H), 6.90–6.96 (m, 4H, 30-H,
300-H), 7.20–7.25 (m, 1H, 5-H), 7.42–7.48 (m, 4H, 20-H, 200-H),
8.41 (s, 1H, NH). dC (126 MHz, CDCl3) 14.1, 22.7, 26.0, 26.1,
29.2, 29.3, 29.4, 29.5, 29.6, 31.9, 40.3, 68.1, 68.1, 68.3, 106.9,
111.9, 112.0, 114.7, 127.6, 130.6, 133.3, 133.3, 138.3, 158.2,
158.7, 160.6. m/z (ESI) C43H66N3Oþ3 673 [Mþ]. m/z (HRMS
ESI) 672.5102. C43H66N3Oþ3 [Mþ] requires 672.5099. Anal.
Calc. for C43H66BF4N3O3: C 67.97, H 8.76, N 5.53. Found:
C 67.85, H 8.87, N 5.36 %. DSC: Cr1 115 (15.1 kJ molꢀ1),
Cr2 129 (15.2 kJ molꢀ1), SmA 135 (4.0 kJ molꢀ1), I.
N00-{3-[(10-{[40-(Decyloxy)-1,10-biphenyl-4-yl]oxy}
decyl)oxy]phenyl}-N,N,N’,N’-tetramethyl
.
Guanidinium Iodide (m-3a I)
Yield: 24 mg (quant.) of a colourless solid. nmax/cmꢀ1 2956,
2934, 2917, 2849, 1629, 1605, 1555, 1500, 1473, 1463, 1430,
1394, 1327, 1313, 1273, 1249, 1226, 1178, 1158, 1137, 1067,
1033, 1011, 995, 951, 920, 906, 846, 824, 808, 769, 723, 689,
643, 594, 566, 550. dH (500 MHz, CDCl3) 0.88 (t, J 6.9, 3H,
CH3), 1.23–1.50 (m, 26H, 13 ꢁ CH2), 1.72–1.82 (m, 6H, 3 ꢁ
OCH2CH2), 3.06 (s, 12H, N(CH3)2), 3.94–4.01 (m, 6H, 3 ꢁ
OCH2), 6.60–6.64 (m, 1H, 4-H), 6.69–6.73 (m, 1H, 6-H), 6.86–
6.89 (m, 1H, 2-H), 6.91–6.96 (m, 4H, 30-H, 300-H), 7.20–7.24 (m,
1H, 5-H), 7.43–7.48 (m, 4H, 20-H, 200-H), 10.01 (s, 1H, NH).
dC (126 MHz, CDCl3) 14.1, 22.7, 26.0, 26.1, 29.2, 29.3, 29.4,
29.5, 29.6, 31.9, 41.2, 68.1, 68.1, 68.4, 107.1, 112.0, 112.3,
114.7, 127.6, 130.4, 133.3, 133.3, 138.3, 158.2, 158.3, 160.4.
m/z (ESI) 673 [M]þ. m/z (HRMS ESI) 672.5115. C43H66N3O3þ
[M]þ requires 672.5099. Anal. Calc. for C43H66IN3O3: C 64.57,
H 8.32, N 5.25. Found: C 64.49, H 8.49, N 4.87 %. DSC: Cr1
115 (10.0 kJ molꢀ1), Cr2 124 (16.9 kJ molꢀ1), [SmA 127
(3.4 kJ molꢀ1)], I.
N00-{3-[(10-{[40-(Decyloxy)-1,10-biphenyl-4-yl]oxy}
decyl)oxy]phenyl}-N,N,N’,N’-tetramethyl
.
Guanidinium Hexafluorophosphate (m-3a PF6)
Yield: 23 mg (quant.) of a colourless solid, mp (DSC) 1238C.
max/cmꢀ1 2926, 2854, 1630, 1608, 1562, 1499, 1470, 1434,
n
1399, 1270, 1242, 1175, 1160, 1036, 904, 842, 822, 723, 687,
649, 594, 557. dH (500 MHz, CDCl3) 0.88 (t, J 6.9, 3H, CH3),
1.21–1.50 (m, 26H, 13 ꢁ CH2), 1.72–1.83 (m, 6H, 3 ꢁ
OCH2CH2), 2.96 (s, 12H, N(CH3)2), 3.94 (t, J 6.5, 2H, C3-
OCH2), 3.96–4.00 (m, 4H, 2 ꢁ biphenyl-OCH2), 6.47–6.50 (m,
1H, 4-H), 6.57–6.60 (m, 1H, 2-H), 6.70–6.74 (m, 1H, 6-H),
6.91–6.96 (m, 4H, 30-H, 300-H), 7.21–7.26 (m, 1H, 5-H), 7.42–
7.49 (m, 4H, 20-H, 200-H), 7.71 (s, 1H, NH). dC (126 MHz,
CDCl3) 14.1, 22.7, 26.0, 26.1, 29.1, 29.3, 29.4, 29.5, 29.6, 31.9,
40.2, 68.1, 68.1, 68.3, 106.9, 112.2, 112.2, 114.7, 127.6, 130.7,
133.3, 133.3, 138.0, 158.2, 158.2, 158.6, 160.6. m/z (ESI)
C43H66N3Oþ3 673 [Mþ]. m/z (HRMS ESI) 672.5097.
C43H66N3Oþ3 [M]þ requires 672.5099. m/z (ESI) F6Pꢀ 145
[A]ꢀ. m/z (HRMS ESI) 144.9644. F6Pꢀ [A]ꢀ requires
144.9639. Anal. Calc. for C43H66F6N3O3P: C 63.14, H 8.13,
N 5.14. Found: C 69.98, H 8.26, N 4.71 %. DSC: Cr1 111
(16.6 kJ molꢀ1), Cr2 127 (27.5 kJ molꢀ1), I.
N00-{3-[(10-{[40-(Decyloxy)-1,10-biphenyl-4-yl]oxy}
decyl)oxy]phenyl}-N,N,N’,N’-tetramethyl
.
Guanidinium Triflate (m-3a OTf)
Yield: 26 mg (96 %) of a colourless solid. nmax/cmꢀ1 2934,
2920, 2852, 2252, 1639, 1607, 1563, 1499, 1471, 1433, 1400,
1288, 1271, 1242, 1223, 1175, 1158, 1066, 1030, 995, 905, 845,
824, 807, 726, 689, 650, 636, 595, 573. dH (500 MHz, CDCl3)
0.88 (t, J 7.0, 3H, CH3), 1.22–1.50 (m, 26H, 13 ꢁ CH2), 1.72–
1.83 (m, 6H, 3 ꢁ OCH2CH2), 2.98 (s, 12H, N(CH3)2), 3.91–4.01
(m, 6H, 3 ꢁ OCH2), 6.46–6.49 (m, 1H, 4-H), 6.60–6.64 (m, 1H,
N00-{3-[(10-{[40-(Decyloxy)-1,10-biphenyl-4-yl]oxy}
decyl)oxy]phenyl}-N,N,N’,N’-tetramethyl
.
Guanidinium Acetate (m-3a OAc)
Yield: 26 mg (96 %) of a colourless solid, mp (DSC) 848C.
max/cmꢀ1 3068, 3041, 2957, 2935, 2918, 2850, 2790, 1672,
n

1098
J. C. Haenle et al.
1606, 1580, 1536, 1500, 1474, 1463, 1424, 1390, 1377, 1329,
1309, 1273, 1249, 1232, 1176, 1149, 1138, 1048, 1032, 1011,
994, 952, 916, 862, 842, 824, 808, 780, 729, 707, 689, 644, 595,
561, 549. dH (500 MHz, CDCl3) 0.88 (t, J 6.9, 3H, CH3),
1.21–1.50 (m, 26H, 13 ꢁ CH2), 1.72–1.84 (m, 6H, 3 ꢁ
OCH2CH2), 2.72 (s, 12H, N(CH3)2), 3.92 (t, J 6.6, 2H, C3-
OCH2), 3.96–4.02 (m, 4H, 2 ꢁ biphenyl-OCH2), 6.25–6.28
(m, 1H, 4-H), 6.31–6.35 (m, 1H, 2-H), 6.40–6.45 (m, 1H, 6-
H), 6.89–6.97 (m, 4H, 30-H, 300-H), 7.04–7.11 (m, 1H, 5-H),
7.42–7.49 (m, 4H, 20-H, 200-H). dC (126 MHz, CDCl3) 14.1, 22.7,
26.1, 29.3, 29.4, 29.5, 29.6, 31.9, 39.6, 67.8, 68.1, 68.1, 106.9,
107.8, 114.1, 114.7, 127.6, 129.2, 133.3, 152.5, 158.2, 159.9,
160.0. m/z (ESI) C43H66N3Oþ3 673 [M]þ. m/z (HRMS ESI)
672.5080. C43H66N3Oþ3 [M]þ requires 672.5099. Anal. Calc.
for C45H69N3O5: C 73.83, H 9.50, N 5.74. Found: C 74.71,
H 9.67, N 5.65 %. DSC: Cr 87 (91.4 kJ molꢀ1) I.
Powder X-Ray Diffraction
Measurements were performed on a Bruker AXS Nanostar C
˚
with a monochromatic CuKa1 beam (l 1.5405 A), which was
obtained by using a ceramic tube generator (1500 W) with cross-
coupled Go¨bel mirrors as the monochromator. Samples were
prepared using glass tubes (0.7 mm outside diameter) from
Hilgenberg GmbH.
Supplementary Material
Further synthetic procedures, concentration-dependent 1H
NMR spectra of m-3b Cl as well as spectroscopic ( H, 13C) and
1
.
MS data of all new compounds are available on the Journal’s
website.
Acknowledgements
Generous financial support by the Ministerium fu¨r Wissenschaft, Forschung
und Kunst des Landes Baden-Wu¨rttemberg, the Bundesministerium fu¨r
Bildung und Forschung(shared instrumentation grant # 01 RI 05177) and the
Fonds der Chemischen Industrie (Kekule´ fellowship for S.B.) is gratefully
acknowledged.
N00-{3-[(10-{[40-(Decyloxy)-1,10-biphenyl-4-yl]oxy}
decyl)oxy]phenyl}-N,N,N’,N’-tetramethyl
.
Guanidinium Thiocyanate (m-3a SCN)
Yield: 22 mg (quant.) of a colourless solid. nmax/cmꢀ1 2958,
2934, 2918, 2850, 2252, 2055, 1629, 1606, 1563, 1500, 1472,
1431, 1397, 1328, 1314, 1272, 1249, 1227, 1178, 1159, 1066,
1034, 1011, 995, 905, 846, 824, 808, 728, 689, 648, 595, 554. dH
(500 MHz, CDCl3) 0.88 (t, J 6.9, 3H, CH3), 1.19–1.51 (m, 26H,
13 ꢁ CH2), 1.73–1.84 (m, 6H, 3 ꢁ OCH2CH2), 3.01 (s, 12H,
N(CH3)2), 3.93–4.01 (m, 6H, 3 ꢁ OCH2), 6.48–6.52 (m, 1H,
4-H), 6.62–6.65 (m, 1H, 2-H), 6.68–6.72 (m, 1H, 6-H), 6.91–
6.96 (m, 4H, 30-H, 300-H), 7.20–7.25 (m, 1H, 5-H), 7.42–7.47 (m,
4H, 20-H, 200-H), 10.66 (s, 1H, NH). dC (126 MHz, CDCl3) 14.1,
22.7, 26.0, 26.1, 29.2, 29.3, 29.4, 29.5, 29.6, 31.9, 40.6, 68.1,
68.1, 68.4, 107.1, 111.7, 112.3, 114.7, 127.6, 130.5, 133.3, 138.7,
158.2, 158.6, 160.5. m/z (ESI) C43H66N3Oþ3 673 [M]þ. m/z
(HRMS ESI) 672.5094. C43H66N3Oþ3 [M]þ requires 672.5099.
Anal. Calc. for C44H66N4O3S: C 72.29, H 9.10, N 7.66. Found:
C 71.74, H 9.29, N 6.95 %. DSC: Cr1 113 (83.7 kJ molꢀ1), Cr2
125 (28.7 kJ molꢀ1), [SmA 127 (4.4kJ molꢀ1)], I.
References
[1] T. Ishikawa, Chem. Pharm. Bull. (Tokyo) 2010, 58, 1555. doi:10.1248/
CPB.58.1555
[2] M. P. Coles, Chem. Commun. 2009, 3659. doi:10.1039/B901940E
[3] S. Herres-Pawlis, Nachr. Chem. 2009, 57, 20. doi:10.1002/
NADC.200960857
[4] T. Ishikawa, T. Kumamoto, Synthesis 2006, 737. doi:10.1055/
S-2006-926325
[5] A. R. Katritzky, B. V. Rogovoy, ARKIVOC 2005, 2005, 49.
doi:10.3998/ARK.5550190.0006.406
[6] J. Sundermeyer, V. Raab, E. Gaoutchenova, U. Garrelts, N. Abacilar,
K. Harms, in Activating Unreactive Substrates (Eds C. Bolm,
F. E. Hahn) 2009, pp. 17–37 (Wiley-VCH Verlag GmbH: Weinheim).
[7] K. Vazdar, R. Kunetskiy, J. Saame, K. Kaupmees, I. Leito, U. Jahn,
Angew. Chem. 2014, 126, 1459. doi:10.1002/ANGE.201307212
[8] O. Bienemann, A. Hoffmann, S. Herres-Pawlis, Rev. Inorg. Chem.
2011, 31, 83. doi:10.1515/REVIC.2011.003
[9] F. T. Edelmann, in Advances in Organometallic Chemistry (Eds
A. F. Hill, M. J. Fink) 2008, pp. 183–352 (Academic Press: London).
[10] M. P. Coles, Dalton Trans. 2006, 985. doi:10.1039/B515490A
[11] A. Peters, E. Kaifer, H.-J. Himmel, Eur. J. Org. Chem. 2008, 5907.
doi:10.1002/EJOC.200800900
[12] P. Selig, Synthesis 2013, 45, 703. doi:10.1055/S-0032-1318154
[13] K. Nagasawa, Y. Sohtome, in Science of Synthesis, Asymmetric
Organocatalysis (Eds B. List, K. Maruoka) 2012, pp. 1–40 (Thieme
Medical Publishers: New York, NY).
Analysis
NMR Spectroscopy
NMR spectra were recorded on a Bruker Avance 300 or
1
Avance 500 spectrometer operating at 300 or 500 MHz for H
and 75 or 126 MHz for 13C using tetramethylsilane (TMS) as a
reference. The chemical shift (d) was measured in ppm down-
field from TMS.
[14] J. E. Taylor, S. D. Bull, J. M. J. Williams, Chem. Soc. Rev. 2012, 41,
2109. doi:10.1039/C2CS15288F
[15] M. Odagi, K. Furukori, T. Watanabe, K. Nagasawa, Chem. – Eur. J.
FT-IR Spectroscopy
IR spectra were recorded on a Bruker Vekor 22 apparatus
with MKII Golden Gate Single Reflection Diamant ATR.
2013, 19, 16740. doi:10.1002/CHEM.201303006
[16] D. Basavaiah, K. Venkateswara Rao, B. Sekhara Reddy, Tetrahedron
Asymmetry 2006, 17, 1036. doi:10.1016/J.TETASY.2006.03.020
[17] J. Y. Quek, T. P. Davis, A. B. Lowe, Chem. Soc. Rev. 2013, 42, 7326.
doi:10.1039/C3CS60065C
[18] C. C. Huval, S. R. Holmes-Farley, W. H. Mandeville, J. S. Petersen,
R. J. Sacchiero, C. Maloney, P. K. Dhal, J. Macromol. Sci. A 2004, 41,
231. doi:10.1081/MA-120028203
Mass Spectrometry
Mass spectra and high-resolution mass spectra were recorded
on a Bruker micrOTOF-Q with electrospray ionisation or a
Varian MAT711 spectrometer with EI ionisation.
Differential Scanning Calorimetry
[19] D. S. Kim, A. Labouriau, M. D. Guiver, Y. S. Kim, Chem. Mater. 2011,
DSC curves were recorded on a Mettler Toledo DSC822e
with a heating/cooling rate of 5 K minꢀ1 using the Software
STAR to determine phase transition temperatures.
23, 3795. doi:10.1021/CM2016164
[20] M. K. Rauf, Imtiaz-ud-Din, A. Badshah, Expert Opin. Drug Dis. 2014,
9, 39. doi:10.1517/17460441.2013.857308
[21] A. Mishra, S. Batra, Curr. Top. Med. Chem. 2013, 13, 2011.
doi:10.2174/15680266113139990126
Polarizing Optical Microscopy
Textures were obtained using an Olympus BX 50 polarizing
microscope with a Linkam LTS 350 hot stage.
[22] F. Sa˛czewski, Ł. Balewski, Expert Opin. Ther. Pat. 2013, 23, 965.
doi:10.1517/13543776.2013.788645

Alkoxybiphenyl-Guanidinium ILCs
1099
[23] R. G. S. Berlinck, A. E. Trindade-Silva, M. F. C. Santos, Nat. Prod.
Rep. 2012, 29, 1382. doi:10.1039/C2NP20071F
[47] Ionic Liquids in Synthesis, 2nd edn (Eds P. Wasserscheid, T. Welton)
2008 (Wiley-VCH: Weinheim).
[24] S. S. Ebada, P. Proksch, Mini Rev. Med. Chem. 2011, 11, 225.
doi:10.2174/138955711795049862
[48] Electrodeposition from Ionic Liquids (Eds F. Endres, D. MacFarlane,
A. Abbott) 2008 (Wiley-VCH: Weinheim).
[25] R. G. S. Berlinck, A. C. B. Burtoloso, A. E. Trindade-Silva,
S. Romminger, R. P. Morais, K. Bandeira, C. M. Mizuno, Nat. Prod.
Rep. 2010, 27, 1871. doi:10.1039/C0NP00016G
[26] F. Saczewski, Ł. Balewski, Expert Opin. Ther. Pat. 2009, 19, 1417.
doi:10.1517/13543770903216675
[27] R. G. S. Berlinck, A. C. B. Burtoloso, M. H. Kossuga, Nat. Prod. Rep.
[49] Ionic Liquids IIIA: Fundamentals, Progress, Challenges, and Oppor-
tunities (Eds R. D. Rogers, K. R. Seddon) 2005, Vol. 901, ACS
Symposium Series (American Chemical Society: Washington DC).
[50] Ionic Liquids IIIB: Fundamentals, Progress, Challenges, and Oppor-
tunities (Eds R. D. Rogers, K. R. Seddon) 2005, Vol. 902, ACS
Symposium Series (American Chemical Society: Washington DC).
[51] Handbook of Liquid Crystals (Eds J. W. Goodby, P. J. Collings,
T. Kato, C. Tschierske, H. F. Gleeson, P. Raynes) 2014, Vols 1–8
(Wiley-VCH: Weinheim).
2008, 25, 919. doi:10.1039/B507874C
[28] R. G. S. Berlinck, M. H. Kossuga, Nat. Prod. Rep. 2005, 22, 516.
doi:10.1039/B209227C
[29] S. Su, I. B. Seiple, I. S. Young, P. S. Baran, J. Am. Chem. Soc. 2008,
[52] C. Tschierske, Angew. Chem. Int. Ed. 2013, 52, 8828. doi:10.1002/
ANIE.201300872
130, 16490. doi:10.1021/JA8074852
[30] F. Mathevet, P. Masson, J.-F. Nicoud, A. Skoulios, J. Am. Chem. Soc.
2005, 127, 9053. doi:10.1021/JA051312A
[53] C. Tschierske, Isr. J. Chem. 2012, 52, 935. doi:10.1002/
IJCH.201200053
[31] D. Kim, S. Jon, H.-K. Lee, K. Baek, N.-K. Oh, W.-C. Zin, K. Kim,
Chem. Commun. 2005, 5509. doi:10.1039/B511517E
[32] S. M. Martin, J. Yonezawa, M. J. Horner, C. W. Macosko, M. D. Ward,
Chem. Mater. 2004, 16, 3045. doi:10.1021/CM049594L
[33] F. Mathevet, P. Masson, J.-F. Nicoud, A. Skoulios, Chem. – Eur. J.
2002, 8, 2248. doi:10.1002/1521-3765(20020517)8:10,2248::AID-
CHEM2248.3.0.CO;2-B
[34] L. M. Antill, M. M. Neidhardt, J. Kirres, S. Beardsworth, M. Mansueto,
A. Baro, S. Laschat, Liq. Cryst. 2014, 41, 976. doi:10.1080/02678292.
2014.896052
[35] M. Butschies, M. Mansueto, J. C. Haenle, C. Schneck,
S. Tussetschla¨ger, F. Giesselmann, S. Laschat, Liq. Cryst. 2014, 41,
821. doi:10.1080/02678292.2014.885600
[36] M. Butschies, M. M. Neidhardt, M. Mansueto, S. Laschat,
S. Tussetschla¨ger, Beilstein J. Org. Chem. 2013, 9, 1093. doi:10.3762/
BJOC.9.121
[54] G. Ungar, X. Zeng, Soft Matter 2005, 1, 95. doi:10.1039/B502443A
[55] K. Goossens, P. Nockemann, K. Driesen, B. Goderis, C. Go¨rller-
Walrand, K. Van Hecke, L. Van Meervelt, E. Pouzet, K. Binnemans,
T. Cardinaels, Chem. Mater. 2008, 20, 157. doi:10.1021/CM702321C
[56] S. K. Pal, S. Kumar, Tetrahedron Lett. 2006, 47, 8993. doi:10.1016/
J.TETLET.2006.09.167
[57] S. Kumar, S. K. Gupta, Tetrahedron Lett. 2010, 51, 5459. doi:10.1016/
J.TETLET.2010.08.022
[58] J. Motoyanagi, T. Fukushima, T. Aida, Chem. Commun. 2005, 101.
doi:10.1039/B414649B
[59] H. Yoshizawa, T. Mihara, N. Koide, Mol. Cryst. Liq. Cryst. 2004, 423,
61. doi:10.1080/15421400490502481
[60] L. Cui, V. Sapagovas, G. Lattermann, Liq. Cryst. 2002, 29, 1121.
doi:10.1080/02678290210155589
[61] W. Davids, J. J. Roberts, W. C. J. Ross, J. Chem. Soc. 1955, 890.
doi:10.1039/JR9550000890
[37] M. Butschies, J. C. Haenle, S. Tussetschla¨ger, S. Laschat, Liq. Cryst.
[62] S. K. Lee, Y. Naito, L. Shi, M. Tokita, H. Takezoe, J. Watanabe, Liq.
Cryst. 2007, 34, 935. doi:10.1080/02678290701541538
[63] W. Kantlehner, E. Haug, W. W. Mergen, P. Speh, T. Maier,
J. J. Kapassakalidis, H.-J. Bra¨uner, H. Hagen, Liebigs Ann. Chem.
1984, 108. doi:10.1002/JLAC.198419840112
2013, 40, 52. doi:10.1080/02678292.2012.732617
[38] M. Butschies, W. Frey, S. Laschat, Chem. – Eur. J. 2012, 18, 3014.
doi:10.1002/CHEM.201101925
[39] M. Butschies, S. Sauer, E. Kessler, H.-U. Siehl, B. Claasen, P. Fischer,
W. Frey, S. Laschat, ChemPhysChem 2010, 11, 3752. doi:10.1002/
CPHC.201000444
[64] J. N. Sarmousakis, M. J. D. Low, J. Phys. Chem. 1956, 60, 1139.
doi:10.1021/J150542A028
[40] S. Sauer, S. Saliba, S. Tussetschla¨ger, A. Baro, W. Frey,
F. Giesselmann, S. Laschat, W. Kantlehner, Liq. Cryst. 2009, 36, 275.
doi:10.1080/02678290902850027
[41] S. Sauer, N. Steinke, A. Baro, S. Laschat, F. Giesselmann,
W. Kantlehner, Chem. Mater. 2008, 20, 1909. doi:10.1021/
CM702967C
[42] T. Kato, M. Yoshio, in Electrochemical Aspects of Ionic Liquids
(Ed. H. Ohno) 2011, pp. 375–392 (Wiley: Hoboken, NJ).
[43] K. V. Axenov, S. Laschat, Materials 2011, 4, 206. doi:10.3390/
MA4010206
[65] Y. Marcus, J. Chem. Soc., Faraday Trans. 1993, 89, 713. doi:10.1039/
FT9938900713
[66] P. H. J. Kouwer, T. M. Swager, J. Am. Chem. Soc. 2007, 129, 14042.
doi:10.1021/JA075651A
[67] N. Yamanaka, R. Kawano, W. Kubo, N. Masaki, T. Kitamura,
Y. Wada, M. Watanabe, S. Yanagida, J. Phys. Chem. B 2007, 111,
4763. doi:10.1021/JP0671446
[68] X. Pan, M. Wang, X. Fang, C. Zhang, Z. Huo, S. Dai, Sci. China Chem.
2013, 56, 1463. doi:10.1007/S11426-013-4904-Y
[69] W. S. Chi, H. Jeon, S. J. Kim, D. J. Kim, J. H. Kim, Macromol. Res.
2013, 21, 315. doi:10.1007/S13233-013-1097-3
[44] T. Kato, N. Mizoshita, K. Kishimoto, Angew. Chem. Int. Ed. 2006, 45,
38. doi:10.1002/ANIE.200501384
[70] S. Balamurugan, P. Kannan, K. Yadupati, A. Roy, J. Mol. Struct. 2011,
1001, 118. doi:10.1016/J.MOLSTRUC.2011.06.027
[71] A. Das, B. Maity, D. Koley, S. Ghosh, Chem. Commun. 2013, 49, 5757.
doi:10.1039/C3CC42808G
[45] K. Binnemans, Chem. Rev. 2005, 105, 4148. doi:10.1021/CR0400919
[46] L. Douce, J.-M. Suisse, D. Guillon, A. Taubert, Liq. Cryst. 2011, 38,
1653. doi:10.1080/02678292.2011.610474