Polar groups and arylsulfonamides: A good combination with which to obtain supramolecular columnar liquid crystals

Article abstract of DOI:10.1002/ejoc.201300222

Mesomorphic arylsulfonamide derivatives containing four long alkyl chains and polar groups (fluoro, cyano or amino) have been synthesized and characterized by polarized optical microscopy, differential scanning calorimetry, and X-ray diffraction on the me

Full text of DOI:10.1002/ejoc.201300222

Job/Unit: O30222
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Date: 03-07-13 10:26:20
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FULL PAPER
Liquid Crystals
Polar groups play an important role in the
organization of arylsulfonamide derivatives
in mesophases. Hydrogen-bonding interac-
A. Zennaro, C. A. Hincapié, A. Martos,
R. M. Sebastián,* J. Barberá,
J. L. Serrano, T. Sierra* ................. 1–11
tions
between
amino
groups
or
dipole···dipole interactions between CF or
CN groups are responsible for the forces
that characterize the cohesion of molecules
in hexagonal columnar mesophases.
Polar Groups and Arylsulfonamides: A
Good Combination with which to Obtain
Supramolecular Columnar Liquid Crystals
Keywords: Liquid crystals
/ Hydrogen
bonds / Electrostatic interactions / Sulfon-
amides / Macrocycles
0000, 0–0
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Job/Unit: O30222
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Pages: 11
R. M. Sebastián, T. Sierra et al.
FULL PAPER
DOI: 10.1002/ejoc.201300222
Polar Groups and Arylsulfonamides: A Good Combination with which to
Obtain Supramolecular Columnar Liquid Crystals
Angela Zennaro,[a] Cesar Augusto Hincapié,[a] Alba Martos,[a] Rosa M. Sebastián,*[a]
Joaquín Barberá,[b] José Luis Serrano,[c] and Teresa Sierra*[b]
Keywords: Liquid crystals / Hydrogen bonds / Electrostatic interactions / Sulfonamides / Macrocycles
Mesomorphic arylsulfonamide derivatives containing four
long alkyl chains and polar groups (fluoro, cyano or amino)
organization of these molecules have allowed a better under-
standing of the noncovalent driving forces (dipole···dipole
have been synthesized and characterized by polarized op- and hydrogen-bonding interactions) responsible for the self-
tical microscopy, differential scanning calorimetry, and X-ray
diffraction on the mesophase. Studies of the supramolecular
assembly, which is mainly due to the presence of the polar
groups.
ence of a fluoro substituent in LC molecules has also been
studied, mainly because of its small size, high electronega-
tivity, and large C–F bond-dissociation energy. Intermo-
lecular dipole···dipole interactions between C–F bonds have
been employed to influence the mesomorphism of calamitic
mesogens,[14] or bent-core mesogens;[15] however, this effect
has rarely been studied for the generation of columnar me-
sophases.[16]
Introduction
Noncovalent intermolecular interactions are mainly re-
sponsible for the spontaneous self-assembly of simple mole-
cules in liquid crystalline materials. Hydrogen-bonding,
dipole···dipole, ionic, π-π stacking, and van der Waals
forces are the most commonly used interactions in the prep-
aration of these materials with organization-dependent
properties.[1–4]
We previously reported that several 15-membered tri-
olefinic azamacrocycles prepared from arylsulfonamides
containing long hydrocarbon or polyfluorinated chains and
their open chain precursors showed liquid crystalline prop-
erties.[11] The rigidity of backbones in macrocyclic mo-
lecules, together with the presence of long tails and the exis-
tence of terminal sulfonamides (NHSO2R) in open precur-
sors, favored the organization of molecules in mesophases.
The aim of the present work was to analyze how the pres-
ence of polar functional groups, such as fluoro, cyano, and
amino, could affect the organization of this type of mole-
cule and the generation of liquid crystalline behavior. Ac-
cordingly, we designed new macrocycles that contain a total
of four alkoxy tails linked to two of the aromatic rings (two
chains per ring), and a polar group such as a fluoro (6a and
7a), a cyano (6b and 7b), or amino (6c and 7c) in the para
position of the third aromatic ring. For comparative pur-
poses, this series was completed with the corresponding
compounds bearing a hydrogen atom instead of polar
groups (6d and 7d). The new macrocycles and their open
precursors were studied by polarized optical microscopy
(POM), differential scanning calorimetry (DSC), and X-ray
diffraction techniques. The presence of intermolecular in-
teractions (mainly hydrogen bonds or dipole···dipole inter-
actions) was considered in order to develop models for the
molecular organization in the mesophases.
Columnar liquid crystals (LC) are well-known examples
of supramolecular assemblies and have received consider-
able interest as functional materials for applications in or-
ganic electronics and optoelectronics.[5–7] Hydrogen-bond-
ing has been used to organize discotic molecules[8,9] or to
arrange complementary precursors to form discs that can
be self-assembled into columns.[10,11] Dipole···dipole inter-
actions between polar groups have also been used in the
latter approach.[12] For example, bent-core mesogens with
cyano groups can be used to achieve columnar organiza-
tions with a macroscopic dipole along the column,[13] which
may show ferroelectric switching.[13b,13c] Likewise, the influ-
[a] Department of Chemistry, Universitat Autònoma de Barcelona,
08193 Cerdanyola del Vallès (Barcelona), Spain
E-mail: rosamaria.sebastian@uab.es
Homepage: http://www.uab.es/
[b] Institute of Materials Science of Aragón, Dep. Química
Orgánica, Facultad de Ciencias, University of Zaragoza –
CSIC,
50009 Zaragoza, Spain
E-mail: tsierra@unizar.es
Homepage: http://www.icma.unizar-csic.es/WebICMA/
[c] Institute of Nanoscience of Aragón, Dep. Química Orgánica,
Facultad de Ciencias, University of Zaragoza,
50009 Zaragoza, Spain
Homepage: http://www. unizar.es
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201300222.
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Arylsulfonamides as Supramolecular Columnar Liquid Crystals
Macrocycles 7a, 7b, and 7d were obtained by cyclization
Results and Discussion
of compounds 6a, 6b, and 6d, respectively, with (E)-1,4-di-
bromo-2-butene, using potassium carbonate base in an-
hydrous acetonitrile (Scheme 2). The same reaction on 6c
was unsuccessful; in this case a complex reaction mixture
was obtained, probably due to competition in the reaction
between sulfonamido and amino groups. Another strategy
was therefore used for the synthesis of 7c[17] that involved
the introduction of sulfonamide 4c in the last step. This
procedure was used to obtain 7c in good yield from dibrom-
oderivative 9 (Scheme 3).
Synthesis
The Boc-protected derivative (2) of 3,4-bis(dodecyloxy)-
benzenesulfonamide (1) was used to prepare the alkylated
compound 3 as described previously (Scheme 1).[11a] The
combination in a basic medium of two molecules of 3 with
one molecule of four different arylsulfonamides, substituted
in the para position with fluoro, cyano and amino groups
(4a–c, respectively, Scheme 2) and the nonsubstituted deriv-
ative 4d allowed the preparation of trisulfonamides 5a–d,
which were subsequently deprotected in an acidic medium
(trifluoroacetic acid/CH2Cl2, 1:1) to give the corresponding
open precursors 6a–d in good to excellent yields (61–99%).
Mesomorphic Behavior
The thermal behavior of compounds 6a–d and 7a–d was
studied by POM and DSC; the results are gathered in
Table 1.
The open precursors 6a and 6b showed monotropic
mesomorphic behavior and displayed poorly defined tex-
tures by POM that are indicative of Colh mesophases. The
stability of the mesophase of 6a was very low and it was
seen too be under kinetic control upon cooling the isotropic
liquid at a rate of 20 °C/min (Figure 1, a). When cooling at
10 °C/min, the mesophase coexisted with the crystalline
phase (Table 1), and at 5 °C/min no mesomorphic behavior
but crystallization was observed (see the Supporting Infor-
mation). For 6b, the mesophase was only observed on cool-
ing from the isotropic liquid (Figure 1, b). In contrast, the
Scheme 1. Synthesis of macrocyclic precursors derived from aryl-
sulfonamide 1.
Scheme 2. Synthesis of open precursors 5 and 6 and macrocycles 7a, 7b, and 7d.
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R. M. Sebastián, T. Sierra et al.
FULL PAPER
Scheme 3. Synthesis of macrocycle 7c.
Table 1. Thermal and thermodynamic properties calculated during
the second heating-cooling cycle (DSC experiments recorded at
10 °C/min). Temperatures are given in °C. Enthalpies are given in
kJmol–1 and appear in parentheses.
Thermal and thermodynamic properties
6a[a] C 94.5 (83.0) I
[b]
I 67.2 (1.9) Cr + I 57.8 (2.0) Cr + Colh 37.6 (30.6) Cr
6b[a] Cr 98.0 (57.1) I
I 79.3 (2.4) Colh 49.2 (32.6) Cr
6c
6d
7a
7b
Cr 40.2 (28.7) Colh 92.6 (1.3) I
I 90.3 (1.2) Colh 31.2 (21.0) Cr
Cr 40.4 (31.8) Colh 45[c]
I
I 42.2 (1.5) Colh 31.0 (23.9) Cr
Cr 40.0[d] (7.6) Colh 60.4 (4.3) I
I 59.2 (5.0) Colh 34.0[d] (8.5) Cr
Cr 55.4[d] (8.2) Colh 83.2 (4.1) I
I 82.5 (5.3) Colh 49.2[c] (5.9) Cr
7c
7d
Cr 56[e]
I
Colh1 30.4 (5.9) Colh2 47.9 (2.0) I 53.3 (–34.8)[f] Cr 77.2
(34.2) I
I 45.7 (4.1) Colh2 35.8 (3.9) Colh1
[a] Monotropic behavior. [b] Crystal phase coexisted with isotropic
liquid or mesophase (see the Supporting Information). [c] Shoulder
of the peak corresponding to melting. [d] Temperatures taken at
the maximum of the broad peaks. [e] Temperature taken by POM.
[f] Cold crystallization.
amino derivative 6c showed an enantiotropic mesophase
over a broad temperature range. The focal-conic texture of
this mesophase, which appeared on cooling the isotropic
state (Figure 1, c), is consistent with a hexagonal columnar
organization.
For open precursors 6a–c it is envisaged that competition
between different types of noncovalent interactions leads to
the different thermal behavior. Thus, for fluoro and cyano
derivatives 6a and 6b, respectively, strong dipole···dipole in-
teractions must compete with the possibility of H-bonding
interactions between sulfonamide groups[11a] and with the
subtle forces responsible for mesomorphic arrangements,
and therefore crystal structures are produced rather than
stable fluid mesophases. This is not the case for compound
6c, which has a much lower melting temperature than 6a
and 6b. This compound has the possibility of forming inter-
molecular hydrogen bonds promoted by amino groups and
Figure 1. (a) Texture of the mesophase observed for 6a, at 55 °C,
at a cooling rate of 20 °C/min from the isotropic liquid (ϫ20).
(b) Texture of the Colh mesophase observed for 6b, at 73 °C (ϫ20).
(c) Focal conic texture observed for 6c, at 97 °C (ϫ20). (d) Texture
of the Colh mesophase observed for 6d, at 38 °C, on cooling (ϫ20).
these could account for the stability of the mesophase. In and later supported by X-ray diffraction, intermolecular H-
terms of explaining the formation of a stable mesophase, bonds between sulfonamide groups can be ruled out be-
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Arylsulfonamides as Supramolecular Columnar Liquid Crystals
cause the final supramolecular structure would require a
In comparison to the corresponding open precursors 6a
disposition of flexible tails that is not favorable for meso- and 6b, melting temperatures decrease significantly for
phase formation. Compound 6d showed undefined textures fluoro (7a) and cyano (7b) derivatives, respectively. It can be
through the POM, reminiscent of Colh mesomorphism. For deduced that dipole···dipole interactions must not be strong
the stability of this mesophase, it can be deduced that inter- enough to favor crystalline behavior as observed for 6a and
molecular interactions are less favored given the lower melt- 6b, and a stable mesomorphic state is observed. Further-
ing and clearing temperatures, compared to 6a–c. Even more, when compared with previously described azamacro-
though the mesophase is enantiotropic according to the cyclic structures that contain two long alkoxy tails in each
thermogram recorded at 10 °C/min (see the Supporting In- aromatic ring,[11a] it is significant that the latter showed
formation), the mesomorphic range is very short, especially shorter mesomorphic temperature ranges than 7a and 7b
compared with cyano and amino derivatives.
(45.3–46.7 °C and 20–30 °C, respectively), while main-
Macrocycles 7a and 7b showed stable mesophases with taining the same type of mesophase. This fact leads one to
hexagonal columnar organizations identified by their tex- consider dipole···dipole interactions as a crucial factor that
tures by POM (Figure 2, a and b). In contrast, compound favors mesomorphic properties in these molecules, and this
7c did not present mesomorphic behavior. Unsubstituted will affect the models proposed for the organization of mo-
compound 7d showed a rather complex thermal behavior lecules in the mesophase (see below). Furthermore, when
with metastable Colh mesomorphism, which undergoes cold compared with the unsubstituted macrocycle 7d, it can be
crystallization on heating. On cooling, the thermogram pre- deduced that the presence of polar groups clearly stabilizes
sented two peaks. The first, at 45.7 °C, is associated with the Colh mesomorphism, likely due to dipole···dipole inter-
the transition between the isotropic liquid and a Colh meso- actions. Once again, these results are in contrast to those
phase, which showed a poorly defined texture. A second found for the amino derivative 7c, which did not show
exothermic peak was visible at 30.4 °C, which should corre- mesomorphic behavior. The melting temperature of 7c is
spond to a thermal transition to a second mesophase that, similar to that of 7b, which means that the difference is not
however, did not show clear texture differences (Figure 2, a matter of stabilization of the crystalline state but that the
c).
mesomorphic behavior in this case is not favored on in-
creasing the rigidity of the constituent molecules by cycliza-
tion. The variable influence of dipole···dipole and H-bond-
ing interactions on mesomorphism is related to the presence
or absence of the macrocyclic ring and this confirms that
mesomorphism is the result of a subtle balance of intermo-
lecular forces.
X-ray Diffraction
X-ray diffraction studies were performed on the liquid
crystal phases of the five mesogenic compounds that
showed enantiotropic mesophases (compounds 6c, 6d, 7a,
7b, and 7d; Table 2). The monotropic character of mesoph-
ases of 6a and 6b precluded their characterization by X-ray
diffraction. They crystallized during the X-ray experiments
because their isotropic-mesophase transition temperature is
well below their melting point.
The X-ray patterns confirm that the mesophase of 6c is
unambiguously Colh. A sharp, strong maximum at 38.9 Å
and two reflections of medium intensity at 22.8 and 19.3 Å
in the small-angle region were observed. These results
correspond to a reciprocal spacing ratio 1:31/2:2, associated,
respectively, to the (10), (11), and (20) reflections of a two-
dimensional hexagonal liquid crystalline lattice, with a lat-
tice constant a of 45 Å (Table 2). This constant is larger
than the value obtained for the similar derivative containing
two long hydrocarbon chains in the aromatic ring instead
of the amino compound (35.6 Å),[11a] despite the smaller
size of the molecule. From the measured lattice constant,
the column cross section can be calculated as S = a2√3/2,
with a value of 1775 Å2 obtained for 6c. This value is too
high for stacking of single molecules and is consistent with
Figure 2. Photomicrographs of the textures observed by polarizing
optical microscopy on cooling from the isotropic state: (a) Com-
pound 7a Colh mesophase at 53.1 °C (ϫ20); (b) Compound 7b
Colh mesophase at 70.0 °C (ϫ20). (c) Texture of the Colh1 meso-
phase observed for 6d at 28 °C (left) and of the Colh2 at 38 °C
(right) (ϫ20).
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Table 2. Structural data for the mesophases measured by X-ray dif-
fraction.[a]
[b]
T [°C] Mesophase Parameters [Å]
dexp
dcal
Z[d]
6c
70
Colh
a = 45.0
38.9
22.8
19.3
39.0
22.5
19.5
3
4.5 diff
35.2
4.5 diff
33.3
4.7 diff
37.4
6d
7a
7b
7d
44
60
Colh
Colh
Colh
Colh1
Colh2
a = 40.6
a = 38.4
a = 43.2
a = 45.4
a = 41.2
35.2
33.3
37.4
39.3
35.7
2–3
2
70
3
4.7 diff
39.3
t.a.
3
4.4[c]
41
35.7
2–3
[a] The columns list, respectively, the compound number, the tem-
perature of the experiment, the mesophase type, the measured pa-
rameters (a: lattice constant in the columnar mesophase), the ex-
perimentally-measured spacing, the calculated spacing, and the es-
timated number of molecules per lattice. [b] diff signifies diffuse.
[c] Relatively narrow, strong halo. [d] See text.
the existence of aggregates in which hydrogen-bonding in-
teractions between amino groups in the center of the col-
umn and external van der Waals interactions between long
chains favor stack formation (Figure 3, a).
When macrocycles 7a and 7b were studied by X-ray dif-
fraction, only one small-angle maximum was observed and
this can be assigned to the (10) reflection of a hexagonal
columnar (Colh) mesophase. The deduced hexagonal lattice
constants a are 38.4 and 43.2 Å, respectively (Table 2). The
difference of around 5 Å shows that the organization of the
molecules in the mesophases should be drastically different;
replacement of a fluoro-substituent by a cyano group
should not produce such a change if only steric effects are
considered (volume change). Calculated cross sections are
1279 Å for 7a and 1616 Å for 7b. Once more, these values
are too large for stacking of single molecules. It can be pre-
dicted on the basis of density estimations that each disc of
the columns should be composed of several molecules, as
shown in Figure 3 (b and c). This kind of structure is in
reasonable agreement with other similar structures pro-
posed by us.[11] The aggregation phenomenon must be due
to the dipole···dipole interactions between C–F bonds and
CϵN groups, respectively.
The number (Z) of molecules per disc (column stratum)
can be estimated on the basis of the expected density for
typical organic compounds. The density ρ in gcm–3 of a
columnar mesophase can be calculated using the equation:
ρ = (M·Z·1024)/(V·NA)
where M is the molar mass in g, V the unit cell volume in
Å3 and NA Avogadro’s number. Assuming that the density
of the organic compounds is close to 1 gcm–3 and taking
into account that the volume of the unit cell is S·c, where
S and c are the cross-sectional area and the height of the
cell, respectively, Z can be estimated as:
Z = (S·c·NA)/(M·1024)
In this equation, c (height of the unit cell or thickness of
a column stratum) is unknown because of the absence of a
Figure 3. Simplified models for (a) 6c, (b) 7a, and (c) 7b showing
hydrogen bond interactions or dipole···dipole interactions.
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Arylsulfonamides as Supramolecular Columnar Liquid Crystals
scattering maximum due to the stacking distance as a con- ciated molecules to be in the same plane because they de-
sequence of the lack of long-range periodicity along the col- part from planarity at the nitrogen atoms. Therefore, the
umn axis. However, it is reasonable to consider that a rough estimated Z values have to be considered an approximation
value can be deduced from the diffuse halo recorded at high and, furthermore, they do not need to be integer numbers.
angles in the scattering patterns (see Table 2). On the basis However, it can be safely concluded that, depending of the
of these assumptions it is estimated that about three mole- estimated Z value, the cross-section of the columns is con-
cules (Z = 3) of compound 6c, two molecules (Z = 2) of 7a, sistent with the presence in each case of a larger or smaller
and three molecules (Z = 3) of 7b are needed on average to number of molecules filling the column section.
fill a column stratum with a thickness of about 4–4.5 Å (see
Figure 3). The stratum thickness would increase to about
4.5–5 Å considering a density of 0.9 gcm–3. In all cases, the
outside of the columns should be coated with a large
number of hydrocarbon chains (eight or twelve for Z values
of two or three, respectively), as usually found in classical
columnar mesophases generated by single disc-shaped mo-
lecules.
Conclusions
New liquid crystalline molecules have been obtained by
combining two molecules of an arylsulfonamide that bear
two long hydrocarbon chains linked to each aromatic ring
and a second containing a polar group in the para position
(fluoro, cyano or amino group). These polar groups play
an important role in the organization of molecules in the
mesophases; hydrogen-bonding interactions between amino
groups or dipole···dipole interactions between C–F or –CN
groups are responsible for the forces that characterize the
cohesion of molecules in hexagonal columnar mesophases.
Indeed, the stability of the columnar mesophases is much
higher than that observed for the corresponding com-
pounds devoid of polar groups. The presence of long alkyl
chains coating the outside of columns should also be con-
sidered, because they are fluid and disordered, allowing the
highly dynamic nature of columnar phases.
In cyclic derivatives 7a and 7c, the presence of these in-
teractions produces a clear increase in the mesomorphic
thermal range, in comparison with similar macrocycles that
contain only long alkyl chains. A favorable or unfavorable
balance between the different types of interactions (hydro-
gen bonding between terminal sulfonamides and
dipole···dipole interactions) could account for the mono-
tropic behavior found for open precursors 6a and 6b and
the nonmesomorphic behavior of macrocycle 7c. It was ob-
served that the variation of the molecular architecture al-
lows control of thermotropic properties and the design of
discotic mesophases. Studies of the supramolecular organi-
zation of these molecules have provided a better under-
standing of the noncovalent driving force responsible for
their self-assembly. Thus, it has been shown that the col-
umns are formed by supramolecular aggregates that are
formed through dipole···dipole interactions (fluoro and
cyano derivatives) or H-bonding interactions (amino deriv-
atives).
The dipole···dipole interactions between the C–F or
CϵN groups take place by antiparallel arrangement of
these groups. Indeed, in the case of 7b, there is a two-by-two
association of molecules with an antiparallel orientation of
their C–F dipoles to maximize the electrostatic interactions
(Figure 3, b). For 7c, a similar kind of antiparallel arrange-
ment occurs, but X-ray results suggest that, in this case,
the molecules associate in groups of three, preserving the
antiparallel orientation of the polar groups (Figure 3, c).
X-ray diffractograms of the nonsubstituted analogues 6d
and 7d were difficult to obtain due to the narrow thermal
range of their mesophases and the tendency for cold
crystallization of 7d. For this reason, only short-exposure-
time patterns were recorded. Only one small-angle reflec-
tion was obtained and this can be assigned to the (10) re-
flection of a hexagonal columnar (Colh) mesophase. The
two mesophases exhibited by 7d yielded similar patterns,
except for the narrower and stronger character of the large-
angle halo for the lower-temperature phase. This denotes
that this phase is more ordered than the higher-temperature
mesophase, for which this scattering halo is practically not
observed. Furthermore, the hexagonal lattice constant a
changes noticeably, probably due to a different kind of
intermolecular association. The estimated Z values for 6d
and 7d are between two and three (Table 2), although this
association must be weaker than for compounds bearing
polar groups.
The absence of (11) and (20) reflections in the X-ray pat-
terns of 6d, 7a, 7b, and 7d is related to the low electron
density of the central core of the supramolecular disc. This
produces a poor contrast in the electron density function
and therefore the intensity of the peaks is reduced as their
angle increases. In addition, the structure is smeared out
compared with the amino-substituted analogue due to the
weaker character of the dipolar forces or van der Waals
interactions compared with hydrogen-bonding.[18]
It must be pointed out that the structures proposed are
idealized models. Due to the fluid nature of the mesophases,
the molecule positions fluctuate, so intermolecular associa-
tion do not need to be within the same plane (supramolec-
ular disc) but can also arise between adjacent planes along
Experimental Section
General: Melting points were determined with a Kofler apparatus.
IR spectra were recorded in attenuated total reflectance mode
(ATR) with a Bruker Tensor 27 spectrophotometer. NMR spectra
were recorded with Bruker ARX200, DPX250, DPX360 or Bruker
AV400 spectrometers. 1H and 13C{1H} NMR chemical shifts are
reported relative to tetramethylsilane; coupling constants are re-
ported in Hz. The assignments of H and 13C NMR spectra were
carried out using DEPT, NOE, COSY, HMQC, HMBC, and
1
the column. In fact, it is not possible for the mutually-asso- TOCSY experiments when necessary. High-resolution MALDI-
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TOF spectra were obtained with a Bruker spectrometer, model
BIFLEX (Bruker-Franzen Analityk) with a Modus Reflecton. The
ionization was achieved by using a laser source (337 nm with a
voltage of 19 kV). Several matrixes were used and details are given
in the experimental part for each compound. High-resolution mass
spectrometry with electrospray ionization (HRMS-ESI) was per-
formed with a Bruker MicroTOF-Q, using sodium formiate as ex-
ternal reference.
(complex signal group, 72 H), 0.87 (t, J = 6.5 Hz, 12 H) ppm. 13C
NMR (62.5 MHz, CDCl3): δ = 153.6, 150.9, 148.8, 133.3, 131.6,
131.4, 127.9, 126.7, 122.0, 113.2, 112.1, 84.4, 69.9, 69.5, 48.0, 47.8,
32.1, 29.8, 29.5, 29.3, 29.2, 28.1, 26.1, 22.8, 14.2 ppm. IR (ATR):
ν = 2922, 2852, 2232, 1726, 1508, 1353, 1137, 922, 719, 626 cm–1.
˜
MALDI-TOF MS (Ditranol): m/z calcd. for C85H140N4O14S3
[M]+ 1536.9; found 1575.8 [M + K]+. C85H140N4O14S3 (1537.23):
calcd. C 66.37, H 9.17, N 3.64; found C 66.64, H; 9.42, H 3.95.
Thermal Properties and Liquid Crystalline Behavior: Differential
(E,E)-6-[(4-Aminophenyl)sulfonyl]-1,11-bis(tert-butyloxycarbonyl)-
scanning calorimetry (DSC) and thermogravimetric analysis
1,11-bis{[(3,4-didodecyloxy)phenyl]sulfonyl}-1,6,11-triazaundeca-
(TGA) were performed with DSC-MDSC TA instruments Q-1000 3,8-diene (5c): Isolated yield: 0.50 g (75%); oil at room temperature.
and Q-2000; and TA Q-5000, respectively. Liquid crystal textures
were studied with an Olympus BX-50 polarizing microscope
equipped with a Linkam TMS91 hot-stage and a CS196 hot-stage
central processor. Microphotographs were taken with an Olympus
DP12–2 digital camera.
1H NMR (250 MHz, CDCl3): δ = 7.58 (d, J = 8.8 Hz, 2 H), 7.37
(d, J = 2.2 Hz, 2 H), 7.43 (dd, J = 8.3, 2.2 Hz, 2 H), 6.92 (d, J =
8.3 Hz, 2 H), 6.68 (d, J = 8.8 Hz, 2 H), 5.72 (m, 2 H), 5.63 (m, 2
H), 4.23 (d, J = 6.2 Hz, 4 H), 4.08 (br. s, 2 H, NH), 4.02 (m, 8 H),
3.78 (d, J = 6.2 Hz, 4 H), 1.82 (m, 8 H), 1.38 (s, 18 H), 1.54–1.26
(complex signal group, 72 H), 0.87 (t, J = 6.5 Hz, 12 H) ppm. 13C
NMR (62.5 MHz, CDCl3): δ = 153.6, 150.9, 148.7, 131.5, 130.2,
129.2, 128.0, 126.3, 122.1, 113.1, 112.1, 84.3, 69.9, 69.4, 48.0, 32.1,
Mesophase Structure: XRD measurements were carried out at
room temperature with a Pinhole camera (Anton-Paar) operating
with a point-focused Ni-filtered Cu-Kα beam. The sample was held
in Lindemann glass capillaries (1 mm diameter) perfectly sealed
and heated, when necessary, with a variable-temperature attach-
ment. The diffraction patterns were collected on a flat photo-
graphic film held perpendicular to the X-ray beam.
29.8, 29.5, 29.2, 28.1, 26.1, 22.8, 14.2 ppm. IR (ATR): ν = 3478,
˜
3380, 2921, 2852, 1726, 1506, 1351, 1137, 918, 719, 626 cm–1
.
MALDI-TOF MS (dithranol): m/z calcd. for C84H142N4O14S3
[M]+ 1526.8; found 1565.8 [M + K]+. C84H142N4O14S3 (1528.24):
calcd. C 66.02, H 9.37, N 3.67; found C 66.40, H 9.61, N 3.99.
Synthesis of Precursors: Compounds 1–3 were prepared as reported
previously.[10a] Sulfonamides 4a–d were commercially available
(Sigma–Aldrich).
(E,E)-1,11-Bis(tert-butyloxycarbonyl)-1,11-bis{[(3,4-didodecyloxy)-
phenyl]sulfonyl}-6-(phenylsulfonyl)-1,6,11-triazaundeca-3,8-diene
(5d): Compound purified by column chromatography (hexane/
EtOAc, 8:2). Isolated yield: 1.20 g (81%); oil at room temperature.
1H NMR (360 MHz, CDCl3): δ = 7.83 (d, J = 7.1 Hz, 2 H), 7.55
(m, 3 H), 7.44 (dd, J = 8.6, 2.0 Hz, 2 H), 7.38 (d, J = 2.0 Hz, 2 H),
6.93 (d, J = 8.6 Hz, 2 H), 5.76 (m, 2 H), 5.57 (m, 2 H), 4.35 (d, J
= 5.4 Hz, 4 H), 4.03 (dt, J = 10.6, 6.5 Hz, 8 H), 3.85 (d, J = 6.2 Hz,
4 H), 1.90–1.80 (m, 8 H), 1.47 (m, 8 H), 1.35 (s, 18 H), 1.27 (br. s,
64 H), 0.89 (t, J = 6.7 Hz, 12 H) ppm. 13C NMR (90 MHz, CDCl3):
δ = 153.2, 150.7, 148.4, 140.2, 132.6, 131.2, 130.3, 129.2, 127.8,
127.1, 121.9, 121.8, 112.8, 112.7, 111.8, 84.2, 69.6, 69.2, 48.1, 47.7,
31.9, 29.7, 29.6, 29.4, 29.1, 29.0, 28.2, 27.9, 27.7, 26.0, 22.7,
Synthesis of Protected Derivatives 5: Sulfonamides 5b–d were ob-
tained by following the same experimental procedure described for
5a (Scheme 2).
(E,E)-1,11-Bis(tert-butyloxycarbonyl)-1,11-bis{[(3,4-didodecyloxy)-
phenyl]sulfonyl}-6-[(4-fluorophenyl)sulfonyl]-1,6,11-triazaundeca-
3,8-diene (5a): Sulfonamide 2 (2.30 g, 3.1 mmol) was dissolved in
anhydrous CH3CN (85 mL) by heating, and 4a (0.23 g. 1.3 mmol)
and K2CO3 (1.1 g, 8.0 mmol) were added. The mixture was heated
to reflux for 24 h. Salts were filtered off, washed with hot CH3CN,
and the filtrates were evaporated. The residue was purified by col-
umn chromatography (hexane/EtOAc, 9:1). Compound 5a (1.83 g,
90%) was isolated as an oil. 1H NMR (360 MHz, CDCl3): δ = 7.80
(dd, J = 8.9, JH,F = 5.0 Hz, 2 H), 7.42 (dd, J = 8.6, JH–F = 2.2 Hz,
2 H), 6.91 (d, J = 8.6 Hz, 2 H), 5.73 (m, 2 H), 5.51 (m, 2 H), 4.34
(d, J = 5.4 Hz, 4 H), 4.02 (dt, J = 10.2, 6.6 Hz, 8 H), 3.84 (d, J =
6.2 Hz, 4 H), 1.82 (m, 8 H), 1.33 (s, 18 H), 1.43 (m, 8 H), 1.25
(complex signal group, 64 H), 0.87 (t, J = 6.8 Hz, 12 H) ppm. 13C
NMR (90 MHz, CDCl3): δ = 163.6 (d, JC,F = 254.1 Hz), 153.3,
150.7, 148.4, 136.4 (d, JC,F = 3.3 Hz), 131.3, 130.6, 129.8 (d, JC,F
= 9.3 Hz), 127.3, 121.9, 116.3 (d, JC,F = 22.6 Hz), 112.7, 111.7,
84.2, 69.6, 69.2, 47.8, 47.7, 31.9, 29.7, 29.8, 29.6, 29.4, 29.1, 29.0,
27.9, 26.0, 25.9, 22.7, 14.1 ppm. 19F NMR (235 MHz, CDCl3): δ =
14.1 ppm. IR (ATR): ν = 2923, 2853, 1727, 1587, 1509, 1468, 1355,
˜
1262, 1158, 1140 cm–1. MALDI-TOF MS (dithranol/NaTFA): m/z
calcd. for C84H141N3O14S3 [M]+ 1511.96; found 1334.9 {M[-OC-
(CH3)3] + Na}+. C84H141N3O14S3 (1513.23): calcd. C 66.67, H 9.39,
N 2.78; found C 66.50, H 9.55, N 2.89.
Synthesis of Open Precursors 6: Compounds 6b–d were obtained
by following the same experimental procedure described for 6a
(Scheme 2).
(E,E)-1,11-Bis{[(3,4-didodecyloxy)phenyl]sulfonyl}-6-[(4-fluorophen-
yl)sulfonyl]-1,6,11-triazaundeca-3,8-diene (6a): Compound 5a
(1.2 g, 0.81 mmol) was dissolved in CH2Cl2 (15 mL). Trifluoro-
acetic acid (TFA; 15 mL) was added and the mixture was stirred
for 4 h at room temperature. The solvent and excess of acid were
evaporated and the residue was dissolved in CH2Cl2 and extracted
three times with water. The organic phase was dried with anhydrous
Na2SO4, filtered, and the filtrate was evaporated. The residue was
105.7 ppm. IR (ATR): ν = 2922, 2852, 1728, 1589, 1508, 1355,
˜
1263, 1140 cm–1. MS (ESI): m/z calcd. for C84H140FN3O14S3 [M]+
1529.86; found 685.0 {M[-OC(CH3)3] + Ca}2+. C84H140FN3O14S3
(1531.22): calcd. C 65.90, H 9.20, N 2.74; found C 66.30, H 9.53,
N 3.14.
purified by flash column chromatography to give 6a, yield 0.65 g
1
(E,E)-1,11-Bis(tert-butyloxycarbonyl)-6-[(4-cyanophenyl)sulfonyl]-
1,11-bis{[(3,4-didodecyloxy)phenyl]sulfonyl}-1,6,11-triazaundeca-
3,8-diene (5b): Isolated yield: 0.40 g (65%); oil at room temperature.
1H NMR (250 MHz, CDCl3): δ = 7.91 (d, J = 8.5 Hz, 2 H), 7.82
(61%). H NMR (250 MHz, CDCl3): δ = 7.79 (dd, J = 8.5, JH,F
=
5.0 Hz, 2 H), 7.42 (dd, J = 8.5, JH,F = 2.0 Hz, 2 H), 7.33 (d, J =
2.0 Hz, 2 H), 7.19 (t, J = 8.5 Hz, 2 H), 6.89 (d, J = 8.5 Hz, 2 H),
5.56 (m, 4 H), 5.07 (t, J = 6.3 Hz, 2NH), 4.02 (t, J = 6.5 Hz, 4 H),
(d, J = 8.5 Hz, 2 H), 7.42 (dd, J = 8.5, 2.1 Hz, 2 H), 7.35 (d, J = 3.96 (t, J = 6.5 Hz, 4 H), 3.70 (d, J = 5.4 Hz, 4 H), 3.47 (t, J =
2.1 Hz, 2 H), 6.91 (d, J = 8.5 Hz, 2 H), 5.79 (m, 2 H), 5.53 (m, 2
H), 4.35 (d, J = 5.1 Hz, 4 H), 4.03 (app. q, J = 6.6 Hz, 8 H), 3.89
(d, J = 6.2 Hz, 4 H), 1.86–1.68 (m, 8 H), 1.34 (s, 18 H), 1.54–1.24
5.4 Hz, 4 H), 1.79 (m, 8 H), 1.43 (m, 8 H), 1.26 (complex signal
group, 64 H), 0.88 (t, J = 6.7 Hz, 12 H) ppm. 13C NMR (62.5 MHz,
CDCl3): δ = 163.7 (d, JC,F = 254.9 Hz), 152.8, 149.2, 135.9 (d, JC,F
8
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Arylsulfonamides as Supramolecular Columnar Liquid Crystals
= 3.3 Hz), 131.0, 129.9 (d, JC,F = 9.3 Hz), 127.9, 120.9, 116.4 (d,
JC,F = 22.5 Hz), 112.2, 111.4, 69.6, 69.3, 49.2, 44.4, 32.0, 29.8,
29.77, 29.5, 29.2, 29.1, 26.1, 22.8, 14.2 ppm. 19F NMR (235 MHz,
25 mL) heated to reflux was slowly added a solution of 6a (0.49 g,
0.37 mmol) and (2E)-1,4-dibromo-2-butene (0.09 g. 0.40 mmol) in
CH3CN/THF (40 mL/15 mL). After the addition, the mixture was
heated to reflux for 24 h. The salts were filtered off, and the solid
CDCl ): δ = 105.6 ppm. IR (ATR): ν =3313, 2918, 2850, 1589,
˜
3
1508, 1323, 1259, 1140, 1091, 833 cm–1. HRMS (MALDI+): m/z was washed with hot CH3CN. The solvent from the filtrates was
calcd. for C74H124FNaN3O10S3 [M + Na]+ 1352.8325; found
1352.8310.
evaporated and the residue was purified by column chromatog-
raphy (hexane/EtOAc, 8:2) to give 7a, yield 0.37 g (73%). 1H NMR
(250 MHz, CDCl3): δ = 7.78 (dd, J = 8.9, JH,F = 5.1 Hz, 2 H), 7.31
(dd, J = 8.4, JH,F = 1.9 Hz, 2 H), 7.14 (m, 4 H), 6.91 (d, J = 8.5 Hz,
2 H), 4.01 (q, J = 6.7 Hz, 8 H), 5.58 (s, 6 H), 3.66 (s, 12 H), 1.81
(s, 8 H), 1.43 (m, 8 H), 1.25 (complex signal group, 64 H), 0.86 (t,
J = 6.3 Hz, 12 H) ppm. 13C NMR (62.5 MHz, CDCl3): δ = 163.1
(d, JC,F = 255.1 Hz), 153.0, 149.2, 135.4 (d, JC,F = 2.6 Hz), 130.3,
130.0, 129.8 (d, JC,F = 9.5 Hz), 129.6, 129.1, 121.0, 116.3 (d, JC,F
= 22.6 Hz), 112.4, 111.8, 69.6, 69.3, 50.8, 50.7, 32.0, 29.8, 29.7,
29.6, 29.5, 29.4, 29.2, 29.1, 26.0, 22.7, 21.2, 14.2 ppm. 19F NMR
(E,E)-6-[(4-Cyanophenyl)sulfonyl]-1,11-bis{[(3,4-didodecyloxy)-
phenyl]sulfonyl}-1,6,11-triazaundeca-3,8-diene (6b): Isolated yield:
0.19 g (99%). 1H NMR (250 MHz, CDCl3): δ = 7.91 (d, J = 8.6 Hz,
2 H), 7.83 (d, J = 8.6 Hz, 2 H), 7.42 (dd, J = 8.6, 2.2 Hz, 2 H),
7.33 (d, J = 2.2 Hz, 2 H), 6.90 (d, J = 8.6 Hz, 2 H), 5.61 (app. q, J
= 4.9 Hz, 4 H), 4.96 (t, J = 6.3 Hz, 2 H, NH), 4.03 (t, J = 6.8 Hz,
4 H), 3.98 (t, J = 6.8 Hz, 4 H), 3.76 (m, 4 H), 3.49 (app. t, J =
5.1 Hz, 4 H), 1.96–1.73 (complex signal group, 8 H), 1.48–1.28
(complex signal group, 72 H), 0.88 (t, J = 6.6 Hz, 12 H) ppm. 13C
NMR (62.5 MHz CDCl3): δ = 152.9, 149.3, 144.1, 133.2, 130.9,
130.8, 127.8, 127.4, 120.9, 112.1, 111.4, 69.6, 69.3, 49.6, 44.2, 32.0,
(235 MHz, CDCl ): δ = 105.6 ppm. IR (ATR): ν =2920, 2851,
˜
3
1587, 1508, 1466, 1329, 1261, 1230, 1139, 1091, 904 cm–1. MS
(MALDI+) (dithranol): m/z calcd. for C78H128FN3O10S3 [M]+
1381.87; found 1404.9 [M + Na]+. C78H128FN3O10S3 (1383.06):
calcd. C 67.74, H 9.33, N 3.04; found C 67.91, H 9.14, N 3.13.
29.8, 29.5, 29.2, 29.1, 26.1, 22.8, 14.2 ppm. IR (ATR): ν = 3272,
˜
2918, 2849, 2359, 1586, 1510, 1322.1263, 1137, 1091, 629 cm–1
.
MALDI-TOF MS (dithranol): m/z calcd. for C75H124N4O10S3
[M]+ 1336.9; found 1337.8 [M]+, 1359.8 [M + Na]+, 1375.8 [M +
K]+. C75H124N4O10S3 (1338.01): calcd. C 67.32, H 9.34, N 4.19;
found C 67.48, H 9.56, N 4.33.
(E,E,E)-1-[(4-Cyanophenyl)sulfonyl]-6,11-bis{[(3,4-didodecyloxy)-
phenyl]sulfonyl}-1,6,11-triazacyclopentadeca-3,8,13-triene (7b):
Compound 7b was not purified by column chromatography. The
residue obtained after evaporation of the solvent was suspended in
a mixture of diethyl ether/methanol (1:1), then filtered and dried to
(E,E)-6-[(4-Aminophenyl)sulfonyl]-1,11-bis{[(3,4-didodecyloxy)-
phenyl]sulfonyl}-1,6,11-triazaundeca-3,8-diene (6c): Isolated yield:
0.54 g (91%). 1H NMR (250 MHz, CDCl3): δ = 7.53 (d, J = 8.3 Hz,
2 H), 7.42 (dd, J = 8.3, 2.0 Hz, 2 H), 7.31 (d, J = 2.0 Hz, 2 H),
6.90 (d, J = 8.3 Hz, 2 H), 6.69 (d, J = 8.8 Hz, 2 H), 5.54 (br. s, 4
H), 4.75 (t, J = 6.4 Hz, 2 H, NH), 4.15 (br. s, 2 H, NH2), 4.03 (t,
J = 6.6 Hz, 4 H), 3.98 (t, J = 6.6 Hz, 4 H), 3.65 (m, 4 H), 3.46 (m,
4 H), 1.85–1.75 (complex signal group, 8 H), 1.38–1.22 (complex
signal group, 72 H), 0.87 (t, J = 6.5 Hz, 12 H) ppm. 13C NMR
(62.5 MHz CDCl3): δ = 152.9, 150.7, 149.3, 131.1, 129.5, 128.6,
127.9, 121.0, 114.3, 112.3, 111.6, 69.7, 69.4, 68.1, 49.3, 44.5, 32.1,
1
obtain pure compound 7b. Isolated yield: 0.04 g (50%). H NMR
(250 MHz, CDCl3): δ = 7.89 (app. d, J = 8.5 Hz, 2 H), 7.86 (app. d,
J = 8.5 Hz, 2 H), 7.33 (dd, J = 8.4, 2.1 Hz, 2 H), 7.22 (d, J =
2.1 Hz, 2 H), 6.92 (d, J = 8.4 Hz, 2 H), 5.63 (s, 6 H), 4.04 (t, J =
6.8 Hz, 4 H), 4.01 (t, J = 6.5 Hz, 4 H), 3.75 (d, J = 4.7 Hz, 4 H),
3.66 (s, 8 H), 1.95–1.68 (m, 8 H), 1.54–1.39 (m, 8 H), 1.27 (s, 64
H), 0.88 (t, J = 6.5 Hz, 12 H) ppm. 13C NMR (62.5 MHz CDCl3):
δ = 153.2, 149.4, 144.0, 133.2, 130.8, 130.4, 129.9, 128.6, 127.9,
121.2, 117.4, 116.6, 112.6, 112.2, 69.9, 69.5, 51.1, 50.9, 50.7, 32.1,
28.83, 29.79, 29.6, 29.5, 29.3, 29.2, 26.2, 22.8, 14.2 ppm. IR (ATR):
29.8, 29.5, 29.3, 29.1, 26.1, 25.8, 22.8, 14.3 ppm. IR (ATR): ν =
˜
ν = 2920, 2851, 2231, 1586, 1508, 1329, 1261, 1155, 1137, 1090,
˜
3491, 3381, 3272, 2917, 2849, 1742, 1586, 1317, 1135, 736,
679 cm–1. C74H126N4O10S3 (1328.01): calcd. C 66.93, H 9.56, N
4.22, S 7.24; found C 66.80 and 66.85, H 9.68 and 9.70, N 4.30
and 4.34, S 6.80 and 6.75.
906, 721 cm– 1. MALDI-TOF MS (dithranol): calcd. for
C79H128N4O10S3 [M]+ 1388.9; found 1412.8, [M + Na]+.
C79H128N4O10S3 (1390.08): calcd. C 68.26, H 9.28, N 4.03, S 6.92;
found C 67.95, H 9.30, N 3.75, S 6.68.
(E,E)-1,11-Bis{[(3,4-didodecyloxy)phenyl]sulfonyl}-6-(phenylsulfonyl)-
1
(E,E,E)-1,6-Bis{[(3,4-didodecyloxy)phenyl]sulfonyl}-11-(phenyl)sulf-
onyl-1,6,11-triazacyclopentadeca-3,8,13-triene (7d): Isolated yield:
0.14 g (54%). 1H NMR (250 MHz, CDCl3): δ = 7.80 (d, J = 7.1 Hz,
2 H), 7.58 (m, 3 H), 7.35 (dd, J = 8.5, 2.0 Hz, 2 H), 7.24 (d, J =
2.0 Hz, 2 H), 6.94 (d, J = 8.5 Hz, 2 H), 5.56 (s, 6 H), 4.05 (dd, J =
15.0, 6.5 Hz, 8 H), 3.69 (s, 12 H), 1.93–1.78 (complex signal group,
8 H), 1.57–1.17 (complex signal group, 72 H), 0.90 (t, J = 6.5 Hz,
12 H) ppm. 13C NMR (62.5 MHz, CDCl3): δ = 153.2, 149.5, 139.5,
133.1, 130.6, 130.1, 130.0, 129.7, 129.6, 127.5, 121.3, 112.7, 112.2,
70.0, 69.6, 51.2, 32.3, 30.11, 30.10, 30.07, 30.0, 29.83, 29.8, 29.6,
1,6,11-triazaundeca-3,8-diene (6d): Isolated yield: 0.36 g (95%). H
NMR (360 MHz, CDCl3): δ = 7.77 (d, J = 7.1 Hz, 2 H), 7.54 (m,
3 H), 7.42 (dd, J = 8.5, 2.0 Hz, 2 H), 7.34 (d, J = 2.0 Hz, 2 H),
6.90 (d, J = 8.5 Hz, 2 H), 5.53 (m, 4 H), 5.24 (t, J = 6.2 Hz, 2 H,
NH), 4.02 (t, J = 6.5 Hz, 4 H), 3.96 (t, J = 6.4 Hz, 4 H), 3.69. (d,
J = 5.5 Hz, 4 H), 3.46 (t, J = 5.2 Hz, 4 H), 1.91–1.71 (complex
signal group, 8 H), 1.50–1.26 (complex signal group, 72 H), 0.89
(t, J = 6.4 Hz, 12 H) ppm. 13C NMR (90 MHz, CDCl3): δ = 152.7,
149.1, 139,7, 130.8, 129.9, 129.2, 127.9, 127.1, 120.9, 112.0, 111.3,
111.2, 69.4, 69.2, 49.0, 44.3, 31.9, 29.8, 29.7, 29.67, 29.6, 29.5, 29.4,
29.4, 26.4, 26.39, 23.1, 14.5 ppm. IR (ATR): ν = 2921, 2852, 1586,
˜
29.38, 29.1, 29.0, 26.0, 22.7, 14.2, 14.1 ppm. IR (ATR): ν = 3273,
˜
1508, 1467, 1446, 1412, 1330, 1261, 1231, 1156, 1138, 1092, 971,
908, 625 cm–1. HR-MALDI-TOF MS (dithranol/NaTFA): m/z
calcd. for C78H129N3O10S3 [M]+ 1363.884; found 1386.873 [M +
Na]+.
2919, 2850, 1586, 1509, 1464, 1414, 1393, 1320, 1263, 1232, 1153,
1135, 1090, 1047, 1022, 1001, 987, 969, 848, 761, 688, 677,
621 cm–1. HR-MALDI-TOF MS (dithranol/NaTFA): m/z calcd.
for C74H125N3O10S3 [M]+ 1311.853; found 1334.839 [M + Na]+.
Compound 7c: Prepared by following the method outlined in
Scheme 3.
Synthesis of Macrocycles 7: Compounds 7b and 7d were obtained
by following the same experimental procedure described for 7a
(Scheme 2).
(E)-N,NЈ-Bis{[(3,4-didodecyloxy)phenyl]sulfonyl}-2-buten-1,4-di-
amine (8): Compound 2 (2.63 g, 4.20 mmol) was dissolved in an-
hydrous CH3CN (100 mL), and (E)-1,4-dibromo-2-butene (0.46 g,
2.10 mmol) and K2CO3 (1.74 g, 12.6 mmol) were added. The mix-
(E,E,E)-1,6-Bis{[(3,4-didodecyloxy)phenyl]sulfonyl}-11-[(4-fluoro-
phenyl)sulfonyl]-1,6,11-triazacyclopentadeca-3,8,13-triene (7a): To a
suspension of K2CO3 (0.30 g, 2.20 mmol) in CH3CN/THF (60 mL/
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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R. M. Sebastián, T. Sierra et al.
FULL PAPER
ture was stirred overnight, then the salts were filtered off before the
reaction mixture had cooled. Salts were washed twice with anhy-
drous CH3CN. The CH3CN solution was evaporated and 8 (pro-
compound 9 (0.10 g, 0.07 mmol) was then added. The mixture was
heated at 70 °C for 15 min, then a solution of sulfonamide 4c
(0.01 g, 0.07 mmol) in CH3CN/THF (3:2, 10 mL) was added drop-
wise over 2 h. The mixture was heated to reflux overnight, then the
tected with Boc groups) was isolated, yield 2.68 g (98%); m.p. 71–
1
73 °C. H NMR (250 MHz, CDCl3): δ = 7.44 (dd, J = 8.5, 2.2 Hz, salts were filtered off and washed with the same mixture of hot
2 H), 7.40 (d, J = 2.2 Hz, 2 H), 6.88 (d, J = 8.5 Hz, 2 H), 5.92–
solvents. Filtrates were evaporated and the residue was purified by
5.88 (m, 2 H), 4.43 (br. s, 4 H), 4.01 (t, J = 6.5 Hz, 8 H), 1.94–1.70 column chromatography (hexane/EtOAc, 8:2) to give 7c (0.06 g,
1
(m, 8 H), 1.34 (s, 18 H), 1.58–1.26 (complex signal group, 72 H),
0.88 (t, J = 6.6 Hz, 12 H) ppm. 13C NMR (90 MHz, CDCl3): δ =
153.2, 150.7, 148.3, 131.24, 129.16, 122.0, 112.9, 111.9, 84.1, 77.4,
77.0, 76.7, 69.6, 69.2, 47.6, 31.9, 29.7, 29.67, 29.63, 29.41, 29.38,
60%), m.p. 56 °C. H NMR (250 MHz, CDCl3): δ = 7.54 (d, J =
8.3 Hz, 2 H), 7.32 (d, J = 8.5 Hz, 2 H), 7.22 (s, 2 H), 6.92 (d, J =
8.5 Hz, 2 H), 6.68 (d, J = 8.3 Hz, 2 H), 5.59 (s, 6 H), 4.13 (br. s, 2
H, NH2), 4.02 (m, 8 H), 3.65 (s, 12 H), 1.83–1.72 (complex signal
group, 8 H), 1.60–1.06 (complex signal group, 72 H), 0.88 (t, J =
6.5 Hz, 12 H) ppm. 13C NMR (62.5 MHz, CDCl3): δ = 153.0,
150.7, 149.2, 130.3, 129.9, 129.7, 129.5, 121.1, 114.3, 112.4, 112.0,
69.8, 69.4, 50.92, 50.88, 32.1, 29.9, 29.84, 29.81, 29.77, 29.6, 29.5,
29.1, 27.9, 25.98, 25.96, 22.7, 14.1 ppm. IR (ATR): ν = 2916, 2849,
˜
1732, 1585, 1418, 1245, 1141, 717 cm–1. C74H130N2O12S (1271.91):
calcd. C 68.16, H 10.05, N 2.15; found C 68.32 and 68.07, H 10.26
and 10.06, N 2.12 and 2.14.
29.3, 29.2, 26.14, 26.12, 14.3 ppm. IR (ATR): ν = 2918, 2850, 1588,
˜
Protected compound 8 (2.65 g, 0.16 mmol) was dissolved in
CH2Cl2 (5 mL) and an excess of TFA (4 mL) was added. The mix-
ture was stirred for 6 h and the solvent was evaporated. The residue
was dissolved in CH2Cl2 (15 mL) and extracted with water (3ϫ
15 mL). The organic phase was dried with anhydrous Na2SO4, fil-
tered, and the filtrate was evaporated. The residue was purified by
column chromatography (hexane/EtOAc, 7:3) to give 8 (0.35 g,
96 %) as a white solid; m.p. 110–112 °C. 1H NMR (250 MHz,
CDCl3): δ = 7.39 (dd, J = 8.5, 2.2 Hz, 2 H), 7.29 (d, J = 2.2 Hz, 2
H), 6.91 (d, J = 8.5 Hz, 2 H), 5.54 (t, J = 2.9 Hz, 2 H), 4.43 (t, J
= 6.2 Hz, 2 H, NH), 4.02 (m, 8 H), 3.48 (m, 4 H), 2.02–1.75 (m, 8
H), 1.55–1.14 (m, 72 H), 0.88 (t, J = 6.6 Hz, 12 H) ppm. 13C NMR
(90 MHz, CDCl3): δ = 153.2, 149.4, 131.4, 128.9, 121.2, 112.6,
112.3, 77.5, 77.2, 76.8, 69.95, 65.55, 44.67, 32.07, 29.83, 29.80,
29.76, 29.6, 29.53, 29.49, 29.4, 29.3, 26.1, 22.8, 14.2 ppm. IR
1509, 1323, 1259, 1014, 863, 794, 673 cm–1. MALDI-TOF MS
(DCTB/NaTFA): m/z calcd. for C78H130N4O10S3 [M]+ 1379.1;
found 1402.1 [M + Na]+. C78H130N4O10S3 (1380.09): calcd. C
67.88, H 9.49, N 4.06; found C 68.02, H 9.53, N 4.31.
Supporting Information (see footnote on the first page of this arti-
cle): Contains 1H and 13C NMR spectra of previously reported
compound 1–3, 1H, 13C and 19F NMR spectra, IR spectra, and
some MS experiments for the new compounds (5a–d, 6a–d, 7a–d,
8 and 9). DSC thermograms are also gathered for compounds 6a–
d and 7a, 7b, and 7d.
Acknowledgments
Financial support from the Spanish Ministerio de Ciencia e Innov-
ación (MICINN), now: Ministerio de Economía y Competitividad
(MINECO) (grant numbers CTQ2011-22649, MAT2009-14636-
C03-01, CTQ2009-09030, MAT2012-38538-C03-01, CTQ2012-
35692), Consolider INGENIO 2010 (grant numbers CSD2007-
00006, CSD2006-00012), Generalitat de Catalunya (projects
2005SGR003305 and 2009SGR1441), Fondos Europeos para el
Desarrollo Regional (FEDER) and the Aragon Government. The
Generalitat de Catalunya is also gratefully acknowledged for pre-
doctoral scholarship to A. Z. The authors also acknowledge the
Universitat Autònoma de Barcelona for a predoctoral scholarship
to C. H.
(ATR): ν = 3325, 3271, 2954, 2916, 2848, 1585, 1509, 1469, 1319,
˜
1263, 1231, 1135, 718 cm–1. C64H114N2O8S2 (1103.73): calcd. C
69.64, H 10.41, N 2.54; found C 69.61 and 69.85, H 10.52 and
10.52, N 2.43 and 2.54.
(E,E,E)-1,14-Dibromo-5,10-bis{[(3,4-didodecyloxy)phenyl]sulfonyl}-
5,10-diazatetradeca-2,7,12-triene (9): Compound 8 (0.20 g,
0.18 mmol) was dissolved in a hot mixture of CH3CN/THF (2:1,
6 mL), and K2CO3 (0.12 g, 0.90 mmol) was added. The suspension
was stirred at 60 °C for 15 min, then (E)-1,4-dibromo-2-butene
(0.46 g, 2.20 mmol) was added to the mixture, which was heated to
reflux overnight. Salts were filtered off and the filtrate was evapo-
rated. The residue was washed three times with a mixture of diethyl
ether/methanol (1:1), filtered, and dried. Compound 9 (0.21 g, 56%
yield) was isolated in almost pure form, but could not be purified
further by column chromatography due to its low stability in the
presence of silica gel and alumina. This compound was used in the
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1
preparation of compound 7c, m.p. 72–78 °C. H NMR (250 MHz,
CDCl3): δ = 7.31 (dd, J = 8.5, 2.1 Hz, 2 H), 7.21 (d, J = 2.1 Hz, 2
H), 6.92 (d, J = 8.5 Hz, 2 H), 5.77 (dt, J = 15.7, 6.0 Hz, 2 H), 5.55
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˜
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10
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Job/Unit: O30222
/KAP1
Date: 03-07-13 10:26:20
Pages: 11
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[18] Concerning the intensity of the peaks, diffraction theory shows
that the amplitude of the wave scattered F(Q) is given by the
Fourier transform of the “structure”. For X-rays, the “struc-
ture” means the electron density distribution within the sample,
ρ(r). The observed intensity is then the modulus-squared of the
amplitude: I(Q) = |F(Q)|2.
Received: February 11, 2013
Published Online: ᭿
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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11