Nanostructured columnar and cubic liquid-crystalline assemblies consisting of unconventional rigid mesogens based on triphenylmethanes

Article abstract of DOI:10.1016/j.tet.2008.06.034

Liquid-crystalline (LC) molecules of unconventional shapes that form columnar and micellar cubic structures have been synthesized using triarylmethyl moieties as building blocks. The molecules have bowl- and dumbbell-shape. Despite the rigidity and bulkiness of the triarylmethyl moieties, the molecules form columnar and micellar cubic LC phases. The bowl-shaped molecules containing one triarylmethyl moiety show LC phases. The LC temperature ranges of the dumbbell-shaped molecules containing two triarylmethyl moieties connected by rigid rods are wider than those of bowl-shaped molecules containing one triarylmethyl moiety. The UV-vis spectroscopy of the dumbbell-shaped molecules having a terphenyl moiety reveals that the terphenyl moieties aggregate in the mesophase.

Full text of DOI:10.1016/j.tet.2008.06.034

Tetrahedron 64 (2008) 8368–8380
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Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Nanostructured columnar and cubic liquid-crystalline assemblies consisting of
unconventional rigid mesogens based on triphenylmethanes
*
Tsukasa Hatano, Takashi Kato
Department of Chemistry and Biotechnology, School of Engineering, The University of Tokyo, Bunkyo-ku, Tokyo, 113-8656, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
Liquid-crystalline (LC) molecules of unconventional shapes that form columnar and micellar cubic
structures have been synthesized using triarylmethyl moieties as building blocks. The molecules have
bowl- and dumbbell-shape. Despite the rigidity and bulkiness of the triarylmethyl moieties, the mole-
cules form columnar and micellar cubic LC phases. The bowl-shaped molecules containing one triaryl-
methyl moiety show LC phases. The LC temperature ranges of the dumbbell-shaped molecules
containing two triarylmethyl moieties connected by rigid rods are wider than those of bowl-shaped
molecules containing one triarylmethyl moiety. The UV–vis spectroscopy of the dumbbell-shaped
molecules having a terphenyl moiety reveals that the terphenyl moieties aggregate in the mesophase.
Ó 2008 Elsevier Ltd. All rights reserved.
Received 26 March 2008
Received in revised form 9 June 2008
Accepted 11 June 2008
Available online 13 June 2008
Keywords:
Liquid crystals
Nanostructures
Self-assembly
Photoluminescence
Mesogen
1. Introduction
Herein, we report on the synthesis and LC properties of bowl-
shaped and dumbbell-shaped mesogens based on triarylmethyl
Soft materials such as liquid crystals, gels, and polymers have
attracted a great deal of attention because of their structures and
dynamic properties.1 Liquid crystals are unique in soft materials
because they combine molecular order and dynamic properties.2
Liquid-crystalline (LC) molecular assemblies have great potential
for dynamically functional materials.3–12 For example, nematic
liquid crystals have been widely used in display devices because of
their anisotropic nature and dynamic behavior responsive to elec-
tric fields.2 Recently, intensive studies have focused on nano-
structured liquid crystals that exhibit smectic, columnar, and cubic
phases.2–12 They have been developed as new nanostructured
functional materials in a variety of fields such as electrooptics,
photonics, transportation of electron, ion, or molecules, sensory,
catalysis, and bio-activity.2–12 For the design of smectic and co-
lumnar liquid crystals, rod-like and disk-like molecular shapes are
standard, respectively (Fig. 1). A number of new mesogens forming
columnar and micellar cubic phases have been developed.3–12 For
example, fan-shaped,13 bowl-shaped,14 and polycatenar11,15 meso-
gens have been reported to form 1D functional columnar liquid
crystals. Furthermore, new aggregated structures of micellar cubic
phases have received attention recently.5,8,9,16–20
moieties (Figs. 1 and 2). Molecules composed of triarylmethyl
moieties designed as new mesogens in the present study are shown
in Figures 3 and 4. Compounds 1–4 having bowl-shaped structures
have triarylmethyl moieties with various groups (Fig. 3). Until now,
a number of molecules such as metallomesogens,14a calixarenes,14b
cyclotriveratrylenes,14c dendrons,14d C60 derivatives,14e,f and tri-
phenylphosphine oxides21a have been used as structural parts of
bowl-shaped mesogens. The linking of two triarylmethyl moieties
via rigid spacers gives dumbbell-shaped compounds 5–8 (Figs. 2
and 4), which leads to the formation of a new mesogen.
2. Results and discussion
2.1. Synthesis of 1–8
Compounds 1 and 2 were synthesized by the nucleophilic
substitution of the hydroxy groups of tris(4-hydroxyphenyl)-
methane (9) and tris(4-hydroxyphenyl)ethane (10) with benzyl
chloride derivatives, respectively (Scheme 1).21 The reaction of 4-
methoxyphenylmagnesium bromide with aromatic esters 11 and
12 yielded triphenylmethanol derivatives 13 and 14, respectively.
The tetraphenylmethane derivatives 15 and 16 were synthesized by
acid-catalyzed reaction of the triphenylmethanol derivatives 13
and 14 with phenol. After the BBr3 demethylation of the methoxy
groups in 15 and 16, nucleophilic substitution of the phenol groups
with 3,4,5-tridodecyloxybenzyl chloride afforded compounds 3
* Corresponding author. Tel.: þ81 3 5841 7440; fax: þ81 3 5841 8661.
E-mail address: kato@chiral.t.u.-tokyo.ac.jp (T. Kato).
0040-4020/$ – see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2008.06.034

T. Hatano, T. Kato / Tetrahedron 64 (2008) 8368–8380
8369
Figure 1. Schematic illustration of several representative mesogens forming nanostructured liquid-crystalline structures.
and 4 (Scheme 1). Compounds 5–7 were prepared as outlined in
Scheme 2. Rod-shaped aromatic compounds with diester moieties
19, 20, and 27 were reacted with 4-methoxyphenylmagnesium
bromide. The hydroxy groups in the generated alchols, 21, 22, and
28 were substituted for phenol groups with acid catalysis. Deme-
thylation of the methoxy goups for 23, 24, and 29 with BBr3 and the
following reaction with 3,4,5-tridodecyloxybenzyl chloride gave
compounds 5–7. Compound 8 has a terphenyl moiety substituted at
the 4- and 400-position for the triarylmethyl groups. The terphenyl
moieties were synthesized by cross-coupling reaction of 4-
bromophenyltriarylmethane (34) and 1,4-phenyldiboronic acid.
Following the demethylation reaction with BBr3 and the nucleo-
philic substitution gave compound 8 (Scheme 3).
2.2. Liquid-crystalline properties of bowl-shaped
molecules 1–4
Figure 2. Molecular structure of the dumbbell-shaped liquid crystal composed of rigid
rod (red part) and bowls (blue parts).
Compounds 1–4 have one triarylmethyl group and the hydro-
gen, methyl, phenyl, and pyridyl groups as a head group. We
Figure 3. Structures of the bowl-shaped liquid crystals containing one triarylmethane moiety.

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T. Hatano, T. Kato / Tetrahedron 64 (2008) 8368–8380
Figure 4. Structures of the dumbbel-shaped liquid crystals containing two triarylmethane moieties.
examined the effects of the structural bulkiness of the head groups
on the LC properties. Compounds 1, 2, and 4 show polarizing mi-
crographs typical for columnar phases, while 3 shows a polydomain
texture (Fig. 5). The DSC thermogram of 1 is shown in Figure 6. The
exothermic peaks observed at 28 and 0 ꢀC on cooling are ascribed to
the isotropic–LC transition and the crystallization, respectively. The
transition peaks due to the crystalline–LC transition and the iso-
tropization are also seen on heating. The phase sequence, transition
temperatures, and transition enthalpies are presented in Table 1.
The crystalline–LC transition temperatures of the compounds be-
come lower as the structural bulkiness of the head group increases.
For example, the crystalline–LC transition temperature of 1 is 12 ꢀC,
while that of 3 is 7 ꢀC. The structural bulkiness of 3 and 4 may
disturb the close molecular packing in the crystalline states. The
isotropization temperatures also decrease with the increase of
the structural bulkiness except for 4 having the pyridyl moiety. The
intermolecular dipole–dipole interactions of the pyridyl group may
stabilize the LC state. The X-ray diffraction pattern of 1 shows re-
flection peaks at 34.2, 19.4, and 16.9 Å, which can be indexed as
[100], [110], and [200], respectively (Fig. 7). The broad peak at 8 Å
can be ascribed to the distance of the molecular stacking of 1, since
the value is similar to those obtained for the single crystals of tri-
phenylmethane derivatives.22 Compounds 2 and 4 give XRD pat-
terns similar to that of 1. The reflections for 1, 2 and 4 are listed in

T. Hatano, T. Kato / Tetrahedron 64 (2008) 8368–8380
8371
Scheme 1. Synthesis of liquid crystals 1–4: (i) 3,4,5-tridodecyloxybenzyl chloride, K2CO3, DMF; (ii) 4-bromoanisole, Mg, THF; (iii) phenol, methanesulfonic acid; (iv) BBr3, CH2Cl2.
Table 2. The reciprocal d-spacing of 1:31/2:41/2 for these materials is
characteristic of hexagonal columnar structures. The intercolumnar
distances of 1, 2, and 4 are 39.5, 40.8, and 40.5 Å, respectively.
Despite the large difference in the structural bulkiness of the head
groups, the intercolumnar distances of 1, 2, and 4 show almost the
same value. Triarylmethane derivatives can be assembled into one-
dimensional columnar structure in the single crystal by the simple
stacking of molecules.22 The columnar structures of 1–4 may be
formed upon the stacking of the bowl-shaped molecules.
structure. The SAXD pattern of 7 suggests that the replacement by
the pyridyl moiety does not affect the phase structure. The SAXD
profile for the cubic phase of 8 is rather complicated, which pre-
vents the determination of the lattice parameter.
2.4. Emission properties of dumbbell-shaped molecule 8
The aggregated structures of 8 having the terphenyl group have
been examined by spectroscopic methods. Figure 11a shows the
UV–vis absorption spectra of 8 in the cubic phase and in hexane
solution (4 m
mol dmꢁ3). The absorption peaks due to the terphenyl
2.3. Liquid-crystalline properties of dumbbell-shaped
molecules 5–8
group are observed at 292 and 288 nm in the cubic phase and in
hexane solution, respectively. The absorption maximum for the
cubic phase is red-shifted from that for the hexane solution, which
suggests the formation of an aggregated structure of the terphenyl
group in the cubic phase. The emission spectrum of 8 in the cubic
phase shows two peaks at 341 and 362 nm and a shoulder around
390 nm, while the spectrum obtained for the hexane solution
represents two peaks at 332 and 353 nm and a shoulder around
380 nm (Fig. 11b). This observation also supports the aggregation of
the terphenyl groups in the cubic phase.23 Terphenyl derivatives
show excimer emission at around 400 nm upon the parallel
stacking of their long axis of the molecules.24 As no excimer
emission peak is seen in the spectrum of 8 in the cubic phase, the
terphenyl groups should aggregate with random orientations in the
cubic phase. Recently, luminescent liquid crystals have been pre-
pared as new functional liquid crystals.25–27 These dumbbell-
shaped mesogens based on the terphenyl moiety may be used as
new photo-functional molecular assemblies.
Compounds 5–8 have dumbbell-shaped structures composed
of two bowl-shaped triphenylmethane moieties connected by
p-phenylenes that function as rod-shaped rigid spacers. The DSC
thermograms of 5–8 are shown in Figure 8 and the thermal prop-
erties are listed in Table 3. The linkage of two tirarylmethane de-
rivatives by the rigid spacers induces transition temperatures that
are higher than those of 1–4. Figure 9 shows polarized optical
microscopic images of the LC phases of 5. A typical texture for
columnar liquid crystals is observed for 5 (Fig. 9). It is of interest
that compounds 6–8 show no birefringence in their mesophases,
suggesting the formation of cubic phases. Compounds 6–8
having longer phenylene spacers show cubic phases for wider
temperature ranges. The isotropization temperature of 6 containing
the biphenyl spacer is the highest among the dumbbell-shaped
liquid crystals prepared in the present study. The replacement of the
biphenyl group by the bipyridyl group induces a slight decrease of
the isotropization temperature. The calculated molecular structures
of 5 and 8 are shown in Figure 10. The wider space around the rod-
shaped part of 8 may promote the aggregation of the terphenyl core,
which results in the formation the micellar cubic phase. The SAXD
pattern of 5 at 68 ꢀC shows only the (100) reflection at 32.6 Å. For
compound 6, the SAXD profile for the cubic phase at 80 ꢀC presents
the reflections of 31.3, 22.1,18.1, and 15.6 Å. The reciprocal d-spacing
of 1:21/2:31/2:41/2 for 6 can be ascribed to a primitive cubic lattice
3. Conclusion
Bowl- and dumbbell-shaped LC molecules have been synthe-
sized by using triarylmethyl moieties as building blocks. The ther-
mal stability of the LC phases for the bowl-shaped molecules is
dependent on the structural bulkiness and the polarity of the
molecules. The LC properties of the dumbbell-shaped molecules are

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T. Hatano, T. Kato / Tetrahedron 64 (2008) 8368–8380
Scheme 2. Synthesis of liquid crystals 5–7: (i) 4-bromoanisole, Mg, THF; (ii) phenol, methanesulfonic acid; (iii) BBr3, CH2Cl2; (iv) 3,4,5-tridodecyloxybenzyl chloride, K2CO3, DMF.
greatly dependent on the length of the rigid spacers. Recently,
a variety of LC molecular objects, such as dendrons,10,28 rotax-
anes,29,30 catenanes,31 and nanoclusters32 have been prepared. The
mesogens reported in the present paper represent new building
blocks for these LC objects.
spherical 40–50 mm). Recycling preparative GPC was carried out
with a Japan Analytical Industry LC-908 chromatograph. 3,4,5-
Tridodecyloxybenzylchloride21 and diethyl-2,20-bipyridyl-5,50-
dicarboxylate33 were prepared by similar procedures reported in
the literature.
4. Experimental section
4.1. Materials
4.2. Instrumentation
1H and 13C NMR spectra were recorded on a JEOL JNM-LA400
spectrometer. Mass spectra were obtained with a PerSeptive Bio-
systems Voyager-DE STR spectrometer. Elemental analyses were
carried out with a Yanaco MT-6 CHN autocorder. Differential scan-
ning calorimetry (DSC) measurements were performed on a Mettler
DSC 30 at a scanning rate of 5 ꢀC minꢁ1. Transition temperatures
were taken at the maximum of transition peaks. A polarizing optical
All reagents and solvents were purchased from Aldrich, Tokyo
Kasei, and Wako, and were used as-received. Analytical thin layer
chromatography (TLC) was performed on silica gel plates from
E. Merck (silica gel F254). Silica gel column chromatography was
carried out with silica gel 60 from Kanto Chemicals (silica gel 60,

T. Hatano, T. Kato / Tetrahedron 64 (2008) 8368–8380
8373
Scheme 3. Synthesis of the liquid crystal 8: (i) 4-bromoanisole, Mg, THF; (ii) phenol, methanesulfonic acid; (iii) CH3I, K2CO3, DMF; (iv) 1,4-phenyldiboronic acid, Pd(PPh3)4, Na2CO3,
THF, H2O; (v) BBr3, CH2Cl2; (vi) 3,4,5-tridodecyloxybenzyl chloride, K2CO3, DMF.
Figure 5. Polarized optical microscopic images of (a) 1 at 25 ꢀC and (b) 4 at 20 ꢀC.
microscope Olympus BH-51 equipped with Mettler FP82 HT hot
stage was used for visual observation. X-ray diffraction (XRD) pat-
terns were obtained using a Rigaku RINT-2500 diffractometer with
characterized by 1H and 13C NMR to provide basic proof of identity
and were then fully used in the ongoing synthetic pathway.
a heating stage using Ni-filtered Cu K
and photoluminescence (PL) spectra were measured with a Agilent
8453 and a JASCO FP-777 W spectrometers, respectively.
a
radiation. UV–vis absorption
4.3.1. Tris[4-(3,4,5-tridodecyloxybenzyloxy)phenyl]methane (1)
To a 10 ml of DMF solution of tris(4-hydroxyphenyl)methane 9
(28 mg, 96 mmol) and 3,4,5-tridodecyloxybenzyl chloride (200 mg,
0.29 mmol) was added K2CO3 (138 mg, 1.0 mmol). The reaction
mixture was then stirred under Ar atmosphere at 70 ꢀC for 6 h. To
the reaction mixture water was added and extracted with hexane.
The collected organic fraction was washed with water, dried over
Na2SO4, and filtered. The solvent of the filtrate was removed under
4.3. Synthesis
All target liquid-crystalline compounds were fully characterized
by all available techniques. Intermediate compounds were

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T. Hatano, T. Kato / Tetrahedron 64 (2008) 8368–8380
Figure 6. DSC heating and cooling trace of 1 (5 ꢀC minꢁ1).
Table 1
Thermal properties of 1–4a
Compounds
Transition temperature/ꢀC
(enthalpy/kJ molꢁ1
)
1
2
3
4
Cr 12 (23.3) Colh 34 (6.1) Iso
Cr 12 (25.0) Colh 28 (5.5) Iso
Cr 7 (13.3) M 22 (4.8) Iso
Cr 3 (24.5) Colh 32 (4.4) Iso
a
Determined by DSC on heating (5 ꢀC minꢁ1), Cr¼crystalline, Colh¼hexagonal
columnar, M¼mesophase, Iso¼isotropic.
Figure 8. DSC thermograms of (a) 5, (b) 6, (c) 7, and (d) 8 on heating and cooling
(5 ꢀC minꢁ1).
Table 3
a
Thermal properties of 5–8 determined by DSC on heating (5 ꢀC minꢁ1
)
Compounds
Transition temperature/ꢀC
(enthalpy/kJ molꢁ1
)
Figure 7. XRD pattern of 1 at 25 ꢀC.
5
6
7
8
Cr ꢁ3 (92.1) Col 63 (4.8) Col 76 (12.5) Iso
Cr ꢁ13 (86.3) M 55 (7.0) Cub 128 (8.4) Iso
Cr ꢁ6 (105.2) Cr 68 (51.3) Cub 119 (5.3) Iso
Cr ꢁ15 (79.1) Cub 110 (13.4) Iso
Table 2
X-ray diffraction data of 1, 2, and 4 obtained from XRD measurements
a
Compounds
Temperature/ꢀC
d/Å
Cr¼crystalline, Col¼columnar, M¼mesophase, Cub¼cubic, Iso¼isotropic.
[100]
[110]
[200]
1
2
4
25
15
15
34.2
35.3
35.0
19.4
20.0
19.8
16.9
17.3
17.2
(d, J¼8.8 Hz, 6H, ArH), 6.61 (s, 6H, ArH), 5.42 (s, 1H, Ar3CH), 4.90 (s,
6H, OCH2Ar), 3.98–3.92 (m, 18H, CH2CH2O), 1.82–1.72 (m, 18H,
CH2CH2CH2O), 1.49–1.41 (br d, 18H, CH2CH2CH2CH2O), 1.30–1.24 (br
d, 144H,CH2), 0.88 (t, J¼7.2 Hz, 27H, CH3); 13C{1H} NMR (100 MHz,
reduced pressure. Purification with GPC (JAIGEL 1H and 2.5H,
CHCl3, 3.8 ml minꢁ1) and column chromatography (silicagel, hex-
ane–ethyl acetate¼20:1) gave a white highly viscous oil (0.13 g,
CDCl3):
d 157.21, 153.26, 137.90, 136.99, 131.86, 130.21, 114.48,
106.19, 73.40, 70.44, 69.17, 31.94, 31.92, 30.32, 29.76, 29.73, 29.70,
29.66, 29.63, 29.62, 29.41, 29.40, 29.36, 26.13, 26.09, 22.69, 14.12;
61%). 1H NMR (400 MHz, CDCl3):
d
7.02 (d, J¼8.4 Hz, 6H, ArH), 6.90

T. Hatano, T. Kato / Tetrahedron 64 (2008) 8368–8380
8375
Figure 9. Polarized optical microscopic images of 5 at 70 ꢀC.
Figure 11. (a) UV–vis absorption spectra of 8 in the cubic phase (d) and on hexane
solution (- - -) at 25 ꢀC and (b) emission spectra of 8 in the cubic phase (d, excitation at
317 nm) and on hexane solution (- - -, excitation at 317 nm).
4.3.2. Tris[4-(3,4,5-tridodecyloxybenzyloxy)phenyl]ethane (2)
To a DMF (10 ml) solution of tris(4-hydroxyphenyl)ethane 10
(41 mg, 0.13 mmol) and 3,4,5-tridodecyloxybenzyl chloride
(300 mg, 0.44 mmol) was added K2CO3 (138 mg, 1.0 mmol). The
reaction mixture was then stirred under Ar atmosphere at 70 ꢀC for
6 h. To the reaction mixture, water (100 ml) was added and
extracted with hexane. The collected organic fraction was washed
with water, dried over Na2SO4, and filtered. The solvent of the fil-
trate was removed under reduced pressure. Purification with GPC
(JAIGEL 1H and 2.5H, CHCl3, 3.8 ml minꢁ1) and column chroma-
tography (silicagel, hexane/ethyl acetate¼20:1) gave a white highly
viscous oil (0.27 g, 93%). 1H NMR (400 MHz, CDCl3):
d 7.02 (d,
J¼8.4 Hz, 6H, ArH), 6.90 (d, J¼8.8 Hz, 6H, ArH), 6.61 (s, 6H, ArH),
4.90 (s, 6H, OCH2Ar), 3.98–3.92 (m, 18H, CH2CH2O), 2.12 (s, 3H,
Ar3CCH3), 1.82–1.72 (m, 18H, CH2CH2CH2O), 1.49–1.41 (br d, 18H,
CH2CH2CH2CH2O),1.30–1.24 (br d,144H,CH2), 0.88 (t, J¼7.2 Hz, 27H,
CH3); 13C{1H} NMR (100 MHz, CDCl3):
d 156.85, 153.26, 142.01,
137.91, 131.87, 129.60, 113.90, 106.21, 73.39, 70.41, 69.06, 50.63,
31.94, 31.91, 30.32, 29.75, 29.73, 29.69, 29.65, 29.63, 29.62, 29.41,
29.39, 29.36, 26.12, 26.09, 22.68, 14.10; m/z (MALDI-TOF) 2235.1
(calcd [M]þ¼2235.6); IR (neat): 2924, 2852, 1591, 1505, 1463, 1435,
1378, 1334, 1291, 1235, 1180, 1116, 1010, 828, 721, 583 cmꢁ1; Anal.
Calcd for C149H252O12: C, 80.05; H, 11.36. Found: C, 79.89; H, 11.43.
Figure 10. Molecular structures of 5 and 8 calculated by molecular mechanics; the red
and blue parts show rod and bowl moieties, respectively.
m/z (MALDI-TOF) 2222.4 (calcd [MþH]þ¼2222.5); IR (neat): 2921,
2851, 1591, 1505, 1467, 1439, 1377, 1334, 1235, 1174, 1117, 1000, 848,
720, 579 cmꢁ1; Anal. Calcd for C148H250O12: C, 80.02; H, 11.34.
Found: C, 80.07; H, 11.56.
4.3.3. Bis(4-methoxyphenyl)phenylmethanol (13)
In an oven-dried 50 ml three-necked flask equipped with
a condenser, mechanical stirrer, and argon system were placed
magnesium turnings (0.58 g, 24 mmol) with dry THF (20 ml).

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T. Hatano, T. Kato / Tetrahedron 64 (2008) 8368–8380
4-Bromoanisole (3.0 g, 16 mmol) was added dropwise with gentle
heating until the reaction was started. The reaction was allowed to
go for 1 h. A brown color was observed. Ethyl benzoate 11 (1.2 g,
8.0 mmol) was added. The mixture was stirred overnight under
argon. The reaction mixture was neutralized with 5 wt % HCl aq and
extracted with CHCl3. The collected organic fraction was washed
with water, dried over Na2SO4, and filtered. The filtrate was con-
centrated and chromatographed on silica with 20% ethyl acetate in
hexane to afford compound 13 as a reddish oil (2.2 g, 86%). 1H NMR
gave a colorless oil (0.27 g, 84%). 1H NMR (400 MHz, CDCl3):
d 7.26–
7.15 (5H, m, PhH), 7.10 (6H, d, J¼8.8 Hz, ArH), 6.86 (6H, d, J¼9.2 Hz,
ArH), 6.61 (6H, s, ArH), 4.90 (6H, s, ArCH2O), 3.99–3.91 (18H, m,
CH2CH2O), 1.87–1.70 (18H, m, CH2CH2CH2O), 1.52–1.37 (18H, br,
CH2CH2CH2CH2O), 1.37–1.19 (144H, br, CH2), 0.88 (27H, t, J¼6.8 Hz,
CH3); 13C{1H} NMR (100 MHz, CDCl3):
d 156.74, 153.25, 147.40,
139.66, 137.90, 132.05, 131.80, 130.97, 127.33, 125.77, 113.42, 106.22,
73.38, 70.36, 69.03, 62.94, 31.93, 31.91, 30.32, 29.75, 29.72, 29.69,
29.64, 29.63, 29.61, 29.40, 29.39, 29.36, 26.13, 26.08, 22.69, 22.67,
14.10; m/z (MALDI-TOF) 2296.1 (calcd [M]þ¼2295.9); IR (neat):
2921,1592,1505,1463,1435,1378,1334,1295,1235,1181,1115,1013,
897, 824, 756, 721, 704, 591 cmꢁ1; Anal. Calcd for C154H254O12: C,
80.50; H, 11.14. Found: C, 80.46; H, 11.38.
(400 MHz, CDCl3):
ArH), 6.82 (4H, d, J¼8.8 Hz, ArH), 3.76 (6H, s, OCH3), 2.77 (1H, s, OH);
13C{1H} NMR (100 MHz, CDCl3):
158.55, 147.27, 139.40, 129.09,
d
7.30–7.24 (5H, m, PhH), 7.17 (4H, d, J¼8.8 Hz,
d
127.81, 127.72, 127.03, 113.11, 81.37, 55.20; IR (neat): 3501, 3002,
2954, 2835, 1606, 1505, 1446, 1413, 1296, 1247, 1176, 1115, 1032, 899,
826, 754, 702, 667, 634, 585 cmꢁ1
.
4.3.7. Bis(4-methoxyphenyl)-4-pyridylmethanol (14)
In an oven-dried 50 ml three-necked flask equipped with
a condenser, mechanical stirrer, and argon system were placed
magnesium turnings (0.66 g, 27 mmol) with dry THF (30 ml). 4-
Bromoanisole (3.4 g, 18 mmol) was added dropwise with gentle
heating until the reaction was started. The reaction was allowed to
go for 1 h. A brown color was observed. Methyl isonicotinate 12
(1.0 g, 7.3 mmol) was added. The mixture was stirred overnight
under argon. The reaction mixture was neutralized with 5 wt % HCl
aq and extracted with CHCl3. The collected organic fraction was
washed with water, dried over Na2SO4, and filtered. The filtrate was
concentrated and chromatographed on silica with CHCl3–methanol
(10:1) to afford compound 14 as a white solid (2.0 g, 85%). Mp
4.3.4. 4-[Bis(4-methoxyphenyl)phenylmethyl]phenol (15)
In a 100 ml flask equipped with a condenser, mechanical stirrer,
and argon system was placed bis(4-methoxyphenyl)phenyl-
methanol 13 (2.2 g, 6.9 mmol) with phenol (3.2 g, 34 mmol). A few
drops of methanesulfonic acid were added with gentle heating. A
deep-red solution was obtained. The reaction mixture was stirred
for 36 h at 120 ꢀC. The reaction mixture was poured into water and
extracted with ethyl acetate. The organic layer was dried with so-
dium sulfate and concentrated. The crude compound was chro-
matographed on silica with 25% ethyl acetate in hexane to afford
compound 15 as a reddish oil (1.9 g, 70%). Mp 176.6–182.7 ꢀC; 1H
NMR (400 MHz, CDCl3):
d
7.28–7.15 (5H, m, PhH), 7.08 (4H, d,
152.6–157.2 ꢀC; 1H NMR (400 MHz, CDCl3):
d
8.52 (2H, d, J¼5.6 Hz,
J¼8.8 Hz, ArH), 7.03 (2H, d, J¼8.8 Hz, ArH), 6.77 (4H, d, J¼8.8 Hz,
PyH), 7.27 (2H, d, J¼4.4 Hz, PyH), 7.15 (4H, d, J¼8.8 Hz, ArH), 6.85
ArH), 6.70 (2H, d, J¼8.8 Hz, ArH), 3.79 (6H, s, OCH3); 13C{1H} NMR
(4H, d, J¼8.8 Hz, ArH), 3.81 (6H, s, OCH3), 2.97 (1H, s, OH); 13C{1H}
(100 MHz, CDCl3):
d
157.32, 153.54, 147.45, 139.46, 132.22, 132.02,
NMR (100 MHz, CDCl3): d 158.93, 155.97, 149.29, 138.16, 129.04,
130.94,127.32,125.73,114.12,112.59, 62.85, 55.15; m/z (MALDI-TOF)
396.29 (calcd [M]þ¼396.17); IR (KBr): 3407, 3031, 2950, 2834, 1034,
1506, 1461, 1442, 1351, 1289, 1251, 1179, 1116, 1034, 825, 757, 727,
127.70, 122.55, 114.12, 113.40, 80.55, 55.26; IR (KBr): 3074, 2835,
1606, 1579, 1508, 1457, 1440, 1413, 1305, 1276, 1248, 1177, 1032,
1006, 924, 826, 782, 674, 639, 610, 591 cmꢁ1; Anal. Calcd for
705, 600, 580, 533 cmꢁ1
.
C20H19NO3: C, 74.75; H, 5.96; N, 4.36. Found: C, 74.56; H, 6.10;
N, 4.26.
4.3.5. Tris(4-hydroxyphenyl)phenylmethane (17)
4-[Bis(4-methoxyphenyl)phenylmethyl]phenol 15 (1.9 g,
4.8 mmol) was placed in a 100 ml two-neck flask equipped with
mechanical stirrer and argon system. Dry CH2Cl2 (50 ml) was added
and the mixture was kept at ꢁ78 ꢀC. A 1.0 M solution of BBr3 in
methylene chloride (9.6 ml, 9.6 mmol) was slowly added. The
temperature was slowly raised to 25 ꢀC and the mixture was stirred
for 12 h at 25 ꢀC. The reaction was quenched with water at 0 ꢀC and
generated precipitate was filtered. Reddish brown solid was
obtained by washing with water and chloroform (1.2 g, 68%). The
compound was used without further purification. 1H NMR
4.3.8. 4-[Bis(4-methoxyphenyl)-4-pyridylmethyl]phenol (16)
In a 100 ml flask equipped with a condenser, mechanical stirrer,
and argon system were placed bis(4-methoxyphenyl)phenyl-
methanol 14 (0.50 g, 1.6 mmol) with phenol (1.5 g, 16 mmol). A few
drops of methanesulfonic acid were added with gentle heating. A
dark-purple solution was obtained. The reaction mixture was stir-
red for 18 h at 120 ꢀC. The reaction mixture was poured into water
and extracted with ethyl acetate. The organic layer was dried with
sodium sulfate and concentrated. The crude compound was chro-
matographed on silica with ethyl acetate–CHCl3 (1:2) to afford
compound 16 as a white solid (0.28 g, 46%). 1H NMR (400 MHz,
(400 MHz, DMSO-d6):
d 9.34 (3H, s, OH), 7.24–7.12 (3H, m, PhH),
7.04 (2H, d, J¼7.6 Hz, PhH), 6.83 (6H, d, J¼8.8 Hz, ArH), 6.62 (6H, d,
CDCl3):
d
8.46 (2H, d, J¼6.4 Hz, PyH), 7.19 (2H, d, J¼5.6 Hz, PyH), 7.04
J¼8.8 Hz, ArH); 13C{1H} NMR (100 MHz, DMSO-d6):
d
155.05,147.82,
(4H, d, J¼8.8 Hz, ArH), 7.04 (4H, d, J¼8.8 Hz, ArH), 6.96 (2H, d,
J¼8.8 Hz, ArH), 6.79 (4H, d, J¼8.8 Hz, ArH), 6.75 (2H, d, J¼8.8 Hz,
137.59, 131.51, 130.45, 127.33, 125.56, 114.14, 62.27; m/z (MALDI-
TOF) 368.36 (calcd [M]þ¼398.14); IR (KBr): 3676, 1595, 1507, 1437,
ArH), 3.79 (6H, s, OCH3); 13C{1H} NMR (100 MHz, CDCl3):
d 157.47,
1363, 1176, 826, 703, 581 cmꢁ1
.
156.73, 155.34, 148.69, 137.89, 136.22, 131.65, 131.63, 125.80, 114.45,
112.67, 62.44, 55.00; m/z (MALDI-TOF) 398.53 (calcd [MþH]þ¼
398.18); IR (KBr): 2998, 2834, 1601, 1507, 1463, 1414, 1252, 1177,
4.3.6. Tris[4-(3,4,5-tridodecyloxybenzyloxy)phenyl]phenyl-
methane (3)
1117, 1070, 1032, 1011, 828, 813, 667, 590 cmꢁ1
.
To a DMF (10 ml) solution of tris(4-hydroxyphenyl)phenyl-
methane 17 (50 mg, 0.14 mmol) and 3,4,5-tridodecyloxybenzyl
chloride (305 mg, 0.45 mmol) was added K2CO3 (138 mg,
1.0 mmol). The reaction mixture was then stirred under Ar atmo-
sphere at 70 ꢀC for 6 h. To the reaction mixture, water (100 ml) was
added and extracted with hexane. The collected organic fraction
was washed with water, dried over Na2SO4, and filtered. The sol-
vent of the filtrate was removed under reduced pressure. Purifi-
cation with GPC (JAIGEL 1H and 2.5H, CHCl3, 3.8 ml minꢁ1) and
column chromatography (silicagel, hexane–ethyl acetate¼15:1)
4.3.9. Tris(4-hydroxyphenyl)-4-pyridylmethane (18)
4-[Bis(4-methoxyphenyl)-4-pyridylmethyl]phenol 16 (0.25 g,
0.63 mmol) was placed in a 100 ml two-neck flask equipped with
mechanical stirrer and argon system. Dry CH2Cl2 (15 ml) was added
and the mixture was kept at ꢁ78 ꢀC. A 1.0 M solution of BBr3 in
methylene chloride (2.5 ml, 2.5 mmol) was slowly added. The
temperature was slowly raised to 25 ꢀC and the mixture was stirred
for 12 h at 25 ꢀC. The reaction was quenched with water at 0 ꢀC and
extracted with ethyl acetate. The collected organic fraction was

T. Hatano, T. Kato / Tetrahedron 64 (2008) 8368–8380
8377
washed with water, dried over Na2SO4, and filtered. Removal of the
solvent gave a white solid (0.18 g, 78%). The compound was used
J¼9.2 Hz, ArH), 6.69 (4H, d, J¼8.8 Hz, ArH), 4.69 (2H, s, OH), 3.78
(12H, s, OCH3); 13C{1H} NMR (100 MHz, CDCl3):
157.36, 153.45,
d
without further purification. 1H NMR (400 MHz, DMSO-d6):
d
9.40
144.76, 139.56, 139.45, 132.26, 132.04, 129.96, 114.03, 112.51, 65.47,
55.17; IR (KBr): 3420, 3032, 2952, 2834, 1606, 1506, 1463, 1441,
(3H, s, OH), 8.45 (2H, d, J¼6.4 Hz, PyH), 7.06 (2H, d, J¼4.4 Hz, PyH),
6.84 (6H, d, J¼8.8 Hz, PhH), 6.67 (6H, d, J¼8.8 Hz, ArH); 13C{1H}
1293, 1249, 1179, 1116, 1034, 824, 599, 581 cmꢁ1
.
NMR (100 MHz, DMSO-d6):
d 156.48, 155.51, 148.96, 136.11, 131.32,
125.41, 114.44, 62.00; m/z (MALDI-TOF) 370.26 (calcd [MþH]þ¼
4.3.13. 1,4-Bis[tris(4-hydroxyphenyl)methyl]benzene (25)
370.14); IR (KBr): 3421, 1601, 1508, 1453, 1381, 1255, 1177, 1070,
1,4-Bis[bis(4-methoxyphenyl)-4-hydroxyphenylmethyl]-
benzene 23 (0.60 g, 0.84 mmol) was placed in a 100 ml two-neck
flask equipped with mechanical stirrer and argon system. Dry
CH2Cl2 (50 ml) was added and the mixture was kept at ꢁ78 ꢀC. A
1.0 M solution of BBr3 in methylene chloride (6.4 ml, 6.4 mmol) was
slowly added. The temperature was slowly raised to 25 ꢀC and the
mixture was stirred for 12 h at 25 ꢀC. The reaction was quenched
with water at 0 ꢀC and generated precipitate was filtered. Reddish
brown solid was obtained by washing with water and chloroform
(0.35 g, 63%). The compound was used without further purification.
1010, 825, 601, 579 cmꢁ1
.
4.3.10. Tris[4-(3,4,5-tridodecyloxybenzyloxy)phenyl]-4-
pyridylmethane (4)
To a DMF (10 ml) solution of tris(4-hydroxyphenyl)-4-pyridyl-
methane 18 (50 mg, 0.14 mmol) and 3,4,5-tridodecyloxybenzyl
chloride (0.28 g, 0.41 mmol) was added K2CO3 (0.19 g, 1.4 mmol).
The reaction mixture was then stirred under Ar atmosphere at
70 ꢀC for 6 h. To the reaction mixture, water (100 ml) was added
and extracted with hexane. The collected organic fraction was
washed with water, dried over Na2SO4, and filtered. The solvent of
the filtrate was removed under reduced pressure. Purification with
GPC (JAIGEL 1H and 2.5H, CHCl3, 3.8 ml minꢁ1) and column chro-
matography (silicagel, hexane–ethyl acetate¼6:1) gave a white
1H NMR (400 MHz, DMSO-d6):
d 9.28 (6H, s, OH), 6.93 (4H, s, ArH),
6.82 (12H, d, J¼8.4 Hz, ArH), 6.62 (12H, d, J¼8.4 Hz, ArH); 13C{1H}
NMR (100 MHz, DMSO-d6):
d 155.03, 144.87, 137.55, 131.46, 129.37,
114.06, 61.86; IR (KBr): 3364, 1609, 1507, 1437, 1363, 1235, 1178,
1014, 826, 600, 577 cmꢁ1
.
highly viscous oil (0.18 g, 57%). 1H NMR (400 MHz, CDCl3):
d 8.49
(2H, d, J¼6.4 Hz, PyH), 7.13 (2H, d, J¼6.4 Hz, ArH), 7.06 (6H, d,
J¼8.8 Hz, ArH), 6.88 (6H, d, J¼8.8 Hz, ArH), 6.61 (6H, s, ArH), 4.91
(6H, s, ArCH2O), 3.99–3.91 (18H, m, CH2CH2O), 1.84–1.70 (18H, m,
CH2CH2CH2O), 1.50–1.40 (18H, br, CH2CH2CH2CH2O), 1.40–1.20
(144H, br, CH2), 0.88 (27H, t, J¼6.8 Hz, CH3); 13C{1H} NMR
4.3.14. 1,4-Bis[tris(4-(3,4,5-tridodecyloxybenzyloxy)phenyl)-
methyl]benzene (5)
To a DMF (10 ml) solution of 1,4-bis[tris(4-hydroxyphenyl)-
methyl]benzene 25 (25 mg, 0.038 mmol) and 3,4,5-tridodecyloxy-
benzyl chloride (0.31 g, 0.45 mmol) was added K2CO3 (0.14 g,
1.0 mmol). The reaction mixture was then stirred under Ar atmo-
sphere at 70 ꢀC for 6 h. To the reaction mixture, water (100 ml) was
added and extracted with hexane. The collected organic fraction
was washed with water, dried over Na2SO4, and filtered. The sol-
vent of the filtrate was removed under reduced pressure. Purifi-
cation with GPC (JAIGEL 1H and 2.5H, CHCl3, 3.8 ml minꢁ1) and
column chromatography (silicagel, hexane–ethyl acetate¼20:1)
gave a white highly viscous oil (83 mg, 48%). 1H NMR (400 MHz,
(100 MHz, CDCl3):
d 157.04, 156.35, 153.24, 149.11, 138.16, 137.93,
131.81, 131.61, 125.82, 113.74, 106.17, 73.33, 70.36, 69.01, 62.66,
31.89, 31.88, 30.23, 29.71, 29.69, 29.65, 29.59, 29.57, 29.37, 29.36,
29.32, 26.09, 26.06, 22.66, 22.64, 14.06; m/z (MALDI-TOF) 2299.3
(calcd [MþH]þ¼2299.6); IR (neat): 2922, 1590, 1505, 1463, 1435,
1378, 1334, 1236, 1182, 1115, 1012, 825, 721, 658, 634, 593 cmꢁ1
;
Anal. Calcd for C153H253NO12: C, 79.94; H, 11.09; N, 0.61. Found: C,
79.78; H, 11.31; N, 0.69.
CDCl3):
d
7.10–7.04 (16H, m, ArH), 6.86 (12H, d, J¼9.2 Hz, ArH), 6.61
4.3.11. 1,4-Bis[bis(4-methoxyphenyl)hydroxymethyl]benzene (21)
In an oven-dried 50 ml three-necked flask equipped with
a condenser, mechanical stirrer, and argon system were placed
magnesium turnings (0.53 g, 22 mmol) with dry THF (30 ml). 4-
Bromoanisole (3.0 g, 16 mmol) was added dropwise with gentle
heating until the reaction was started. The reaction was allowed to
go for 1 h. A brown color was observed. Dimethyl terephthalate 19
(0.73 g, 3.7 mmol) was added. The mixture was stirred overnight
under argon. The reaction mixture was neutralized with 5 wt % HCl
aq and extracted with CHCl3. The collected organic fraction was
washed with water, dried over Na2SO4, and filtered. The filtrate was
concentrated and reprecipitated with ethyl acetate–hexane (1:2) to
afford compound 21 as a white solid (2.1 g, 78%). 1H NMR (400 MHz,
(12H, s, ArH), 4.89 (12H, s, ArCH2O), 3.99–3.91 (36H, m, CH2CH2O),
1.87–1.70 (36H, m, CH2CH2CH2O), 1.52–1.37 (36H, br,
CH2CH2CH2CH2O), 1.37–1.19 (288H, br, CH2), 0.89–0.85 (54H, m,
CH3); 13C{1H} NMR (100 MHz, CDCl3):
d 156.79, 153.25, 144.74,
139.65, 137.95, 132.08, 131.74, 130.00, 113.31, 106.25, 73.36, 70.37,
69.04, 62.55, 31.92, 31.89, 30.32, 29.73, 29.72, 29.68, 29.63, 29.62,
29.40, 29.38, 29.35, 26.12, 26.09, 22.66, 14.08; IR (neat): 2922, 1589,
1505, 1435, 1377, 1334, 1239, 1181, 1115, 1012, 821, 721, 635, 599,
542 cmꢁ1; Anal. Calcd for C302H502O24: C, 80.30; H, 11.20. Found: C,
80.12; H, 11.44.
4.3.15. 4,40-Bis[bis(4-methoxyphenyl)-4-hydroxyphenylmethyl]-
biphenyl (24)
CDCl3):
d
7.21–7.14 (12H, m, ArH), 6.82 (8H, d, J¼8.8 Hz, ArH), 3.80
In an oven-dried 50 ml three-necked flask equipped with
a condenser, mechanical stirrer, and argon system were placed
magnesium turnings (0.58 g, 24 mmol) with dry THF (30 ml). 4-
Bromoanisole (3.0 g, 16 mmol) was added dropwise with gentle
heating until the reaction was started. The reaction was allowed to
go for 1 h. A brown color was observed. Dimethyl 4,40-biphe-
nyldicarboxylate 20 (1.1 g, 4.0 mmol) was added. The mixture was
stirred overnight under argon. The reaction mixture was neutral-
ized with 5 wt % HCl aq and extracted with CHCl3. The collected
organic fraction was washed with water, dried over Na2SO4, and
filtered. The solvent was removed in vacuo and crude compound of
4,40-bis[bis(4-methoxyphenyl)hydroxymethyl]biphenyl 22 was
obtained as a reddish oil. In a 100 ml flask equipped with a con-
denser, mechanical stirrer, and argon system were placed the crude
22 with phenol (3.8 g, 40 mmol). A few drops of methanesulfonic
acid were added with gentle heating. A deep-red solution was
(12H, s, OCH3); 13C{1H} NMR (100 MHz, CDCl3):
d
158.29, 142.97,
136.11, 130.05, 127.67, 112.93, 86.25, 55.16; IR (KBr): 3496, 2951,
2834, 1723, 1608, 1508, 1463, 1440, 1303, 1251, 1176, 1113, 1069,
1034, 826, 595 cmꢁ1
.
4.3.12. 1,4-Bis[bis(4-methoxyphenyl)-4-hydroxyphenylmethyl]-
benzene (23)
In a 100 ml flask equipped with a condenser, mechanical stirrer,
and argon system was placed 1,4-bis[bis(4-methoxyphenyl)-
hydroxymethyl]benzene 21 (2.1 g, 2.9 mmol) with phenol (3.5 g,
38 mmol). A few drops of methanesulfonic acid were added with
gentle heating. A deep-red solution was obtained. The reaction
mixture was stirred for 18 h at 120 ꢀC. Reprecipitation with meth-
anol–H2O (10:1) afforded compound 23 as a white solid (1.2 g, 43%).
1H NMR (400 MHz, CDCl3):
d 7.06–7.00 (16H, m, ArH), 6.76 (8H, d,

8378
T. Hatano, T. Kato / Tetrahedron 64 (2008) 8368–8380
obtained. The reaction mixture was stirred for 36 h at 120 ꢀC.
Reprecipitation with methanol–H2O (6:1) and following washing
with CHCl3 afforded compound 24 as a pale yellow solid (0.91 g,
chromatographed on silica with CHCl3–methanol (10:1) to afford
compound 28 as a white solid (0.13 g, 25%). 1H NMR (400 MHz,
CDCl3):
d
8.58 (2H, s, PyH), 8.31 (2H, d, J¼8.4 Hz, PyH), 7.78 (2H, d,
23%). 1H NMR (400 MHz, DMSO-d6):
d
9.40 (2H, s, OH), 7.55 (4H, d,
J¼8.4 Hz, PyH), 7.19 (8H, d, J¼9.6 Hz, ArH), 6.85 (8H, d, J¼8.8 Hz,
J¼8.4 Hz, ArH), 7.13 (4H, d, J¼8.4 Hz, ArH), 7.00 (8H, d, J¼8.8 Hz,
ArH), 6.88 (4H, d, J¼8.8 Hz, ArH), 6.83 (8H, d, J¼8.8 Hz, ArH), 6.66
(4H, d, J¼8.8 Hz, ArH), 3.70 (12H, s, OCH3).
ArH), 3.81 (12H, s, OCH3), 2.76 (12H, s, OH); 13C{1H} NMR (100 MHz,
CDCl3):
d 158.15, 153.73, 148.65, 143.07, 138.81, 135.87, 128.76,
119.44, 112.72, 54.84; m/z (MALDI-TOF) 641.66 (calcd
[MþH]þ¼641.27); IR (KBr): 3299, 2955, 2835, 1608, 1509, 1463,
4.3.16. 4,40-Bis[tris(4-hydroxyphenyl)methyl]biphenyl (26)
1298, 1254, 1175, 1035, 915, 830, 747, 608, 589 cmꢁ1
.
1,4-Bis[bis(4-methoxyphenyl)-4-hydroxyphenylmethyl]-
benzene 24 (0.72 g, 0.91 mmol) was placed in a 100 ml two-neck
flask equipped with mechanical stirrer and argon system. Dry
CH2Cl2 (50 ml) was added and the mixture was kept at ꢁ78 ꢀC. A
1.0 M solution of BBr3 in methylene chloride (4.0 ml, 4.0 mmol) was
slowly added. The temperature was slowly raised to 25 ꢀC and the
mixture was stirred for 12 h at 25 ꢀC. The reaction was quenched
with water at 0 ꢀC and generated precipitate was filtered. Reddish
brown solid was obtained by washing with water and chloroform
(0.59 g, 88%). The compound was used without further purification.
4.3.19. 5,50-Bis[bis(4-methoxyphenyl)-4-hydroxyphenylmethyl]-
2,20-bipyridyl (29)
In a 100 ml flask equipped with a condenser, mechanical stirrer,
and argon system were placed 5,50-bis[bis(4-methoxyphenyl)hy-
droxymethyl]-2,20-bipyridyl 28 (0.13 g, 0.20 mmol) with phenol
(0.38 g, 4.0 mmol). A few drops of methanesulfonic acid were
added with gentle heating. A deep-red solution was obtained. The
reaction mixture was stirred for 18 h at 120 ꢀC. Reprecipitation with
methanol–H2O (1:1) afforded compound 29 as a white solid (0.11 g,
1H NMR (400 MHz, DMSO-d6):
d
9.34 (6H, s, OH), 7.55 (4H, s, ArH),
67%). 1H NMR (400 MHz, DMSO-d6: CDCl3¼1:10):
d 8.49 (2H, s,
7.12 (4H, d, J¼8.4 Hz, ArH), 6.88 (12H, d, J¼8.8 Hz, ArH), 6.65 (12H, d,
PyH), 8.23–8.19 (4H, m, OH and PyH), 7.63 (2H, d, J¼6.0 Hz, PyH),
7.08 (8H, d, J¼8.8 Hz, ArH), 6.98 (4H, d, J¼8.8 Hz, ArH), 6.78 (8H, d,
J¼8.8 Hz, ArH), 6.74 (4H, d, J¼8.4 Hz, ArH), 3.79 (12H, s, OCH3).
J¼8.8 Hz, ArH); 13C{1H} NMR (100 MHz, DMSO-d6):
d 155.10,146.96,
137.52, 136.79, 131.50, 130.97, 125.46, 114.19, 62.06; m/z (MALDI-
TOF) 734.05 (calcd [M]þ¼734.27); IR (KBr): 3360, 1609, 1594, 1507,
1437, 1362, 1237, 1177, 1111, 1014, 1004, 825, 583 cmꢁ1
.
4.3.20. 5,50-Bis[tris(4-hydroxyphenyl)methyl]-2,20-bipyridyl (30)
5,50-Bis[bis(4-methoxyphenyl)-4-hydroxyphenylmethyl]-2,20-
bipyridyl 29 (50 mg, 0.063 mmol) was placed in a 100 ml two-neck
flask equipped with mechanical stirrer and argon system. Dry
CH2Cl2 (20 ml) was added and the mixture was kept at ꢁ78 ꢀC. A
1.0 M solution of BBr3 in methylene chloride (1.0 ml, 1.0 mmol) was
slowly added. The temperature was slowly raised to 25 ꢀC and the
mixture was stirred for 12 h at 25 ꢀC. The reaction was quenched
with water at 0 ꢀC and generated precipitate was filtered. A pale
yellow solid was obtained by washing with water and chloroform
(30 mg, 65%). The compound was used without further purification.
4.3.17. 1,4-Bis[tris(4-(3,4,5-tridodecyloxybenzyloxy)phenyl)-
methyl]biphenyl (6)
To a DMF (15 ml) solution of 4,40-bis[tris(4-hydroxyphenyl)-
methyl]biphenyl 26 (60 mg, 0.082 mmol) and 3,4,5-tridodecyloxy-
benzyl chloride (0.40 g, 0.60 mmol) was added K2CO3 (0.28 g,
2.0 mmol). The reaction mixture was then stirred under Ar atmo-
sphere at 70 ꢀC for 6 h. To the reaction mixture, water (150 ml) was
added and extracted with hexane. The collected organic fraction
was washed with water, dried over Na2SO4, and filtered. The sol-
vent of the filtrate was removed under reduced pressure. Purifi-
cation with GPC (JAIGEL 1H and 2.5H, CHCl3, 3.8 ml minꢁ1) and
column chromatography (silicagel, hexane–ethyl acetate¼20:1)
gave a white highly viscous oil (0.23 g, 61%). 1H NMR (400 MHz,
1H NMR (400 MHz, DMSO-d6):
d 9.41 (6H, s, OH), 8.31 (2H, s, PyH),
8.28 (2H, d, J¼8.4 Hz, PyH), 7.69 (2H, d, J¼8.4 Hz, PyH), 6.87 (12H, d,
J¼8.4 Hz, ArH), 6.67 (12H, d, J¼8.0 Hz, ArH); 13C{1H} NMR
(100 MHz, DMSO-d6):
d 155.64, 148.06, 146.63, 146.27, 142.19,
CDCl3):
d
7.49 (4H, d, J¼8.4 Hz, ArH), 7.24 (4H, d, J¼8.4 Hz, ArH), 7.12
135.88, 131.31, 121.82, 114.75, 60.79; m/z (MALDI-TOF) 737.48 (calcd
(12H, d, J¼8.8 Hz, ArH), 6.88 (12H, d, J¼8.8 Hz, ArH), 6.62 (12H, s,
ArH), 4.90 (12H, s, ArCH2O), 3.99–3.91 (36H, m, CH2CH2O), 1.87–
1.70 (36H, m, CH2CH2CH2O), 1.52–1.37 (36H, br, CH2CH2CH2CH2O),
1.37–1.19 (288H, br, CH2), 0.89–0.85 (54H, m, CH3); 13C{1H} NMR
[MþH]þ¼737.27); IR (KBr): 3283,1609,1546,1509,1469,1436,1374,
1262, 1177, 1113, 1013, 829, 733, 587 cmꢁ1
.
4.3.21. 5,50-Bis[tris(4-(3,4,5-tridodecyloxybenzyloxy)phenyl)-
methyl]-2,20-bipyridyl (7)
(100 MHz, CDCl3):
d 156.79, 153.24, 146.48, 139.59, 137.92, 137.71,
132.04, 131.75, 131.47, 125.67, 113.44, 106.23, 73.35, 69.02, 62.71,
31.92, 31.89, 30.32, 29.73, 29.71, 29.68, 29.61, 29.59, 29.37, 29.34,
26.11, 26.08, 22.67, 22.66, 14.08; m/z (MALDI-TOF) 4594.9 (calcd
[MþH]þ¼4594.3); IR (neat): 2922, 2852, 1590, 1505, 1467, 1439,
To a DMF (15 ml) solution of 4,40-bis[tris(4-hydroxyphenyl)-
methyl]biphenyl 30 (50 mg, 0.068 mmol) and 3,4,5-tridodecyloxy-
benzyl chloride (0.33 g, 0.49 mmol) was added K2CO3 (0.30 g,
2.2 mmol). The reaction mixture was then stirred under Ar atmo-
sphere at 70 ꢀC for 6 h. To the reaction mixture, water (150 ml) was
added and extracted with hexane. The collected organic fraction
was washed with water, dried over Na2SO4, and filtered. The sol-
vent of the filtrate was removed under reduced pressure. Purifi-
cation with GPC (JAIGEL 1H and 2.5H, CHCl3, 3.8 ml minꢁ1) and
column chromatography (silicagel, hexane–ethyl acetate¼10:1)
gave a white highly viscous oil (0.12 g, 38%). 1H NMR (400 MHz,
1377, 1334, 1294, 1239, 1182, 1116, 1004, 824, 721, 592, 529 cmꢁ1
;
Anal. Calcd for C308H506O24: C, 80.54; H, 11.10. Found: C, 80.39; H,
11.29.
4.3.18. 5,50-Bis[bis(4-methoxyphenyl)hydroxymethyl]-2,20-
bipyridyl (28)
In an oven-dried 50 ml three-necked flask equipped with
a condenser, mechanical stirrer, and argon system were placed 4-
bromoanisole (0.90 g, 4.8 mmol) with dry THF (30 ml). A 1.6 M
solution of buthyllithium in hexane (3.3 ml, 5.3 mmol) was added
dropwise at ꢁ78 ꢀC. After the reaction was kept for 1 h, the tem-
perature of the reaction mixture was raised to 0 ꢀC. Dimethyl 2,20-
bipyridyl-5,50-dicarboxylate 27 (0.24 g, 0.80 mmol) was added and
the mixture was stirred overnight under argon. The reaction
mixture was neutralized with 5 wt % HCl aq and extracted with
CHCl3. The collected organic fraction was washed with water, dried
over Na2SO4, and filtered. The filtrate was concentrated and
CDCl3):
d
8.51 (2H, s, PyH), 8.26 (2H, d, J¼8.0 Hz, PyH), 7.65 (2H, d,
J¼8.4 Hz, PyH), 7.00 (12H, d, J¼8.0 Hz, ArH), 6.88 (12H, d, J¼8.8 Hz,
ArH), 6.62 (12H, s, ArH), 4.90 (12H, s, ArCH2O), 3.99–3.92 (36H, m,
CH2CH2O), 1.85–1.70 (36H, m, CH2CH2CH2O), 1.52–1.37 (36H,
br, CH2CH2CH2CH2O), 1.37–1.19 (288H, br, CH2), 0.89–0.85 (54H,
m, CH3); 13C{1H} NMR (100 MHz, CDCl3):
d 157.06, 153.27, 153.09,
151.81, 143.09, 138.87, 138.56, 137.97, 131.85, 131.63, 119.44,
113.76, 106.26, 73.38, 70.45, 69.05, 61.25, 31.92, 31.90, 30.32, 29.96,
29.74, 29.71, 29.68, 29.63, 29.40, 29.38, 29.35, 26.11, 26.08, 22.68,
22.66, 14.09; m/z (MALDI-TOF) 4595.7 (calcd [M]þ¼4595.3); IR

T. Hatano, T. Kato / Tetrahedron 64 (2008) 8368–8380
8379
(neat): 2922, 2852, 1733, 1589, 1505, 1464, 1436, 1378, 1334, 1238,
0.39 mmol), Pd(PPh3)4 (100 mg), and sodium carbonate (0.54 g,
5.1 mmol) in 10 ml of THF and 2.5 ml of water was degassed and
stirred at 80 ꢀC for 48 h. The mixture was cooled to room temper-
ature and diluted with 100 ml of chloroform. The organic layer was
collected, washed with water, dried over sodium sulfate, and then
the solvent was removed. The residue was chromatographed on
silica with chloroform and then obtained solid was washed with
ethyl acetate to give the desired compounds as a white solid (0.21 g,
1181, 1115, 1012, 825, 721, 595 cmꢁ1; Anal. Calcd for C306H504N2O24
C, 79.98; H, 11.05; N, 0.61. Found: C, 79.69; H, 11.23; N, 0.64.
:
4.3.22. Bis(4-methoxyphenyl)-4-bromophenylmethanol (32)
In an oven-dried 50 ml three-necked flask equipped with
a condenser, mechanical stirrer, and argon system were placed
magnesium turnings (0.50 g, 21 mmol) with dry THF (30 ml). 4-
Bromoanisole (3.0 g, 16 mmol) was added dropwise with gentle
heating until the reaction was started. The reaction was allowed to
go for 1 h. A brown color was observed. Ethyl 4-bromobenzoate 31
(1.8 g, 7.6 mmol) was added. The mixture was stirred overnight
under argon. The reaction mixture was neutralized with 5 wt % HCl
aq and extracted with CHCl3. The collected organic fraction was
washed with water, dried over Na2SO4, and filtered. The filtrate was
concentrated and chromatographed on silica with 20% ethyl acetate
in hexane to afford compound 13 as a reddish oil (2.5 g, 82%). 1H
60%). 1H NMR (400 MHz, CDCl3):
d 7.65 ppm (4H, s, ArH), 7.52 (4H,
d, J¼8.8 Hz, ArH), 7.25 (4H, d, J¼8.8 Hz, ArH), 7.13 (12H, d, J¼9.2 Hz,
ArH), 6.80 (12H, d, J¼8.4 Hz, ArH), 3.80 (18H, s, OCH3); 13C{1H} NMR
(100 MHz, CDCl3):
d 157.44, 146.74, 139.39, 139.32, 137.74, 132.02,
131.39, 127.19, 125.76, 112.65, 62.67, 55.16; IR (KBr): 3030, 2949,
2834, 1605, 1581, 1507, 1488, 1462, 1442, 1304, 1288, 1252, 1182,
1117, 1034, 823, 812, 590, 581 cmꢁ1
.
4.3.26. 4,400-Bis[tris(4-hydroxyphenyl)methyl]-[1,10,40,100]-
NMR (400 MHz, CDCl3):
d
7.42 (2H, d, J¼8.8 Hz, ArH), 7.17 (2H, d,
terphenyl (36)
J¼8.8 Hz, ArH), 7.14 (4H, d, J¼8.8 Hz, ArH), 6.83 (4H, d, J¼8.8 Hz,
4,400-Bis[tris(4-methoxyphenyl)methyl]-[1,10,40,100]-terphenyl 35
(0.72 g, 0.91 mmol) was placed in a 100 ml two-neck flask equipped
with mechanical stirrer and argon system. Dry CH2Cl2 (50 ml) was
added and the mixture was kept at ꢁ78 ꢀC. A 1.0 M solution of BBr3
in methylene chloride (4.0 ml, 4.0 mmol) was slowly added. The
temperature was slowly raised to 25 ꢀC and the mixture was stirred
for 12 h at 25 ꢀC. The reaction was quenched with water at 0 ꢀC and
generated precipitate was filtered. Reddish brown solid was
obtained by washing with water and chloroform (0.59 g, 88%). The
compound was used without further purification. 1H NMR
ArH), 3.80 (6H, s, OCH3), 2.70 (1H, s, OH); 13C{1H} NMR (100 MHz,
CDCl3):
113.07, 80.90, 55.01; IR (neat): 3486, 2955, 2836, 1605, 1463, 1243,
1116, 1072, 1009, 905, 826, 733, 585 cmꢁ1
Anal. Calcd for
21H19BrO3: C, 63.17; H, 4.80. Found: C, 62.95; H, 4.79.
d 158.44, 146.31, 138.78, 130.64, 129.48, 128.92, 120.89,
;
C
4.3.23. 4-[Bis(4-methoxyphenyl)-4-bromophenylmethyl]-
phenol (33)
In a 100 ml flask equipped with a condenser, mechanical stirrer,
and argon system were placed bis(4-methoxyphenyl)-4-bromo-
phenylmethanol 32 (4.5 g, 11 mmol) with phenol (6.0 g, 64 mmol).
A few drops of methanesulfonic acid were added with gentle
heating. A deep-red solution was obtained. The reaction mixture
was stirred for 18 h at 120 ꢀC. The reaction mixture was poured into
water and extracted with ethyl acetate. The organic layer was dried
with sodium sulfate and concentrated. The crude compound was
chromatographed on silica with 25% ethyl acetate in hexane to af-
ford compound 33 as a reddish oil (3.4 g, 65%). 1H NMR (400 MHz,
(400 MHz, DMSO-d6): d 9.33 (6H, s, OH), 7.75 (4H, s, ArH), 7.64 (4H,
d, J¼8.8 Hz, ArH), 7.16 (4H, d, J¼8.8 Hz, ArH), 6.90 (12H, d, J¼8.8 Hz,
ArH), 6.66 (12H, d, J¼8.4 Hz, Ar); 13C{1H} NMR (100 MHz, DMSO-
d6):
d 155.09, 147.22, 138.42, 137.50, 136.52, 131.49, 131.02, 126.93,
125.40, 114.20, 62.08; IR (KBr): 3559, 1699, 1610, 1593, 1507, 1488,
1440, 1362, 1235, 1177, 1111, 1014, 1004, 823, 579 cmꢁ1
.
4.3.27. 4,400-Bis[tris(4-(3,4,5-tridodecyloxybenzyloxy)phenyl)-
methyl]-[1,10,40,100]-terphenyl (8)
CDCl3):
(2H, d, J¼9.2 Hz, ArH), 6.71 (2H, d, J¼8.8 Hz, ArH), 3.79 (6H, s,
OCH3); 13C{1H} NMR (100 MHz, CDCl3):
157.50, 153.58, 146.66,
d
7.35 (2H, d, J¼8.4 Hz, ArH), 7.07–6.98 (6H, m, ArH), 6.78
To a DMF (10 ml) solution of 4,400-bis[tris(4-hydroxyphenyl)-
methyl]-[1,10,40,100]-terphenyl 36 (50 mg, 0.062 mmol) and 3,4,5-
tridodecyloxybenzyl chloride (0.30 g, 0.44 mmol) was added K2CO3
(0.14 g, 1.0 mmol). The reaction mixture was then stirred under Ar
atmosphere at 70 ꢀC for 6 h. To the reaction mixture, water (100 ml)
was added and extracted with hexane. The collected organic frac-
tion was washed with water, dried over Na2SO4, and filtered. The
solvent of the filtrate was removed under reduced pressure. Puri-
fication with GPC (JAIGEL 1H and 2.5H, CHCl3, 3.8 ml minꢁ1) and
column chromatography (silicagel, hexane–ethyl acetate¼10:1)
d
139.05, 138.90, 132.68, 132.10, 131.89, 130.41, 119.85, 114.27, 112.75,
62.54, 55.18; m/z (MALDI-TOF) 474.54 (calcd [M]þ¼474.08); IR
(neat): 3868, 3033, 2834, 1606, 1505, 1247, 1177, 1034, 1009, 907,
817, 752, 580, 539 cmꢁ1
.
4.3.24. Tris(4-methoxyphenyl)-4-bromophenylmethane (34)
4-[Bis(4-methoxyphenyl)-4-bromophenylmethyl]phenol
33
(3.4 g, 7.2 mmol) and K2CO3 (2.0 g, 15 mmol) were placed in
a 100 ml two-neck flask equipped with mechanical stirrer and ar-
gon system. Dry DMF (50 ml) and methyliodide (2.0 g, 14 mmol)
were added and the reaction mixture was stirred at 25 ꢀC for 12 h.
The reaction mixture was neutralized with 5 wt % HCl aq and
extracted with CHCl3. The collected organic fraction was washed
with water, dried over Na2SO4, and filtered. The filtrate was con-
centrated and chromatographed on silica with CHCl3–hexane (1:1)
to afford compound 34 as a white solid (2.4 g, 68%). 1H NMR
gave a colorless oil (0.14 g, 49%). 1H NMR (400 MHz, CDCl3):
d 7.66
(4H, s, ArH), 7.53 (4H, d, J¼8.8 Hz, ArH), 7.26 (4H, m, ArH), 7.14 (12H,
d, J¼8.4 Hz, ArH), 6.88 (12H, d, J¼8.8 Hz, Ar), 6.61 (12H, s, ArH), 4.91
(12H, s, ArCH2O), 3.99–3.92 (36H, m, CH2CH2O), 1.85–1.70 (36H, m,
CH2CH2CH2O), 1.52–1.37 (36H, br, CH2CH2CH2CH2O), 1.37–1.19
(288H, br, CH2), 0.89–0.85 (54H, m, CH3); 13C{1H} NMR (100 MHz,
CDCl3):
d 156.80, 153.26, 146.66, 139.59, 139.28, 137.93, 137.77,
132.04, 131.78, 131.39, 127.16, 125.74, 113.49, 106.24, 73.37, 70.38,
69.04, 62.74, 31.92, 31.90, 30.32, 29.74, 29.72, 29.68, 29.63, 29.62,
29.60, 29.40, 29.38, 29.35, 26.12, 26.08, 22.66, 14.09; m/z (MALDI-
TOF) 4676.8 (calcd [MþLi]þ¼4676.3); IR (neat): 2923, 1591, 1505,
1439, 1377, 1334, 1238, 1181, 1116, 1004, 908, 824, 721, 635, 593,
540 cmꢁ1; Anal. Calcd for C314H510O24: C, 80.77; H, 11.01. Found: C,
80.67; H, 11.14.
(400 MHz, CDCl3):
d
7.35 (2H, d, J¼8.4 Hz, ArH), 7.07–7.03 (8H, m,
ArH), 6.78 (6H, d, J¼9.2 Hz, ArH), 3.79 (6H, s, OCH3); 13C{1H} NMR
(100 MHz, CDCl3):
d 157.53, 146.72, 138.91, 132.69, 131.89, 130.41,
119.85, 112.74, 62.54, 55.15; IR (KBr): 3035, 2948, 2834, 1605, 1576,
1508, 1457, 1392, 1292, 1250, 1180, 1034, 1009, 822, 580 cmꢁ1
.
4.3.25. 4,400-Bis[tris(4-methoxyphenyl)methyl]-[1,10,40,100]-
terphenyl (35)
Acknowledgements
A mixture of tris(4-methoxyphenyl)-4-bromophenylmethane
34 (0.40 g, 0.82 mmol), 1,4-phenyldiboronic acid (65 mg,
Partial financial support of Grant-in-Aid for Creative Scientific
Research of ‘Invention of Conjugated Electric Structures and Novel

8380
T. Hatano, T. Kato / Tetrahedron 64 (2008) 8368–8380
Matsuo, Y.; Kanie, K.; Kato, T.; Nakamura, E. Nature 2002, 419, 702–705; (f)
Matsuo, Y.; Muramatsu, A.; Kamimawa, Y.; Kato, T.; Nakamura, E. J. Am. Chem.
Soc. 2006, 128, 9586–9587.
Functions’ (No. 16GS0209) (T.K. and T.H.) from the Japan Society for
the Promotion of Science (JSPS) and for The Global COE program for
Chemistry Innovation from the Ministry of Education, Culture,
Sports, Science and Technology is gratefully acknowledged. The
authors thank Mr. Satoshi Kajiyama and Mr. Shogo Yamane for
technical assistance.
ˆ
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