Synthesis and characterization of anthracene-clustering dendrimers: Observation of fluorescence resonance energy transfer in the multichromophoric system

Article abstract of DOI:10.1016/j.tet.2004.09.096

A series of anthracene-clustering dendrimers bearing various aliphatic substituents at the terminal positions were synthesized using a direct coupling strategy. A remarkable effect of the side chains was imparted to chemical properties of the dendrimers s

Full text of DOI:10.1016/j.tet.2004.09.096

Tetrahedron 60 (2004) 11771–11781
Synthesis and characterization of anthracene-clustering
dendrimers: observation of fluorescence resonance energy
transfer in the multichromophoric system
a,*
b
Masaki Takahashi, Hironao Morimoto, Yousuke Suzuki, Tomoya Odagi,
a
b
a
Mitsuji Yamashita and Hideki Kawai
c
a
Department of Materials Science and Chemical Engineering, Faculty of Engineering, Shizuoka University, 3-5-1 Johoku, Hamamatsu,
Shizuoka 432-8561, Japan
b
Graduate School of Science and Engineering, Shizuoka University, 3-5-1 Johoku, Hamamatsu, Shizuoka 432-8561, Japan
c
Research Institute of Electronics, Shizuoka University, 3-5-1 Johoku, Hamamatsu, Shizuoka 432-8011, Japan
Received 27 August 2004; revised 28 September 2004; accepted 29 September 2004
Available online 18 October 2004
Abstract—A series of anthracene-clustering dendrimers bearing various aliphatic substituents at the terminal positions were synthesized
using a direct coupling strategy. A remarkable effect of the side chains was imparted to chemical properties of the dendrimers such as
drastically increased solubility. Although the multibranched anthracene arrays in the dendritic architectures exhibited no cooperativity in
terms of the absorption feature and behaved as single chromophoric systems, investigations focusing on fluorescence properties revealed that
a type of cooperativity was present as expressed in the reduced quantum yields of fluorescence. An alternative approach utilizing time-
resolved fluorescence decay measurements clearly demonstrated that the most reasonable mechanism of the cooperative action should
involve two discernible channels of intramolecular fluorescence resonance energy transfer (FRET) occurring from one chromophore to the
others within and across junctions of the branching units.
q 2004 Elsevier Ltd. All rights reserved.
1. Introduction
system since the light-harvesting step is the first critical
1
3
event in the natural photosynthetic processes. In this
regard, anthracene is envisaged as a potentially function-
alized candidate for use in the light-harvesting dendrimers
due to its high absorption coefficient as well as its high
fluorescence quantum yield. Recently, we have reported that
a primitive type of anthracene-clustering dendrimer 1 (RZ
H in Fig. 1), which represents an aggregated form of
anthracene chromophores immobilized in a dendritic
framework, exhibited an energy transport property within
the supramolecular framework. Although this property
has been shown to be of direct relevance to practical
fabrication of fluorescence resonance dendritic antennae,
the resulting dendrimer exhibited poor solubility in common
organic solvents and certain structural modification should
therefore be given to establish more practical molecular
systems. As part of our continuing efforts in synthesis and
investigation of the designed molecules, we report here a
convenient and general protocol for the preparation of
anthracene-clustering dendrimers bearing various aliphatic
side chains at their peripheral positions. During the course
of studying effects of the substituents on physical and
chemical properties of the dendrimers, we found that the
presence of aliphatic auxiliaries markedly affected the
solubility in a wide range of organic solvents without
Nature has developed the most sophisticated solar energy
storage systems in photosynthetic organisms, which contain
large numbers of porphyrins held in particular three-
1
,2
dimensional arrays. These complex assemblies capture
photons at the light-harvesting antenna pigments and
transport them into reaction centers for initiation of the
photosynthetic reaction cascades. Based on this fact, a
considerable effort has been devoted to mimic the natural
light-harvesting system in order to create artificial photo-
1
4
3
–8
synthetic models. Since it has been shown that aromatic
dendrimers exhibited the collective phenomena from light-
harvesting peripheral units into molecular centers of their
globular structures, there is much current interest in the
study directed towards designing and synthesizing effective
light-harvesting dendrimers capable of converting solar
9
–12
energy into useable photonic power.
Accordingly,
ensuing search for effective light-collecting antennae may
offer versatile solutions to produce more potential photonic
Keywords: Anthracene; Dendrimer; Fluorescence resonance energy
transfer.
*
Corresponding author. Tel./fax: C81 53 478 1621;
e-mail: tmtakah@ipc.shizuoka.ac.jp
0040–4020/$ - see front matter q 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2004.09.096

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M. Takahashi et al. / Tetrahedron 60 (2004) 11771–11781
of the corresponding Grignard reagents to the carbonyl
group of anthrone, aromatization after acidic dehydration of
the resulting benzhydrol intermediate giving rise to a series
of 9-alkylanthracenes 6, and subsequent chloromethylation
1
5,16
to form the corresponding 4 (Scheme 2).
Alternatively,
one could synthesize the dendritic backbone 5 via catalytic
hydrogenolysis of the Fr e´ chet type dendrimer 7 in
methanolic solvent, which could be prepared by esterifica-
tion of commercially available 3,5-bis(benzyloxy)benzyl
alcohol with trimesoyl chloride under the basic condition
1
7
(
Scheme 3). All these structural components of the
dendritic architectures were purified by recrystallization of
the crude materials prior to their reactions.
Figure 1. Structures of dendrimer 1 and its structurally simplified
analogues 2 and 3.
altering their own photophysical properties. One of the most
remarkable findings in this context is that the aggregated
chromophoric groups exhibited pronounced cooperative
actions of energy transfer from one dendritic branch to the
others as expressed in reduced quantum yields as well as
faster transient decay profiles of their fluorescence signals
relative to monomeric anthracene analogues.
Scheme 2. Synthesis of 4. Conditions: (a) RMgX (XZBr or I)/ether,
benzene (1:1), reflux; (b) (CH O) /HClaq, AcOH, rt.
2 n
2
. Results and discussion
Our previous report has shown that a successive convergent
strategy can be used to construct a multichromophoric array
of anthracenes in the dendritic framework. In this manner,
synthetic route was established in several steps involving
ether bond formation and subsequent esterification to
connect all structural components of the dendritic archi-
tecture. Despite the noteworthy synthetic achievement
with high yields (75–98%) in all steps, the proposed
synthetic strategy employed a multistep sequence of bond-
forming events resulting in low yield recovery of the final
product. To gain convenient access to the functionalized
dendrimers, we decided to pursue an alternative approach of
in situ coupling between anthracene units 4 and a dendritic
backbone 5 as a useful and practical protocol (Scheme 1).
Scheme 3. Synthesis of 5. Conditions: (a) Trimesoyl chloride, Et
3
N/
benzene, rt; (b) cat. Pd–C, H /CHCl , CH OH (1:1).
2
3
3
With two components in hand, a series of dendrimers 1a–g
were synthesized by a straightforward way carrying out the
reaction of 5 with an excess of the corresponding anthryl
chlorides 4. As a result, nucleophilic attacks of phenolate
ions onto 4 preferentially occurred at the multiple reaction
sites of 5, giving rise to the variously substituted dendrimers
1
4
1
(
a–g in predominant yields (50–62%) for all cases
Scheme 4). These dendrimers were purified by recrystal-
lization from chloroform–methanol solutions and were fully
characterized by elemental analyses and a range of
Scheme 1. Retrosynthetic analysis of 1.
All 10-alkyl-substituted 9-anthryl chlorides 4 were prepared
from anthrone according to an established literature
procedure used for preparation of 9-chloromethyl-10-
methylanthracene 4a, which involved nucleophilic addition
Scheme 4. Syntheses of 1, 2, and 3. Conditions: (a) 4 (8.0 equiv), K
2
CO
2
CO
2
CO
3
3
3
(
(
8.0 equiv), 18-Crown-6 (3.0 equiv)/DMF, 55 8C; (b) 4 (2.5 equiv), K
2.5 equiv), 18-Crown-6 (1.0 equiv)/DMF, 55 8C; (c) 4 (1.5 equiv), K
(1.5 equiv), 18-Crown-6 (0.15 equiv)/DMF, 55 8C.

M. Takahashi et al. / Tetrahedron 60 (2004) 11771–11781
11773
Table 1. Size exclusion chromatography (SEC) results and side chain effects on solubilities of dendrimers 1
a
n
a
b
Entry
Formula
M
w
/M
Nominal M
w
M
w
[1] (mmol/mL)
1
1
1
1
1
1
1
a
b
c
d
e
f
C
C
C
C
C
C
C
126
H
132
H
138
H
144
H
156
H
168
H
180
H
96
O
12
1.006
1.003
1.003
1.002
1.004
1.003
1.003
1801
1885
1969
2053
2221
2389
2558
1385
1497
1666
1799
2074
2307
2567
0.6
3.7
5.9
6.6
10.0
37.7
44.5
108
120
132
156
180
204
O
12
12
12
12
12
12
O
O
O
O
O
g
a
Calibrated with narrow-dispersity polystyrene standards.
Maximum concentrations dissolved in chloroform at 20 8C.
b
spectroscopies. In terms of structural details, structural
homogeneity of the products was well confirmed by
with a less steep downward slope as seen in Figure 2. It has
been well recognized in this context that dendritic structures
should be denser and more compact than linear polymers,
giving underestimated values when determining the mol-
1
13
observation of simplicity in the H and C NMR spectra
due to their highly symmetric nature, wherein all the
building components should be equivalent as previously
1
8
ecular weights by calibration with the linear polymers.
1
4
demonstrated. Consequently, this direct synthetic protocol
provides an important strategic advantage over the previous
methodology in accessing higher generation dendritic
systems since this method has simplicity of synthesis
allowing us to form highly ordered symmetric arrays of the
molecular units rapidly. On the other hand, this synthetic
strategy can be applied in the construction of structurally
simpler analogous systems 2 and 3 that possess a small
number of anthracenes, employing the corresponding
phenolic backbones 8 and 9, respectively, instead of 5.
These reactions worked well with less molar equivalents of
Thus, this rule also seems to be applicable to our
macromolecular system functionalized with a range of
alkyl groups at the surfaces of the commonly used dendritic
motif. Table 1 summarizes the molecular weights of the
dendrimers (M ) determined by SEC calibrated with the
w
polystyrene standards. As can be surveyed in Table 1,
the estimated data for the longer chained homologues 1f–g
are close to the nominal molecular weights, whereas those
for the smaller-sized dendrimers should be extremely
deviated from the theoretical values with up to 23% weight
loss. These observations indicate that the longer chained
molecules were behaving as flexible spheres like linear
polymers, which could change substantially in size or shape
through the efficient interaction with solvent molecules.
This correlation may exist only if relative contribution of the
longer alkyl moieties to the macromolecular properties
should be much larger than that of the rigid dendritic shell.
4
and gave rise to the mono- and bichromophoric products
in excellent yields (90–98%) as confirmed by complete
characterization data (Scheme 4).
Size effects of the external functional groups on the
dendritic shell can be inferred from comparison of retention
volumes on the size exclusion chromatography (SEC). This
demonstrated each dendrimer gave a sharp and symmetrical
peak in chloroform with a polydispersity index (PDI)
M /M !1.01 that should be in the range typically found for
In this regard, degree of solvation is suggested to be more
important in interpreting concomitant influence of the
external alkyl groups on the lipophilic nature of dendrimers.
It can be obviously seen that increasing chain length of the
alkyl groups markedly enhanced the relative solubility of
dendrimers in common organic solvents such as chloroform,
THF, and toluene. Table 1 also includes maximum
solubilities of the dendrimers, which were determined by
dissolving the samples in chloroform and measuring their
UV absorption maxima around 380 nm. From these data,
significant difference was observed in the solubility among
the dendrimer derivatives, where the critical concentrations
ranged from 0.6 to 44.5 mmol/L. As a consequence, the
structural modification significantly improved these values
showing the maximum difference to be as large as nearly
w
n
1
7
unified dendrimers (Table 1). Figure 2 shows correlation
diagrams for a series of polystyrene standards, indicating
that retention volumes of the polystyrenes exhibited a linear
dependence on logarithmic number of their averaged
molecular weights following reverse order paralleling the
molecular sizes. Such a trend was observed for the dendritic
system (1a–g), giving the monomodal distribution, albeit
74-fold. These results can be explained on the basis of a
change in hydrodynamic radius of the dendrimers in the
1
8
organic solvents. In general, flexible dendrimers have
mobile structures displaying large changes in hydrodynamic
radii in various solvent systems, whereas rigid dendrimers
are intuitively much more shape persistent and thus show
little change in hydrodynamic radii as a function of
1
9
solvent. The experimental results of our preliminary
studies are in good agreement with this theoretical proposal,
which clearly demonstrates the local structural alteration at
the external surfaces of dendrimers gives the larger
Figure 2. Semilogarithmic plot of average molecular weight versus SEC
retention volumes for polystyrene standards (:) and dendrimers (%).

11774
M. Takahashi et al. / Tetrahedron 60 (2004) 11771–11781
a
hydrodynamic radii and thus renders the resulting molecules
soluble in a wide range of solvents.
Table 2. Fluorescence quantum yields (F
F
) of 1–3
Entry
1
2
3
a
b
c
d
e
f
0.09
0.17
0.20
0.20
0.20
0.20
0.19
0.26
0.32
0.33
0.34
0.36
0.38
0.38
0.36
0.41
0.42
0.43
0.44
0.44
0.44
As part of our continuing interest in the fundamental aspects
of the multichromophoric dendrimer system, we focused
attention on some of their photophysical properties in order
to gain insight into the electronic details of polyaromatic
aggregates. Figure 3 shows representative absorption and
fluorescence spectra for constituent members of ethyl side
chain analogues 1b–3b composed of one to six anthracene
groups, where all signals were normalized with respect to
the corresponding absorption maxima and optical densities
of the chromophoric units, respectively. As shown in
Figure 3, three discrete spectra of 1b–3b exhibited a closely
overlapping feature around three typical absorption maxima
at 359, 378, and 399 nm attributed to p,p* transitions of the
anthracene excitation, while the corresponding molar
absorption coefficients were found to be approximately
proportional to the number of the anthracene units. These
results suggest that the anthracene groups of 1b and 2b
behave like monomeric species and thus the contribution of
each chromophoric unit to the absorption character is
virtually the same in the ground-state, providing little or no
intramolecular electronic interaction. However, pronounced
differences were noticed in the fluorescence emission
spectra of these systems. Figure 3 also illustrates the
steady-state fluorescence spectra of 1b–3b exhibiting the
emission maxima at 407, 430, and 455 nm attributed to
emission from the anthracene groups. It should be noted that
three individual molecules showed markedly different
g
a
20
Determined by referring to the value of anthracene as a standard.
photoproducts in any significant quantities during all
measurements, and neither showed any sign of aggregate
and excimer formation when all these solutions were
dilute enough that intermolecular interactions should be
negligible. While these processes causing a serious decrease
in fluorescence quantum yields can be discounted, intra-
molecular energy transfer mechanism from one branch to
the others provides a plausible rationale for the systematic
decrease of quantum yields. Besides, it was found that a
specific geometrical bias of the methyl group at the C10-
position on the anthracene rings was also attributed to
significant decrease in the quantum yields, where the
methyl-substituted series 1a–3a exhibited the markedly
lowered quantum efficiencies of fluorescence in comparison
to the other series. The interpretation of this effect was that
rotational motion of the methyl group should lead to
effective free rotor radiationless deactivation over the others
as a result of less steric constraints.
intensity levels, whose quantum efficiencies (F ) decreased
F
In our efforts to address a question as to how the
multichromophoric molecular frameworks affect the fluor-
escence efficiencies, we explored an alternative approach
utilizing time-resolved fluorescence decay measurements,
which allow us to gain some further insights into
photodynamic characters during the fluorescence emission
processes. The measurements were performed on the ethyl-
substituted anthracene series 1b–3b, where the samples
were dissolved in THF solutions and the fluorescence decay
traces were recorded at excitation wavelengths of 355 nm as
depicted in Figure 4. The decay traces for the mono-
with an increase in the number of chromophores. This can
be rationalized by assuming that the relative contribution of
each fluorescent unit in the multichromophoric systems
such as 1 and 2 to the emission behavior clearly changed as
expressed in the reduced quantum yields of fluorescence.
Table 2 summarizes estimated values of fluorescence
quantum yields for all dendrimers and their related
analogues. In agreement with the above result, the other
members also showed similar trends of their fluorescence
quantum efficiencies following the order 3O2O1 through-
out the whole given series of molecules. Additionally, the
bi- and multichromophoric systems 1–2 did not produce
chromophoric system 3b followed
a
simple
Figure 3. Absorption (ABS) and steady-state fluorescence spectra (FL) of a
series of 1b (solid line), 2b (dotted line), and 3b (dashed line) in chloroform
solutions. The absorption spectra are normalized at the anthracene maxima
(378 nm). The fluorescence spectra were obtained by excitation at 387 nm
and are normalized to the same optical density at the excitation wavelength.
All measurements were conducted in sufficiently low concentrations
K8 K6
10 –10 mol/mL) of the analytes to exclude the possibilities of
(
intermolecular interactions.
Figure 4. Fluorescence decay profiles of 1b–3b in THF solutions at the
excitation wavelength of 355 nm.

M. Takahashi et al. / Tetrahedron 60 (2004) 11771–11781
11775
monoexponential decrease with a lifetime of 7.3 ns, which
is close to the values reported for 9,10-disubstituted
general and simple methodology. This synthetic procedure
is beneficial and gives many practical and potential
applications for the construction of a variety of higher
generation dendrimer systems composed of anthracene
residues as a functional repeat unit. Investigations of the
physical and chemical properties of the dendrimer deriva-
tives revealed that functionalization of the surface groups of
the dendritic architectures should play critical roles in the
solubility in common organic solvents. Furthermore, we
have demonstrated that these dendrimers exhibited
intriguing photophysical properties in terms of the intra-
molecular FRET between the peripheral chromophoric
units. This photophysical outcome was noticed in the
reduced quantum yields of fluorescence, the emission
spectra, and the more complex time-dependent behavior
due to the chromophore-clustering nature of the dendritic
system. A detailed investigation of this property based on
the time-resolved transient emission measurements revealed
unambiguously that the dendrimer system offered two
discrete channels for the FRET processes occurring from
one chromophore to the others within and across the
junctions of branching units. The results of our preliminary
studies of the dendrimers indicate that this supramolecular
system may act as a potential mediator for energy transport
of absorbed photons and thus offer many advantages for
applications in design and synthesis of artificial light-
harvesting nanostructured materials.
2
1
anthracenes. Under identical conditions, the bichromo-
phoric system 2b behaved similarly attending a mono-
exponential mode of action but with a significantly short
lifetime decay of 5.6 ns. The observation of reduced lifetime
for 2b suggests strongly that a type of cooperativity, which
may be interpreted in terms of intramolecular energy
migration from one chromophore to another, is present in
this molecular system. As a matter of fact, the feasibility of
intramolecular energy transfer step depends to a large extent
upon accessible orientation of neighboring nonbonded
chromophores in the multichromophoric systems. The
structural description of 2b guarantees that two anthracenes
are immobilized in close proximity to interact as confirmed
previously by X-ray structural analysis and molecular
1
4
modeling study. Therefore, it appears that the origin of
energy delocalization responsible for the fast fluorescence
decay can be a result of structurally unique disposal of the
chromophoric groups. In contrast to the relative behavior of
these two examples, the dendritic system 1b showed a
remarkable difference in the decay profile, which follows a
double exponential curve with a much faster decay rate. The
decay curve was well fitted with a double exponential
function, which provides two product distributions classi-
fied into a longer-lived component (5.6 ns, 66%) and a
short-lived component (1.6 ns, 34%). The decay time of the
longer-lived component is in good agreement with that of
2
b and is therefore assigned to originate from the
bichromophoric character of interactions between closely
disposed chromophores within the branching units. From
this, it can be deduced that the presence of the faster decay
component should be explained on the basis of another
radiationless deactivation channel emerging from chromo-
phore-clustering domains in the three-dimensional molecu-
lar framework. As a consequence of these considerations,
we can draw a speculative conclusion that the short-lived
component is attributed to a fluorescence emission involv-
ing interactions from one bichromophoric unit to the other
chromophores. On the other hand, strength of the F o¨ rster-
type energy transfer interactions may depend largely on the
amount of spectral overlap between absorption spectra of
chromophoric acceptors and emission profiles of chromo-
4. Experimental
4.1. General
All solvents and reagents were of reagent grade quality from
Wako Pure Chemicals used without further purification. A
series of polystyrene standards (molecular weightsZ800,
1300, 2000, 2500, and 4000) were purchased from Pressure
1
Chemical Co. and used without further purification. The H
1
3
and C nuclear magnetic resonance (NMR) spectra
operating at the frequencies of 300 and 75 MHz, respect-
ively, were recorded on a JEOL JNM-AL300 spectrometer
in chloroform-d (CDCl ) or acetone-d ((CD ) CO).
3
6
3 2
Chemical shifts are reported in parts per million (ppm)
relative to TMS and the solvent used as internal standards,
and the coupling constants are reported in Hertz (Hz).
Fourier transform infrared (FT-IR) spectra were recorded on
a JASCO FT/IR-410 spectrometer as KBr disks. Absorption
spectra were recorded on a JASCO model V-570 UV-VIS-
NIR spectrophotometer. Fluorescence spectra were
measured on a Hitachi F-4500 spectrofluorometer.
Melting points were determined on a Yanaco MP-S3
melting point apparatus. Fast atom bombardment (FAB)
mass spectra were determined by a JASCO JMS-HX110A
using a 3-nitrobenzyl alcohol matrix. Elemental analyses
were obtained from Perkin-Elmer-240 instrument. Size
exclusion chromatography (SEC) was performed on a
system consisting of a JASCO model 880-PU pump at a
flow rate of 0.5 mL/min and JASCO 875-UV absorbance
detector (254 nm) equipped with a Shodex K-802 column,
where chloroform was used as mobile phase. Time-resolved
fluorescence decay measurements were performed on a
system consisting of a Hamamatsu C5094 imaging spectro-
graph and a B. M. Industries 5022 D. PS. DP.10
2
2–25
phoric donors.
In this context, all three series of
compounds 1–3 showed a considerable degree of spectral
overlap between the absorption and fluorescence spectra
attributed to the anthracene groups, where the absorption
tails extend over the region of the emission bands beyond
4
00 nm (Fig. 3). This spectroscopic feature may offer an
opportunity for the fluorescence resonance energy transfer
FRET), which ultimately provides the energy transport
(
character of the multichromophoric systems. We therefore
conclude that the multichromophoric dendrimer systems
offer a number of opportunities for the intramolecular FRET
pathways available to the efficient energy transport of
captured photons within the nanoscopic dimension of
molecular architectures.
3. Conclusion
In conclusion, we have developed a new synthetic approach
to the anthracene-clustering dendrimers employing a

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M. Takahashi et al. / Tetrahedron 60 (2004) 11771–11781
passively/actively mode-locked Nd:YAG laser employing
the third harmonic at 355 nm. The decays were fitted with
the least-squares (LS) method to evaluate the fluorescence
lifetimes. The quality of the fits has been judged from the
estimated values and residuals. Samples of 9-chloromethyl-
4.2.3. Tris[3,5-bis((10-propyl-9-anthracenediyl)methoxy)-
benzyl] benzene-1,3,5-tricarboxylate 1c. This compound
was obtained (0.20 g, 59%) as a pale yellow powdery
material from chloroform–methanol solution; mp 189–
190 8C; UV (CHCl ) 360 nm (3 40,900), 379 nm (3
3
1
6
K1
66,000), 400 nm (3 63,300); IR (KBr) 1594 cm (C]C),
1
cene 4b, 9-chloromethyl-10-butylanthracene 4d, and a
0-methylanthracene 4a, 9-chloromethyl-10-ethylanthra-
2
6
27
K1
1728 cm
(C]O); MS (FABC) m/z 1969 (MC), 1970
1
5,28–31
1
series of 9-alkylanthracenes 6a–g
were prepared by
(MHC); H NMR (CDCl ) d 1.14 (t, JZ7.3 Hz, 18H,
3
the sequence of procedures reported in the literature. Their
physical properties and spectroscopic data were in full
agreement with those reported earlier. The fluorescence
quantum yields of 1–3 were measured in comparison to
CH CH CH ), 1.82 (sext, JZ7.9 Hz, 12H, CH CH CH ),
2
2
3
2
2
3
3.55 (t, JZ8.0 Hz, 12H, CH CH CH ), 5.41 (s, 6H, CH ),
2
2
3
2
5.86 (s, 12H, CH ), 6.8–6.9 (m, 9H, ArH), 7.4–7.5 (m, 24H,
2
1
3
ArH), 8.2–8.3 (m, 24H, ArH), 9.01 (s, 3H, BzH); C NMR
(CDCl ) d 14.7 (CH ), 24.6 (CH ), 30.4 (CH ), 63.0 (CH ),
2
0
anthracene in ethanol solution (F Z0.27) as a standard.
F
3
3
2
2
2
6
7.3 (CH ), 102.0 (CH), 107.5 (CH), 124.6 (CH), 124.98
2
4
.2. General procedure for the synthesis of 1
(CH), 125.04 (C), 125.1 (C), 125.2 (CH), 126.0 (CH), 129.4
C), 130.9 (C), 133.3 (C), 135.1 (CH), 137.8 (C), 138.1 (C),
160.7 (C), 164.8 (C). Anal. Calcd for C138 12: C,
84.12; H, 6.14; N, 0.00. Found: C, 84.01; H, 6.13; N, 0.02.
(
All dendrimers 1 were prepared as described in the
following typical procedure. For example, synthesis of 1a
was exemplified as follows.
H O
120
4
.2.4. Tris[3,5-bis((10-butyl-9-anthracenediyl)methoxy)-
4
.2.1.
Tris[3,5-bis((10-methyl-9-anthracenediyl)-
benzyl] benzene-1,3,5-tricarboxylate 1d. This compound
was obtained (0.20 g, 56%) as a pale yellow powdery
material from chloroform–methanol solution; mp 187–
methoxy)benzyl] benzene-1,3,5-tricarboxylate 1a. A
solution containing 4a (0.33 g, 1.39 mmol), 5 (0.10 g,
0
1
.17 mmol), potassium carbonate (0.19 g, 1.39 mmol), and
8-crown-6 (0.14 g, 0.52 mmol) in DMF (5 mL) was heated
188 8C; UV (CHCl
64,300), 400 nm (3 61,700); IR (KBr) 1594 cm (C]C),
) 360 nm (3 39,600), 379 nm (3
3
K1
K1
at 55 8C with stirring under argon atmosphere. After 4 h, the
reaction mixture was then precipitated in ice-cold diluted
HCl solution (50 mL). The precipitate was collected by
filtration, intensively washed with water, and dried in a
vacuum to afford a pale yellow solid. After complete
vacuum drying, the solid sample was purified by
recrystallization from chloroform–methanol, affording 1a
1728 cm
(C]O); MS (FABC) m/z 2053 (MC), 2054
1
(MHC); H NMR (CDCl
(CH CH ), 1.57 (sext, JZ7.3 Hz, 12H, (CH
1.7–1.8 (m, 12H, CH CH CH CH ), 3.55 (t, JZ7.9 Hz,
12H, CH (CH CH ), 5.40 (s, 6H, CH ), 5.83 (s, 12H,
CH ), 6.8–6.9 (s, 9H, ArH), 7.4–7.5 (m, 24H, ArH), 8.2–8.3
(m, 24H, ArH), 9.00 (s, 3H, BzH); C NMR (CDCl
) d 1.00 (t, JZ7.3 Hz, 18H,
3
)
)
CH CH ),
2
3
3
2
2
2
3
2
2
2
3
)
2
2
2
3
2
2
1
3
) d 14.0
), 63.0 (CH ), 67.3
), 102.0 (CH), 107.5 (CH), 124.6 (CH), 125.0 (CH),
3
(
0.16 g, 50%) as a pale yellow powdery material; mp 192–
(CH
(CH
3
), 23.4 (CH
2
), 28.1 (CH
2
), 33.5 (CH
2
2
1
3
1
93 8C; UV (CHCl ) 359 nm (3 40,200), 378 nm (3 64,500),
3
2
K1
99 nm (3 60,900); IR (KBr) 1593 cm
732 cm (C]O); MS (FABC) m/z 1801 (sMC), 1802
(C]C),
125.1 (CH), 126.0 (CH), 129.3 (C), 130.9 (C), 131.3 (C),
135.1 (CH), 138.0 (C), 138.1 (C), 160.7 (C), 164.8 (C).
Anal. Calcd for C144H O12: C, 84.18; H, 6.48; N, 0.00.
132
K1
1
(
MHC); H NMR (CDCl ) d 3.05 (s, 18H, CH ), 5.42 (s,
3
3
6
7
H, CH ), 5.83 (s, 12H, CH ), 6.8–6.9 (m, 9H, ArH), 7.4–
2
Found: C, 84.27; H, 6.33; N, 0.09.
2
.5 (m, 24H, ArH), 8.2–8.3 (m, 24H, ArH), 9.02 (s, 3H,
1
3
BzH); C NMR (CDCl ) d 14.4 (CH ), 63.0 (CH ), 67.4
3
4.2.5. Tris[3,5-bis((10-hexyl-9-anthracenediyl)methoxy)-
benzyl] benzene-1,3,5-tricarboxylate 1e. This compound
was obtained (0.20 g, 54%) as a pale yellow powdery
material from chloroform–methanol solution; mp 184–
3
2
(
CH ), 102.2 (CH), 107.6 (CH), 124.5 (CH), 124.9 (CH),
2
1
1
25.3 (CH), 126.0 (CH), 129.9 (C), 130.7 (C), 132.7 (C),
35.1 (CH), 138.0 (C), 160.7 (C), 164.8 (C). Anal. Calcd for
C126H O : C, 83.98; H, 5.37; N, 0.00. Found: C, 83.89; H,
185 8C; UV (CHCl ) 360 nm (3 40,600), 379 nm (3
3
96
12
K1
65,900), 400 nm (3 63,300); IR (KBr) 1594 cm (C]C),
5
.60; N, 0.00.
K1
1
730 cm
(C]O); MS (FABC) m/z 2221 (MC), 2222
1
4
.2.2. Tris[3,5-bis((10-ethyl-9-anthracenediyl)methoxy)-
(MHC); H NMR (CDCl
(CH CH ), 1.3–1.4 (m, 24H, (CH
(m, 12H, (CH CH (CH CH ), 1.7–1.8 (m, 12H, CH2-
CH (CH CH ), 3.55 (t, JZ7.9 Hz, 12H, CH (CH CH ),
5.42 (s, 6H, CH ), 5.85 (s, 12H, CH ), 6.8–6.9 (s, 9H, ArH),
7.4–7.5 (m, 24H, ArH), 8.2–8.3 (m, 24H, ArH), 9.02 (s, 3H,
3
) d 0.91 (t, JZ7.3 Hz, 18H,
benzyl] benzene-1,3,5-tricarboxylate 1b. This compound
was obtained (0.19 g, 60%) as a pale yellow powdery
material from chloroform–methanol solution; mp 191–
2
)
5
3
2
)
3
(CH CH ), 1.5–1.6
2
)
2
3
)
)
2
2
2
2
2
3
)
)
4
2
2
3
3
2
2
3
1
6
1
92 8C; UV (CHCl ) 359 nm (3 42,100), 378 nm (3
3
2
2
K1
6,600), 399 nm (3 63,800); IR (KBr) 1593 cm (C]C),
729 cm
K1
13
(C]O); MS (FABC) m/z 1885 (MC), 1886
BzH); C NMR (CDCl
3
) d 14.1 (CH
), 31.4 (CH ), 31.8 (CH
), 102.1 (CH), 107.5 (CH), 124.7 (CH), 125.0 (CH),
3
), 22.7 (CH
2
), 28.5
), 67.4
2
1
(
MHC); H NMR (CDCl ) d 1.41 (t, JZ7.3 Hz, 18H,
(CH
(CH
2
), 30.1 (CH
2
2
2
), 63.1 (CH
3
CH CH ), 3.59 (q, JZ7.3 Hz, 12H, CH CH ), 5.41 (s, 6H,
2
2
3
2
3
CH ), 5.84 (s, 12H, CH ), 6.8–6.9 (m, 9H, ArH), 7.4–7.5 (m,
125.1 (CH), 126.0 (CH), 129.3 (C), 130.9 (C), 131.4 (C),
135.4 (CH), 135.1 (C), 138.1 (C), 160.7 (C), 164.8 (C).
Anal. Calcd for C156H O12: C, 84.29; H, 7.07; N, 0.00.
156
2
2
1
3
2
4H, ArH), 8.2–8.3 (m, 24H, ArH), 9.00 (s, 3H, BzH);
NMR (CDCl ) d 15.5 (CH ), 21.4 (CH ), 63.0 (CH ), 67.3
C
3
3
2
2
(
CH ), 102.0 (CH), 107.5 (CH), 124.7 (CH), 124.9 (CH),
2
Found: C, 84.29; H, 7.00; N, 0.06.
1
25.1 (CH), 126.0 (CH), 128.9 (C), 130.9 (C), 131.3 (C),
35.1 (CH), 138.1 (C), 139.1 (C), 160.7 (C), 164.8 (C).
Anal. Calcd for C132H108O : C, 84.05; H, 5.77; N, 0.00.
1
4.2.6. Tris[3,5-bis((10-octyl-9-anthracenediyl)methoxy)-
benzyl] benzene-1,3,5-tricarboxylate 1f. This compound
was obtained (0.25 g, 61%) as a pale yellow powdery
12
Found: C, 84.11; H, 5.52; N, 0.05.

M. Takahashi et al. / Tetrahedron 60 (2004) 11771–11781
11777
material from chloroform–methanol solution; mp 181–
CH ), 5.40 (s, 2H, CH ), 5.93 (s, 4H, CH ), 6.92 (s, 3H,
3 2 2
1
6
1
82 8C; UV (CHCl ) 360 nm (3 40,800), 379 nm (3
3
ArH), 7.4–7.6 (m, 11H, ArH), 8.0–8.2 (m, 2H, BzH), 8.2–
8.4 (m, 8H, ArH); C NMR (CDCl ) d 14.5 (CH ), 63.1
(CH ), 66.5 (CH ), 101.4 (CH), 107.1 (CH), 124.6 (CH),
2 2
125.0 (CH), 125.4 (CH), 126.1 (CH), 128.4 (CH), 129.8
(CH), 130.0 (C), 130.1 (C), 130.8 (C), 132.5 (C), 133.1
(CH), 138.7 (C), 160.7 (C), 166.4 (C).
K1
6,200), 400 nm (3 63,600); IR (KBr) 1595 cm (C]C),
13
3
3
K1
731 cm
(C]O); MS (FABC) m/z 2390 (MC), 2391
1
(
(
(
MHC); H NMR (CDCl ) d 0.88 (t, JZ6.8 Hz, 18H,
CH ) CH ), 1.2–1.4 (m, 48H, (CH ) (CH ) CH ), 1.5–1.6
m, 12H, (CH ) CH (CH ) CH ), 1.7–1.8 (m, 12H, CH -
3
2
7
3
2 3
2 4
3
2
2
2
2 4
3
2
CH (CH ) CH ), 3.54 (t, JZ8.0 Hz, 12H, CH (CH ) CH ),
2
2 5
3
2
2 6
3
5
.41 (s, 6H, CH ), 5.84 (s, 12H, CH ), 6.8–6.9 (m, 9H, ArH),
2 2
4
.3.2. 3,5-Bis[(10-ethyl-9-anthracenediyl)methoxy]-
benzyl benzoate 2b. This compound was obtained
0.27 g, 95%) as a pale yellow powdery material from
chloroform–hexane solution; mp 146–147 8C; UV (CHCl3)
7.4–7.5 (m, 24H, ArH), 8.2–8.3 (m, 24H, ArH), 9.01 (s, 3H,
BzH); C NMR (CDCl ) d 14.1 (CH ), 22.7 (CH ), 28.4
1
3
3
3
2
(
(
CH ), 29.3 (CH ), 29.5 (CH ), 30.4 (CH ), 31.4 (CH ), 31.9
2 2 2 2 2
(
CH ), 63.0 (CH ), 67.3 (CH ), 102.1 (CH), 107.5 (CH),
2 2 2
359 nm (3 13,600), 378 nm (3 21,800), 399 nm (3 21,100);
IR (KBr) 1594 cm
1
1
1
8
24.7 (CH), 125.0 (CH), 125.1 (CH), 126.0 (CH), 129.3 (C),
30.9 (C), 131.3 (C), 135.1 (CH), 138.0 (C), 138.1 (C),
60.7 (C), 164.8 (C). Anal. Calcd for C168H180O : C,
12
K1
K1
(C]C), 1719 cm (C]O); MS
FABC) m/z 681 (MC), 682 (MHC); HRMS (FABC) m/z
(
calcd for C H O : 680.2927, found 680.2955; H NMR
1
4
8 40 4
4.38; H, 7.59; N, 0.00. Found: C, 84.09; H, 7.56; N, 0.03.
(CDCl ) d 1.45 (t, JZ7.5 Hz, 6H, CH CH ), 3.66 (q, JZ
3 2 3
7
6
8
.5 Hz, 4H, CH CH ), 5.41 (s, 2H, CH ), 5.91 (s, 4H, CH ),
.92 (s, 3H, ArH), 7.4–7.6 (m, 11H, ArH), 8.09 (d, JZ
.4 Hz, 2H, BzH), 8.1–8.4 (m, 8H, ArH); C NMR (CDCl3)
2 3 2 2
4
.2.7. Tris[3,5-bis((10-decyl-9-anthracenediyl)methoxy)-
benzyl] benzene-1,3,5-tricarboxylate 1g. This compound
was obtained (0.27 g, 62%) as a pale yellow powdery
material from chloroform–methanol solution; mp 174–
13
d 15.5 (CH ), 21.5 (CH ), 63.0 (CH ), 66.5 (CH ), 101.3
2
3
2
2
(
CH), 107.0 (CH), 124.7 (CH), 125.0 (CH), 125.1 (CH),
1
6
1
75 8C; UV (CHCl ) 360 nm (3 41,300), 379 nm (3
3
126.1 (CH), 128.4 (CH), 129.0 (C), 129.8 (CH), 130.0 (C),
130.9 (C), 133.1 (CH), 138.7 (C), 139.2 (C), 160.7 (C),
166.4 (C).
K1
6,400), 400 nm (3 64,000); IR (KBr) 1594 cm (C]C),
K1
730 cm
(C]O); MS (FABC) m/z 2558 (MC), 2559
1
(
(
(
MHC); H NMR (CDCl ) d 0.87 (t, JZ6.8 Hz, 18H,
CH ) CH ), 1.2–1.4 (m, 72H, (CH ) (CH ) CH ), 1.5–1.6
m, 12H, (CH ) CH (CH ) CH ), 1.7–1.8 (m, 12H, CH -
3
2
9
3
2 3
2 6
3
4
.3.3. 3,5-Bis[(10-propyl-9-anthracenediyl)methoxy]-
2
2
2
2 6
3
2
benzyl benzoate 2c. This compound was obtained
0.29 g, 91%) as a pale yellow powdery material from
CH (CH ) CH ), 3.54 (t, JZ7.9 Hz, 12H, CH (CH ) CH ),
2
2 7
3
2
2 8
3
(
5
.41 (s, 6H, CH ), 5.85 (s, 12H, CH ), 6.8–6.9 (m, 9H, ArH),
2 2
chloroform–hexane solution; mp 202–203 8C; UV (CHCl3)
360 nm (3 13,700), 379 nm (3 22,200), 400 nm (3 21,500);
7.4–7.5 (m, 24H, ArH), 8.2–8.3 (m, 24H, ArH), 9.01 (s, 3H,
BzH); C NMR (CDCl ) d 14.1 (CH ), 22.7 (CH ), 28.4
1
3
3
3
2
K1
K1
IR (KBr) 1593 cm
(C]C), 1726 cm
FABC) m/z 709 (MC), 710 (MHC); HRMS (FABC) m/z
(C]O); MS
(
CH ), 29.3 (CH ), 29.6 (CH ), 29.65 (CH ), 29.70 (CH ),
2 2 2 2 2
(
calcd for C H O : 708.3240, found 708.3250; H NMR
3
1
1
1
0.4 (CH ), 31.4 (CH ), 31.9 (CH ), 63.0 (CH ), 67.4 (CH ),
2 2 2 2 2
1
5
0 44 4
02.0 (CH), 107.5 (CH), 124.6 (CH), 124.9 (C), 125.0 (CH),
25.1 (CH), 126.0 (CH), 129.3 (C), 130.9 (C), 131.3 (C),
35.1 (CH), 138.1 (C), 160.7 (C), 164.8 (C). Anal. Calcd for
(CDCl ) d 1.16 (t, JZ7.3 Hz, 6H, (CH ) CH ), 1.86 (sext,
3 2 2 3
JZ7.7 Hz, 4H, CH CH CH ), 3.5–3.7 (m, JZ8.1 Hz, 4H,
CH CH CH ), 5.41 (s, 2H, CH ), 5.91 (s, 4H, CH ), 6.92 (s,
2
2
3
2
2
3
2
2
C180H204O : C, 84.47; H, 8.03; N, 0.00. Found: C, 84.45;
12
H, 7.97; N, 0.04.
3
8
H, ArH), 7.3–7.6 (m, 11H, ArH), 8.0–8.2 (m, 2H, BzH),
.2–8.4 (m, 8H, ArH); C NMR (CDCl ) d 14.7 (CH ), 24.7
1
3
3
3
(
CH ), 30.4 (CH ), 63.1 (CH ), 66.5 (CH ), 101.4 (CH),
2 2 2 2
4
.3. General procedure for the synthesis of 2
1
1
1
1
07.1 (CH), 124.7 (CH), 125.0 (CH), 125.1 (C), 125.2 (CH),
26.1 (CH), 128.4 (CH), 129.4 (C), 129.8 (CH), 130.1 (C),
30.9 (C), 133.0 (CH), 137.9 (C), 138.7 (C), 160.7 (C),
66.4 (C).
All bichromophoric compounds 2 were prepared as
described in the following typical procedure. For example,
synthesis of 2a was exemplified as follows.
4
.3.1. 3,5-Bis[(10-methyl-9-anthracenediyl)methoxy]-
benzyl benzoate 2a. A solution containing 4a (0.25 g,
.02 mmol), 8 (0.10 g, 0.41 mmol), potassium carbonate
0.14 g, 1.02 mmol), and 18-crown-6 (0.11 g, 0.41 mmol) in
4.3.4. 3,5-Bis[(10-butyl-9-anthracenediyl)methoxy]-
benzyl benzoate 2d. This compound was obtained
(0.30 g, 93%) as a pale yellow powdery material from
chloroform–hexane solution; mp 189–190 8C; UV (CHCl3)
360 nm (3 13,400), 379 nm (3 21,900), 400 nm (3 21,200);
1
(
DMF (5 mL) was heated at 55 8C with stirring under argon
atmosphere. After 3 h, the reaction mixture was then
precipitated in ice-cold diluted HCl solution (50 mL). The
precipitate was collected by filtration, intensively washed
with water, and dried in a vacuum to afford a pale yellow
solid. After complete vacuum drying, the solid sample was
purified by recrystallization from chloroform–hexane sol-
ution, affording 2a (0.24 g, 90%) as a pale yellow powdery
K1
K1
IR (KBr) 1593 cm
(C]C), 1716 cm
(C]O); MS
(FABC) m/z 736 (MC), 737 (MHC); HRMS (FABC) m/z
1
calcd for C H O : 736.3553, found 736.3517; H NMR
5
2 48 4
(CDCl ) d 1.02 (t, JZ7.3 Hz, 6H, (CH ) CH ), 1.60 (sext,
3
2 3
3
JZ7.3 Hz, 4H, (CH ) CH CH ), 1.7–1.9 (m, 4H, CH -
2
2
2
3
2
CH CH CH ), 3.61 (t, JZ7.9 Hz, 4H, CH (CH ) CH ),
2
2
3
2
2 2
3
5.41 (s, 2H, CH ), 5.90 (s, 4H, CH ), 6.92 (s, 3H, ArH), 7.3–
7.6 (m, 11H, ArH), 8.0–8.2 (m, 2H, BzH), 8.2–8.4 (m, 8H,
ArH); C NMR (CDCl ) d 14.0 (CH ), 23.4 (CH ), 28.1
2
2
material; mp 243–244 8C; UV (CHCl ) 359 nm (3 13,600),
3
K1
13
3
(
78 nm (3 21,700), 399 nm (3 20,900); IR (KBr) 1595 cm
C]C), 1719 cm (C]O); MS (FABC) m/z 653 (MC),
3
3
2
K1
(CH ), 33.5 (CH ), 63.1 (CH ), 66.5 (CH ), 101.4 (CH),
2 2 2 2
6
6
54 (MHC); HRMS (FABC) m/z calcd for C H O :
6 36 4
107.1 (CH), 124.7 (CH), 125.0 (CH), 125.2 (CH), 126.1
(CH), 128.4 (CH), 129.4 (C), 129.8 (CH), 130.1 (C), 130.9
4
1
52.2614, found 652.2594; H NMR (CDCl ) d 3.13 (s, 6H,
3

11778
M. Takahashi et al. / Tetrahedron 60 (2004) 11771–11781
(
1
C), 131.0 (C), 133.0 (CH), 138.1 (C), 138.7 (C), 160.8 (C),
66.4 (C).
129.3 (CH), 129.8 (C), 130.0 (C), 130.9 (C), 133.1 (C),
138.2 (C), 138.7 (C), 160.7 (C), 166.4 (C).
4
.3.5. 3,5-Bis[(10-hexyl-9-anthracenediyl)methoxy]-
4.4. General procedure for the synthesis of 3
benzyl benzoate 2e. This compound was obtained
0.31 g, 94%) as a pale yellow powdery material from
chloroform–hexane solution; mp 136–137 8C; UV (CHCl3)
(
All monochromophoric compounds 3 were prepared as
described in the following typical procedure. For example,
synthesis of 3a was exemplified as follows.
3
IR (KBr) 1595 cm
(
calcd for C H O : 792.4179, found 792.4208; H NMR
60 nm (3 13,500), 379 nm (3 22,000), 400 nm (3 21,300);
K1
K1
(C]C), 1715 cm (C]O); MS
FABC) m/z 792 (MC), 793 (MHC); HRMS (FABC) m/z
4.4.1. 3-[(10-Methyl-9-anthracenediyl)methoxy]benzyl
benzoate 3a. A solution containing 4a (0.32 g,
1
5
6 56 4
(
8
CDCl ) d 0.92 (t, JZ7.0 Hz, 6H, (CH ) CH ), 1.3–1.5 (m,
1.32 mmol), 9 (0.20 g, 0.88 mmol), potassium carbonate
(0.18 g, 1.32 mmol), and 18-crown-6 (0.04 g, 0.13 mmol) in
DMF (5 mL) was heated at 55 8C with stirring under argon
atmosphere. After 3 h, the reaction mixture was then
quenched by slow addition of 1.0 mol/L HCl. The resulting
mixture was extracted with ethyl acetate, and the combined
organic extracts were intensively washed with water,
3
2 5
3
H, (CH ) (CH ) CH ), 1.5–1.7 (m, 4H, (CH ) CH (CH ) -
2 3 2 2 3 2 2 2 2 2
CH ), 1.7–1.9 (m, 4H, CH CH (CH ) CH ), 3.61 (t, JZ
8
CH ), 6.92 (s, 3H, ArH), 7.3–7.6 (m, 11H, ArH), 8.0–8.2 (m,
2
(
3
2
2
2 3
3
.2 Hz, 4H, CH (CH ) CH ), 5.41 (s, 2H, CH ), 5.91 (s, 4H,
2 2 4 3 2
2
1
3
H, BzH), 8.2–8.4 (m, 8H, ArH); C NMR (CDCl ) d 14.1
3
CH ), 22.7 (CH ), 28.5 (CH ), 30.0 (CH ), 31.4 (CH ), 31.8
3 2 2 2 2
(
CH ), 63.1 (CH ), 66.5 (CH ), 101.4 (CH), 107.1 (CH),
2
saturated NaHCO solution, and brine. The organic layer
3
2
2
1
24.7 (CH), 125.0 (CH), 125.2 (CH), 126.1 (CH), 128.4
was separated, dried over anhydrous Na SO , filtered, and
2
4
(
(
CH), 129.3 (C), 129.8 (CH), 130.1 (C), 130.9 (C), 133.0
CH), 138.1 (C), 138.7 (C), 160.7 (C), 166.4 (C).
concentrated under vacuum to give pale yellow oily residue.
Purification of the residue by silica-gel column chromato-
graphy (50% chloroform, 50% hexane) gave 3a as a pale
yellow crystalline mass (0.36 g, 95%). Further purification
was achieved by recrystallization from chloroform–metha-
nol solution affording purely pale yellow needles; mp 148–
4
.3.6. 3,5-Bis[(10-octyl-9-anthracenediyl)methoxy]-
benzyl benzoate 2f. This compound was obtained (0.35 g,
8%) as a pale yellow powdery material from chloroform–
hexane solution; mp 166–167 8C; UV (CHCl ) 360 nm (3
9
149 8C; UV (CHCl
399 nm (3 10,400); IR (KBr) 1584 cm
1714 cm
) 359 nm (3 7200), 378 nm (3 11,100),
3
3
K1
1
1
8
3,500), 379 nm (3 22,100), 400 nm (3 21,300); IR (KBr)
594 cm (C]C), 1724 cm (C]O); MS (FABC) m/z
48 (MC), 849 (MHC); HRMS (FABC) m/z calcd for
(C]C),
(C]O); MS (FABC) m/z 432 (MC), 433
(MHC); HRMS (FABC) m/z calcd for C30
K1
K1
K1
H O :
24 3
1
1
C H O : 848.4805, found 848.4846; H NMR (CDCl ) d
6
0
432.1725, found 432.1710; H NMR (CDCl
3H, CH ), 5.38 (s, 2H, CH ), 5.93 (s, 2H, CH ), 7.1–7.2 (m,
2H, ArH), 7.22 (br s, 1H, ArH), 7.3–7.6 (m, 8H, ArH), 8.0–
3
) d 3.12 (s,
0
64
4
3
.89 (t, JZ6.8 Hz, 6H, (CH ) CH ), 1.2–1.5 (m, 16H,
3
2
2
2
7
3
(
CH ) (CH ) CH ), 1.5–1.7 (m, 4H, (CH ) CH (CH ) -
2 3 2 4 3 2 2 2 2 4
1
3
CH ), 1.7–1.9 (m, 4H, CH CH (CH ) CH ), 3.62 (t, JZ
8.1 (m, 2H, BzH), 8.2–8.4 (m, 4H, ArH); C NMR (CDCl
)
3
3
2
2
2 5
3
8
CH ), 6.93 (s, 3H, ArH), 7.3–7.6 (m, 11H, ArH), 8.0–8.2 (m,
.2 Hz, 4H, CH (CH ) CH ), 5.41 (s, 2H, CH ), 5.94 (s, 4H,
d 14.5 (CH ), 62.9 (CH ), 66.5 (CH ), 114.5 (CH), 114.6
3
2
2
2
2 6
3
2
(CH), 120.7 (CH), 124.6 (CH), 124.9 (CH), 125.1 (C), 125.4
(CH), 126.0 (CH), 128.4 (CH), 129.7 (CH), 129.8 (CH),
129.9 (C), 130.1 (C), 130.7 (C), 132.8 (C), 133.0 (CH),
137.8 (C), 159.5 (C), 166.4 (C).
2
1
3
2
H, BzH), 8.2–8.4 (m, 8H, ArH); C NMR (CDCl ) d 14.1
3
(
CH ), 22.7 (CH ), 28.5 (CH ), 29.3 (CH ), 29.5 (CH ), 30.4
3 2 2 2 2
(
CH ), 31.4 (CH ), 31.9 (CH ), 63.1 (CH ), 66.5 (CH ),
2 2 2 2 2
1
01.4 (CH), 107.1 (CH), 124.7 (CH), 125.0 (CH), 125.2
(
(
1
CH), 126.1 (CH), 128.4 (CH), 129.4 (C), 129.8 (CH), 130.1
C), 131.0 (C), 133.0 (CH), 138.2 (C), 138.7 (C), 160.8 (C),
66.4 (C).
4.4.2. 3-[(10-Ethyl-9-anthracenediyl)methoxy]benzyl
benzoate 3b. This compound was obtained (0.38 g, 96%)
as a pale yellow powdery material from chloroform–
methanol solution; mp 140–141 8C; UV (CHCl ) 359 nm
3
4
.3.7. 3,5-Bis[(10-decyl-9-anthracenediyl)methoxy]-
(3 7000), 378 nm (3 11,100), 399 nm (3 10,500); IR (KBr)
1583 cm (C]C), 1720 cm (C]O); MS (FABC) m/z
446 (MC), 447 (MHC); HRMS (FABC) m/z calcd for
K1
K1
benzyl benzoate 2g. This compound was obtained
0.36 g, 96%) as a pale yellow powdery material from
chloroform–hexane solution; mp 130–131 8C; UV (CHCl3)
(
1
C
H
O
: 446.1882, found 446.1875; H NMR (CDCl
) d
),
), 7.1–7.2 (m, 2H, ArH),
7.23 (br s, 1H, ArH), 7.3–7.6 (m, 8H, ArH), 8.0–8.1 (m, 2H,
31
26
3
3
3
IR (KBr) 1596 cm
60 nm (3 13,500), 379 nm (3 22,100), 400 nm (3 21,400);
1.46 (t, JZ7.6 Hz, 3H, CH
5.39 (s, 2H, CH ), 5.93 (s, 2H, CH
2
), 3.67 (q, JZ7.6 Hz, 2H, CH
3 2
K1
K1
(C]C), 1714 cm (C]O); MS
FABC) m/z 904 (MC), 905 (MHC); HRMS (FABC) m/z
2
(
calcd for C H O : 904.5431, found 904.5424; H NMR
1
13
BzH), 8.2–8.4 (m, 4H, ArH); C NMR (CDCl
(CH ), 21.5 (CH ), 62.9 (CH ), 66.5 (CH ), 114.4 (CH),
) d 15.5
3
6
4 72 4
(
CDCl ) d 0.90 (t, JZ7.0 Hz, 6H, (CH ) CH ), 1.2–1.5 (m,
3
2
2
2
3
2 9
3
2
4H, (CH ) (CH ) CH ), 1.5–1.7 (m, 4H, (CH ) CH -
114.5 (CH), 120.7 (CH), 124.7 (CH), 125.0 (CH), 125.1
(CH), 125.2 (C), 126.0 (CH), 128.4 (CH), 129.0 (C), 129.7
(CH), 129.8 (CH), 130.1 (C), 131.0 (C), 133.0 (CH), 137.8
(C), 139.2 (C), 159.5 (C), 166.4 (C).
2
3
2 6
3
2 2
2
(
(
(
CH ) CH ), 1.7–1.9 (m, 4H, CH CH (CH ) CH ), 3.64
2 6 3 2 2 2 7 3
t, JZ7.9 Hz, 4H, CH (CH ) CH ), 5.44 (s, 2H, CH ), 5.95
s, 4H, CH ), 6.95 (s, 3H, ArH), 7.44 (t, JZ7.2 Hz, 9H),
2
2 8
3
2
2
7
8
.5–7.6 (m, 9H, ArH), 8.13 (d, JZ7.2 Hz, 2H, BzH), 8.3–
13
.4 (m, 8H, ArH); C NMR (CDCl ) d 14.1 (CH ), 22.7
4.4.3. 3-[(10-Propyl-9-anthracenediyl)methoxy]benzyl
benzoate 3c. This compound was obtained (0.38 g, 95%)
as a pale yellow powdery material from chloroform–
3
3
(
2
6
CH ), 28.5 (CH ), 29.3 (CH ), 29.57 (CH ), 29.63 (CH ),
2 2 2 2 2
9.7 (CH ), 30.4 (CH ), 31.4 (CH ), 31.9 (CH ), 63.0 (CH ),
2 2 2 2 2
6.5 (CH ), 101.3 (CH), 107.0 (CH), 124.6 (CH), 124.96
2
methanol solution; mp 130–131 8C; UV (CHCl ) 360 nm
3
(
CH), 125.04 (CH), 125.2 (CH), 126.1 (CH), 128.4 (CH),
(3 7100), 379 nm (3 11,400), 400 nm (3 10,800); IR (KBr)

M. Takahashi et al. / Tetrahedron 60 (2004) 11771–11781
11779
K1 K1
585 cm (C]C), 1715 cm (C]O); MS (FABC) m/z
60 (MC), 461 (MHC); HRMS (FABC) m/z calcd for
1
4
0.90 (t, JZ6.8 Hz, 3H, (CH ) CH ), 1.2–1.5 (m, 8H,
2 9 3
(CH ) (CH ) CH ), 1.59 (quint, JZ7.7 Hz, 2H, (CH ) -
2 3 2 4 3 2 2
1
C H O : 460.2038, found 460.2053; H NMR (CDCl ) d
3
CH (CH ) CH ), 1.82 (quint, JZ7.8 Hz, 2H, CH CH -
2 2 4 3 2 2
3
2
28
3
1
2
2
.17 (t, JZ7.4 Hz, 3H, (CH ) CH ), 1.87 (sext, JZ7.7 Hz,
(CH ) CH ), 3.61 (t, JZ8.2 Hz, 2H, CH (CH ) CH ), 5.38
(s, 2H, CH ), 5.92 (s, 2H, CH ), 7.1–7.2 (m, 2H, ArH), 7.22
2 2
2
2
3
2 5 3 2 2 6 3
H, CH CH CH ), 3.5–3.7 (m, 2H, CH CH CH ), 5.39 (s,
H, CH ), 5.92 (s, 2H, CH ), 7.1–7.2 (m, 2H, ArH), 7.23 (br
2
2
3
2
2
3
(br s, 1H, ArH), 7.3–7.6 (m, 8H, ArH), 8.0–8.1 (m, 2H,
BzH), 8.2–8.4 (m, 4H, ArH); C NMR (CDCl ) d 14.1
2
2
1
3
s, 1H, ArH), 7.3–7.6 (m, 8H, ArH), 8.0–8.1 (m, 2H, BzH),
8
3
1
.2–8.4 (m, 4H, ArH); C NMR (CDCl ) d 14.7 (CH ), 24.7
3
(CH ), 22.7 (CH ), 28.5 (CH ), 29.3 (CH ), 29.5 (CH ), 30.4
3
3
3
2
2
2
2
(
CH ), 30.4 (CH ), 63.0 (CH ), 66.5 (CH ), 114.4 (CH),
2
(CH ), 31.4 (CH ), 31.9 (CH ), 62.9 (CH ), 66.5 (CH ),
2 2 2 2 2
2
2
2
1
14.5 (CH), 120.7 (CH), 124.7 (CH), 125.0 (CH), 125.2
114.4 (CH), 114.5 (CH), 120.7 (CH), 124.7 (CH), 125.0
(CH), 125.1 (C), 125.2 (CH), 126.0 (CH), 128.4 (CH), 129.3
(C), 129.7 (CH), 129.8 (CH), 130.1 (C), 130.9 (C), 133.0
(CH), 137.8 (C), 138.1 (C), 159.5 (C), 166.4 (C).
(
(
(
CH), 126.0 (CH), 128.4 (CH), 129.4 (C), 129.7 (CH), 129.8
CH), 130.1 (C), 131.0 (C), 133.0 (CH), 137.8 (C), 137.9
C), 159.5 (C), 166.4 (C).
4.4.4. 3-[(10-Butyl-9-anthracenediyl)methoxy)benzyl
benzoate 3d. This compound was obtained (0.40 g, 96%)
4.4.7. 3-[(10-Decyl-9-anthracenediyl)methoxy)benzyl
benzoate 3g. This compound was obtained (0.48 g, 97%)
as a pale yellow powdery material from chloroform–
as a pale yellow powdery material from chloroform–
methanol solution; mp 134–135 8C; UV (CHCl ) 360 nm
methanol solution; mp 93–94 8C; UV (CHCl ) 360 nm (3
3
3
(
1
4
3 6900), 379 nm (3 11,200), 400 nm (3 10,600); IR (KBr)
6900), 379 nm (3 11,200), 400 nm (3 10,600); IR (KBr)
K1 K1
584 cm (C]C), 1715 cm (C]O); MS (FABC) m/z
74 (MC), 475 (MHC); HRMS (FABC) m/z calcd for
K1
K1
1583 cm (C]C), 1714 cm (C]O); MS (FABC) m/z
558 (MC), 559 (MHC); HRMS (FABC) m/z calcd for
C H O : 558.3134, found 558.3121; H NMR (CDCl ) d
1
1
C H O : 474.2195, found 474.2210; H NMR (CDCl ) d
3
3
3
30
3
39 42
3
3
1
2
3
5
.04 (t, JZ7.3 Hz, 3H, (CH ) CH ), 1.61 (sext, JZ7.5 Hz,
0.89 (t, JZ6.5 Hz, 3H, (CH ) CH ), 1.2–1.5 (m, 12H,
(CH ) (CH ) CH ), 1.5–1.7 (m, 2H, (CH ) CH (CH ) -
2 3 2 6 3 2 2 2 2 6
2
3
3
2 9 3
H, (CH ) CH CH ), 1.7–1.9 (m, 2H, CH CH CH CH ),
.63 (t, JZ8.2 Hz, 2H, CH (CH ) CH ), 5.39 (s, 2H, CH ),
2
2
2
3
2
2
2
3
CH ), 1.7–1.9 (m, 2H, CH CH (CH ) CH ), 3.61 (t, JZ
2
2 2
3
2
3 2 2 2 7 3
.93 (s, 2H, CH ), 7.1–7.2 (m, 2H, ArH), 7.23 (br s, 1H,
2
8.2 Hz, 2H, CH (CH ) CH ), 5.39 (s, 2H, CH ), 5.92 (s, 2H,
2 2 8 3 2
ArH), 7.3–7.6 (m, 8H, ArH), 8.0–8.1 (m, 2H, BzH), 8.2–8.4
(
CH ), 7.1–7.2 (m, 2H, ArH), 7.23 (br s, 1H, ArH), 7.3–7.6
2
1
3
m, 4H, ArH); C NMR (CDCl ) d 14.0 (CH ), 23.4 (CH ),
(m, 8H, ArH), 8.0–8.1 (m, 2H, BzH), 8.2–8.4 (m, 4H, ArH);
C NMR (CDCl ) d 14.1 (CH ), 22.7 (CH ), 28.5 (CH ),
3 3 2 2
3
3
2
1
3
2
8.1 (CH ), 33.5 (CH ), 63.0 (CH ), 66.5 (CH ), 114.5
2
2
2
2
(
CH), 114.6 (CH), 120.7 (CH), 124.7 (CH), 125.0 (CH),
29.3 (CH ), 29.56 (CH ), 29.63 (CH ), 29.7 (CH ), 30.4
2 2 2 2
125.2 (CH), 126.0 (CH), 128.4 (CH), 129.4 (C), 129.7 (CH),
129.8 (CH), 130.1 (C), 131.0 (C), 133.0 (CH), 137.8 (C),
138.0 (C), 159.5 (C), 166.4 (C).
(CH ), 31.4 (CH ), 31.9 (CH ), 63.0 (CH ), 66.5 (CH ),
2 2 2 2 2
114.4 (CH), 114.5 (CH), 120.7 (CH), 124.7 (CH), 125.0
(CH), 125.2 (CH), 126.0 (CH), 128.4 (CH), 129.3 (C), 129.7
(CH), 129.8 (CH), 130.1 (C), 130.9 (C), 133.0 (CH), 137.8
(C), 138.1 (C), 159.5 (C), 166.4 (C).
4.4.5. 3-[(10-Hexyl-9-anthracenediyl)methoxy)benzyl
benzoate 3e. This compound was obtained (0.42 g, 95%)
as a pale yellow powdery material from chloroform–
methanol solution; mp 93–94 8C; UV (CHCl ) 360 nm (3
4.5. General procedure for the synthesis of 4
3
7
1
5
000), 379 nm (3 11,300), 400 nm (3 10,700); IR (KBr)
585 cm (C]C), 1718 cm (C]O); MS (FABC) m/z
All 10-alkyl-9-chloromethylanthracenes 4 were synthesized
according to the established literature procedure used for
preparation of 4a. For example, synthesis of 4c was
exemplified as follows.
K1
K1
02 (MC), 503 (MHC); HRMS (FABC) m/z calcd for
1
C H O : 502.2508, found 502.2529; H NMR (CDCl ) d
3
5
34
3
3
0
.93 (t, JZ7.1 Hz, 3H, (CH ) CH ), 1.3–1.5 (m, 4H,
2 5 3
(
CH ) (CH ) CH ), 1.5–1.7 (m, 2H, (CH ) CH (CH ) -
4.5.1. 9-Chloromethyl-10-propylanthracene 4c. A sol-
ution containing 6c (1.0 g, 4.54 mmol), paraformaldehyde
(1.0 g), and concd HCl (10 mL) in acetic acid (20 mL) was
heated at room temperature with vigorous stirring. After
14 h, the reaction mixture was then precipitated in ice-cold
(50 mL). The precipitate was collected by filtration,
intensively washed with water, and dried in a vacuum to
afford a pale yellow solid. After complete vacuum drying,
the solid sample was purified by recrystallization from
chloroform–hexane solution, affording 4c (1.1 g, 92%) as a
2
3
2 2
3
2 2
2
2 2
CH ), 1.7–1.9 (m, 2H, CH CH (CH ) CH ), 3.61 (t, JZ
3
2
2
2 3
3
8
2
7
.3 Hz, 2H, CH (CH ) CH ), 5.39 (s, 2H, CH ), 5.93 (s,
H, CH ), 7.1–7.2 (m, 2H, ArH), 7.23 (br s, 1H, ArH), 7.3–
2 2 4 3 2
2
.6 (m, 8H, ArH), 8.0–8.1 (m, 2H, BzH), 8.2–8.4 (m, 4H,
1
3
ArH); C NMR (CDCl ) d 14.1 (CH ), 22.7 (CH ), 28.5
3
(
(
1
1
1
3
2
CH ), 30.1 (CH ), 31.4 (CH ), 31.8 (CH ), 63.0 (CH ), 66.5
2 2 2 2 2
CH ), 114.4 (CH), 114.5 (CH), 120.7 (CH), 124.7 (CH),
2
25.0 (CH), 125.2 (C), 126.0 (CH), 128.4 (CH), 129.3 (C),
29.7 (CH), 129.8 (CH), 130.1 (C), 130.9 (C), 133.0 (CH),
37.8 (C), 138.1 (C), 159.5 (C), 166.4 (C).
pale yellow powdery material; mp 123–124 8C; IR (KBr)
7
K1
59, 1249, 1444, 1478 cm ; MS (FABC) m/z 268 (MC),
1
4.4.6. 3-[(10-Octyl-9-anthracenediyl)methoxy]benzyl
benzoate 3f. This compound was obtained (0.46 g, 98%)
269 (MHC); H NMR (CDCl ) d 1.14 (t, JZ7.5 Hz, 3H,
3
CH CH CH ), 1.82 (sext, JZ7.5 Hz, 2H, CH CH CH ),
2
2
3
2
2
3
as a pale yellow powdery material from chloroform–
methanol solution; mp 98–99 8C; UV (CHCl ) 360 nm (3
3.5–3.6 (m, 2H, CH ), 5.57 (s, 2H, CH ), 7.4–7.6 (m, 4H,
2 2
1
ArH), 8.2–8.4 (m, 4H, ArH); C NMR (CDCl ) d 14.7
3
3
3
6
1
5
800), 379 nm (3 11,000), 400 nm (3 10,000); IR (KBr)
584 cm (C]C), 1714 cm (C]O); MS (FABC) m/z
(CH ), 24.7 (CH ), 30.4 (CH ), 39.5 (CH ), 124.1 (CH),
3
2
2
2
K1
K1
125.1 (CH), 125.4 (CH), 126.2 (C), 126.3 (CH), 129.5 (C),
129.9 (C), 138.2 (C). Anal. Calcd for C H Cl: C, 80.43; H,
6.38; N, 0.00. Found: C, 80.51; H, 6.49; N, 0.05.
30 (MC), 531 (MHC); HRMS (FABC) m/z calcd for
1
8 17
1
C H O : 530.2821, found 530.2795; H NMR (CDCl ) d
38
3
7
3
3

11780
M. Takahashi et al. / Tetrahedron 60 (2004) 11771–11781
4
.5.2. 9-Chloromethyl-10-hexylanthracene 4e. This com-
pound was obtained (1.1 g, 89%) from 6e (1.0 g,
.82 mmol) as a pale yellow powdery material from
chloroform–hexane solution; mp 114–115 8C; IR (KBr)
Purification of the residue by column chromatography (67%
ethyl acetate, 33% hexane) and recrystallization from
hexane–ethyl acetate gave 5 (0.51 g, 78%) as a white
3
K1
powdery material; mp 219–220 8C; IR (KBr) 1608 cm
K1
K1
K1
7
56, 1246, 1446, 1459, 1479 cm ; MS (FABC) m/z 310
(C]C), 1714 cm
(FABC) m/z 576 (MC), 578 (MHC); HRMS (FABC)
(C]O), 3391 cm
(OH); MS
1
(
MC), 311 (MHC); H NMR (CDCl ) d 0.91 (t, JZ7.0 Hz,
3
1
m/z calcd for C H O : 576.1268, found 576.1245; H
3
H, (CH ) CH ), 1.3–1.5 (m, 4H, (CH ) (CH ) CH ), 1.56
2
5
3
2 3
2 2
3
30 24 12
(
quint, JZ7.3 Hz, 2H, (CH ) CH (CH ) CH ), 1.77 (quint,
NMR (acetone-d ) d 5.31 (s, 6H, CH ), 6.34 (t, JZ2.1 Hz,
2
2
2
2 2
3
6
2
JZ7.5 Hz, 2H, CH CH (CH ) CH ), 3.56 (t, JZ8.2 Hz,
3H, PhH), 6.49 (d, JZ2.1 Hz, 6H, PhH), 8.32 (s, 6H, OH),
8.85 (s, 3H, BzH); C NMR (acetone-d ) d 68.3 (CH ),
6 2
103.5 (CH), 107.4 (C), 132.7 (C), 135.3 (CH), 139.3 (C),
159.8 (C), 166.0 (C).
2
2
2 3
3
13
2
ArH), 8.2–8.4 (m, 4H, ArH); C NMR (CDCl ) d 14.1
H, CH (CH ) CH ), 5.56 (s, 2H, CH ), 7.4–7.6 (m, 4H,
2
2 4
3
2
1
3
3
(
CH ), 22.7 (CH ), 28.5 (CH ), 30.0 (CH ), 31.4 (CH ), 31.7
3 2 2 2 2
(
CH ), 39.5 (CH ), 124.1 (CH), 125.2 (CH), 125.3 (CH),
2 2
126.1 (C), 126.30 (CH), 129.33 (C), 129.9 (C), 138.4 (C).
Anal. Calcd for C H Cl: C, 81.14; H, 7.46; N, 0.00.
Found: C, 81.25; H, 7.50; N, 0.00.
4
.5.6. Preparation of tris(3,5-bis(benzyloxy)benzyl)
benzene-1,3,5-tricarboxylate 7. To a solution containing
,5-bis(benzyloxy)benzyl alcohol (0.56 g, 1.75 mmol) and
triethylamine (0.34 mL, 2.44 mmol) in anhydrous benzene
20 mL) was added dropwise to a solution trimesoyl
chloride (0.15 g, 0.55 mmol) in anhydrous benzene
20 mL) at 0 8C. The reaction mixture was stirred at room
2
1 23
3
4
.5.3. 9-Chloromethyl-10-octylanthracene 4f. This com-
pound was obtained (0.99 g, 85%) from 6f (1.0 g,
.45 mmol) as a pale yellow powdery material from
chloroform–hexane solution; mp 96–97 8C; IR (KBr) 760,
(
3
(
temperature for 12 h, quenched by slow addition of 1.0 mol/
L HCl, and then extracted with an additional benzene
(150 mL). The combined organic layers were washed with
brine, dried over anhydrous Na SO , filtered, and concen-
trated in vacuo. Silica-gel column chromatography (50%
chloroform, 50% hexane) of the crude sample furnished 7
K1
1
3
248, 1445, 1459, 1479 cm ; MS (FABC) m/z 338 (MC),
1
39 (MHC); H NMR (CDCl ) d 0.88 (t, JZ7.0 Hz, 3H,
3
(
CH ) CH ), 1.2–1.4 (m, 8H, (CH ) (CH ) CH ), 1.56
2 7 3 2 3 2 4 3
2
4
(
quint, JZ7.6 Hz, 2H, (CH ) CH (CH ) CH ), 1.79
2 2 2 2 4 3
(
quint, JZ7.7 Hz, 2H, CH CH (CH ) CH ), 3.58 (t, JZ
2 2 2 5 3
8
4
.2 Hz, 2H, CH (CH ) CH ), 5.59 (s, 2H, CH ), 7.4–7.6 (m,
2 2 6 3 2
(0.60 g, 98%) as a colorless crystalline mass. Further
1
H, ArH), 8.2–8.4 (m, 4H, ArH); C NMR (CDCl ) d 14.1
3
3
purification was achieved by recrystallization from chloro-
form–hexane giving a purely powdery material; mp 123–
1
MS (FABC) m/z 1117 (MC), 1118 (MHC); H NMR
(
CH ), 22.7 (CH ), 28.5 (CH ), 29.3 (CH ), 29.5 (CH ), 30.4
3 2 2 2 2
(
CH ), 31.5 (CH ), 31.9 (CH ), 39.6 (CH ), 124.1 (CH),
2
K1 K1
24 8C; IR (KBr) 1597 cm (C]C), 1724 cm (C]O);
2
2
2
1
1
8
25.2 (CH), 125.4 (CH), 126.1 (C), 126.3 (CH), 129.4 (C),
29.9 (C), 138.5 (C). Anal. Calcd for C H Cl: C, 81.51; H,
.03; N, 0.00. Found: C, 81.52; H, 8.21; N, 0.00.
1
2
3 27
(CDCl ) d 5.00 (s, 12H, CH ), 5.33 (s, 6H, CH ), 6.58 (t, JZ
3 2 2
2
3
.2 Hz, 3H, PhH), 6.67 (d, JZ2.2 Hz, 6H, PhH), 7.2–7.4 (m,
13
0H, ArH), 8.90 (s, 3H, BzH); C NMR (CDCl ) d 67.2
3
4
.5.4. 9-Chloromethyl-10-decylanthracene 4g. This com-
(
CH ), 70.1 (CH ), 102.0 (CH), 107.3 (CH), 127.5 (CH),
2 2
pound was obtained (0.96 g, 83%) from 6g (1.0 g,
.14 mmol) as a pale yellow powdery material from
chloroform–hexane solution; mp 95–96 8C; IR (KBr) 760,
1
1
28.0 (CH), 128.6 (CH), 131.2 (C), 135.0 (CH), 136.7 (C),
37.7 (C), 160.2 (C), 164.7 (C). Anal. Calcd for C H O :
3
7
2 60 12
C, 77.40; H, 5.41; N, 0.00. Found: C, 77.41; H, 5.27; N,
.07.
K1
1
3
249, 1445, 1459, 1477 cm ; MS (FABC) m/z 366 (MC),
0
1
67 (MHC); H NMR (CDCl ) d 0.88 (t, JZ7.0 Hz, 3H,
3
(
CH ) CH ), 1.2–1.4 (m, 12H, (CH ) (CH ) CH ), 1.57
2 9 3 2 3 2 6 3
(
quint, JZ7.3 Hz, 2H, (CH ) CH (CH ) CH ), 1.79 (quint,
2
2
2
2 6
3
JZ7.7 Hz, 2H, CH CH (CH ) CH ), 3.57 (t, JZ8.2 Hz,
Acknowledgements
2
2
2 7
3
2
ArH), 8.2–8.4 (m, 4H, ArH); C NMR (CDCl ) d 14.1
H, CH (CH ) CH ), 5.57 (s, 2H, CH ), 7.4–7.6 (m, 4H,
2 2 8 3 2
1
3
This research was supported by a Grant-in-Aid for Scientific
Research from the Ministry of Education, Culture, Sports,
Science, and Technology, Japan (Grant 13740393) and
Suzuki Foundation. We thank Mr. Shirae, Ms. Hasegawa,
and Prof. Masami Sakamoto of Chiba University, Japan for
their help measuring elemental analyses and recording low-
and high-resolution mass spectra.
3
(
CH ), 22.7 (CH ), 28.5 (CH ), 29.3 (CH ), 29.55 (CH ),
3 2 2 2 2
2
9.62 (CH ), 29.7 (CH ), 30.4 (CH ), 31.5 (CH ), 31.9
2 2 2 2
(
CH ), 39.5 (CH ), 124.1 (CH), 125.2 (CH), 125.4 (CH),
2 2
126.1 (C), 126.3 (CH), 129.4 (C), 129.9 (C), 138.5 (C).
Anal. Calcd for C H Cl: C, 81.82; H, 8.51; N, 0.00.
Found: C, 82.04; H, 8.57; N, 0.02.
2
5 31
4
1
.5.5. Preparation of tris(3,5-dihydroxybenzyl) benzene-
,3,5-tricarboxylate 5. The following synthetic procedure
was also used for the sample preparations of benzoyl 3,5-
dihydroxybenzylate 8 and benzoyl 3-hydroxybenzylate 9.
To a solution of 7 (1.26 g, 1.13 mmol) in a mixture of HPLC
grade methanol (20 mL) and chloroform (20 mL) was added
a catalytic amount of 10% Pd–C (0.1 g) in some portions at
room temperature. The mixture was stirred under a
hydrogen gas atmosphere at ambient temperature for 20 h.
The catalyst was removed by filtration and the filtrate was
then evaporated to dryness to obtain a colorless oily residue.
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