Synthesis of cyclotriveratrylene-phenylacetylene derivatives and a photophysical investigation of rigid conjugated cyclotriveratrylene dendrimers

Article abstract of DOI:10.1002/ejoc.201201024

Various functionalized host molecules and building blocks can be derived from the cone-shaped cyclotriveratrylene (CTV). In this article, we report on the synthesis of CTV-I₃ derivatives 3a and 3b and their Sonogashira cross-coupling with various terminal aryl-alkynes, to synthesize CTV-phenylacetylene derivatives in moderate to good yields. In this way, three star-like conjugated dendrimers with rigid macrocyclic cores 4k-m, which showed good photophysical properties, were also synthesized. The band gaps of 4k-m are 3.49, 3.49 and 3.45 eV, and the fluorescence quantum yields are 0.64, 0.78, 0.48 (2-aminopyridine as a standard and excited at 310 nm), respectively. Electrochemical studies revealed their HOMO and LUMO energy levels. Our research disclosed that these CTV dendrimers could potentially be used as host materials in OLEDs. Copyright

Full text of DOI:10.1002/ejoc.201201024

FULL PAPER
DOI: 10.1002/ejoc.201201024
Synthesis of Cyclotriveratrylene–Phenylacetylene Derivatives and a
Photophysical Investigation of Rigid Conjugated Cyclotriveratrylene
Dendrimers
Xiao-Na Han,[a] Jian-Ming Chen,[a] Zhi-Tang Huang,[a] and Qi-Yu Zheng*[a]
Keywords: Dendrimers / Macrocycles / Cross-coupling / Molecular modeling
Various functionalized host molecules and building blocks
can be derived from the cone-shaped cyclotriveratrylene
(CTV). In this article, we report on the synthesis of CTV-I3
derivatives 3a and 3b and their Sonogashira cross-coupling
with various terminal aryl-alkynes, to synthesize CTV-phen-
ylacetylene derivatives in moderate to good yields. In this
way, three star-like conjugated dendrimers with rigid macro-
cyclic cores 4k–m, which showed good photophysical proper-
ties, were also synthesized. The band gaps of 4k–m are 3.49,
3.49 and 3.45 eV, and the fluorescence quantum yields are
0.64, 0.78, 0.48 (2-aminopyridine as a standard and excited at
310 nm), respectively. Electrochemical studies revealed their
HOMO and LUMO energy levels. Our research disclosed
that these CTV dendrimers could potentially be used as host
materials in OLEDs.
tions of phenyl, 4-tolyl, or 4-(ethoxycarbonyl)phenyl bo-
ronic acid with CTV-Br3 did give the desired products, but
the yields were far from satisfactory. Further study showed
that the more reactive indolylphosphane ligand was re-
quired. Because the coupling reactivity of iodides are supe-
rior to bromides,[11] more reactive reactants such as iodide-
substituted CTV were investigated. Collet reported the syn-
thesis of CTV-I3 in 1995.[12] However, its synthesis required
many steps and harsh reaction conditions. Gosse[13] re-
ported an efficient route to synthesize the same CTV-I3
starting from 3-hydroxy-4-iodobenzoic acid in three steps
with 47% overall yield. Due to the low solubility of this
CTV-I3, we replaced the methyl group with propyl or butyl
groups and improved Gosse’s procedures to obtain the
CTV-I3 derivatives 3a and 3b. A series of CTV-phenylacetyl-
ene derivatives were then obtained in moderate to good
yields through Sonogashira cross-coupling from 3a and 3b.
Dendrimers are precisely defined, three-dimensional
structures that combine properties of both polymers and
nonpolymers. They are designed on the basis of the Cayley
tree topology and are composed of repeating units that,
overall, result in high overall molecular weight compounds,
but are monodisperse, well-defined molecules. It is always
important for the design of functional macromolecules to
investigate their physical or chemical properties, which are
affected by their molecular structure. Previous work showed
that CTV functionalized with polybenzyl ether dendrons af-
forded an internal cavity with appropriate dimensions and
shape for forming a 1:1 complex with C60.[14] The Ka values
of the complex increase significantly with the generation
number of the surrounding dendritic substituents. Percec
and co-workers reported a series of dendritic CTVs that
Introduction
The rigid, cone-shaped molecule of cyclotriveratrylene
(CTV) is a macrocyclic host that has been investigated in
detail in recent decades.[1] Numerous studies have been un-
dertaken to synthesize CTV analogues.[2] In most cases, new
CTV derivatives have been developed with etherification or
esterification at the upper rims of cyclotricatechylene (CTC)
and cyclotriguaiacylene (CTG), which gave flexible ex-
tended arms.[3] These CTV analogues possess deeper cavi-
ties and various functional groups. CTV and its derivatives
have shown wide applications in fields such as host-guest
chemistry,[4] organic or metallo-supramolecular assembl-
ies,[5] ion-sensing,[6] and bio-sensing.[7]
The latest work disclosed that CTV analogues with rigid
arms contain deeper cavities that provide unique advan-
tages when constructing functional materials.[8] This stimu-
lated our curiosity to synthesize CTV derivatives with even
larger rigid cavities. The convenient synthetic strategy in-
[9]
volving bromide-substituted reactant CTV-Br3 makes it
possible to prepare the rigid CTV derivatives through
Suzuki–Miyaura coupling or Sonogashira coupling reac-
tions. Recently, we have reported the use of classical
Suzuki–Miyaura coupling conditions with CTV-Br3 in the
presence of [Pd(PPh3)4] and anhydrous K2CO3.[10] Reac-
[a] Beijing National Laboratory for Molecular Sciences, CAS Key
Laboratory of Molecular Recognition and Function, Institute
of Chemistry, Chinese Academy of Sciences,
Beijing, 100190, China
Fax: +86-10-6255-4449
E-mail: zhengqy@iccas.ac.cn
Homepage: http://zhengqy.iccas.ac.cn
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201201024.
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self-assemble into a hexagonal columnar lattice and/or into hydrofuran (THF), NaBH4, and methanol at reflux tem-
chiral supramolecular spheres depending on the type of chi- perature within 4 h (conversion was determined by TLC
ral dendrimer used.[15] On the other hand, Moore reported analysis). Treatment of 2a and 2b with P2O5 and Et2O un-
the first fluorescent phenylacetylene dendrimers.[16] Sub- der reflux gave the cyclotribenzylene compounds 3a and 3b,
sequently, numerous studies on acetylene-linked dendrimers which could be purified by recrystallization from CHCl3/
were inspired by Moore’s models and applied in areas such hexane. In contrast to the method developed by Gosse,[13]
as OLEDs[17] and sensors,[18] among others.[19] The excellent NaBH4 was used to reduce propyl or butyl ester intermedi-
performance of 3a and 3b made it possible to synthesize ate without deiodination instead of diisobutylaluminum hy-
CTV-phenylacetylene dendrimers 4k–m. The photophysical dride, which was used at –80 °C. Because of the good solu-
and electrochemical properties of these conjugated CTV- bility of 3a and 3b, less solvent was required for elution and
phenylacetylene dendrimers have been investigated and are recrystallization.
discussed herein.
The palladium-catalyzed Sonogashira coupling of 3 with
aryl-alkynes is shown in Scheme 2.[22] Sonogashira cross-
coupling reaction of 3a and 3b with terminal alkynes pro-
ceeded smoothly at 50 °C. Heating contributed to the dis-
solution of 3a and 3b. Through the use of [PdCl2(PPh3)2]
as a catalyst, CuI as a cocatalyst, and an excess amount of
Et3N as solvent, the reaction afforded moderate to good
yields. For aryl-alkynes, the product yield depended on the
substitution pattern of the phenyl ring. Electron-rich phen-
ylacetylenes gave better yields (Table 1, entries 1–4) than
electron-poor alkynes (Table 1, entries 5–10).[23]
Results and Discussion
Synthesis
As mentioned above, functionalized C3-cyclotrivera-
trylenes could be obtained by cyclodehydration of certain
3,4-disubstituted benzyl alcohol derivatives.[20] In this
method, acetic acid was usually required as solvent and per-
chloric acid as catalyst to generate the benzylic cation.
However, to our dismay, by using this method we did not
obtain the desired product CTV-I3 starting from 4-iodo-3-
methoxybenzyl alcohol. In the synthesis of CTV-Br3, Cram
et al.[9] commented that the bromine in 4-bromo-3-meth-
oxybenzyl alcohol acted as a group that protects the 4-posi-
tion from alkylation by the benzyl cation. So it seems that
4-iodo-3-methoxybenzyl alcohol could also work by using
this protocol. We have found that the methoxy-substituted
CTV-I3 derivative synthesized by Collet and Gosse showed
poor solubility in common solvents and could be only
solved in dimethyl sulfoxide (DMSO). Isolation of the
product from the reaction system by increasing the solubil-
ity seems to be the key problem. Collet pointed out that a
strongly electron-donating group para to the CH2OH moi-
ety was required. Furthermore, the importance of having a
strongly electron-donating substituent meta to CH2OH was
also demonstrated.[1a] Thus, the introduction of propyloxy
and butoxy groups meta to CH2OH seemed to be a promis-
ing approach.
Scheme 2. Palladium-catalyzed Sonogashira coupling of 3 with
aryl-alkynes.
The preparation of 3a and 3b is shown in Scheme 1.
Starting from 3-hydroxybenzoic acid, iodination took place
according to the reported method.[21] Alkylation and esteri-
Phenylacetylene monodendrons D-k, D-l, and D-m (Fig-
fication of 3-hydroxy-4-iodobenzoic acid were carried out ure 1) were synthesized according to the reported conver-
using Cs2CO3 as base. Although the reaction only provided gent method.[24] The higher generation of none tert-butyl
a moderate yield, the unreacted material could be acidified substituted dendron was not obtained because of its poor
with concentrated HCl and recycled. Reduction of 1a and solubility. When these monodendrons reacted with 3b, low
1b to the benzyl alcohol proceeded in a mixture of tetra- yields were obtained. There are two main reasons for this
Scheme 1. Syntheses of C3-cyclotriveratrylenes iodine derivatives.
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Synthesis and Investigation of Cyclotriveratrylene Derivatives
Table 1. Palladium-catalyzed Sonogashira coupling of 3 with aryl-
alkynes.[a,b]
Figure 1. Chemical structures of D-k, D-l, D-m and the CTV core.
result: the diacetylene byproduct of Glaser coupling in-
creases with increasing generation,[16,24] and steric hin-
drance became more apparent with increasing generation
and size. Moreover, generations higher than D-m were not
synthesized because of the lower fluorescence quantum
yields of the product and because Glaser coupling would
become more significant.[24]
Visualization and Simulation
[a] Reaction conditions for entries 1–8: 3a (0.365 mmol), aryl-alkynes
(1.3 mmol, 1.2 equiv.), CuI (0.016 mmol, 4 mol-%), [PdCl2(PPh3)2]
(0.014 mmol, 4 mol-%), Et3N (10 mL), anhydrous THF (10 mL),
50 °C, 24 h. [b] Entries 9 and 11–13 use 3b in the reactions, other
conditions are same as above. [c] Yield of isolated product.
The structures of dendrimers 4k–m were modeled by the
AM2 method in the Gaussian 09 program;[25] the results are
displayed in Figure 2. All three compounds exhibit ‘wind-
mill-like’ shape. Although 4k–m all bear large dendron
Figure 2. Molecular models of 4k–m optimized by the AM2 method in the Gaussian 09 program.
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structures at the upper rims, the cone shape conformation
at the center remains unchanged, which can be confirmed
1
by their H NMR spectra. In the cone-shaped CTV, the
methylene groups in the CTV skeleton show a pair of dou-
blets around δ = 3.6 and 4.7 ppm, whereas in the saddle-
shaped CTV only a singlet was found (δ = 3.8 ppm).[26]
The three dendrimers 4k–m can adopt two stereoiso-
meric forms: P and M (the dendrimers in Figure 2 are de-
picted as M). Their optimized structures show that the
phenylacetylene monodendrons on the upper rim twist in
the same direction. It seems that even a large chiral cavity
could be realized by introducing the phenylacetylene mono-
dendrons to CTV.
Compared with 4m, CTV dendrimers 4k and 4l, with
smaller dendrons at their periphery, show better co-planar-
ity of all the phenyl groups. Compound 4m possesses more
arms at its periphery and the outermost arms are not in the
same plane with the phenyl in the CTV core due to steric
hindrance. In contrast, the dendrons at the periphery of 4k
and 4l have good conjugation with the phenyl in the CTV
core.
Figure 4. Fluorescence spectra of 4k–m in CH2Cl2 excited at
310 nm. From top to bottom: 4l, 4k, and 4m.
Table 2. Photophysical properties.
λmax [nm][a]
ε [105 L·mol–1·cm–1]
2.70, 2.76, 2.61, 0.83 3.49
2.91, 2.58, 0.84 3.49
6.70, 6.55, 7.08, 0.92 3.45
ΔE [eV][b]
4k
4l
287, 296, 303, 338
297, 310, 338
293, 299, 310, 338
284, 302
4m
D-k
D-l
D-m
0.66, 0.63
–
Photophysical Properties
290, 307
291, 299, 310
1/3 4k 287, 304, 325
0.64, 0.63
1.99, 1.88, 2.22
0.91, 0.84, 0.22
–
–
3.64
The absorption spectra of dendrimeric CTVs 4k–m,
phenylacetylene monodendrons D-k, D-l, D-m, the CTV
core, and 1/3 4k are shown in Figure 3. The fluorescence
spectra of 4k–m are shown in Figure 4. The photophysical
data are summarized in Table 2 and Table 3.
[a] In CH2Cl2. [b] Estimated from the absorption edge.
Table 3. Photophysical properties of 4k–m.
λ FLmax [nm][a]
ΦFL
[b]
4k
391
389
398
383
0.64
0.78
0.48
0.34
4l
4m
1/3 4k
[a] Excited at 310 nm. [b] Determined with 2-aminopyridine as a
standard, when excited at 310 nm.
of the former is probably covered by the absorption bands
of phenylacetylene dendrons.
The molar extinction coefficient (ε) of compound 4m is
somewhat larger than that of compounds 4k and 4l. This is
consistent with phenylacetylene monodendrons D-k, D-l,
and D-m, for which the molar extinction coefficient in-
creases with increasing generation. It is interesting that the
spectra of 4k–m contain absorption bands around 340 nm;
these bands, which are the lowest energy absorption peaks,
did not appear in the spectra of D-k, D-l, D-m, or the CTV
core. The peaks increase with increasing generations and
also shift to red with increasing size, which is typical of
conjugated organic molecules.[16] We attribute this absorp-
Figure 3. Absorption spectra of 4k–m, D-k, D-l, D-m, 1/3 4k, and
the CTV core in CH2Cl2. (Green) 4m, (red) D-m, (orange) 4k,
(blue) 4l, (black) 1/3 4k, (brown) D-k, (purple) D-l, (deep-blue)
CTV core. The concentrations are normalized to 3.2ϫ10–6 L·mol–1
for 4k–m, CTV core, and 9.6ϫ10–6 L·mol–1 for D-k, D-l, D-m, 1/
3 4k.
From the absorption spectra displayed in Figure 3, it can tion band to the conjugation between phenylacetylene mon-
be seen that the phenylacetylene monodendrons D-k, D-l, odendron and phenyl in the CTV core. To gain a better
and D-m have almost the same absorption bands as their understanding of the origins of this absorption band, 1/3
corresponding CTV derivatives. Therefore, the intense ab- 4k was synthesized (Scheme 3). As can be observed in its
sorption bands around 290–310 nm of 4k–m are due to the spectrum, the absorption band around 340 nm shifts to
phenylacetylene dendrons. When the spectra of the CTV 330 nm and the intensity is lower than 4k at the same con-
core is compared with those of 4k–m, the absorption band centration. We assumed that the CTV core makes a signifi-
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Synthesis and Investigation of Cyclotriveratrylene Derivatives
cant contribution to this absorption band, and it may facili-
The experiments were carried out in 0.1 m Bu4NPF6/
tate intramolecular π-interaction of the attached conjugated CH2Cl2 at a scan rate of 100 mV/s, and poorly resolved re-
dendrons.
versible oxidation peaks were observed for 4k–m. The
HOMO energy levels, which were estimated on the basis
of roughly evaluated onset oxidation potentials (HOMO =
Eox
+ 4.7 eV), were calculated to be –6.07, –6.10, and
onset
–5.92 eV, respectively. The LUMO energy levels were calcu-
lated from the HOMO energy level and energy band gap
(Eg), which was determined by the UV/Vis absorption edge
(LUMO = HOMO – Eg eV); LUMO energy levels of 4k–
m were thus calculated to be –2.58, –2.61, and –2.47 eV,
respectively.
Scheme 3. Synthesis of 1/3 4k.
Conclusions
The band-gaps of 4k–m estimated from the correspond-
ing absorption edge are 3.49, 3.49 and 3.45 eV. The energy
gaps decreased with increasing generation because of the
extended conjugation. As a result of this unique character-
istic, 4k–m could be used as potential host material in
OLEDs.
The fluorescence spectra show that the fluorescence
maximum does not shift significantly between 4k and 4l,
but a bathochromic shift of 9 nm between 4l and 4m can
be seen, which is a characteristic for conjugated systems.
The fluorescence intensity decreases with higher generation,
which is also a character for dendrimeric systems.[16] The
fluorescence quantum yields of 4k–m (determined with 2-
aminopyridine as a standard when excited at 310 nm) were
0.64, 0.78, and 0.48, respectively. This result is consistent
with the conclusion that the higher generation dendrimers
normally have lower quantum yields.[16]
This work describes a simple and useful synthetic route,
starting with 3-hydroxybenzoic acid, to prepare the key re-
actants CTV-I3 3a and 3b for cross-coupling reactions,
which showed very good activity when reacted with aryl-
alkynes. A series of functionalized macrocyclic CTV-phen-
ylacetylene derivatives was synthesized. Sonogashira reac-
tions of 3b with phenylacetylene monodendrons D-k, D-
l, and D-m provided the star-like molecules 4k–m. These
compounds show good photophysical properties. The fluo-
rescence quantum yield of 4k and 4l are as high as 0.64 and
0.78. The band-gaps of 4k–m, estimated from absorption
edges, are 3.49, 3.49 and 3.45 eV, respectively, which make
these compounds suitable as potential materials for
OLEDs. The HOMO energy levels of 4k–m, which were
investigated by cyclic voltammetry, are –6.07, –6.10, and
–5.92 eV, respectively, whereas the LUMO energy levels are
–2.58, –2.61, and –2.47 eV.
Electrochemical Properties
The excellent performance of CTV-I3 derivatives in Son-
ogashira cross-coupling reactions makes it possible to intro-
duce various functional groups to the CTV upper rim, and
the assembly of these new macrocycles is ongoing in our
laboratory.
To gain a better understanding of the character of 4k–m
for their application in functional materials, their electro-
chemical properties were investigated by cyclic voltamme-
try, which allowed their HOMO and LUMO energy levels
to be calculated.[27] The cyclic voltammograms are shown
in Figure 5.
Experimental Section
General: All reactions were carried out under argon atmosphere.
Unless otherwise noted, all reagents were purchased from commer-
cial suppliers and used without purification. [PdCl2(PPh3)2] and
CuI were purchased from Aldrich. Anhydrous Et3N was distilled
from KOH. Anhydrous THF was distilled from Na. Melting points
were recorded with an electrothermal melting point apparatus. IR
spectra were recorded with an FTIR-480 spectrometer using KBr
discs. The UV/Vis and fluorescence experiments were recorded with
Gangdong F-380 and Persee TU-1810, spectrophotometers, respec-
tively. All the electrochemical experiments were carried out with a
CHI620D potentiostat. The measurements were carried out in
0.1 m Bu4NPF6/CH2Cl2 with Ag/AgCl/KCl as the reference elec-
trode and a platinum coil as the counter electrode. Mass spectra
were recorded with a Micromass GCT and a Bruker autoflex III
1
instrument. H and 13C NMR spectra were recorded at 25 °C with
a Bruker (400 MHz) NMR spectrometer with TMS as internal
standard.
Figure 5. Cyclic voltammograms of (from top to bottom) dendri-
mers 4m, 4l, and 4k in 0.1 m Bu4NPF6/CH2Cl2, scan rate 100 mV/
s.
[PdCl2(PPh3)2]-Catalyzed Sonogashira Coupling Reactions on (؎)-
2,7,12-Tris(propyloxy)-3,8,13-triiodo-10,15-dihydro-5H-tribenzo-
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[a,d,g]cyclonoene. General Procedure: Under argon, CuI (0.003 g,
1
1724 (C=O) cm–1. H NMR (400 MHz, CDCl3): δ = 8.00 (d, J =
0.016 mmol, 4 mol-%), [PdCl2(PPh3)2] (0.01 g, 0.014 mmol, 4 mol- 8.4 Hz, 6 H), 7.54 (d, J = 8.4 Hz, 6 H), 7.45 (s, 3 H), 6.89 (s, 3 H),
%), 3a (0.2 g, 0.365 mmol), and Et3N (10 mL) were loaded into a
Schlenk tube equipped with a Teflon®-coated magnetic stirring bar.
After 30 min, the corresponding acetylene (1.3 mmol, 1.2 equiv.) in
anhydrous THF (10 mL) was added. The mixture was stirred at
50 °C for 24 h. Upon completion of the reaction, solvents were
evaporated and the residue was dissolved in CH2Cl2 (50 mL). The
organic layer was washed with water and dried with Na2SO4. After
filtration and concentration, the residue was purified by column
chromatography (petroleum ether/CH2Cl2) to give the desired
product.
4.72 (d, J = 13.6 Hz, 3 H), 4.07–4.02 (m, 6 H), 3.92 (s, 9 H), 3.63
(d, J = 13.6 Hz, 3 H), 1.88–1.83 (m, 6 H), 1.07 (t, J = 14.4 Hz,
9 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 166.6, 158.7, 141.8,
134.6, 131.3, 130.8, 129.5, 129.2, 128.6, 114.0, 111.4, 92.3, 89.1,
70.6, 52.2, 36.7, 22.6, 10.5 ppm. HRMS (ESI+): calcd. for
C60H54O9 919.3841; found 919.3882.
(؎)-2,7,12-Tris(propyloxy)-3,8,13-tris[(4-fluorophenyl)ethynyl]-
10,15-dihydro-5H-tribenzo[a,d,g]cyclonoene (4f): Yield 78 %; m.p.
240–241 °C. IR (KBr): ν = 2963, 2877 (CH , CH ), 2212
˜
3
2
(CϵC) cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.49–7.46 (m, 9 H),
(؎)-2,7,12-Tris(propyloxy)-3,8,13-tris(phenylethynyl)-10,15-dihydro- 7.04–6.99 (m, 6 H), 6.86 (s, 3 H), 4.70 (d, J = 13.6 Hz, 3 H), 4.05–
5H-tribenzo[a,d,g]cyclonoene (4a): Yield 84%; m.p. 268–269 °C. IR
3.99 (m, 6 H), 3.60 (d, J = 13.6 Hz, 3 H), 1.88–1.79 (m, 6 H), 1.06
(KBr): ν = 2963, 2934, 2876 (CH , CH ), 2211 (CϵC) cm–1. 1H
(t, J = 14.8 Hz, 9 H ppm. 13C NMR (100 MHz, CDCl3): δ = 163.5,
˜
3
2
NMR (400 MHz, CDCl3): δ = 7.51–7.49 (m, 6 H), 7.43 (s, 3 H), 161.1, 158.5, 141.3, 134.4, 133.3, 133.2, 130.8, 120.0, 119.9, 115.6,
7.34–7.29 (m, 9 H), 6.87 (s, 3 H), 4.68 (d, J = 13.6 Hz, 3 H), 4.07– 115.4, 114.0, 111.7, 91.8, 85.5, 70.5, 36.6, 22.5, 10.5 ppm. MS
3.98 (m, 6 H), 3.60 (d, J = 13.6 Hz, 3 H), 1.88–1.79 (m, 6 H), 1.07 (MALDI-TOF): m/z = 798.2, 821.2 [M + Na+], 837.2 [M + K+].
(t, J = 14.8 Hz, 9 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 158.5,
141.3, 134.5, 131.5, 130.8, 128.2, 127.9, 123.9, 114.1, 111.9, 92.9,
85.9, 70.6, 36.6, 22.6, 10.5 ppm. MS (MALDI-TOF): m/z = 744.2,
767.2 [M + Na+], 783.2 [M + K+]. C54H48O3 (744.97): calcd. C
87.09, H 6.34; found C 86.73, H 6.53.
C54H45F3O3 (798.94): calcd. C 81.10, H 5.52; found C 81.44, H
5.54.
(؎)-2,7,12-Tris(propyloxy)-3,8,13-tris[(3-acetylphenyl)ethynyl]-
10,15-dihydro-5H-tribenzo[a,d,g]cyclonoene (4g): Yield 71%; m.p.
167–169 °C. IR (KBr): ν = 2965, 2935, 2876 (CH , CH ), 2213
˜
3
2
1
(؎)-2,7,12-Tris(propyloxy)-3,8,13-tris[(p-tolyl)ethynyl]-10,15-di-
hydro-5H-tribenzo[a,d,g]cyclonoene (4b): Yield 77 %; m.p. 247–
(CϵC), 1690 (C=O) cm–1. H NMR (400 MHz, CDCl3): δ = 8.09
(s, 3 H), 7.89–7.87 (m, 3 H), 7.69–7.66 (m, 3 H), 7.46–7.41 (m, 6 H),
248 °C. IR (KBr): ν = 2964, 2927, 2874 (CH , CH ), 2211 6.90 (s, 3 H), 4.73 (d, J = 13.6 Hz, 3 H), 4.10–4.02 (m, 6 H), 3.64
˜
3
2
(CϵC) cm–1. H NMR (400 MHz, CDCl3): δ = 7.42 (s, 3 H), 7.39 (d, J = 13.6 Hz, 3 H), 2.61 (s, 9 H), 1.89–1.83 (m, 6 H), 1.09 (t, J
1
(d, J = 8.0 Hz, 6 H), 7.12 (d, J = 8.0 Hz, 6 H), 6.86 (s, 3 H), 4.67
(d, J = 13.6 Hz, 3 H), 4.04–3.99 (m, 6 H), 3.59 (d, J = 13.6 Hz,
3 H), 2.35 (s, 9 H), 1.85–1.80 (m, 6 H), 1.06 (t, J = 14.8 Hz,
9 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 158.4, 141.1, 137.9,
134.4, 131.4, 130.9, 129.0, 120.9, 114.1, 112.1, 93.0, 85.3, 70.6, 36.6,
22.6, 21.5, 10.5 ppm. MS (MALDI-TOF): m/z = 786.3, 809.3 [M
+ Na+], 825.3 [M + K+]. C57H54O3 (787.05): calcd. C 87.01, H
6.78; found C 86.96, H 7.06.
= 14.8 Hz, 9 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 197.4,
158.7, 141.7, 137.2, 135.7, 134.5, 131.4, 130.8, 128.6, 127.5, 124.5,
114.0, 111.5, 91.9, 87.0, 70.6, 36.6, 26.6, 22.5, 10.5 ppm. MS
(MALDI-TOF): m/z = 893.2 [M + Na+]. C60H54O6 (871.08): calcd.
C 82.68, H 6.12; found C 82.98, H 6.14.
(؎)-2,7,12-Tris(propyloxy)-3,8,13-tris[(3-formylphenyl)ethynyl]-
10,15-dihydro-5H-tribenzo[a,d,g]cyclonoene (4h): Yield 53%; m.p.
231–232 °C. IR (KBr): ν = 2964, 2935, 2876 (CH , CH ), 2211
˜
3
2
(؎)-2,7,12-Tris(propyloxy)-3,8,13-tris{[4-(tert-butyl)phenyl]- (CϵC), 1695 (C=O) cm–1. 1H NMR (400 MHz, CDCl3): δ = 10.00
ethynyl}-10,15-dihydro-5H-tribenzo[a,d,g]cyclonoene (4c): Yield
(s, 3 H), 7.99 (s, 3 H), 7.82–7.79 (m, 6 H), 7.75–7.72 (m, 6 H), 6.90
(s, 3 H), 4.72 (d, J = 13.6 Hz, 3 H), 4.10–4.01 (m, 6 H), 3.64 (d, J
= 13.6 Hz, 3 H), 1.90–1.81 (m, 6 H), 1.08 (t, J = 14.8 Hz, 9 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 191.6, 158.7, 141.8, 137.0, 136.5,
82%; m.p. 263–264 °C. IR (KBr): ν = 2963, 2872 (CH , CH ), 2211
˜
3
2
(CϵC) cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.43 (t, J = 8.3 Hz,
9 H), 7.34 (d, J = 8.2 Hz, 6 H), 6.86 (s, 3 H), 4.66 (d, J = 13.6 H,
3 H), 4.06–3.96 (m, 6 H), 3.59 (d, J = 13.6 Hz, 3 H), 1.86–1.78 (m, 134.6, 132.7, 130.8, 129.0, 128.7, 125.1, 113.9, 111.4, 91.4, 87.6,
6 H), 1.31 (s, 27 H), 1.06 (t, J = 14.8 Hz, 9 H) ppm. 13C NMR
70.5, 36.6, 22.5, 10.5 ppm. MS (MALDI-TOF): m/z = 851.3.
(100 MHz, CDCl3): δ = 158.5, 151.1, 141.1, 134.4, 131.2, 130.9, C57H48O6 (829.00): calcd. C 82.53, H 5.69; found C 82.60, H 5.62.
125.2, 120.9, 114.2, 112.2, 92.9, 85.3, 70.6, 36.6, 34.7, 31.2, 22.6,
(؎)-2,7,12-Tris(butyloxy)-3,8,13-tris[(4-nitrophenyl)ethynyl]-10,15-di-
hydro-5H-tribenzo[a,d,g]cyclonoene (4i): Yield 40 %; m.p. 310–
10.5 ppm. MS (MALDI-TOF): m/z = 912.4, 935.4 [M + Na+],
951.4 [M + K+]. C66H72O3·0.5H2O: C 85.95, H 7.98; found C 85.72,
H 7.81.
311 °C. IR (KBr): ν = 2957, 2935, 2876 (CH , CH ), 2210 (CϵC),
˜
3
2
1341 (N=O) cm–1. 1H NMR (400 MHz, CDCl3): δ = 8.20 (d, J=8.8,
6 H), 7.60 (d, J = 8.8 Hz, 6 H), 7.46 (s, 3 H), 6.91(s, 3 H), 4.77 (d,
J = 13.6 Hz, 3 H), 4.12–4.08 (m, 6 H), 3.67 (d, J = 13.6 Hz, 3 H),
(؎)-2,7,12-Tris(propyloxy)-3,8,13-tris[(4-methoxyphenyl)ethynyl]-
10,15-dihydro-5H-tribenzo[a,d,g]cyclonoene (4d): Yield 80 %; m.p.
239–240 °C. IR (KBr): ν = 2963, 2934, 2875 (CH , CH ), 2211 1.84–1.79 (m, 6 H), 1.58–1.49 (m, 6 H), 0.98 (t, J = 14.8 Hz,
˜
3
2
(CϵC), 1248 (C–O) cm–1. H NMR (400 MHz, CDCl3): δ = 7.43 9 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 158.9, 146.8, 142.4,
1
(t, J = 8.6 Hz, 9 H), 6.85 (d, J = 8.0 Hz, 9 H), 4.68 (d, J = 13.6
134.7, 132.0, 130.8, 130.7, 123.6, 113.8, 110.9, 91.5, 91.4, 68.8, 36.7,
Hz, 3 H), 4.04–4.00 (m, 6 H), 3.81 (s, 9 H), 3.59 (d, J = 13.6 Hz,
31.1, 19.2, 13.8 ppm. MS (EI+): m/z = 921. C57H51N3O9 (922.04):
3 H), 1.88–1.79 (m, 6 H), 1.06 (t, J = 14.8 Hz, 9 H) ppm. 13C NMR calcd. C 74.07, H 5.44; found C 74.03, H 5.70.
(100 MHz, CDCl3): δ = 159.4, 158.3, 140.9, 134.3, 132.9, 130.9,
(؎)-2,7,12-Tris(butyloxy)-3,8,13-tri(pyridin-4-yl)-10,15-dihydro-5H-tri-
benzo[a,d,g]cyclonoene (4j): Yield 70%; m.p. 266–267 °C. IR (KBr):
116.1, 114.2, 113.9, 112.2, 92.8, 84.5, 70.6, 55.3, 36.6, 22.6,
10.5 ppm. MS (MALDI-TOF): m/z = 834.3, 857.2 [M + Na+],
873.2 [M + K+]. C57H54O6·0.5H2O: C 81.11, H 6.57; found C 81.05,
H 6.64.
ν = 2965, 2934, 2876 (CH , CH ), 2214 (CϵC), 1591, 1405,
˜
3
2
1253 cm–1. H NMR (400 MHz, CDCl3): δ = 8.57 (d, J = 5.6 Hz,
6 H), 7.43 (s, 3 H), 7.33 (d, J = 5.6 Hz, 6 H), 6.85 (s, 3 H), 4.57 (d,
J = 13.6 Hz, 3 H), 4.04–3.96 (m, 6 H), 3.54 (d, J = 13.6 Hz, 3 H),
1.84–1.79 (m, 6 H), 1.05 (t, J = 14.8 Hz, 9 H) ppm. 13C NMR
1
(؎)-2,7,12-Tris(butyloxy)-3,8,13-tris[4-(methoxycarbonyl)phenyl]-
10,15-dihydro-5H-tribenzo[a,d,g]cyclonoene (4e): Yield 54 %; m.p.
231–232 °C. IR (KBr): ν = 2964, 2876 (CH , CH ), 2211 (CϵC), (100 MHz, CDCl3): δ = 158.9, 149.7, 142.3, 134.7, 131.9, 130.7,
˜
3
2
6900
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© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2012, 6895–6903

Synthesis and Investigation of Cyclotriveratrylene Derivatives
125.4, 113.7, 110.7, 90.8, 90.4, 70.4, 36.5, 22.5, 10.5 ppm. HRMS Compound 1a: Yield 6.85 g (65%). 1H NMR (400 MHz, CDCl3): δ
(ESI+): calcd. for C51H46O3N3: 748.3534; found 748.3548.
= 7.83 (d, J = 8.0 Hz, 1 H), 7.42 (d, J = 8.0 Hz, 1 H), 7.36–7.34
(m, 1 H), 4.27 (t, J = 13.2 Hz, 2 H), 4.05 (t, J = 12.4 Hz, 2 H),
1.91–1.74 (m, 4 H), 1.10 (t, J = 14.8 Hz, 3 H), 1.02 (t, J = 14.8 Hz,
3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 166.2, 157.7, 139.3,
131.9, 123.0, 112.2, 93.1, 70.9, 66.8, 22.4, 22.1, 10.7, 10.4 ppm.
HRMS (EI+): calcd. for C13H17O3I [M + H+] 348.0222; found
348.0227.
(؎)-2,7,12-Tris(butyloxy)-3,8,13-tris{3,5-bis[(phenylethynyl)-
phenyl]ethynyl}-10,15-dihydro-5H-tribenzo[a,d,g]cyclonoene (4k):
Yield 41%; m.p. 246–247 °C. IR (KBr): ν = 2956, 2869 (CH , CH ),
˜
3
2
2213 (CϵC) cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.62–7.60 (m,
9 H), 7.53–7.51 (m, 12 H), 7.45 (s, 3 H), 7.36–7.34 (m, 18 H), 6.90
(s, 3 H), 4.73 (d, J = 13.6 Hz, 3 H), 4.13–4.09 (m, 6 H), 3.64 (d, J
= 13.6 Hz, 3 H), 1.88–1.81 (m, 6 H), 1.63–1.50 (m, 6 H), 1.01 (t, J
= 14.8 Hz, 9 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 158.8,
141.6, 134.6, 133.9, 133.7, 131.7, 130.8, 128.5, 128.4, 124.6, 123.9,
122.9, 114.0, 111.5, 91.4, 90.3, 87.9, 87.3, 68.9, 36.7, 31.3, 29.7,
19.3, 13.9 ppm. MS (MALDI-TOF): m/z = 1410.5 [M + Na+].
C57H54O3·0.5H2O: C 90.29, H 5.70; found C 90.05, H 5.67.
1
Compound 1b: Yield 6.67 g (58%). H NMR (400 MHz, CDCl3): δ
= 7.83 (d, J = 8.0 Hz, 1 H), 7.41 (s, 1 H), 7.35 (d, J = 8.0 Hz, 1 H),
4.31 (t, J = 13.2 Hz, 2 H), 4.08 (t, J = 12.8 Hz, 2 H), 1.86–1.80
(m, 2 H), 1.76–1.71 (m, 2 H), 1.59–1.43 (m, 4 H), 1.02–0.96 (m,
6 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 166.2, 157.7, 139.3,
131.9, 123.0, 112.2, 93.1, 69.1, 65.1, 31.0, 30.7, 19.3, 19.2, 13.8,
13.7 ppm. HRMS (EI+): calcd. for C15H21O3I [M + H+] 376.0535;
found 376.0540.
(؎)-2,7,12-Tris(butyloxy)-3,8,13-tris(3,5-bis{[(4-tert-butylphenyl)-
ethynyl]phenyl}ethynyl)-10,15-dihydro-5H-tribenzo[a,d,g]cyclo-
noene (4l): Yield 25%; m.p. 275–276 °C. IR (KBr): ν = 2961, 2869
˜
Synthesis of 2a and 2b. General Procedure: Compound 1a (5 g,
14.4 mmol) and NaBH4 (10 g, 263 mmol) were dissolved in anhy-
drous THF (150 mL) in a 500 mL two-neck round-bottomed flask.
After heating to reflux for 30 min, methanol (8 mL) was added over
30 min. The mixture was heated for 4 h at reflux and, after cooling
to room temperature, the reaction mixture was quenched by the
addition of saturated aqueous NH4Cl. The aqueous solution was
extracted with ethyl acetate and dried (Na2SO4). The concentrated
residue was purified by column chromatography (petroleum ether/
ethyl acetate) to give the product as a colorless oil.
Compound 2a: Yield 3.77 g (90%). 1H NMR (400 MHz, CDCl3): δ
= 7.71 (d, J = 8.0 Hz, 1 H), 6.83 (s, 1 H), 6.68–6.66 (m, 1 H), 4.64
(d, J = 4.8 Hz, 2 H), 3.98 (t, J = 12.8 Hz,2 H), 1.90–1.81 (m, 2 H),
1.09 (t, J = 15.2 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
157.8, 142.8, 139.3, 120.5, 110.5, 85.3, 70.7, 64.8, 22.5, 10.7 ppm.
HRMS (EI+): calcd. for C10H13O2I [M + H+] 291.9960; found
291.9964.
Compound 2b: Yield 3.78 g (93%). 1H NMR (400 MHz, CDCl3): δ
= 7.69 (d, J = 11.2 Hz, 1 H), 6.81 (d, J = 11.2 Hz, 1 H), 6.66–6.63
(m, 1 H), 4.60 (s, 2 H), 4.00 (t, J = 11.8 Hz,2 H), 1.83–1.79 (m,
2 H), 1.58–1.52 (m, 2 H), 0.99 (t, J = 14.8 Hz, 3 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 157.9, 142.8, 139.3, 120.5, 110.5, 85.3, 68.9,
64.7, 31.2, 19.3, 13.8 ppm. HRMS (EI+): calcd. for C11H15O2I [M
+ H+] 306.0117; found 306.0120.
1
(CH3, CH2), 2213 (CϵC) cm–1. H NMR (400 MHz, CDCl3): δ =
7.60–7.58 (m, 9 H), 7.45 (d, J = 8.4 Hz, 15 H), 7.37 (d, J = 8.4 Hz,
12 H), 6.89 (s, 3 H), 4.69 (d, J = 13.6 Hz, 3 H), 4.14–4.06 (m, 6 H),
3.62 (d, J = 13.6 Hz, 3 H), 1.87–1.80 (m, 6 H), 1.63–1.53 (m, 6 H),
1.32 (s, 54 H), 1.02 (t, J = 14.8 Hz, 9 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 158.8, 151.8, 141.6, 134.6, 133.8, 133.6, 131.4, 130.8,
125.4, 124.6, 124.1, 119.9, 113.9, 111.6, 91.5, 90.5, 87.4, 87.2, 68.9,
36.6, 34.8, 31.3, 31.2, 19.4, 14.0 ppm. MS (MALDI-TOF): m/z =
1746.5 [M + Na+]. C129H126O3 (1724.41): calcd. C 89.99, H 7.13;
found C 89.59, H 7.22.
(؎)-2,7,12-Tris(butyloxy)-3,8,13-tris{[3,5-bis({3,5-bis[(4-tert-
butylphenyl)ethynyl]phenyl}ethynyl)phenyl]ethynyl}-10,15-dihydro-
5H-tribenzo[a,d,g]cyclonoene (4m): Yield 28%; m.p. 217–218 °C. IR
(KBr): ν = 2961, 2869 (CH , CH ), 2213 (CϵC) cm–1. 1H NMR
˜
3
2
(400 MHz, CDCl3): δ = 7.64–7.61 (m,26 H), 7.46 (d, J = 8 Hz,
26 H), 7.36 (d, J = 8 Hz, 26 H), 6.93 (s, 3 H), 4.75 (d, J = 13.6 Hz,
3 H), 4.15–4.13 (m, 6 H), 3.67 (d, J = 13.6 Hz, 3 H), 1.90–1.83 (m,
6 H), 1.66–1.60 (m, 6 H), 1.31 (s, 108 H), 1.04 (t, J = 14.8 Hz,
9 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 158.8, 151.9, 141.8,
134.7, 134.3, 133.9, 131.5, 130.8, 125.4, 124.8, 124.3, 123.6, 123.5,
119.8, 114.0, 111.5, 91.3, 90.8, 89.0, 88.8, 87.6, 87.2, 68.9, 36.7,
34.8, 31.2, 31.1, 19.4, 14.0 ppm. MS (MALDI-TOF): m/z = 3284.3
[M + Na+]. C249H222O3·CH2Cl2: C 89.70, H 6.74; found C 89.49,
H 6.68.
Synthesis of 3a and 3b. General Procedure: To a rapidly stirred mix-
ture of P2O5 (16 g, 113 mmol) suspended in anhydrous ether
(200 mL) was slowly added 2a (8 g, 27.4 mmol). The mixture was
warmed to reflux temperature and stirred for 2 d. The ether was
evaporated and the residue was triturated with CHCl3. A fine white
product was formed in this CHCl3 solution on cooling to 0 °C over-
night. The product was filtered and washed with water, then dried
under vacuum.
Compound 3a: Yield 2.25 g (30%); m.p. 306–307 °C. 1H NMR
(400 MHz, CDCl3): δ = 7.69 (s, 3 H), 6.70 (s, 3 H), 4.61 (d, J =
13.6 Hz, 3 H), 4.03–3.91 (m, 6 H), 3.54 (d, J = 13.6 Hz, 3 H), 1.84–
1.79 (m, 6 H), 1.06 (t, J = 14.8 Hz, 9 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 156.6, 140.7, 140.3, 132.8, 113.4, 84.9, 70.9, 36.0, 22.4,
10.7 ppm. MS (MALDI-TOF): m/z = 821.8, 844.8 [M + Na+],
860.2 [M + K+]. C30H33I3O3 (822.30): calcd. C 3.82, H 4.05; found
C 43.91, H 4.08.
{5-[(2-Butoxyphenyl)ethynyl]-1,3-phenylene}bis(ethyne-2,1-diyl)-
dibenzene (1/3 D-k): Yield 82%. H NMR (400 MHz, CDCl3): δ =
1
7.51 (s, 3 H), 7.49–7.37 (m, 4 H), 7.37–7.27 (m, 7 H), 6.94–6.89 (m,
2 H), 4.09–4.04 (t, J = 12.4 Hz, 2 H), 1.91–1.84 (m, 2 H), 1.66–1.53
(m, 2 H), 1.04 (t, J = 14.8 Hz, 3 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 159.9, 134.0, 133.7, 133.3, 131.7, 130.0, 128.5, 128.4,
124.6, 123.9, 122.9, 120.3, 112.5, 112.1, 91.7, 90.3, 87.9, 87.3, 68.5,
31.3, 19.3, 13.9 ppm. HRMS (EI+): calcd. for C34H26O [M + H+]
450.1984; found 450.1988.
Synthesis of 1a and 1b. General Procedure: A 500 mL two-neck
round-bottomed flask was charged with 3-hydroxy-4-iodobenzoic
acid (8 g, 30.3 mmol), Cs2CO3 (40 g, 2 equiv.), RBr (C3H7Br, 9 g,
1.2 equiv. C4H9Br, 10 g, 1.2 equiv.) and acetone (200 mL). The mix-
ture was heated a further 12 h at reflux, then the inorganic solids
were filtered off, and the solvent was evaporated. The residue was
extracted several times with water and dichloromethane. The com-
bined organic layer was dried (Na2SO4) and the aqueous layer was
combined and acidified with concd. HCl. The unreacted material
that remained in water could be recycled. After filtration, dichloro-
methane was evaporated to yield 1 as a colorless oil, which was
pure enough for the next step.
Compound 3b: Yield 2.11 g (28%); m.p. 263–264 °C. 1H NMR
(400 MHz, CDCl3): δ = 7.68 (s, 3 H), 6.69 (s, 3 H), 4.55 (d, J =
13.6 Hz, 3 H), 4.06–3.93 (m, 6 H), 3.49 (d, J = 13.6 Hz, 3 H), 1.80–
1.74 (m, 6 H), 1.56–1.47 (m, 6 H), 0.97 (t, J = 14.8 Hz, 9 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 156.6, 140.5, 140.3, 132.8, 113.4,
Eur. J. Org. Chem. 2012, 6895–6903
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
6901

X.-N. Han, J.-M. Chen, Z.-T. Huang, Q.-Y. Zheng
FULL PAPER
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84.9, 69.1, 36.0, 31.0, 19.3, 13.8 ppm. MS (MALDI-TOF): m/z =
886.8 [M + Na+]. C33H39I3O3 (864.38): calcd. C 45.85, H 4.55;
found C 45.64, H 4.59.
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1
cle): H and 13C NMR spectra of all the products, high-resolution
mass spectra of 1a, 1b, 2a, 2b, 1/3 4k, 4e, and 4j.
Acknowledgments
This work was supported by the National Natural Science Founda-
tion of China (NSFC) (grant number 20932004), the Major State
Basic Research Development Program of China (2011CB932501),
and the Chinese Academy of Sciences.
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Received: July 31, 2012
Published Online: November 2, 2012
Eur. J. Org. Chem. 2012, 6895–6903
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
6903