Synthesis and solid-state polymerization of a macrocyclic compound with two butadiyne units

Article abstract of DOI:10.1246/bcsj.20160418

A macrocyclic compound 1 with two butadiyne and four dodecyloxy-substituted benzamide moieties was successfully synthesized, and its ring structure was confirmed by the MALDI-TOF mass spectra and the 1HNMR spectra. Compound 1 showed two modifications depending on solvent for the solidification. Characteristic excitonic absorption bands of polydiacetylene were observed at around 500 nm for one of the modifications after UV irradiation. Quantitative conversion of butadiyne moieties to the corresponding polydiacetylene structure was confirmed by the Raman spectra.

Full text of DOI:10.1246/bcsj.20160418

Advance Publication Cover Page
Synthesis and Solid-State Polymerization of a Macrocyclic Compound with Two
Butadiyne Units
Kohei Kikuchi, Yoko Tatewaki, and Shuji Okada*
Advance Publication on the web January 7, 2017
doi:10.1246/bcsj.20160418
© 2017 The Chemical Society of Japan

Synthesis and Solid-State Polymerization of a Macrocyclic Compound with Two
Butadiyne Units
Kohei Kikuchi,1 Yoko Tatewaki,2 and Shuji Okada*3
1Graduate School of Science and Engineering, Yamagata University, 4-3-16 Jonan, Yonezawa 992-8510
2Division of Applied Chemistry, Tokyo University of Agriculture and Technology, 2-24-16 Nakacho, Koganei 184-8588
3Graduate School of Organic Materials Science, Yamagata University, 4-3-16 Jonan, Yonezawa 992-8510
E-mail: kk.labmail@gmail.com
Abstract
A macrocyclic compound 1 with two butadiyne and four
dodecyloxy-substituted benzamide moieties was successfully
synthesized, and its ring structure was confirmed by the
MALDI-TOF mass spectra and the1H-NMR spectra. Compound
1 showed two modifications depending on solvent for the solid-
ification. Characteristic excitonic absorption bands of polydi-
acetylene were observed at around 500 nm for one of the modi-
fications after UV irradiation. Quantitative conversion of bu-
tadiyne moieties to the corresponding polydiacetylene structure
was confirmed by the Raman spectra.
Figure 1. Structure of the macrocyclic derivative 1, in which
R is a dodecyl group.
1. Introduction
Cyclic compounds have been widely investigated in the
fields of biochemistry, complex chemistry, polymer chemistry,
and electrical chemistry. Typical examples are crown ethers,1 cy-
clodextrins,2,3 calixarenes,4 etc. They can selectively include
ions or molecules. Also, such ring compounds can be used as a
part of supramolecules and their unique functions have been in-
vestigated. On the other hand, ring compounds with polymeriza-
tion sites are interesting for fixing aggregation states of the ring
compounds.
In this study, we synthesized a macrocyclic compound 1
with two butadiyne units (Figure 1). In order to provide self-as-
sembling ability to the macrocyclic compound, trialkoxyphenyl
groups for - stack and hydrophobic interactions and amide
groups for intermolecular hydrogen-bonding were introduced.5-
11
Butadiyne units are for topochemical polymerization. When
butadiyne moieties are aligned in proper translation relations,
regular 1,4-addition polymerization can be stimulated by UV ir-
radiation or thermal annealing to form polydiacetylenes (PDAs)
(Figure 2).12,13 The topochemical polymerization can be easily
confirmed by the color appearance due to formation of -conju-
gated PDA backbones. By combination of the macrocyclic mo-
lecular shape and topochemical polymerization of butadiyne
units, polymers with characteristic structures may be synthesized,
e.g., tube-type polymers and three-dimensionally crosslinked
polymers (Figure 3). There have been several reports on cyclic
butadiyne derivatives.14-21 These compounds had their own
Figure 2. Solid-state polymerization of butadiyne derivatives.
structural characteristics, e.g., methylene chain linkages,14,15
a
glutarate structure,16,17 isophthalamide structures,18,19 m-
acetynylphenyl structure,20 linkages composed of chiral glu-
tamic acid and trans-1,4-cyclohexanediol,21 and fully -conju-
gated cyclic and rigid structures.22-35 On the other hand, the
structure of 1 in this study is composed of trialkoxyphenyl and
amide groups for self-assembling assist and methylene chains
for structure flexibility besides butadiyne moieties. Its character-
ization and polymerization were investigated.
Figure 3. Examples of polymer structures which may be ob-
tained from cyclic compounds with two butadiyne units.

Scheme 1. Synthesis route of 1: (i) SOCl2, pyridine, (ii) NaNH2, liq. NH3, (iii) TsCl, pyridine, (iv) NaN3, (v) PPh3, H2O, (vi)
CH3(CH2)11Br, K2CO3, (vii) KOH aq., (viii) 7, DCC, HOBt, TEA (ix) Br(CH2)9Br, K2CO3, (x) O2, CuCl, TMEDA, (xi) 11, K2CO3. R
is a dodecyl group.
Several spectroscopic measurements were conducted to
2. Results and Discussion
confirm the ring structure of 1. By using 1H-NMR, the spectrum
of 1 was compared with that of 14 (Figure 4). The proton peaks
at propargyl positions of terminal acetylenes were known to shift
to a lower field by the coupling reaction. For the spectrum of 14,
there are the doublet-triplet peak at 2.22 ppm for the propargyl
protons of the terminal acetylenes and the triplet peak at 2.29
Compound 1 was synthesized according to Scheme 1.
Starting from tetrahydrofuran-2-methanol 2, compounds 3－7
were successively prepared referring to the literatures.36,37
Meanwhile, by reacting methyl gallate 8 and two equivalents of
1-bromododecane with potassium carbonate in DMF, two do-
decyl groups were introduced to give 9 in 44% yield. Saponifi-
cation of 9 using potassium hydroxide afforded 10 in 93% yield.
Amide 11 was obtained by condensation between 7 and 10 us-
ing N,N'’-dicyclohexylcarbodiimide, 1-hydroxybenzotriazole
and trimethylamine in 41% yield.38,39 The hydroxy group of 11
and 1,9-dibromononane reacted with potassium carbonate in
DMF to afford 12 in 85% yield. The coupling reaction of 12 was
performed in THF by bubbling oxygen using CuCl-TMEDA as
a catalyst to give 13 in 73% yield. By attaching two species of
11 to 13 using potassium carbonate in DMF, ring precursor 14
was obtained in 53% yield. In the reaction step from 11 to 12,
1,9-dibromononane, i.e., dibromide with odd-number methyl-
enes, was selected to approach the terminal acetylene units of 14
when the methylene chains took the all-trans conformation. Final
oxidative coupling of 14 gave a rise to the desired ring product
1 in 32% yield. We also tried another route for preparation of 1
(Scheme S1). From 1,9-dibromononane and two equimolar
amount of 11, a ring precursor with two terminal acetylenes (21
in Scheme S1) was synthesized, and its oxidative coupling reac-
tion was performed. In this case, monomeric and trimeric ring
products were also obtained besides the desired dimeric ring
product 1. Since separation of these ring products were not easy,
the route in Scheme 1 is better to obtain the pure ring compound
of 1.
Figure 4. 1H-NMR spectra of 1 (upper) and 14 (lower). The
partial structures of 1 and 14 around the aromatic ring and the
acetylenic moieties are inserted.

Figure 5. MALDI-TOF mass spectra of 1. The lower figure is
an expanded spectrum of the upper figure.
Figure 6. UV-vis diffuse reflectance spectra of 1 as a function
of the UV irradiation time. Spectra (a) and (b) are for 1 solidified
from chloroform-methanol mixture and chloroform-hexane mix-
ture, respectively. Spectra obtained after UV irradiation for 0
min, 10 min, 60 min and 240 min are displayed using long-
dashed, dotted, short-dashed and solid lines, respectively.
ppm for the propargyl protons of the butadiyne moiety. However,
for the spectrum of 1, the doublet-triplet peak disappeared and
only propargyl protons of the butadiyne moiety were observed
at 2.29 ppm, indicating that the coupling reaction was successful.
In addition, two aromatic proton peaks were observed at 6.94
and 7.00 ppm for 1 while only one aromatic peak at 6.95 ppm
was found for 14. This difference can be explained as follows.
For ring precursor 14, the aromatic rings can freely rotate and
the aromatic protons (HA and HB of the inserted structure in Fig-
ure 4) were observed equivalently. On the other hand, environ-
ment of the aromatic protons of ring compound 1 became differ-
ent between inside and outside of the ring, and HA and HB were
detected at different chemical shifts.
Figure 7. Structure of the linear-shape monomer 15, in which
R is a dodecyl group.
As mentioned above, we obtained ring compounds with
several ring sizes via Scheme S1, which were clarified by using
the MALDI-TOF mass spectrum (Figure S1). However, we con-
firmed that pure compound of 1 was finally isolated via Scheme
1. Figure 5 shows the MALDI-TOF mass spectrum of 1, in
which ion peaks were observed as Na adducts, i.e., [M+Na]+.
There were no peaks of 14 and its coupling by-products. The
calculated [M+Na]+ of 1 is 2609.11, which almost coincide with
the observed m/z of 2609.15. The result of elementary analysis
also supported the constitution of 1 (see Experimental section).
Thermal characteristics of 1 and 14 were evaluated by DSC
measurements (Figure S2). The melting points of 1 and 14
solidified from chloroform-methanol mixture were 153.5 oC and
107.3 oC, respectively. Large difference of 46 oC in the melting
points in spite of almost the same molecular weight suggested
large difference in molecular shapes and/or packing in the solids.
Topochemical polymerization of 1 was stimulated by UV
irradiation. Figure 6 (a) shows UV-visible diffuse reflectance
spectra of 1 solidified from chloroform-methanol mixture as a
function of the UV irradiation time. The visible absorption band
at around 500 nm, which was assignable to excitonic absorption
of PDA, was gradually developed. Namely, regular 1,4-addition

Table 1. Absorption maximum wavenumbers () for N-H
polymerization of the butadiyne units were suggested, although
there was the conformational disorder judging from the red color.
On the other hand, we found that 1 solidified from chloroform-
hexane mixture did not show such red color upon UV irradiation
as shown in Figure 6 (b), indicating two modifications of 1.
Hereafter, we call 1 solidified from chloroform-methanol mix-
ture as modification I and that solidified from chloroform-hex-
ane mixture as modification II.
stretching vibration
 / cm-1
Compound
Modification I
Modification II
1
3266
3284
15
3266
3272
Similar difference in polymerization behaviors has been
observed for the linear-shape monomer of 15 (Figure 7) with the
chemical structure similar to 1.39 Compound 15 also showed two
modifications, i.e., modification I showing the excitonic absorp-
tion band and modification II showing absorption increase in vis-
ible region without the excitonic band, respectively, upon UV
irradiation. From the FT-IR spectra of 1 and 15 (Figure S3), we
found a common tendency in the intermolecular hydrogen bond-
ing between amide groups. Although the C=O stretching vibra-
tion peaks were observed at 1630±1 cm-1 in any modifications,
the N-H stretching vibration peaks of modification I was ob-
served at a lower wavenumber than that of modification II in
both compounds (Table 1). From these results, the intermolecu-
lar hydrogen bonding of modification I was found to be stronger
than that of modification II, and stronger hydrogen bonding
seemed to cause appropriate polymerizable arrangement of the
monomers in this series of compounds.
Nanostructures of the polymerizable solid of 1 were ob-
served by SEM (Figure 8). In the image of modification I, nano-
fiber structures with the diameter of 80±30 nm was confirmed,
and their fibrous structures were not affected by the photo-in-
duced polymerization. For modification II, such fibrous struc-
tures was not observed (Figure S4).
Figure 8. SEM images of 1 obtained by drop casting of the
chloroform-MeOH solution: (a) Before and (b) after
photopolymerization.
Figure 9 shows diffraction patterns of 1. The result shows
large broad peak at 2 of around 21o. This peak corresponds to
the spacing of 4.3 Å, which is related to be assigned as a distance
between two monomers stacking arrays along the polymeriza-
tion direction.
Figure 10 shows Raman spectra of 1 before and after UV
irradiation for 240 min using a Raman microscope system. For
conventional butadiyne monomers with alkyl substituents, the
Raman peaks on stretching vibration of CC were reported to
appear at between 2260 cm-1 and 2081 cm-1.18, 40-42 Those of
PDAs were observed at 2085 cm-1 and 2116 cm-1 for the blue and
red phases, respectively.43 Modification I showed two acetylene
peaks. The peak at 2250 cm-1, which disappeared in the polymer
spectrum, must be originated from the monomer. On the other
hand, the peak at 2106 cm-1 coincided with the CC peak of the
corresponding PDA. From this fact, we estimated that the solid-
state polymerization progressed during the monomer spectral
measurement and the peak at 2106 cm-1 observed in the mono-
mer spectrum was for the polymer, which contaminated the mon-
omer. Actually, we confirmed that intensity of this peak in-
creased with each microscopic observation accompanying Ra-
man measurements. The most important point was that bu-
tadiyne moieties almost reacted to form the PDA backbones by
UV irradiation. Even in modification II, partial polymerization
during the measurements and almost full conversion to the pol-
ymer were also observed (Figure S5).
Figure 9. Powder XRD measurement of 1.
3. Conclusion
We succeeded to synthesize a cyclic derivative 1 with two
butadiyne moieties and it was characterized by 1H-NMR spectra,
MALDI-TOF mass spectra, the melting point measurement by
DSC, FT-IR spectra, Raman spectra and polymerization behav-
iors. The ring structure and purity were confirmed by the
MALDI-TOF mass spectrum, in which only ion peaks assigna-
ble to the adduct of the cyclic molecule and Na+ were detected.
Figure 10. Raman spectra of 1: Modification II (upper), modi-
fication I (middle) and modification I after photopolymerization
(lower).

In the 1H-NMR spectrum, protons inside and outside of the ring
were clearly distinguished, and this fact was also a good evi-
dence for the ring structure. Two modifications of 1 were ob-
tained by solidified from different mixed solvents. Upon UV ir-
radiation, modification I obtained from chloroform-methanol
mixture became red color, and the absorption bands originated
from the PDA structure were observed at around 500 nm. Since
modification II obtained from chloroform-hexane mixture
showed absorption increase in visible region without excitonic
bands in the course of photopolymerization, the polymer struc-
ture was not so regular. In both modifications, almost quantita-
tive photopolymerization of the butadiyne moieties was con-
firmed by the Raman spectra. As we mentioned in Introduction,
cyclic compound 1 may form polymer displayed in Figure 3.
Since the resulting polymer was soluble in organic solvent such
as chloroform and THF. It is clear that the fully crosslinked pol-
ymer was not obtained. Further studies on the polymer structure
are in progress.
mmol) and 1-hydroxybenzotriazole (HOBt) (0.373 g, 2.76
mmol) were added, the reaction flask was cooled in an ice bath
for 30 min. Then, 7 (0.230 g, 2.36 mmol) and triethylamine
(0.238 g, 2.36 mmol) were added, and the mixture was stirred
overnight at ambient temperature. After filtration, solvent in the
filtrate was evaporated under reduced pressure. The residue was
purified by column chromatography (silica gel, chloroform/ethyl
acetate = 9:1) to give 0.470 g (40.7%) of 11 as white solid: 1H-
NMR (400 MHz, CDCl3): δ 0.88 (6H, t, J = 6.8 Hz), 1.18–1.38
(32H, m), 1.38–1.50 (4H, m), 1.55–1.64 (2H, m), 1.67–1.84 (6H,
m), 1.97 (1H, t, J = 2.5 Hz), 2.23 (2H, dt, J = 2.5 Hz, 6.9 Hz),
3.44 (2H, dt, J = 6.2 Hz), 3.99 (2H, t, J = 6.6 Hz), 4.11 (2H, t, J
= 6.8 Hz), 6.15 (1H, s), 6.34 (1H, t, J = 6.2 Hz), 6.90 (1H, d, J =
2.0 Hz), 7.02 (1H, d, J = 2.0 Hz) ; 13C-NMR (100 MHz, CDCl3)
δ 14.05, 18.00, 22.61, 25.62, 25.86, 26.08, 28.55, 29.17*, 29.30*,
29.37*, 29.57*, 30.10, 31.84, 39.43, 68.65, 68.70, 73.45, 83.96,
104.50, 105.65, 129.82, 137.11, 149.15, 151.73, 167.15.
Asterisks indicate overlapped nonequivalent 13C peaks.
One of the important features of the cyclic compound in
this study is that carbon numbers in methylene chains in the cy-
clic structure and alkyl groups located outside of the cyclic struc-
ture can be easily changed. This results in flexibility in size and
shape of the ring, and further modification of this series of com-
pounds is an interesting subject.
3-(9-Bromononyloxy)-4,5-bis(dodecyloxy)-N-(hex-5-
ynyl)benzamide (12): Compound 11 (0.470 g, 0.802 mmol),
1,9-dibromononane (0.689 g, 2.41 mmol) and potassium car-
bonate (0.333 g, 2.41 mmol) in DMF (10 mL) were stirred over-
night at ambient temperature under a nitrogen atmosphere. Chlo-
roform was added to the reaction mixture, and it was washed
with water. The organic layer was dried over anhydrous magne-
sium sulfate and was filtered. After solvent evaporation from the
filtrate under reduced pressure, the residue was recrystallized
from chloroform-methanol mixture to give 0.540 g (85.2%) of
12 as white solid: 1H-NMR (400 MHz, CDCl3): δ 0.88 (6H, t, J
= 6.9 Hz), 1.20–1.39 (42H, m), 1.40–1.52 (6H, m), 1.59–1.67
(2H, m), 1.68–1.90 (8H, m), 1.98 (1H, t, J = 2.5 Hz), 2.27 (2H,
dt, J = 6.6 Hz, 2.5 Hz), 3.41 (2H, t, J = 6.9 Hz), 3.47 (2H, q, J =
6.9 Hz, 6.0 Hz), 3.98 (2H, t, J = 6.6 Hz), 4.01 (4H, t, J = 6.4 Hz),
6.05 (1H, t, J = 6.0 Hz), 6.92-6.96 (2H, m); 13C-NMR (100 MHz,
CDCl3): δ 14.04, 18.02, 22.61, 25.68, 25.92, 25.99, 28.06, 28.63,
29.16*, 29.23*, 29.30*, 29.49*, 29.57*, 29.64*, 30.22, 31.84,
32.72, 33.86, 39.48, 68.67, 69.17, 73.35, 83.96, 105.44, 105.51,
129.51, 140.85, 152.91, 152.94, 167.33. Asterisks indicate
overlapped nonequivalent 13C peaks.
4. Experimental
Synthesis. Methyl 3,4-bis(dodecyloxy)-5-hydroxyben-
zoate (9): Methyl gallate (8) (0.500 g, 2.94 mmol), 1-bromo-
dodecane (1.47 g, 5.88 mmol) and potassium carbonate (0.897 g,
6.47 mmol) in DMF (10 mL) were stirred overnight at 85 oC un-
der a nitrogen atmosphere. Chloroform was added to the reaction
mixture, and the mixture was washed with water. The organic
layer was dried over anhydrous sodium sulfate and was filtered.
After solvent evaporation from the filtrate under reduced pres-
sure, the residue was purified by column chromatography (silica
gel, chloroform) to give 0.880 g (43.5%) of 9 as white solid: 1H-
NMR (400 MHz, CDCl3): δ 0.88 (6H, t, J = 6.7 Hz), 1.21–1.39
(32H, m), 1.39–1.52 (4H, m), 1.75 (2H, dt, J = 7.3 Hz, 6.9 Hz),
1.82 (2H, dt, J = 7.3 Hz, 6.5 Hz), 3.88 (3H, s), 4.03 (2H, t, J =
6.9 Hz), 4.16 (2H, t, J = 6.5 Hz), 5.85 (1H, brs), 7.17 (1H, d, J =
1.8 Hz), 7.28 (1H, d, J = 1.8 Hz); 13C-NMR (100 MHz, CDCl3):
δ 14.04, 22.64, 25.86, 26.11, 29.21*, 29.32*, 29.37*, 29.57*,
29.61*, 30.16, 31.88, 52.01, 68.77, 73.52, 106.34, 109.41,
125.13, 138.64, 149.13, 151.24, 166.72. Asterisks indicate
overlapped nonequivalent 13C peaks.
N,N'-(Dodeca-5,7-diyne-1,12-diyl)bis(3-(9-bromo-
nonyloxy)-4,5-bis(dodecyloxy)benzamide) (13): Copper(I)
chloride (10.3 mg, 0.104 mmol) and N,N,N’,N’-tetramethyleth-
ylenediamine (TMEDA) (15.5 μL, 0.104 mmol) in THF (5 mL)
were stirred at ambient temperature. To the mixture, 12 (0 .410
g, 0.518 mmol) in THF (10 mL) were added, and stirring was
continued overnight with oxygen bubbling at 70 oC. Solvent of
the mixture was evaporated under reduced pressure. The residue
was purified by column chromatography (silica gel, chloro-
form/ethyl acetate = 9:1) to give 0.300 g (73.3%) of 13 as white
solid: 1H-NMR (400 MHz, CDCl3) δ 0.88 (12H, t, J = 6.6 Hz),
1.19–1.38 (84H, m), 1.39–1.51 (12H, m), 1.59 (4H, dt, J = 6.9
Hz, 6.6 Hz), 1.66–1.89 (16H, m), 2.31 (4H, t, J = 6.6 Hz), 3.37–
3.46 (8H, m), 3.97 (12H, t, J = 6.0 Hz), 6.36 (2H, t, J = 5.7 Hz),
6.97 (4H, s); 13C-NMR (100 MHz, CDCl3) δ 14.07, 18.84, 22.63,
25.54, 25.95, 26.03, 28.09, 28.65, 28.76, 29.19*, 29.25*, 29.33*,
29.53*, 29.59*, 29.68*, 30.25, 31.86, 32.74, 33.92, 39.44, 65.72,
69.17, 73.39, 77.10, 105.41, 105.47, 129.49, 140.85, 152.93,
3,4-Bis(dodecyloxy)-5-hydroxybenzoic acid (10): To 9
o
(3.12 g, 5.99 mmol) in ethanol (40 mL) heated at 80 C, potas-
sium hydroxide (1.35 g, 24.0 mmol) in water (3 mL) was added.
The mixture was refluxed for 3 h under a nitrogen atmosphere.
After addition of 2 mol/L HCl solution (50 mL), the mixture was
extracted with diethyl ether. The combined organic layer was
dried over anhydrous magnesium sulfate. After filtration, solvent
in the filtrate was removed under reduced pressure to give 2.82
g (92.9%) of 10 as white solid: 1H-NMR (400 MHz, CDCl3): δ
0.88 (6H, t, J = 6.8 Hz), 1.19–1.39 (32H, m), 1.39–1.53 (4H, m),
1.76 (2H, dt, J = 7.2 Hz, 6.8 Hz), 1.83 (2H, dt, J = 7.2 Hz, 6.7
Hz), 4.04 (2H, t, J = 6.8 Hz), 4.19 (2H, t, J = 6.7 Hz), 5.88 (1H,
brs), 7.22 (1H, d, J = 1.8 Hz), 7.36 (1H, d, J = 1.8 Hz), the car-
boxyl proton was not clearly detected; 13C-NMR (100 MHz,
CDCl3): δ 14.09, 22.68, 25.91, 26.15, 29.23*, 29.36*, 29.40*,
29.61*, 29.65*, 31.92, 68.90, 73.70, 106.97, 110.13, 124.25,
139.39, 149.19, 151.27, 171.63. Asterisks indicate overlapped
nonequivalent 13C peaks.
152.97, 167.36. Asterisks indicate overlapped nonequivalent 13
peaks.
C
14: The mixture of 13 (80.0 mg, 0.0506 mmol), 11 (67.2
mg, 0.111 mmol) and potassium carbonate (15.4 mg, 0.111
o
mmol) in DMF (2 mL) were stirred overnight at 85 C under a
nitrogen atmosphere. Chloroform was added to the reaction mix-
ture, and it was washed with water. The organic layer was dried
over anhydrous magnesium sulfate and was filtered. After sol-
vent evaporation from the filtrate under reduced pressure, the
3,4-Bis(dodecyloxy)-N-(hex-5-ynyl)-5-hydroxyben-
zamide (11): To 10 (1.00 g, 1.97 mmol) in dichloromethane (30
mL), N,N'-dicyclohexylcarbodiimide (DCC) (0.568 g, 2.76

residue was recrystallized from chloroform-methanol mixture to
give 70.0 mg (53.4%) of 14 as white solid: m.p. 105.0–107.5 oC;
IR (KBr) 3288, 3095, 2923, 2852, 1629, 1581, 1548, 1500, 1467,
1423, 1390, 1336, 1232, 1114, 862, 761, 721 cm-1;1H-NMR (400
MHz, CDCl3): δ 0.84–0.91 (24H, m), 1.19–1.39 (148H, m),
1.40–1.51 (16H, m), 1.54–1.66 (8H, m), 1.67–1.85 (32H, m),
1.97 (2H, t, J = 2.7 Hz), 2.25 (4H, dt, J = 2.7, 6.8 Hz), 2.32 (4H,
t, J = 6.6 Hz), 3.44 (8H, dt, J = 6.8, 6.8 Hz), 3.91–4.05 (24H, m),
6.16–6.25 (4H, m), 6.95 (8H, s); 13C-NMR (100 MHz, CDCl3):
δ 14.01, 17.99, 18.77, 22.58, 25.53, 25.67, 25.84, 25.97, 28.58,
28.71, 29.11*, 29.32*, 29.47*, 29.56*, 29.61*, 30.20, 31.82,
39.47, 65.70, 68.65, 69.07, 73.32, 83.93, 105.44, 105.51, 129.43,
140.79, 152.87, 152.90, 167.35. Asterisks indicate overlapped
nonequivalent 13C peaks.
the experiments using preparative gel permeation chromatog-
raphy. We thank Mr. Daisuke Unabara, Prof. Tsunenobu On-
odera and Prof. Hidetoshi Oikawa for their cooperation on the
MALDI-TOF MS experiments. We thank Prof. Haruya Okimoto,
Prof. Masahito Sano and their coworkers for the Raman spec-
troscopy measurements. Preliminary experimental works of this
study by Mr. Rintaro Takahashi and Mr. Ryohei Tomita are grate-
fully acknowledged.
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1
1425, 1378, 1336, 1232, 1116, 860, 763, 721 cm-1; H-NMR
(400 MHz, CDCl3) δ 0.88 (24H, t, J = 6.9 Hz), 1.20–1.38 (148H,
m), 1.38–1.51 (16H, m), 1.53–1.64 (8H, m), 1.65–1.85 (32H, m),
2.29 (8H, t, J = 6.4 Hz), 3.42 (8H, dt, J = 5.9, 6.4 Hz), 3.88–4.02
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129.48, 140.81, 152.84, 153.05, 167.44. Asterisks indicate
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2.16%. 1H- and 13C-NMR spectra are shown in Figure S6.
Apparatus. The 1H- and 13C-NMR spectra were measured
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720 spectrometer. The Raman spectra were obtained by a
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ative gel permeation chromatography (Japan Analytical Industry
LC-9201 using serially connected columns of JAIGEL3H and
JAIGEL2.5H. Elemental analysis was performed using a Perkin-
Elmer CHN/O 2400 II analyzer.
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Graphical Abstract
<Title>
Synthesis and Solid-State Polymerization of a Macrocyclic Compound with Two Butadiyne Units
<Authors' names>
Kohei Kikuchi, Yoko Tatewaki, and Shuji Okada
<Summary>
A macrocyclic compound with two butadiyne and four dodecyloxy-substituted benzamide moieties was
successfully synthesized. Upon UV irradiation, this compound reacted to form polydiacetylene in almost quantitative
conversion.
<Diagram>