Development of n-type semiconductor based on cyclopentene- or cyclohexene-fused [C60]-fullerene derivatives

Article abstract of DOI:10.1021/acs.joc.5b00530

Properties of cyclopentene- or cyclohexene-fused [C₆₀]-fullerene derivatives as the acceptor in photovoltaic cells have been investigated by use of poly(3-hexylthiophene) (P3HT) as the model donor polymer. Several cyclopentene- or cyclohexene-fused [C₆₀]-fullerene derivatives show high power conversion efficiency (PCE). The highest PCE was obtained for 3′,6′-dihydro-4′-phenoxycarbonyl-6′-methylbenzo[1,9][5,6](C₆₀-I_h)fullerene (3.2%); this is superior to that of [C₆₀]-PCBM with the P3HT polymer under the same experimental conditions. PCE of the OPV devices with alkyl-substituted cyclohexene-fused [C₆₀]-fullerenes depended on the alkyl substituent on the cyclohexene ring; compounds with substituents of odd-number alkyl groups showed better PCE than those compounds possessing even-number alkyl groups.

Full text of DOI:10.1021/acs.joc.5b00530

Article
pubs.acs.org/joc
Development of n‑Type Semiconductor Based on Cyclopentene- or
Cyclohexene-Fused [C60]‑Fullerene Derivatives
Yu Yamane,† Kiyotaka Sugawara,† Naoshi Nakamura,† Shuichi Hayase,† Toshiki Nokami,†,‡
and Toshiyuki Itoh*,†,‡
‡
†Department of Chemistry and Biotechnology, Graduate School of Engineering, and Center for Research on Green Sustainable
Chemistry, Tottori University, 4-101 Koyama-minami, Tottori 680-8552, Japan
S
* Supporting Information
ABSTRACT: Properties of cyclopentene- or cyclohexene-fused [C60]-
fullerene derivatives as the acceptor in photovoltaic cells have been
investigated by use of poly(3-hexylthiophene) (P3HT) as the model
donor polymer. Several cyclopentene- or cyclohexene-fused [C60]-fullerene
derivatives show high power conversion efficiency (PCE). The highest PCE
was obtained for 3′,6′-dihydro-4′-phenoxycarbonyl-6′-methylbenzo[1,9]-
[5,6](C60-Ih)fullerene (3.2%); this is superior to that of [C60]-PCBM with
the P3HT polymer under the same experimental conditions. PCE of the
OPV devices with alkyl-substituted cyclohexene-fused [C60]-fullerenes
depended on the alkyl substituent on the cyclohexene ring; compounds
with substituents of odd-number alkyl groups showed better PCE than those
compounds possessing even-number alkyl groups.
(Figure 1). However, a weak point was also found that [C60]-
FP required a special indium tin oxide (ITO) electrode that
lacked the poly(3,4-ethylenedioxythiophene)−poly-
(styrenesulfonate) (PEDOT−PSS)14 layer to display high
PCE, because the sulfonic acid group of PSS reacted with the
nitrogen atom on the pyrrolidine ring and formed a quarternary
ammonium salt that prevented smooth hole transfer.13 It is
known that PEDOT−PSS works as a hole transport layer
(HTL), which prevents the leakage of current from the active
layer to the ITO electrode, thereby contributing to enhance-
ment of OPV performance, especially fill factor (FF) and open-
circuit voltage (Voc).14 We solved this problem by introducing
two aryl groups on the pyrrolidine ring: the resulting cis-1,3-
diaryl-substituted fulleropyrrolidines, [C60]-Ar2FP, allowed use
of the PEDOT−PSS-coated ITO electrode, due to the
protecting effect of the two aryl groups on the nitrogen atom
in the pyrrolidine moiety.15
INTRODUCTION
■
Organic photovoltaics (OPV) have been attracting much
attention as a next-generation photovoltaic system because of
their light weight and shape flexibility, as well as the potential to
be produced at low cost.1 Use of photovoltaic technology is
now well-recognized as one of the most important ways to
prevent the exhaustion of fossil fuels. Fullerene and its
derivatives are widely used as n-type materials in the active
layer of OPVs due to their high electron mobility and adequate
lowest unoccupied molecular orbital (LUMO) level.2,3
Recently, a hybrid solar cell based on the mesosuperstructured
organometallic halide perovskite has been developed, which
had a strong impact on the field of OPV:4,5 these compounds
are now referred to as “a game changer” in photovoltaics.5a
However, fullerene-based solar cells might be important
candidates for green solar cells. Development of stable fullerene
derivatives with high power conversion efficiency (PCE) is,
therefore, still strongly desired.6 Methyl [6,6]-phenyl-C61-
butyrate ([C60]-PCBM)7 is known to be the standard blending
material among acceptors with poly-3-hexylthiophene (P3HT),
which is a donor partner in polymer solar cells.8 Troshin and
co-workers9 developed various types of methanofullerene
derivatives as acceptors for P3HT. Matsuo and co-workers10
reported OPV devices with silylmethylfullerene (SIMEF) that
showed PCE superior to devices with [C60]-PCBM. Recently,
Matsuo et al.11 also reported excellent simple fullerene
derivatives such as dihydromethane/indene adducts of [C60]
and [C70]-fullerene as acceptor with P3HT.
Recently, Yang et al.16 reported the syntheses of cyclo-
pentene- and cyclohexene-fused [C60]-fullerene derivatives
through [3 + 2] and [4 + 2] cycloaddition reactions of
Morita−Baylis−Hillman adducts with [C60]-fullerene. We are
intrigued by these compounds and decided to investigate their
potential as resources for OPV materials, because these
fullerene derivatives might be free from the influence of
PEDOT−PSS. Herein we report the properties of OPV devices
with cyclopentene- and cyclohexene-fused [C60]-fullerenes, 1
and 2, as n-type materials with P3HT (Figure 1). As expected,
we have established that some cyclopentene- and cyclohexene-
We found that fulleropyrrolidine derivatives ([C60]-FP)12,13
worked as a good acceptor with P3HT and the resulting solar
cell showed higher PCE compared to that of [C60]-PCBM
Received: March 9, 2015
Published: April 9, 2015
© 2015 American Chemical Society
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Figure 2. Typical solar cell designed to evaluate cyclopentene- or
cyclohexene-fused [C60]-fullerene derivatives.
inferior results (entry 2) to the simple phenyl-substituted 1a,
though introduction of the methoxy group on the phenyl
substituent effectively enhanced PCE for fulleropyrrolidine
derivatives.12 Introduction of an electron-withdrawing bromine
atom on the phenyl group also significantly reduced both Jsc
and Voc and afforded poor PCE (entry 3). We next investigated
the influence of the ester group on the cyclopentene ring
toward efficiency of the OPVs.
Introduction of methoxyethoxyethyl (MEM) moiety on the
nitrogen atom of the fulleropyrrolidine ring significantly
increased solubility in chlorobenzene, and this not only allowed
easy preparation of the devices but also contributed to
improved PCE.12 Comparing the results of 1a and 1g, which
have the same aromatic group on the CP ring, 1g showed better
solubility in chlorobenzene than 1a; however, the PCE value of
1g was inferior to that of 1a due to poor FF (entry 7). Upon
switching the ester carbonyl group to the hydroxylmethyl
group, a significant drop in PCE, mainly due to a poor Jsc value
(entry 8), was obtained for 1h.
Figure 1. [C60]-fullerene derivatives as source of OPVs.
fused [C60]-fullerene derivatives showed superior or similar
ability to that of [C60]-PCBM.
RESULTS AND DISCUSSION
■
Design of Cyclopentene-Fused [C60]-Fullerene. Syn-
thesis of cyclopentene-fused [C60]-fullerene ([C60]-CP) and
cyclohexene-fused [C60]-fullerene derivatives ([C60]-CH) has
been accomplished according to the method reported by Yang
and co-workers.16 Using these fullerene derivatives, we
prepared model solar cells (Figure 2) and evaluated their
efficiency. Cyclopentene- or cyclohexene-fused [C60]-fullerene
derivatives were mixed with P3HT (1/1 w/w) in chloroben-
zene, and the resulting solution was spin-coated onto ITO with
PEDOT−PSS14 as a positive electrode to make an active layer
of organic photovoltaic cells. Calcium and aluminum were used
as negative electrode.
It is reported that the Voc of an OPV device is determined by
the difference between the LUMO level of the n-type
conductor and the highest occupied molecular orbital
(HOMO) level of the p-type semiconductor.17 Since it was
expected that LUMO level of the cyclopentene ring might be
modified by introduction of a π-conjugated group,13 we initially
prepared 13 types of aryl-, alkyl, and thiophene-substituted
cyclopentene-fused fullerene derivatives 1a−1m (Figure 3), and
the results of evaluation of corresponding OPV devices are
summarized in Table 1.
Although the levels of PCE of all [C60]-CP were inferior to
that of [C60]-PCBM (entry 14), the OPV prepared with 1a
showed a similar level to that of [C60]-PCBM (entry 1). This
device displayed the high short-circuit current (Jsc), open-circuit
voltage (Voc), and fill factor (FF), and in particular, the Jsc of 1a
was higher than that of [C60]-PCBM. However, due to lower
Voc and FF values, the resulting PCE was slightly inferior to that
of [C60]-PCBM. The methoxyphenyl-substituted 1b showed
It is reported that the Voc of an OPV device is determined by
the difference between the n-type conductor and the HOMO
level of the p-type semiconductor.17 We previously reported
that introduction of π-conjugated thiophene group on the
fulleropyrrolidine effectively modified the LUMO level of the
compound and contributed to the enhancement of PCE of the
corresponding OPVs.13 Therefore, we expected that higher
PCE might be obtained for thiophene-substituted cyclo-
pentene-fused [C60]-fullerenes. Unfortunately, PCE values of
thiophene-substituted compounds were inferior to those of
[C60]-PCBM and 1a (entries 9−13). Among methyl, t-butyl,
and MEM esters of thiophene derivatives (1i, 1j, and 1k), the
best PCE was attained for MEM ester 1k (entry 11). On the
other hand, a better result in PCE was obtained for the simple
methyl ester 1l (entry 12) upon comparing the results obtained
by bithiophene-substituted derivatives 1l and 1m (entries 12
and 13); this was assumed to be from the poor FF value of 1m,
while Jsc was superior to that of 1l.
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Design of Cyclohexene-Fused [C60]-Fullerene. We next
prepared 12 types of cyclohexene-fused [C60]-fullerene
derivatives 2a−2l (Figure 4) and evaluated properties of the
Figure 4. Molecular structures of cyclohexene-fused [C60]-fullerene
derivatives.
Figure 3. Molecular structures of cyclopentene-fused [C60]-fullerene
derivatives.
corresponding OPV devices (Table 2). To our delight, three
devices with 2b, 2g, and 2l gave better PCE than the control
device derived from [C60]-PCBM. In particular, the highest
Table 1. Photovoltaic Performance of P3HT-Based Organic
Photovoltaic Devices with Various Types of Cyclopentene-
a
Fused [C60]-Fullerene Derivatives 1
Table 2. Photovoltaic Performance of P3HT-Based Organic
Photovoltaic Devices with Various Types of Cyclohexene-
entry fullerene derivative PCE (%) Jsc (mA·cm−1
)
Voc (V)
FF
a
Fused [C60]-Fullerene Derivatives 2
1
1a
2.57
2.05
1.60
1.78
1.84
2.15
1.57
1.40
1.97
1.68
2.13
1.88
1.76
2.59
6.76
5.87
5.50
6.88
6.36
6.05
6.38
3.93
6.41
4.71
6.78
5.24
6.16
6.91
0.605
0.604
0.532
0.544
0.541
0.577
0.592
0.592
0.552
0.588
0.544
0.576
0.566
0.601
0.628
0.578
0.548
0.475
0.535
0.617
0.416
0.599
0.556
0.605
0.577
0.623
0.505
0.625
2
1b
entry fullerene derivative PCE (%) Jsc (mA·cm−1
)
Voc (V)
FF
3
1c
1
2a
0.61
2.71
1.14
2.57
0.51
2.26
2.83
1.58
1.47
1.41
1.89
3.20
2.59
2.00
6.96
3.51
6.46
2.43
6.16
7.71
5.64
4.31
5.26
5.24
8.13
6.91
0.522
0.619
0.528
0.627
0.544
0.625
0.625
0.615
0.608
0.652
0.672
0.642
0.601
0.588
0.629
0.616
0.634
0.387
0.587
0.586
0.454
0.561
0.412
0.536
0.614
0.625
4
1d
2
2b
5
1e
3
2c
6
1f
4
2d
7
1g
5
2e
8
1h
6
2f
9
1i
7
2g
10
11
12
13
14
1j
8
2h
1k
9
2i
1l
10
11
12
13
2j
1m
2k
[C60]-PCBM
2l
a
Under the illumination of AM 1.5G, 100 mW/cm2. Jsc, short-circuit
current; Voc, open-circuit voltage; FF, fill factor.
[C60]-PCBM
a
Under the illumination of AM 1.5G, 100 mW/cm2. Jsc, short-circuit
current; Voc, open-circuit voltage; FF, fill factor.
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PCE (3.20%) was attained for methyl-substituted phenyl ester
2l (entry 12): Jsc of 2l reached 8.13 mA·cm−1, and this is the
highest value among 26 types of devices tested in the present
study. On the contrary, the worst PCE value was obtained for
the simple cyclohexene-fused compound 2a due to very poor Jsc
(entry 1).
Furthermore, we discovered the very interesting facts that
PCE depended on the alkyl substituent on the cyclohexene
ring: compounds that have substituents with an odd number of
alkyl groups (2b, 2d, 2f, and 2g) showed better PCE (entries 2,
4, 6, and 7) than those of compounds with an even number of
alkyl groups (2c and 2e) (entries 3 and 5). As shown in Table
2, [C60]-CH with an odd number of alkyl groups generally
showed high Jsc, while compounds with an even number of alkyl
groups showed lower values in Jsc.
Figure 6. Cyclic voltammograms of [C60]-PCBM, 2b, 2k, and 2l
devices in o-dichlorobenzene/CH3CN (4:1 v/v) (0.1 mM) with 0.1 M
n-Bu4NPF6 at a scan rate of 10 mV/s.
We also found that all compounds showed good solubility in
chlorobenzene; hence it was very easy to prepare OPV films.
However, the preparation of fine films sometimes failed when
2c or 2e was used due to the formation of very small particles
during the baking process. It is speculated that alkyl
substituents on the cyclohexene ring significantly influenced
the aggregation state of the fullerene derivatives. Since our
OPVs are bulk heterojunction-type solar cells, the aggregation
state influenced the interaction state with P3HT and this may
have reflected on the results of the OPV properties.
Table 3. Reduction Potentials and LUMO Levels for
Fullerene Derivatives
a
entry fullerene derivative E0 (V) E0 (V) E0 (V) LUMO (eV)
1
2
3
1
2
3
4
[C60]-PCBM
−1.09
−1.15
−1.11
−1.14
−1.49
−1.54
−1.50
−1.55
−2.00
−2.06
−2.04
−2.08
−3.71
−3.65
−3.69
−3.66
2b
2k
2l
a
Potential values in this table are versus Fc/Fc+.
Figure 5 shows current density versus Voc for OPVs derived
from P3HT with typical fullerene derivatives, 1a, 1k, 2b, 2l, and
The LUMO energy levels of the fullerene derivatives were
estimated from their first half-wave potentials (E0 ) indicated in
1
the cyclic voltammograms (Figure 6), and the results are
summarized in Table 3. The E01 values of [C60]-PCBM, 2b, 2k,
and 2l devices were −1.09, −1.15, −1.11, and −1.14 V vs Fc/
Fc+, respectively. The LUMO energy levels of the fullerene
derivatives from the onset reduction potentials were calculated
by use of the following equation: LUMO (eV) = −(E0
+
1
4.80).18 Therefore, the LUMO energy levels of [C60]-PCBM,
2b, 2k, and 2l calculated by this method are −3.71, −3.65,
−3.69, and −3.66 eV, respectively. The LUMO level of 2l is
raised by 0.05 eV in comparison with that of [C60]-PCBM. The
higher LUMO level of 2l is desirable for its application as an
acceptor in the active layer to obtain Voc. It has been reported
that the LUMO level corresponded to Voc value. However, the
highest LUMO level was observed for 2b, while the highest Voc
was recorded for 2k (see Table 2, entries 2 and 11).
Furthermore, the best PCE was attained for the OPV device
with 2l (see Table 2, entry 12).
Therefore, we further investigated LUMO levels of all
cyclopentene- and cyclohexene-fused fullerenes using cyclic
voltammograms and found that almost all compounds, except
1e and 1f, showed slightly higher LUMO levels than that of
[C60]-PCBM (see Experimental Section and Table S1 in
Supporting Information). Although it has been reported that
the LUMO level corresponded to Voc value, only 48% of OPV
cells (11 cells) gave higher Voc than that of [C60]-PCBM, while
acceptor materials possess higher LUMO levels than [C60]-
PCBM (Table S1, Supporting Information). FF values of most
cells are inferior to that of [C60]-PCBM cell except for 1a, 2b,
and 2d.
All films showed a broad π−π* absorption from 300 to 700
nm, and the λmax of these films is around 500 nm. Similar UV−
vis spectra were obtained from films including P3HT with 1a,
2b, 2l, and [C60]-PCBM, though P3HT/1k has distinctive
broad absorption between 350 and 400 nm and strong
absorption around 550 nm, which were assumed to be caused
Figure 5. Current density−potential characteristics of P3HT/[C60]-
CP (1a and 1k) and P3HT/[C60]-CH (2b and 2l) solar cell devices
under illumination by an AM 1.5G solar simulated light (100 mW/
cm2).
control [C60]-PCBM: the 2l cell shows the highest PCE of
3.20% and Jsc of 8.13 mA/cm2. As clearly shown in this I−V
profile, 2l cell displays superior properties to those of [C60]-
PCBM.
Since high PCEs were obtained for cyclohexene-fused [C60]-
fullerene, we investigated more detailed properties of OPV
devices with three derivatives, 2b, 2k, and 2l, by cyclic
voltammogram (CV) analysis, and the results are shown in
Figure 6 and Table 3.
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red1
exact mass 894.0681); E1/2
−3.69 eV.
−1.11, LUMO = −(4.8 + E1/2red1) =
by the thiophene moiety on the cyclopentene molecule (see
Figure S1, Supporting Information). UV−vis spectra of OPV
film prepared by 2k shows a lower level of absorption around
500 nm (see Figure S1, Supporting Information); this also
suggests poor matching of the cyclohexyl ester with P3HT.
These results clearly indicate that PCE levels of these OPVs are
not determined only by LUMO level of the n-type materials
with P3HT.
1b. From [C60]-fullerene (360 mg, 0.50 mmol) and methyl 2-
[hydroxy(4-methoxyphenyl)methyl]acrylate (S3b)19 (172 mg, 0.90
mmol), product 1b was obtained in 34% yield (162 mg, 0.17 mmol) as
a brown amorphous solid. 1H NMR (500 MHz, ppm, CDCl3−CS2) δ
8.04 (d, J = 2.0 Hz, 1H), 7.64 (br s, 1H), 7.55 (br s, 1H), 7.00 (br s,
1H), 6.90 (br s, 1H), 6.16 (d, J = 1.5 Hz, 1H), 3.89 (s, 3H), 3.82 (s,
3H); 13C NMR (125 MHz, ppm, CS2−CDCl3) δ163.82, 158.92,
156.31, 153.95, 151.03, 150.71, 147.30, 147.21, 146.27, 146.21, 146.00,
145.98, 145.93, 145.91, 145.87, 145.75, 145.62, 145.55, 145.46, 145.45,
145.41, 145.32, 145.26, 145.17, 145.03, 144.98, 144.93, 144.86, 144.42,
144.32, 144.28, 144.25, 144.09, 143.03, 142.99, 142.59, 142.50, 142.47,
142.42, 142.38, 142.10, 142.07, 142.05, 141.96, 141.85, 141.71, 141.67,
141.65, 141.51, 140.48, 140.22, 140.04, 139.39, 138.66, 136.77, 136.01,
135.33, 133.99, 132.91, 76.68, 74.68, 62.33, 54.82, 51.89; FT-IR (neat,
cm−1) 2943, 1723, 1608, 1430, 1244, 1094, 824, 765, 690; MALDI-
TOF-MS (matrix SA) found 924.0812 (calcd for C72H12O3 exact mass
CONCLUSION
■
In summary, we have carried out the rational design of
cyclopentene- and cyclohexene-fused [C60]-fullerene derivatives
as acceptors with poly-3-hexylthiophene (P3HT) and estab-
lished that these fullerenes worked as good n-type materials.
High power conversion efficiency was attained for cyclohexene-
fused [C60]-fullerene derivatives, in particular, 3′,6′-dihydro-4′-
phenoxycarbonyl-6′-methylbenzo[1,9][5,6](C60-Ih)fullerene
(2l), which was superior to that of the P3HT-based devices
including [C60]-PCBM. A very interesting effect of alkyl
substituents attached to cyclohexene ring was observed: an
odd number of alkyl group substituents gave better results on
PCEs, while compounds with an even number of alkyl groups
at the cyclohexene ring gave very poor PCE. These results
indicate that both the appropriate band gap level between
LUMO level of the acceptor compounds and HOMO level of
the donor polymer and sufficiently mixed state of both
components determine the total PCE of the OPV devices.
Further investigation into the development of novel donor
polymers as a partner of cyclopentene- and cyclohexene-fused
[C60]-fullerene derivatives will allow the creation of even more
efficient solar cells in the near future.
924.0786); E1/2 −1.11, LUMO = −(4.8 + E1/2red1) = −3.69 eV.
red1
1c. From [C60]-fullerene (359 mg, 0.50 mmol) and methyl 2-
[hydroxy(4-bromophenyl)methyl]acrylate (S3c)19 (418 mg, 1.50
mmol), product 1c was obtained in 33% yield (146 mg, 0.15 mmol)
as a brown amorphous solid. 1H NMR (500 MHz, ppm, CDCl3−CS2)
δ 8.09 (dd, J = 1.0, 1.8 Hz, 1H), 7.62 (br s, 2H), 7.52 (br s, 2H), 6.17
(dd, J = 1.8, 1.1 Hz, 1H), 3.90 (s, 3H); 13C NMR (125 MHz, ppm,
CDCl3-1,2-dichlorobenzene) δ 164.09, 155.83, 153.26, 150.64, 150.32,
147.26, 147.15, 146.20, 146.13, 145.94, 145.88, 145.86, 145.85, 145.81,
145.61, 145.59, 145.52, 145.48, 145.34, 145.32, 145.24, 145.20, 145.20,
145.14, 144.99, 144.93, 144.87, 144.58, 144.21, 144.20, 144.00, 142.90,
142.89, 142.47, 142.43, 142.38, 142.33, 142.21, 141.97, 141.87, 141.78,
141.58, 141.56, 141.53, 141.45, 140.39, 140.30, 140.22, 139.98, 139.32,
137.89, 136.53, 135.94, 135.42, 134.10, 121.93, 76.95, 74.19, 62.53,
52.18; FT-IR (neat, cm−1) 2946, 1720, 1646, 1484, 1430, 1340, 1245,
1186, 1131, 1095, 1011, 889, 819, 765, 691; MALDI-TOF-MS
(matrix: SA) found 971.9761 (calcd for C71H9O2Br exact mass
971.9786); E1/2 −1.11, LUMO = −(4.8 + E1/2red1) = −3.69 eV.
1d. From [C60]-fullerene (362 mg, 0.50 mmol) and methyl 3-
hydroxy-2-methylenehexanoate (S3d)19 (243 mg, 1.54 mmol),
product 1d was obtained in 18% yield (79 mg, 0.17 mmol) as a
red1
EXPERIMENTAL SECTION
■
Materials. [C60]-fullerene was purchased from Frontier Carbon
(nanom purple ST-A), and P3HT was from Aldrich. Silica gel was
purchased from Wako Pure Chemical Industry, Ltd. (Wakogel C-
300E, 45−75 mm, and silica gel 60N).
1
brown amorphous solid. H NMR (500 MHz, ppm, CDCl3−CS2) δ
7.78 (d, J = 1.8 Hz, 1H), 5.01−5.03 (m, 1H), 4.04 (s, 3H), 2.55−2.62
(m, 1H), 2.38−2.45 (m, 1H), 1.94−2.03 (m, 1H), 1.79−1.87 (m, 1H),
1.06 (t, J = 7.4 Hz, 3H); 13C NMR (125 MHz, ppm, CDCl3−CS2) δ
164.69, 156.83, 152.78, 151.28, 151.26, 147.39, 147.26, 146.47, 146.35,
146.30, 146.27, 146.10, 146.08, 146.05, 146.03, 146.00, 145.74, 145.67,
145.55, 145.48, 145.42, 145.40, 145.38, 145.35, 145.26, 145.11, 145.09,
144.81, 144.54, 144.41, 144.27, 143.19, 143.12, 143.05, 142.75, 142.63,
142.54, 142.47, 142.25, 142.23, 142.18, 142.07, 141.97, 141.88, 141.83,
141.70, 141.69, 141.67, 140.51, 140.49, 140.06, 139.98, 139.25, 136.68,
136.43, 135.78, 133.98, 77.46, 73.38, 56.54, 52.04, 36.59, 21.26, 14.68;
FT-IR (neat, cm−1) 2950, 2864, 1718, 1511, 1430, 1342, 1241, 1130,
890, 765, 744; MALDI-TOF-MS (matrix SA) found 860.0819 (calcd
for C68H12O2 exact mass 860.0837); E1/2red1 −1.11, LUMO = −(4.8 +
E1/2red1) = −3.69 eV.
Procedure for Synthesis of Cyclopentene-Fused [C60]-Full-
erenes: 1a.16 A solution of [C60]-fullerene (216 mg, 0.30 mmol),
methyl 2-[hydroxy(phenyl)methyl]acrylate (S3a)19 (172 mg, 0.90
mmol), and N,N-dimethylaminopyridine (110 mg, 0.90 mmol) in dry
toluene (96 mL) was irradiated under ultrasonic conditions for several
minutes to afford a violet solution; then the solution was added to
acetic anhydride (91 mg, 0.90 mmol) and the mixture was stirred for
20 h at 120 °C. After being allowed to cool at room temperature, the
mixture was evaporated under reduced pressure and the residue was
added to methanol. This formed a brown solid, which was collected by
an ultramembrane filter, dissolved in carbon disulfide (CS2), and
purified by silica gel (60N) flash chromatography [CS2/toluene = 1:0,
10:1, and 4:1 (v/v)], affording product 1a (75.0 mg, 0.074 mmol) as a
dark brown amorphous solid in 27% yield; the unreacted fullerene (30
mg) was recovered in 14% yield. 1a showed no clear melting point and
1e. From [C60]-fullerene (360 mg, 0.50 mmol) and (E)-methyl 3-
hydroxy-2-methylene-5-phenylpent-4-enoate (S3e)19 (327 mg, 1.5
mmol), product 1e was obtained in 32% yield (155 mg, 0.16 mmol) as
a brown amorphous solid. 1H NMR (500 MHz, ppm, CS2−CDCl3) δ
7.93 (d, J = 2.0 Hz, 1H), 7.45 (d, J = 7.5 Hz, 2H), 7.32 (t, J = 7.5 Hz,
2H), 7.26 (t, J = 4.5 Hz, 1H), 6.94 (d, J = 15.5 Hz, 1H), 6.76 (dd, J =
10.0, 15.5 Hz, 1H), 5.70 (dd, J = 1.8, 9.7 Hz, 1H), 3.98 (s, 3H); 13C
NMR (125 MHz, ppm, CS2−CDCl3) δ 164.40, 156.07, 153.18,
150.99, 150.74, 147.52, 147.42, 146.45, 146.42, 146.31, 146.23, 146.22,
146.20, 146.18, 146.15, 146.11, 145.90, 145.87, 145.82, 145.76, 145.62,
145.51, 145.35, 145.25, 145.23, 144.62, 144.55, 144.42, 144.31, 144.26,
143.25, 143.18, 142.76, 142.75, 142.70, 142.63, 142.44, 142.32, 142.28,
142.14, 142.11, 142.08, 142.05, 141.95, 141.79, 141.74, 140.60, 140.49,
140.23, 139.95, 138.49, 136.69, 136.66, 136.14, 135.59, 134.24, 134.19,
129.21, 128.70, 128.06, 126.90, 77.02, 73.85, 60.79, 52.24; FT-IR
(neat, cm−1) 3019, 2943, 1724, 1642, 1431, 1225, 1135, 1093, 958,
1
only caused decomposition: H NMR (500 MHz, ppm, CDCl3−CS2)
δ 8.09 (d, J = 2.0 Hz, 1H), 7.74 (br s, 1H), 7.62 (br s, 1H), 7.50 (br s,
1H), 7.39 (br s, 1H), 7.32 (t, J = 7.5 Hz, 1H), 6.21 (d, J = 2.0 Hz, 1H),
3.89 (s, 3H); 13C NMR (125 MHz, ppm, CS2−CDCl3) δ 163.41,
156.09, 153.57, 150.75, 150.55, 147.22, 147.12, 146.20, 146.13, 145.92,
145.91, 145.87, 145.86, 145.83, 145.80, 145.62, 145.53, 145.47, 145.45,
145.37, 145.35, 145.23, 145.18, 145.10, 144.99, 144.90, 144.83, 144.73,
144.32, 144.23, 144.19, 144.01, 142.95, 142.92, 142.52, 142.44, 142.39,
142.35, 142.27, 142.01, 142.00, 141.97, 141.88, 141.77, 141.60, 141.59,
141.57, 141.45, 140.66, 140.42, 140.19, 139.98, 139.23, 138.40, 136.65,
135.90, 135.34, 133.97, 127.74, 76.71, 74.32, 62.94, 51.75; FT-IR
(neat, cm−1) 3020, 2943, 1722, 1646, 1428, 1243, 1095, 767, 694;
MALDI-TOF-MS (matrix SA) found 894.0696 (calcd for C71H10O2
4642
DOI: 10.1021/acs.joc.5b00530
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The Journal of Organic Chemistry
Article
744, 690, 575; MALDI-TOF-MS (matrix SA) found 920.0837 (calcd
for C73H12O2 exact mass 920.0833); E1/2red1 −1.08, LUMO = −(4.8 +
E1/2red1) = −3.72 eV.
1i. From [C60]-fullerene (360 mg, 0.50 mmol) and methyl 2-
[hydroxy(thiophen-2-yl)methyl]acrylate (S3h)24 (297 mg, 1.50
mmol), product 1i was obtained in 52% yield (230 mg, 0.26 mmol)
as a brown amorphous solid. 1H NMR (500 MHz, ppm, CDCl3−CS2)
δ 8.01 (d, J = 1.5 Hz, 1H), 7.28 (t, J = 5.0 Hz, 2H), 7.04 (dd, J = 3.5,
5.0 Hz, 1H), 6.43 (d, J = 1.5 Hz, 1H), 3.91 (s, 3H); 13C NMR (125
MHz, ppm, CS2−CDCl3) δ 163.91, 155.52, 152.98, 150.95, 150.58,
147.44, 147.33, 146.38, 146.33, 146.15, 146.10, 146.07, 146.06, 146.02,
145.99, 145.94, 145.73, 145.69, 145.61, 145.57, 145.55, 145.53, 145.43,
145.37, 145.28, 145.25, 145.14, 145.10, 144.97, 144.88, 144.54, 144.47,
144.39, 144.37, 144.18, 143.09, 143.05, 142.73, 142.62, 142.56, 142.53,
142.39, 142.22, 142.19, 142.07, 141.95, 141.85, 141.81, 141.81, 141.77,
141.69, 141.58, 140.58, 140.32, 140.12, 139.29, 138.09, 137.05, 135.97,
135.69, 134.33, 127.73, 126.69, 125.72, 76.54, 74.71, 57.87, 52.24; FT-
IR (neat, cm−1) 3069, 2843, 1723, 1645, 1430, 1225, 1131, 1095, 894,
1f. From [C60]-fullerene (216 mg, 0.30 mmol) and phenyl 2-
[hydroxy(phenyl)methyl]acrylate (S3f)23 (305 mg, 1.20 mmol),
product 1f was obtained in 37% yield (111 mg, 0.12 mmol) as a
1
brown amorphous solid. H NMR (500 MHz, ppm, CS2−CDCl3) δ
8.30 (d, J = 2.0 Hz, 1H), 7.88 (br s, 1H), 7.66 (br s, 1H), 7.55 (br s,
1H), 7.31−7.41 (m, 5H), 7.04 (d, J = 7.0 Hz, 2H), 6.33 (d, J = 1.5 Hz,
1H); 13C NMR (126 MHz, ppm, CDCl3) δ 162.30, 156.25, 153.72,
150.85, 150.48, 147.54, 147.44, 146.63, 146.52, 146.44, 146.23, 146.18,
146.16, 146.14, 146.10, 145.98, 145.82, 145.80, 145.70, 145.68, 145.63,
145.55, 145.50, 145.41, 145.27, 145.21, 145.15, 145.01, 144.56, 144.53,
144.47, 144.31, 143.23, 143.20, 142.80, 142.73, 142.68, 142.64, 142.51,
142.30, 142.29, 142.21, 142.17, 142.08, 142.04, 141.91, 141.89, 141.87,
141.85, 141.74, 140.93, 140.70, 140.48, 140.25, 139.54, 138.41, 136.98,
136.32, 135.61, 134.27, 129.54, 128.07, 126.14, 121.47, 74.66, 65.98,
63.22; FT-IR (neat, cm−1) 3028, 2913, 1736, 1490, 1217, 1188, 1077,
894, 744, 697, 573; MALDI-TOF-MS (matrix SA) found 956.0821
698; MALDI-TOF-MS (matrix SA) found 900.0233 (calcd for
red1
C69H8O2S exact mass 900.0245); E1/2
−1.10, LUMO = −(4.8 +
E1/2red1) = −3.70 eV.
1j. From [C60]-fullerene (370 mg, 0.51 mmol) and tert-butyl 2-
[hydroxy(thiophen-2-yl)methyl]acrylate (S3i) (365 mg, 1.52 mmol),
product 1j was obtained in 46% yield (219 mg, 0.23 mmol) as a brown
amorphous solid. 1H NMR (500 MHz, ppm, CDCl3−CS2) δ 7.96 (d, J
= 1.9 Hz, 1H), 7.32−7.30 (m, 2H), 7.07 (dd, J = 3.7, 5.5 Hz, 1H), 6.41
(d, J = 1.9 Hz, 1H), 1.53 (s, 9H); 13C NMR (125 MHz, ppm, CDCl3−
CS2) δ 162.66, 155.81, 153.22, 151.20, 150.87, 147.45, 147.33, 146.38,
146.33, 146.16, 146.11, 146.08, 146.06, 146.03, 146.01, 145.99, 145.82,
145.74, 145.65, 145.62, 145.53, 145.44, 145.37, 145.28, 145.23, 145.14,
145.11, 145.01, 144.96, 144.54, 144.41, 144.24, 143.75, 143.11, 143.07,
142.72, 142.62, 142.57, 142.54, 142.41, 142.22, 142.09, 141.98, 141.95,
141.82, 141.81, 141.78, 141.77, 141.60, 140.60, 140.34, 140.11, 140.00,
139.34, 136.90, 135.99, 135.75, 134.35, 127.52, 126.54, 125.46, 81.63,
76.49, 74.78, 58.05, 27.98; FT-IR (neat, cm−1) 3070, 2972, 2926, 1709,
red1
(calcd for C76H12O2 exact mass 956.0837); E1/2 −1.07, LUMO =
−(4.8 + E1/2red1) = −3.73 eV.
1g. From [C60]-fullerene (360 mg, 0.50 mmol) and 2-(2-
methoxyethoxy)ethyl 2-[hydroxy(phenyl)methyl]acrylate (S3g) (420
mg, 1.50 mmol), product 1g was obtained in 32% yield (158 mg, 0.16
mmol) as a brown amorphous solid. 1H NMR (500 MHz, ppm,
CDCl3−CS2) δ 8.13 (d, J = 2.0 Hz, 1H), 7.77 (br s, 1H), 7.63 (br s,
1H), 7.50 (br s, 1H), 7.37 (br s, 1H), 7.31 (t, J = 7.3 Hz, 1H), 6.22 (d,
J = 1.8 Hz, 1H), 4.46−4.51 (m, 1H), 4.38−4.42 (m, 1H), 3.74−3.78
(m, 1H), 3.67−3.71 (m, 1H), 3.61−3.63 (m, 2H), 3.56−3.58 (m, 2H),
3.42 (s, 3H); 13C NMR (125 MHz, ppm, CS2−CDCl3) δ 163.59,
156.27, 153.76, 150.96, 150.73, 147.41, 147.31, 146.38, 146.30, 146.10,
146.05, 146.03, 146.01, 145.97, 145.84, 145.72, 145.69, 145.63, 145.57,
145.54, 145.50, 145.41, 145.37, 145.29, 145.18, 145.13, 145.08, 145.00,
144.91, 144.46, 144.41, 144.37, 144.20, 143.11, 143.08, 142.67, 142.61,
142.56, 142.53, 142.42, 142.18, 142.17, 142.13, 142.06, 141.96, 141.95,
141.77, 141.75, 141.73, 141.62, 140.95, 140.57, 140.35, 140.12, 139.37,
138.45, 136.78, 136.11, 135.50, 134.16, 127.81, 77.41, 77.16, 76.95,
76.91, 74.54, 70.56, 69.12, 64.23, 63.04, 59.04; FT-IR (neat, cm−1)
3109, 2945, 1727, 1645, 1429, 1225, 1094, 801, 765, 697, 575;
1646, 1365, 1248, 1132, 845, 765, 691; MALDI-TOF-MS (matrix SA)
red1
found 942.0670 (C72H14O2S exact mass 942.0715) ; E1/2
−1.11,
LUMO = −(4.8 + E1/2red1) = −3.69 eV.
1k. From [C60]-fullerene (360 mg, 0.50 mmol) and 2-(2-
methoxyethoxy)ethyl 2-[hydroxy(thiophen-2-yl)methyl]acrylate (S3j)
(430 mg, 1.50 mmol), product 1k was obtained in 40% yield (200 mg,
1
0.20 mmol) as a brown amorphous solid. H NMR (500 MHz, ppm,
MALDI-TOF-MS (matrix SA) found 982.1205 (calcd for C75H18O2
exact mass 982.1212); E1/2
−3.70 eV.
CDCl3−CS2) δ 8.10 (d, J = 1.7 Hz, 1H), 7.34 (dd, J = 1.0, 3.6 Hz,
1H), 7.31 (dd, J = 1.0, 4.9 Hz, 1H), 7.07 (dd, J = 3.6, 4.9 Hz, 1H), 6.48
(d, J = 1.8 Hz, 1H), 4.52−4.56 (m, 1H), 4.45−4.49 (m, 1H), 3.80−
3.84 (m, 1H), 3.74−3.78 (m, 1H), 3.66−3.68 (m, 2H), 3.59−3.61 (m,
2H), 3.43 (s, 3H); 13C NMR (125 MHz, ppm, CDCl3−CS2) δ 163.29,
155.47, 152.94, 150.91, 150.51, 147.38, 147.27, 146.33, 146.27, 146.10,
146.04, 146.02, 146.00, 145.96, 145.93, 145.89, 145.67, 145.56, 145.51,
145.49, 145.48, 145.38, 145.32, 145.22, 145.19, 145.07, 145.05, 144.91,
144.47, 144.34, 144.32, 144.14, 143.04, 143.00, 142.67, 142.56, 142.51,
142.48, 142.34, 142.16, 142.13, 142.02, 141.91, 141.81, 141.75, 141.72,
141.65, 141.53, 140.54, 140.27, 140.07, 139.24, 138.02, 138.01, 136.95,
135.95, 135.64, 134.29, 127.63, 126.65, 125.60, 76.50, 74.66, 71.98,
70.56, 69.12, 64.29, 58.99, 57.79; FT-IR (KBr, cm−1) 3075, 2887,
2727, 2328, 1726, 1658, 1438, 1255, 1094, 855, 709, 530; MALDI-
red1
−1.10, LUMO = −(4.8 + E1/2red1) =
1h. A mixture of 1a (57.2 mg, 0.064 mmol) in dry toluene (60 mL)
was irradiated under ultrasonic conditions for several minutes to afford
a clear solution, and then this solution was cooled at −78 °C. To this
was added diisobutylaluminium hydride (DIBAL-H; 0.32 mL, 0.1 M
hexane) at the same temperature, and the mixture was stirred for 19 h
and allowed to warm to room temperature. To this solution was added
20 mL of potassium sodium tartrate tetrahydrate (Rochelle salt)
saturated aqueous solution; the mixture was stirred for 1 h and the
resulting organic layer was collected. The aqueous layer was extracted
with toluene (30 mL, 3 times). The combined organic layers were
washed with brine, dried, and evaporated to dryness. The residue was
dissolved in toluene and purified by silica gel (60N) flash
chromatography [toluene/ethyl acetate = 1:0 and 5:1 (v/v)], affording
1h (39.2 mg, 0.0457 mmol) as a dark brown amorphous solid in 71%
yield: 1H NMR (500 MHz, ppm, CDCl3−CS2) δ 7.88 (d, J = 7.6 Hz,
1H), 7.58 (br s, 2H), 7.32−7.38 (m, 2H), 7.17 (d, J = 1.7 Hz, 1H),
5.96 (s, 1H), 4.84 (dq, J = 4.3, 10.5 Hz, 2H), 1.82 (t, J = 5.3 Hz, 1H);
13C NMR (125 MHz, ppm, CDCl3−1,2-dichlorobenzene) δ 157.39,
154.49, 153.39, 152.70, 152.31, 147.12, 146.98, 146.57, 145.97, 145.90,
145.82, 145.79, 145.75, 145.69, 145.66, 145.61, 145.57, 145.52, 145.40,
145.08, 145.02, 145.00, 144.98, 144.89, 144.80, 144.77, 144.63, 144.17,
144.08, 144.07, 142.81, 142.79, 142.29, 142.26, 142.20, 142.17, 142.09,
141.83, 141.74, 141.69, 141.48, 141.45, 141.41, 141.34, 140.18, 140.14,
140.05, 139.74, 139.01, 135.89, 135.82, 135.49, 134.29, 77.19, 75.38,
64.34, 60.79; FT-IR (neat, cm−1) 3583, 3024, 2857, 1599, 1491, 1426,
TOF-MS (matrix SA) found 988.0806 (calcd for C73H16O4S exact
red1
mass 988.0769); E1/2
eV.
−1.11, LUMO = −(4.8 + E1/2red1) = −3.69
1l. From [C60]-fullerene (360 mg, 0.50 mmol) and methyl 2-[(2,2′-
bithiophen)-5-yl(hydroxyl)methyl]acrylate (S3k) (420 mg, 1.50
mmol), product 1l was obtained in 42% yield (210 mg, 0.21 mmol)
as a brown amorphous solid. 1H NMR (500 MHz, ppm, CDCl3−CS2)
δ 8.05 (d, J = 1.8 Hz, 1H), 7.23 (d, J = 3.5 Hz, 1H), 7.19 (d, J = 5.1
Hz, 1H), 7.16 (d, J = 3.5 Hz, 1H), 7.11 (d, J = 3.5 Hz, 1H), 7.00 (dd, J
= 3.7, 5.1 Hz, 1H), 6.41 (d, J = 1.8 Hz, 1H), 3.96 (s, 3H); 13C NMR
(125 MHz, ppm, CS2−CDCl3) δ 164.02, 155.50, 152.87, 150.88,
150.53, 147.49, 147.39, 146.44, 146.39, 146.20, 146.15, 146.12, 146.08,
146.05, 145.96, 145.75, 145.73, 145.64, 145.60, 145.58, 145.50, 145.42,
145.33, 145.30, 145.25, 145.22, 145.20, 144.96, 144.58, 144.44, 144.42,
144.23, 143.43, 143.13, 143.10, 142.77, 142.67, 142.62, 142.58, 142.41,
142.29, 142.26, 142.13, 142.00, 141.90, 141.89, 141.87, 141.83, 141.62,
140.63, 140.37, 140.17, 139.51, 137.92, 137.90, 137.33, 137.13, 136.00,
1182, 1026, 864, 698, 573; MALDI-TOF-MS (matrix SA) found
red1
866.0719 (calcd for C70H10O exact mass 866.0732); E1/2
−1.14,
LUMO = −(4.8 + E1/2red1) = −3.66 eV.
4643
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Article
135.89, 134.35, 127.87, 127.57, 124.58, 124.10, 123.87, 77.41, 77.16,
76.91, 76.63, 74.74, 58.14, 52.43; FT-IR (neat, cm−1) 3109, 3063,2945,
1727, 1645, 1429, 1225, 1131, 1094, 765, 697, 575; MALDI-TOF-MS
(matrix 9-NA) found 982.0142 (calcd for C73H10O2S2 exact mass
2c. From [C60]-fullerene (362 mg, 0.50 mmol) and methyl 3-
hydroxy-2-methylenehexanoate (S3d)19 (230 mg, 1.45 mmol),
product 2c was obtained in 47% yield (200 mg, 0.23 mmol) as a
1
brown amorphous solid. H NMR (500 MHz, ppm, CDCl3−CS2) δ
red1
982.0122); E1/2 −1.12, LUMO = −(4.8 + E1/2red1) = −3.68 eV.
7.88 (s, 1H), 4.69 (d, J = 15.2 Hz, 1H), 4.18 (d, J = 13.9 Hz, 1H), 3.97
(s, 3H), 3.88 (br s, 1H), 2.84−2.90 (m, 1H), 2.30 (br s, 1H), 1.48 (t, J
= 7.3 Hz, 3H); 13C NMR (125 MHz, ppm, CDCl3−CS2) δ 164.48,
156.75, 156.52, 153.59, 147.46, 147.32, 146.63, 146.40, 146.30, 146.16,
146.04, 145.87, 145.63, 145.38, 145.30, 145.22, 145.15, 145.01, 144.58,
144.53, 144.38, 142.93, 142.50, 142.46, 142.02, 141.94, 141.87, 141.69,
141.60, 141.45, 141.29, 141.20, 140.19, 138.88, 138.75, 136.12, 135.60,
134.86, 134.42, 69.80, 67.21, 51.81, 49.52, 39.19, 26.04, 13.71; FT-IR
(neat, cm−1) 2958, 2868, 1713, 1639, 1511, 1430, 1266, 1131, 1080,
759, 575; HRMS (ESI-TOF) m/z [M + Na+] calcd for C68H12O2Na
1m. From [C60]-fullerene (187 mg, 0.26 mmol) and 2-
methoxyethyl 2-[(2,2′-bithiophen)-5-yl(hydroxyl)methyl]acrylate
(S3l) (259 mg, 0.80 mmol), product 1m was obtained in 33% yield
1
(99 mg, 0.087 mmol) as a brown amorphous solid. H NMR (500
MHz, ppm, CDCl3−CS2) δ 8.08 (d, J = 2.0 Hz, 1H), 7.23 (d, J = 4.0
Hz, 1H), 7.19 (dd, J = 1.0, 5.0 Hz, 1H), 7.15 (d, J = 4.5 Hz, 1H), 7.11
(d, J = 3.5 Hz, 1H), 6.99 (dd, J = 4.0, 5.5 Hz, 1H), 6.42 (d, J = 2.0 Hz,
1H), 4.50−4.54 (m, 1H), 4.42−4.46 (m, 1H), 3.64−3.72 (m, 2H),
3.41 (s, 3H); 13C NMR (125 MHz, ppm, CS2−CDCl3) δ 163.52,
155.50, 152.88, 150.89, 150.50, 147.48, 147.38, 146.43, 146.38, 146.19,
146.14, 146.11, 146.10, 146.07, 146.04, 145.96, 145.76, 145.73, 145.65,
145.64, 145.58, 145.49, 145.42, 145.33, 145.29, 145.24, 145.19, 144.95,
144.56, 144.42, 144.23, 143.46, 143.11, 143.09, 142.75, 142.66, 142.60,
142.57, 142.39, 142.28, 142.24, 142.24, 142.12, 142.00, 141.89, 141.85,
141.83, 141.82, 141.62, 140.62, 140.37, 140.16, 139.51, 137.85, 137.83,
137.35, 137.06, 136.04, 135.87, 134.36, 127.88, 127.60, 124.54, 124.04,
123.81, 76.66, 74.70, 70.47, 64.38, 59.03, 58.09; FT-IR (neat, cm−1)
3066, 2873, 1719, 1646, 1426, 1223, 1127, 1090, 801, 764, 689, 574;
red1
red1
883.0735, found 883.0726; E1/2 −1.15, LUMO = −(4.8 + E1/2
)
= −3.65 eV.
2d. From [C60]-fullerene (357 mg, 0.50 mmol) and methyl 3-
hydroxy-2-methyleneheptanoate (S3o)25 (251 mg, 1.46 mmol),
product 2d was obtained in 48% yield (210 mg, 0.24 mmol) as a
1
brown amorphous solid. H NMR (500 MHz, ppm, CDCl3−CS2) δ
7.86 (s, 1H), 4.68 (d, J = 13.3 Hz, 1H), 4.18 (d, J = 13.3 Hz, 1H), 3.96
(s, 4H), 2.72−2.80 (m, 1H), 2.29 (br s, 1H), 1.99−2.07 (m, 1H),
1.74−1.81 (m, 1H), 1.20 (t, J = 7.6 Hz, 3H); 13C NMR (125 MHz,
ppm, CDCl3−1,2-dichlorobenzene) δ 165.27, 156.81, 153.84, 147.38,
147.26, 146.48, 146.30, 146.26, 146.20, 146.17, 145.94, 145.57, 145.48,
145.24, 145.19, 145.14, 144.96, 144.92, 144.43, 144.32, 142.81, 142.76,
142.37, 142.33, 141.94, 141.90, 141.85, 141.81, 141.68, 141.39, 141.34,
141.18, 141.12, 140.02, 140.01, 138.81, 138.67, 136.02, 135.61, 135.50,
134.92, 134.33, 69.91, 66.10, 51.97, 47.66, 39.28, 34.65, 22.24, 14.28;
IR (neat, cm−1) 2955, 2927, 2855, 1707, 1639, 1513, 1433, 1372, 1269,
MALDI-TOF-MS (matrix 9-NA) found 1026.0351 (calcd for
red1
C75H14O3S2 exact mass 1026.0384); E1/2
−1.12, LUMO = −(4.8
+ E1/2red1) = −3.68 eV.
Procedure for Synthesis of Cyclohexene-Fused [C60]-Full-
erenes: 2b. A solution of [C60]-fullerene (359 mg, 0.50 mmol),
methyl 3-hydroxy-2-methylenepentanoate (S3n)19 (232 mg, 1.55
mmol), and N,N-dimethylaminopyridine (184 mg, 1.51 mmol) in dry
toluene (160 mL) was irradiated under ultrasonic conditions for
several minutes to afford violet solution; then the solution was added
to acetic anhydride (0.14 mL, 1.48 mol) and the mixture was stirred
for 2.5 h at 120 °C. After the mixture was allowed to cool at room
temperature, the solvent was evaporated under reduced pressure and
the residue was added to methanol. This formed a brown solid, which
was collected on an ultramembrane filter, dissolved in carbon disulfide
(CS2), and purified by silica gel (60N) flash chromatography [CS2/
toluene =1:0, 5:1, and 3:1 (v/v)], affording product 2b (211 mg, 0.249
mmol) as a brown amorphous solid in 50% yield; the unreacted
fullerene (62 mg) was recovered in 18% yield. 2b showed no clear
1205, 1132, 1086, 958, 748, 573; HRMS (ESI-TOF) m/z [M + Na+]
red1
calcd for C69H14O2Na 897.0891, found 897.0883; E1/2
−1.16,
LUMO = −(4.8 + E1/2red1) = −3.64 eV.
2e. From [C60]-fullerene (367 mg, 0.51 mmol) and methyl 3-
hydroxy-2-methyleneoctanoate (S3p)25 (272 mg, 1.46 mmol), product
2e was obtained in 41% yield (187 mg, 0.21 mmol) as a brown
amorphous solid. 1H NMR (500 MHz, ppm, CDCl3−CS2) δ 7.85 (br
s, 1H), 4.68 (d, J = 13.8 Hz, 1H), 4.15 (d, J = 14.2 Hz, 1H), 3.98 (m,
4H), 2.75−2.81 (m, 1H), 2.29 (br s, 1H), 1.96 (br s, 1H), 1.69−1.78
(m, 1H), 1.54−1.68 (m, 2H), 1.09 (t, J = 7.2 Hz, 3H); FT-IR (neat,
cm−1) 2947, 2915, 2851, 1708, 1640, 1512, 1430, 1373, 1263, 1210,
1128, 1086, 748, 573; HRMS (ESI-TOF) m/z [M + Na+] calcd for
1
melting point and only caused decomposition: H NMR (500 MHz,
red1
C70H16O2Na 911.1048, found 911.1039 ; E1/2
−1.11, LUMO =
ppm, CDCl3−CS2) δ 7.76 (s, 1H), 4.69 (d, J = 14.3 Hz, 1H), 4.21−
4.13 (m, 2H), 3.97 (s, 3H), 2.15 (d, J = 7.2 Hz, 3H); 13C NMR (125
MHz, ppm, CDCl3−CS2) δ 165.15, 156.88, 156.70, 153.15, 147.77,
147.62, 147.51, 146.67, 146.61, 146.56, 146.55, 146.46, 146.21, 146.18,
146.16, 145.77, 145.76, 145.53, 145.51, 145.50, 145.41, 145.39, 145.36,
145.35, 145.34, 145.12, 144.72, 144.68, 144.55, 144.53, 143.08, 143.07,
142.66, 142.63, 142.61, 142.59, 142.19, 142.17, 142.07, 142.02, 142.00,
141.84, 141.73, 141.57, 141.45, 141.36, 140.30, 140.28, 139.11, 138.94,
136.50, 135.71, 135.66, 134.99, 133.82, 70.02, 66.92, 52.13, 42.38,
39.17, 18.45; FT-IR (neat, cm−1) 2980, 2564, 1714, 1640, 1431, 1364,
1258, 1208, 1127, 746, 575; HRMS (ESI-TOF) m/z [M + Na+] calcd
−(4.8 + E1/2red1) = −3.69 eV. Due to very poor solubility of 2e in all
solvents tested, such as CDCl3 and CS2, we were unable to obtain
reliable 13C NMR spectra.
2f. From [C60]-fullerene (361 mg, 0.50 mmol) and methyl 3-
hydroxy-2-methylenenonanoate (S3q)24 (290 mg, 1.5 mmol), product
2f was obtained in 34% yield (155 mg, 0.17 mmol) as a brown
1
amorphous solid. H NMR (500 MHz, ppm, CDCl3−CS2) δ 7.86 (s,
1H), 4.67 (d, J = 14.0 Hz, 1H), 4.15 (d, J = 12.6 Hz, 1H), 3.97 (m,
4H), 2.71−2.80 (m, 1H), 2.28 (br s, 1H), 1.92−2.01 (m, 1H), 1.67−
1.78 (m, 1H), 1.44−1.56 (m, 4H), 0.99 (t, J = 7.2 Hz, 3H); 13C NMR
(125 MHz, ppm, CDCl3−CS2) δ 164.62, 156.82, 156.57, 153.68,
147.52, 147.37, 146.70, 146.41, 146.32, 146.09, 146.06, 145.68, 145.40,
145.24, 145.07, 144.59, 144.42, 142.98, 142.52, 142.04, 141.95, 141.75,
141.71, 141.61, 141.53, 141.46, 141.30, 141.22, 140.22, 140.19, 138.97,
138.91, 138.84, 138.79, 136.18, 136.16, 136.12, 135.64, 134.98, 134.93,
134.33, 134.27, 69.83, 67.25, 51.89, 51.85, 47.85, 39.20, 32.84, 32.36,
29.11, 23.24, 14.46; FT-IR (neat, cm−1) 2918, 2852, 1710, 1641, 1432,
1374, 1267, 1210, 1128, 1088, 748, 574; HRMS (ESI-TOF) m/z [M +
Na+] calcd for C71H18O2Na 925.1204, found 925.1199; E1/2red1 −1.16,
LUMO = −(4.8 + E1/2red1) = −3.64 eV.
red1
for C67H10O2Na 869.0578, found 869.0579; E1/2 −1.15, LUMO =
−(4.8 + E1/2red1) = −3.65 eV.
2a. From [C60]-fullerene (363 mg, 0.50 mmol) and methyl 3-
hydroxy-2-methylenebutanoate (S3m)19 (222 mg, 1.63 mmol),
product 2a was obtained in 48% yield (201 mg, 0.24 mmol) as a
1
brown amorphous solid. H NMR (500 MHz, ppm, CDCl3−CS2) δ
8.06 (t, J = 5.8 Hz, 1H), 4.39 (s, 2H), 4.22 (d, J = 5.8 Hz, 2H), 3.98 (s,
3H); 13C NMR (125 MHz, ppm, CDCl3−CS2) δ 164.84, 156.16,
156.10, 147.57, 147.52, 146.45, 146.41, 146.16, 146.13, 145.68, 145.47,
145.35, 145.19, 144.99, 144.62, 144.52, 143.03, 142.52, 142.49, 142.09,
142.07, 142.02, 141.92, 141.58, 141.54, 141.44, 140.16, 140.08, 135.73,
135.64, 135.49, 65.48, 64.97, 51.97, 41.10, 38.76; FT-IR (neat, cm−1)
2940, 2836, 1713, 1638, 1511, 1429, 1366, 1262, 1211, 1124, 746;
2g. From [C60]-fullerene (363 mg, 0.50 mmol) and methyl 3-
hydroxy-5-methyl-2-methylenehexanoate (S3r)19 (278 mg, 1.5 mmol),
product 2g was obtained in 32% yield (139 mg, 0.16 mmol) as a
1
brown amorphous solid. H NMR (500 MHz, ppm, CDCl3−CS2) δ
HRMS (ESI-TOF) m/z [M + Na+] calcd for C66H8O2Na 855.0422,
8.05 (s, 1H), 4.70 (d, J = 14.1 Hz, 1H), 4.13 (d, J = 12.9 Hz, 1H), 3.98
(s, 4H), 3.32 (ddt, J = 3.3, 6.8, 13.5 Hz, 1H), 1.44 (d, J = 6.8 Hz, 3H),
1.40 (d, J = 6.6 Hz, 3H); 13C NMR (125 MHz, ppm, CDCl3−1,2-
red1
found 855.0418; E1/2
eV.
−1.14, LUMO = −(4.8 + E1/2red1) = −3.66
4644
DOI: 10.1021/acs.joc.5b00530
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Article
Figure 7. Starting materials for preparing [C60]-CP and [C60]-CH.
dichlorobenzene) δ 165.46, 157.73, 156.69, 154.21, 147.45, 147.30,
146.59, 146.39, 146.33, 146.22, 146.05, 146.01, 145.96, 145.84, 145.68,
145.57, 145.37, 145.27, 145.23, 145.15, 145.09, 145.02, 144.85, 144.50,
144.45, 144.35, 144.31, 143.07, 142.86, 142.48, 142.40, 142.05, 142.01,
141.96, 141.87, 141.74, 141.54, 141.50, 141.36, 141.24, 140.23, 140.07,
138.71, 135.86, 135.61, 134.87, 134.55, 69.93, 67.45, 54.13, 52.17,
39.70, 27.35, 25.35, 19.86; FT-IR (neat, cm−1) 2952, 1709, 1646, 1432,
obtained in 34% yield (146 mg, 0.17 mmol) as a brown amorphous
solid. 1H NMR (500 MHz, ppm, CDCl3−CS2) δ 7.74 (s, 1H), 4.68 (d,
J = 13.3 Hz, 1H), 4.69 (d, J = 14.3 Hz, 1H), 4.37−4.45 (m, 2H), 4.13−
4.20 (m, 2H), 2.16 (d, J = 7.2 Hz, 3H), 1.46 (t, J = 7.2 Hz, 3H); 13C
NMR (125 MHz, ppm, CDCl3−CS2) δ 164.39, 156.85, 156.66,
153.06, 147.52, 147.41, 147.10, 146.59, 146.53, 146.47, 146.46, 146.36,
146.12, 146.09, 146.07, 145.68, 145.45, 145.43, 145.32, 145.30, 145.27,
145.26, 145.03, 144.64, 144.60, 144.46, 144.44, 143.00, 142.98, 142.57,
142.54, 142.52, 142.51, 142.10, 142.09, 141.99, 141.93, 141.77, 141.65,
141.49, 141.37, 141.27, 140.23, 140.21, 139.04, 138.86, 136.46, 135.61,
135.59, 134.90, 134.08, 69.96, 66.85, 61.06, 42.33, 39.10, 18.42, 14.54;
IR (neat, cm−1) 2970, 2849, 1705, 1637, 1511, 1428, 1369, 1246, 1205,
1237, 1208, 1122, 1088, 748, 574; HRMS (ESI-TOF) m/z [M + Na+]
red1
calcd for C69H14O2Na 897.0891, found 897.0886; E1/2
−1.16,
LUMO = −(4.8 + E1/2red1) = −3.64 eV.
2h. From [C60]-fullerene (329 mg, 0.46 mmol) and methyl 3-
hydroxy-2-methylene-4-propoxybutanoate (S3s) (247 mg, 1.31
mmol), product 2h was obtained in 37% yield (153 mg, 0.17 mmol)
as a brown amorphous solid. 1H NMR (500 MHz, ppm, CDCl3−CS2)
δ 7.96 (s, 1H), 5.56 (s, 1H), 4.72 (d, J = 14.5 Hz, 1H), 4.10 (br s, 2H),
3.99 (s, 3H), 3.87−3.94 (m, 1H), 1.80 (sextet, J = 7.3 Hz, 2H), 1.01 (t,
J = 6.9 Hz, 3H); 13C NMR (125 MHz, ppm, CDCl3−CS2) δ 165.18,
156.44, 153.56, 147.64, 146.62, 146.59, 146.59, 146.56, 146.32, 146.26,
146.23, 146.21, 145.86, 145.86, 145.86, 145.81, 145.70, 145.61, 145.48,
145.44, 145.42, 145.42, 145.14, 144.75, 144.68, 144.64, 143.10, 143.07,
142.68, 142.66, 142.66, 142.61, 142.28, 142.25, 142.16, 142.11, 142.11,
142.00, 141.84, 141.64, 141.63, 141.43, 140.32, 140.29, 139.41, 136.04,
135.21, 81.76, 74.31, 70.39, 65.43, 52.52, 38.21, 23.48, 11.11; FT-IR
(neat, cm−1) 2946, 22867, 1716, 1511, 1430, 1364, 1234, 1090, 965,
745, 573; HRMS (ESI-TOF) m/z [M + Na+] calcd for C69H14O3Na
1125, 1060, 1020, 860, 745, 575; HRMS (ESI-TOF) m/z [M + Na+]
red1
calcd for C68H12O2Na 883.0735, found 883.0728; E1/2
−1.15,
LUMO = −(4.8 + E1/2red1) = −3.65 eV.
2j. From [C60]-fullerene (356 mg, 0.49 mmol) and tert-butyl 3-
hydroxy-2-methylenepetanoate (S3u)27 (282 mg, 1.52 mmol), product
2j was obtained in 31% yield (134 mg, 0.15 mmol) as a brown
1
amorphous solid. H NMR (500 MHz, ppm, CDCl3−CS2) δ 7.61 (s,
1H), 4.64 (d, J = 14.0 Hz, 1H), 4.12−4.17 (m, 1H), 4.08 (dd, J = 2.1,
14.3 Hz, 1H), 2.14 (d, J = 7.0 Hz, 3H), 1.64 (s, 9H); 13C NMR (125
MHz, ppm, CDCl3−CS2) δ 164.01, 157.25, 156.89, 153.25, 147.59,
147.47, 146.74, 146.68, 146.53, 146.51, 146.43, 146.41, 146.21, 146.17,
146.15, 146.13, 145.77, 145.76, 145.49, 145.46, 145.41, 145.38, 145.36,
145.33, 145.32, 145.27, 145.09, 144.71, 144.67, 144.54, 144.51, 143.06,
143.04, 142.63, 142.60, 142.56, 142.21, 142.16, 142.15, 142.05, 142.00,
141.84, 141.68, 141.56, 141.42, 141.33, 140.30, 140.23, 139.07, 138.87,
136.56, 135.67, 135.51, 135.48, 134.95, 80.94, 70.10, 67.04, 42.32,
39.22, 28.20,18.49; FT-IR (neat, cm−1) 2969, 2927, 1705, 1640, 1450,
red1
red1
913.0841, found 913.0828; E1/2 −1.11, LUMO = −(4.8 + E1/2
)
= −3.69 eV.
2i. From [C60]-fullerene (359 mg, 0.50 mmol) and ethyl 3-hydroxy-
2-methylenepentanoate (S3t)26 (237 mg, 1.50 mmol), product 2i was
4645
DOI: 10.1021/acs.joc.5b00530
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Article
1364, 1279, 1127, 1079, 847, 745; HRMS (ESI-TOF) m/z [M + Na+]
2-(2-Methoxyethoxy)ethyl 2-[Hydroxy(phenyl)methyl]acrylate
(S3g). To a mixture of 2-(2-methoxyethoxy)ethyl acrylate (1.5 g, 8.6
mmol) and 1,4-diazabicyclo[2.2.2]octane (DABCO) (193 mg, 1.72
mmol) was added benzaldehyde (1.10 g, 10.3 mmol), and the mixture
was stirred for 62 h at room temperature. Then this was diluted with
ethyl acetate (20 mL) and washed with brine (10 mL, three times).
The aqueous phase was extracted with ethyl acetate. The combined
organic layers were dried over Na2SO4, and the filtrate was evaporated
to dryness. The residue was purified by silica gel flash column
chromatography (silica gel 60 N, hexane/ethyl acetate = 5:1, 2:1, then
1:1 v/v) to afford S3g (1.67 g, 5.96 mmol) in 69% yield as a colorless
red1
calcd for C70H16O2Na 911.1048, found 911.1054; E1/2
−1.11,
LUMO = −(4.8 + E1/2red1) = −3.69 eV.
2k. From [C60]-fullerene (370 mg, 0.51 mmol) and cyclohexyl 3-
hydroxy-2-methylenepentanoate (S3v) (319 mg, 1.50 mmol), product
2k was obtained in 31% yield (146 mg, 0.16 mmol) as a brown
1
amorphous solid. H NMR (500 MHz, ppm, CDCl3−CS2) δ 7.72 (s,
1H), 5.04 (septet, J = 4.1 Hz, 1H), 4.69 (d, J = 14.2 Hz, 1H), 4.12−
4.19 (m, 2H), 2.15 (d, J = 7.2 Hz, 3H), 1.98 (br s, 2H), 1.75−1.85 (m,
2H), 1.58−1.70 (m, 3H), 1.44−1.50 (m, 2H), 1.34−1.39 (m, 1H); 13C
NMR (125 MHz, ppm, CDCl3−CS2) δ 164.48, 157.24, 156.90,
154.63, 153.34, 147.67, 147.56, 147.16, 146.82, 146.77, 146.60, 146.51,
146.49, 146.28, 146.25, 146.23, 146.20, 145.85, 145.83, 145.57, 145.53,
145.51, 145.46, 145.44, 145.42, 145.41, 145.32, 145.14, 144.78, 144.61,
143.13, 143.12, 142.70, 142.67, 142.64, 142.28, 142.24, 142.22, 142.13,
142.11, 142.09, 142.07, 141.91, 141.76, 141.62, 141.50, 141.40, 140.34,
140.29, 139.13, 138.94, 136.57, 135.77, 135.62, 135.07, 134.65, 73.31,
70.23, 67.15, 42.36, 39.39, 31.76, 31.68, 25.67, 23.85, 23.75, 18.47; FT-
IR (neat, cm−1) 2926, 2851, 1706, 1641, 1446, 1379, 1248, 1207, 1118,
1
liquid: H NMR (500 MHz, ppm, CDCl3) δ 7.33−7.39 (m, 4H),
7.26−7.30 (m, 1H), 6.38 (s, 1H), 6.00 (s, 1H), 5.80 (t, J = 1.2 Hz,
1H), 5.57 (d, J = 4.8 Hz, 1H), 4.29 (ddd, J = 1.0, 3.8, 5.8 Hz, 2H),
3.66−3.70 (m, 2H), 3.58−3.62 (m, 2H), 3.50−3.54 (m, 2H), 3.37 (s,
3H), 3.15 (d, J = 5.6 Hz, 1H); 13C NMR (125 MHz, ppm, CDCl3) δ
166.1, 142.1, 141.4, 128.4, 127.7, 126.7, 72.9, 70.6, 69.8, 68.9, 66.7,
63.9, 15.2; 13C NMR (125 MHz, ppm, CDCl3) δ 166.14, 142.12,
141.38, 128.35, 127.73, 126.68, 72.91, 70.57, 69.76, 68.85, 66.72,
63.89; IR (neat, cm−1) 3417, 2881, 1714, 1634, 1453, 1266, 1135,
1105, 1042, 1024, 957, 840, 765, 699; HRMS (ESI-TOF) m/z calcd
for [M + Na]+ C15H20O5Na, 303.1208; found, 303.1203.
1012, 746, 574; HRMS (ESI-TOF) m/z [M + Na+] calcd for
red1
C72H18O2Na 937.1204, found 937.1199; E1/2
−1.11, LUMO =
−(4.8+ E1/2red1) = −3.69 eV.
tert-Butyl 2-[Hydroxy(thiophen-2-yl)methyl]acrylate (S3i). To a
mixture of thiophene-2-carbaldehyde (0.92 mL, 10 mmol) and
DABCO (1.12 g, 10 mmol) in 1.0 mL of mixed solvent (1,4-
dioxane/H2O = 1.0 mL, 1:1 v/v) was added tert-butyl acrylate (4.4
mL, 30 mmol), and the mixture was stirred for 48 h at room
temperature. Then this was diluted with water (20 mL) and extracted
with ether (20 mL, 3 times). The combined organic layer was washed
with brine (20 mL) and dried over Na2SO4, and the filtrate was
evaporated to dryness. The residue was purified by silica gel flash
column chromatography (silica gel 60N, hexane/ethyl acetate = 15:1,
10:1, then 3:1 v/v) to afford S3i (0.595 g, 2.48 mmol) in 25% yield as
2l. From [C60]-fullerene (358 mg, 0.50 mmol) and phenyl 3-
hydroxy-2-methylenepentanoate (S3w) (200 mg, 0.97 mmol), product
2l was obtained in 38% yield (173 mg, 0.19 mmol) as a brown
1
amorphous solid. H NMR (500 MHz, ppm, CDCl3−CS2) δ 8.01 (s,
1H), 7.43−7.47 (m, 2H), 7.26−7.30 (m, 3H), 4.80 (d, J = 14.3 Hz,
1H), 4.24−4.30 (m, 2H), 2.22 (d, J = 7.1 Hz, 3H); 13C NMR (125
MHz, ppm, CDCl3−CS2) δ 163.17, 156.82, 156.52, 153.02, 150.74,
149.59, 147.62, 147.50, 146.65, 146.59, 146.56, 146.55, 146.45, 146.20,
146.17, 146.16, 145.76, 145.75, 145.54, 145.52, 145.40, 145.39, 145.37,
145.35, 145.32, 145.06, 144.71, 144.67, 144.53, 144.52, 143.08, 143.07,
142.66, 142.61, 142.60, 142.59, 142.19, 142.16, 142.07, 142.02, 141.98,
141.82, 141.73, 141.58, 141.45, 141.36, 140.34, 140.28, 139.12, 138.96,
136.48, 135.71, 135.61, 135.01, 133.51, 129.49, 125.90, 121.62, 70.01,
66.91, 42.61, 39.20, 18.46; FT-IR (neat, cm−1) 3061, 2960, 1725, 1639,
11589, 1489, 1428, 1245, 1188, 1160, 1115, 1051, 903, 738, 684;
1
a light yellow oil: H NMR (500 MHz, ppm, CDCl3) δ 7.25 (dd, J =
1.2, 4.0 Hz, 1H), 6.94−6,98 (m, 2H), 6.27 (s, 1H), 5.82 (s, 1H), 5.69
(d, J = 7.1 Hz, 1H), 3.45 (d, J = 7.1 Hz, 1H), 1.44 (s, 9H); 13C NMR
(125 MHz, ppm, CDCl3) δ 165.5, 148.3, 142.7, 128.8, 125.1, 124.5,
92.0, 70.0, 29.0; IR (neat, cm−1) 3423, 2978, 2933, 1699, 1630, 1393,
1368, 1288, 1255, 1146, 1025, 957, 848, 762, 697; HRMS (ESI-TOF)
m/z [M + Na+] calcd for C12H16O3SNa, 263.0718; found, 263.0712.
2-(2-Methoxyethoxy)ethyl 2-[Hydroxy(thiophen-2-yl)methyl]-
acrylate (S3j). To a mixture of 2-(2-methoxyethoxy)ethyl acrylate
(1.15 g, 6.6 mmol) and DABCO (0.148 g, 1.32 mmol) was added
thiophene-2-carbaldehyde (0.710 g, 6.6 mmol), and the mixture was
stirred for 72 h at room temperature. Then this was diluted with ethyl
acetate (20 mL) and washed with brine (10 mL, three times). The
aqueous phase was extracted with ethyl acetate. The combined organic
layers were dried over Na2SO4, and the filtrate was evaporated to
dryness. The residue was purified by silica gel flash column
chromatography (silica gel 60N, hexane/ethyl acetate = 5:1, 2:1,
then 1:1 v/v) to afford S3j (1.44 g, 5.03 mmol) in 76% yield as a light
HRMS (ESI-TOF) m/z [M + Na+] calcd for C72H12O2Na 931.0735,
red1
found 931.0728; E1/2
eV.
−1.14, LUMO = −(4.8 + E1/2red1) = −3.66
Preparation of Organic Photovoltaic Device. Photovoltaic
devices were prepared by spin-coating the cyclopentene- or cyclo-
hexene-fused [C60]-fullerene blends from chlorobenzene onto an
indium tin oxide (ITO) glass electrode as follows: To a P3HT (1.0 wt
%) solution of chlorobenzene were added cyclopentene-fused [C60]-
fullerene 1a (equal weight as P3HT) and silica gel (1.0 wt % versus
P3HT solution), and then the mixture was stirred for 12 h at ambient
temperature. It was then filtered through a Teflon (0.2 mm) filter. The
resulting solution was applied to the surface of an ITO plate [with
PEDOT−PSS (AI4083 (pH = 1.8)] by the spin-coating method at a
thickness of ca. 100 nm, and the surface was washed with acetone and
irradiated under UV light and ozone gas for 20 min to decompose the
impurities. After being dried under vacuum for 20 min, the resulting
plate was placed in a vacuum chamber and the surface was coated with
the electrode layers of calcium (4 nm) and aluminum (100 nm) by
evaporation at 10−4 Pa at room temperature. We placed the glass plate
on the resulting film, and the plate was firmly fixed by use of a bonding
agent under an argon atmosphere to produce the solar cell. The PCE
values were obtained with the solar simulator Otento-Sun II (AM1.5G,
100 mW/cm2). Cyclic voltammograms were obtained in acetonitrile
with 0.1 mM tetrabutylammonium hexafluorophosphate (n-Bu4NPF6)
as a supporting electrolyte with glassy carbon (1 mm diameter) as a
working electrode, a Pt counter electrode, and Ag/AgCl reference
electrode.
1
yellow oil: H NMR (500 MHz, ppm, CDCl3) δ 7.25−7.26 (m, 1H),
6.93−6.98 (m, 2H), 6.40 (s, 1H), 5.92 (s, 1H), 5.77 (d, J = 6.8 Hz,
1H), 4.32 (t, J = 4.7 Hz, 2H), 3.67−3.73 (m, 2H), 3.61 (dd, J = 3.3, 5.7
Hz, 2H), 3.53 (dd, J = 3.5, 5.5 Hz, 2H), 3.49 (d, J = 6.9 Hz, 1H), 3.38
(s, 3H); 13C NMR (125 MHz, ppm, CDCl3) δ 165.9, 145.9, 141.4,
126.8, 126.6, 124.7, 71.8, 70.4, 69.4, 68.9, 64.0, 59.1; IR (neat, cm−1)
3407, 2920, 1713, 1629, 1452, 1397, 1259, 1104, 1026, 853, 841, 771,
700; HRMS (ESI-TOF) m/z calcd for [M + Na]+ C13H18O5SNa,
309.0773; found, 309.0763.
Methyl 2-[(2,2′-Bithiophen)-5-yl(hydroxy)methyl]acrylate (S3k).
To a mixture of methyl acrylate (0.86 g, 10 mmol) and , 1,8-
diazabicyclo[5.4.0]undec-7-ene (DBU) (1.52 g, 10 mmol) was added
2,2′-bithiophene-5-carboxyaldehyde (1.94 g, 10 mmol), and the
mixture was stirred for 5 h at room temperature. Then this was
diluted with ethyl acetate (20 mL) and washed with brine (10 mL,
three times). The aqueous phase was extracted with ethyl acetate. The
combined organic layers were dried over Na2SO4, and the filtrate was
evaporated to dryness. The residue was purified by silica gel flash
column chromatography (silica gel 60N, hexane/ethyl acetate = 10:1
Preparation of Starting Materials for [C60]-CP and [C60]-CH.
[C60]-CP and [C60]-CH were synthesized by use of 23 types of α-
methylene-β-hydroxy esters as starting materials (Figure 7). These
esters were prepared following the method developed by Gonzal
́
ez and
co-workers19 through Morita-Baylis-Hillmann reaction.20
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The Journal of Organic Chemistry
Article
then 4:1 v/v) to afford S3k (1.12 g, 4.0 mmol) in 40% yield as a light
yellow oil: 1H NMR (500 MHz, ppm, CDCl3) δ 7.20 (dd, J = 1.1, 5.1
Hz, 1H), 7.13 (dd, J = 1.1, 31.6 Hz, 1H), 7.02 (d, J = 3.7 Hz, 1H), 7.00
(dd, J = 3.6, 5.1 Hz, 1H), 6.86 (dd, J = 0.9, 3.7 Hz, 1H), 6.39 (s, 1H),
6.00 (s, 1H), 5.72 (d, J = 6.8 Hz, 1H), 3.78 (s, 3H), 3.38 (d, J = 6.8
Hz, 1H); 13C NMR (125 MHz, ppm, CDCl3) δ 166.5, 144.7, 140.9,
137.4, 137.3, 127.9, 126.5, 125.5, 124.5, 123.7, 123.4, 69.8, 52.2; IR
(neat, cm−1) 3254. 2959, 1715, 1634, 1435, 1263, 1200, 1156, 1004,
982, 969, 955, 801, 776, 695; HRMS (ESI-TOF) m/z calcd for [M +
Na]+ C13H12O3S2Na, 303.0126; found, 303.0120.
(1.15 g, 10 mmol) in 1.0 mL of mixed solvent (1,4-dioxane/water =
1:1 v/v) was added cyclohexyl acrylate (4.8 mL, 30 mmol), and the
mixture was stirred for 39 h at room temperature and diluted with
water (20 mL) to give the biphasic layer. After collection of the
organic layer, the water layer was extracted with ether (20 mL, three
times). The combined organic layers were washed with brine (20 mL)
and dried over Na2SO4, and the filtrate was evaporated to dryness. The
residue was purified by silica gel flash column chromatography (silica
gel 60N, hexane/ethyl acetate = 10:1 then 8:1 v/v) to give S3v (0.495
g, 2.33 mmol) in 24% yield as a colorless liquid: 1H NMR (500 MHz,
ppm, CDCl3) δ 6.22 (d, J = 1.2 Hz, 1H), 5.74 (t, J = 1.2 Hz, 1H), 4.88
(septet, J = 4.4 Hz, 1H), 4.31 (q, J = 6.7 Hz, 1H), 2.65 (d, J = 7.0 Hz,
1H), 1.84−1.90 (m, 2H), 1.64−1.76 (m, 4H), 1.47−1.57 (m, 3H),
1.36−1.44 (m, 2H), 1.27−1.34 (m, 1H), 0.95 (t, J = 7.4 Hz, 3H); 13C
NMR (125 MHz, ppm, CDCl3) δ 166.2, 142.8, 124.7, 73.3, 73.2, 31.5,
29.3, 25.4, 23.7, 10.3; IR (neat, cm−1) 3431, 2935, 2860, 1707, 1628,
1451, 1259, 1167, 1095, 1038, 1014, 982, 950, 819; HRMS (ESI-TOF)
m/z [M + H+] calcd for C12H21O3, 213.1491; found, 213.1488.
Phenyl 3-Hydroxy-2-methylenepentanoate (S3w). Potassium
carbonate (14 g, 100 mmol) was dissolved in deionized water (25
mL) and acetone (100 mL) in a 500 mL flask and cooled to 0 °C. To
this solution was added acryl chloride (8 mL, 99 mmol) and an
acetone (10 mL) solution of phenol (4.79 g, 51 mmol); the mixture
was stirred for 4 h at 0 °C to cause precipitation. The white precipitate
formed was removed by filtration, the filtrate was evaporated, and the
resulting syrup was dissolved in water (50 mL). This was extracted
with ether (50 mL, three times) and the combined organic layers were
washed with brine (50 mL) and dried over Na2SO4, evaporated to
dryness, and chromatographed on silica gel flash column (silica gel
60N, hexane/ethyl acetate = 12:1 v/v) to give phenylacrylic acid22 (6.0
g, 40.6 mmol) in 80% yield.
2-Methoxyethyl 2-[(2,2′-Bithiophen)-5-yl(hydroxy)methyl]-
acrylate (S3l). To a mixture of methyl acrylate (0.52 g, 4.0 mmol)
and 2,2′-bithiophene-5-carboxyaldehyde (0.79 g, 4.0 mmol) was added
DABCO (0.089 g, 0.8 mmol), and the mixture was stirred for 48 h at
roo, temperature. Then this was diluted with diethyl ether (20 mL)
and washed with brine (10 mL, three times). The aqueous phase was
extracted with ether. The combined organic layers were dried over
Na2SO4, and the filtrate was evaporated to dryness. The residue was
purified by silica gel flash column chromatography (silica gel 60N,
hexane/ethyl acetate = 9:1, 4:1, then 2:1 v/v) to afford S3l (0.844 g,
1
2.6 mmol) in 65% yield as a light yellow oil: H NMR (500 MHz,
1
ppm, CDCl3) H NMR (500 MHz, ppm, CDCl3) δ 7.20 (d, J = 5.0
Hz, 1H), 7.13 (d, J = 3.1 Hz, 1H), 7.02 (d, J = 3.6 Hz, 1H), 7.00 (t, J =
4.5 Hz, 1H), 6.86 (d, J = 3.3 Hz, 1H), 6.43 (s, 1H), 5.99 (s, 1H), 5.73
(s, 1H), 4.32 (t, J = 4.5 Hz, 2H), 3.60 (t, J = 4.5 Hz, 2H), 3.47 (d, J =
6.8 Hz, 1H), 3.36 (s, 3H); 13C NMR (125 MHz, ppm, CDCl3) δ
166.0, 144.8, 141.0, 137.4, 137.3, 127.9, 127.0, 125.5, 124.5, 123.7,
123.4, 70.2, 69.8, 64.1, 59.1; IR (neat, cm−1) 3403, 3101, 2890, 1712,
1638, 1403, 1259, 1200, 1152, 1123, 1028, 960, 838, 801, 695; HRMS
(ESI-TOF) m/z calcd for [M + Na]+ C15H16O4S2Na, 347.0388; found,
347.0383.
Methyl 3-Hydroxy-2-methylene-4-propoxybutanoate (S3s). A
mixture of 1-propanol (4.55 g, 76 mmol), sodium hydroxide (1.95
g, 49 mmol), and 2-bromo-1,1-dimethoxyethane (2.6 g, 15.4 mmol)
was stirred at 80 °C. After stirring for 9 h at the same temperature, 1-
propanol (1.0 g, 17 mmol) was added and the mixture was further
stirred for 6 h. After being allowed to cool at room temperature, the
mixture was diluted with water (30 mL) to give the biphasic layer. The
organic layer formed was collected and the water layer was extracted
with ether (30 mL, five times). The combined organic layers were
dried over anhydrous sodium sulfate (Na2SO4) and evaporated to
dryness. The residue was purified by silica gel flash column
chromatography to afford 1-(2,2-dimethoxyethoxy)propane21 (0.885
g, 5.98 mmol) in 39% yield.
To a solution of 1-(2,2-dimethoxyethoxy)propane in deionized
water (25 mL) was added p-toluenesulfonic acid monohydrate (4.0 g,
21 mmol), and the mixture was stirred for 14.5 h at room temperature
and then extracted with ether (30 mL, five times). The combined
organic layers were washed with brine (30 mL), dried over Na2SO4,
and condensed to ca. 0.5 mL (0.497 g), and then this was diluted with
0.4 mL of mixed solvent (1,4-dioxane/water = 1:1 v/v). To this
solution were added DABCO (0.549 g, 4.9 mmol) and methyl acrylate
(1.3 mL, 14.5 mmol), and the mixture was stirred for 20 h at room
temperature. The resulting solution was diluted with water (10 mL)
and extracted with ether (20 mL, three times). The combined organic
layers were washed with brine (20 mL), dried over Na2SO4, and
evaporated to dryness. The residue was separated by silica gel flash
column chromatography (Wakogel C-300E, hexane/ethyl acetate =
10:1 then 3:1 v/v) to give S3s (0.247 g, 1.31 mmol) in 22% yield (two
steps) as a colorless liquid: 1H NMR (500 MHz, ppm, CDCl3) δ 6.36
(t, J = 1.1 Hz, 1H), 6.02 (t, J = 1.3 Hz, 1H), 4.68−4.72 (m, 1H), 3.77
(s, 3H), 3.87 (dd, J = 3.5, 9.7 Hz, 1H), 3.40−3.49 (m, 2H), 3.33 (dd, J
= 7.4, 9.7 Hz, 1H), 2.89 (d, J = 4.3 Hz, 1H), 1.60 (sext, J = 7.0 Hz,
2H), 0.92 (t, J = 7.2 Hz, 3H); 13C NMR (125 MHz, ppm, CDCl3)
166.5, 139.3, 126.6, 74.1, 73.0, 69.3, 51.9, 22.9, 10.6; IR (neat, cm−1)
3441, 2961, 2876, 1715, 1631, 1439, 1274, 1159, 1080, 939, 819;
HRMS (ESI-TOF) m/z [M + H+] calcd for C9H17O4, 189.1127;
found, 189.1127.
To a solution of phenylacrylic acid (0.445 g, 3.1 mmol) and
DABCO (119 mg, 1.1 mmol) in a mixed solvent of 1,4-dioxane and
H2O (0.1 mL, 1:1 v/v) in a 50 mL flask was added propionaldehyde
(0.07 mL, 0.98 mmol), and the mixture was stirred for 113 h at room
temperature. Then this was diluted with water (10 mL) and extracted
with ether (10 mL, three times). The combined organic layers were
washed with brine (10 mL), dried over Na2SO4, and evaporated to
dryness. The residue was purified by silica gel flash column
chromatography (silica fel 60N, hexane/ethyl acetate = 10:1 then
5:1 v/v) to afford S3w (0.0663 g, 0.32 mmol) in 33% yield as a
1
colorless liquid: H NMR (500 MHz, ppm, CDCl3) δ 7.41 (t, J = 8.0
Hz, 2H), 7.26 (t, J = 8.6 Hz, 1H), 7.12 (d, J = 8.0 Hz, 2H), 6.52 (s,
1H), 6.01 (s, 1H), 4.44 (q, J = 6.7 Hz, 1H), 2.47 (d, J = 6.8 Hz, 1H),
1.71−1.94 (m, 2H), 1.01 (t, J = 7.5 Hz, 3H); 13C NMR (125 MHz,
ppm, CDCl3) δ 165.2, 150.5, 141.9, 129.6, 127.0, 126.1, 121.7, 73.0,
29.3, 10.3; IR (neat, cm−1) 3472, 2968, 2936, 2879, 1728, 1491, 1191,
1162, 1137, 1079, 981, 751, 688; HRMS (ESI-TOF) m/z [M + Na+]
calcd for C12H14O3Na, 229.0841; found, 229.0836.
Spectra of Known Compounds. Spectra of known compounds are
completely identical with those in the literature cited.
S3b:19 1H NMR (500 MHz, ppm, CDCl3) δ 7.29 (d, J = 9.0 Hz,
2H), 6.87 (d, J = 9.0 Hz, 2H), 6.32 (s, 1H), 5.84 (t, J = 1.0 Hz, 1H),
5.53 (d, J = 5.5 Hz, 1H), 3.80 (s, 3H), 3.72 (s, 3H), 2.85 (d, J = 5.5
Hz, 1H); 13C NMR (125 MHz, ppm, CDCl3) δ 166.93, 159.30,
142.13, 133.46, 128.00, 125.90, 113.92, 72.94, 55.38, 52.11.
S3c:19 1H NMR (500 MHz, ppm, CDCl3) δ 7.47 (d, J = 8.5 Hz,
2H), 7.26 (d, J = 8.3 Hz, 2H), 6.34 (s, 1H), 5.83 (t, J = 1.0 Hz, 1H),
5.51 (d, J = 5.7 Hz, 1H), 3.73 (s, 3H), 3.07 (d, J = 5.8 Hz, 1H); 13C
NMR (125 MHz, ppm, CDCl3) δ 166.8, 141.6, 140.4, 131.7, 128.4,
126.6, 121.9, 72.9, 52.2.
S3d:19 1H NMR (500 MHz, ppm, CDCl3) δ 6.22 (s, 1H), 5.79 (s,
1H), 4.40 (q, J = 7.4 Hz, 1H), 3.78 (s, 3H), 2.52 (d, J = 7.0 Hz, 1H),
1.63 (q, J = 7.4 Hz, 2H), 1.48 (sextet, J = 6.7 Hz, 1H), 1.36 (sextet, J =
7.6 Hz, 1H), 0.94 (t, J = 7.2 Hz, 3H); 13C NMR (125 MHz, ppm,
CDCl3) δ 167.1, 142.7, 124.9, 71.3, 51.9, 38.4, 19.1, 13.9.
S3e:19 1H NMR (500 MHz, ppm, CDCl3) δ 7.39 (d, J = 7.0 Hz,
2H), 7.31 (t, J = 7.5 Hz, 2H), 7.23 (d, J = 7.5 Hz, 1H), 6.67 (d, J =
16.0 Hz, 1H), 6.31 (d, J = 14.5 Hz, 1H), 6.30 (t, J = 8.0 Hz, 1H), 5.92
(s, 1H), 5.13 (t, J = 6.5 Hz, 1H), 3.80 (s, 3H), 2.89 (d, J = 5.5 Hz,
Cyclohexyl 3-Hydroxy-2-methylenepentanoate (S3v). To a
mixture of propionaldehyde (0.70 mL, 9.8 mmol) and DABCO
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The Journal of Organic Chemistry
Article
1H); 13C NMR (125 MHz, ppm, CDCl3) δ 166.84, 141.23, 136.46,
131.47, 129.23, 128.63, 127.90, 126.66, 126.02, 72.03, 52.14.
S3f:23 1H NMR (500 MHz, ppm, CDCl3) δ 7.44 (d, J = 7.5 Hz,
2H), 7.30−7.39 (m, 5H), 7.22 (t, J = 7.5 Hz, 1H), 6.99 (d, J = 7.5 Hz,
2H), 6.61 (s, 1H), 6.07 (s, 1H), 5.68 (s, 1H), 2.90 (br s, 1H); 13C
NMR (125 MHz, ppm, CDCl3) δ 164.80, 150.34, 141.80, 141.17,
129.50, 128.59, 128.08, 127.51, 126.83, 126.06, 121.54, 72.99.
S3h:24 1H NMR (500 MHz, ppm, CDCl3) δ 7.25−7.26 (m, 1H),
6.96−6.97 (m, 2H), 6.36 (s, 1H), 5.92 (s, 1H), 5.76 (d, J = 6.5 Hz,
1H), 3.76 (s, 3H), 3.34 (d, J = 7.0 Hz, 1H); 13C NMR (125 MHz,
ppm, CDCl3) δ 166.56, 145.70, 141.28, 126.85, 126.23, 125.30, 124.81,
69.36, 52.13.
ACKNOWLEDGMENTS
■
The present work was supported by a Grant-in-Aid for
Scientific Research of the GSC Center of Tottori University
from the Ministry of Education, Culture, Sports, Science and
Technology of Japan and was also supported by a fund for
Environmental Research from Tottori Prefecture. We are
grateful to Professor Hideyuki Murata and Ryo Itou of Japan
Advanced Institute of Science and Technology for measure-
ment of OPV properties of fullerene derivatives.
S3m:19 1H NMR (500 MHz, ppm, CDCl3) δ 6.22 (s, 1H), 5.83 (t, J
= 1.1 Hz, 1H), 4.62 (quintet, J = 6.5 Hz, 1H), 3.79 (3H, s), 2.64−2.67
(m, 1H), 1.39 (d, J = 6.2 Hz, 3H); 13C NMR (125 MHz, ppm, CDCl3)
δ 167.2, 143.6, 124.3, 67.1, 52.0, 22.2.
REFERENCES
■
(1) Reviews: (a) Prato, M.; Maggini, M. Acc. Chem. Res. 1998, 31,
519−601. (b) Diederich, F.; Kessinger, R. Acc. Chem. Res. 1999, 32,
537−545. (c) Zhou, Z.; Wilson, S. R. Curr. Org. Chem. 2005, 9, 789−
811.
S3n:19 1H NMR (500 MHz, ppm, CDCl3) δ 6.24 (s, 1H), 5.79 (s,
1H), 4.32 (q, J = 6.2 Hz, 1H), 3.78 (s, 3H), 2.53 (d, J = 6.5 Hz, 1H),
1.75−1.63 (sextet, J = 7.5 Hz, 2H), 0.95 (t, J = 7.4 Hz, 3H); 13C NMR
(125 MHz, ppm, CDCl3) δ 167.1, 142.3, 125.2, 72.9, 51.8, 29.1, 10.1.
S3o:25 1H NMR (500 MHz, ppm, CDCl3) δ 6.22 (d, J = 1.0 Hz,
1H), 5.79 (s, 1H), 4.38 (q, J = 6.6 Hz, 1H), 3.78 (s, 3H), 2.52 (d, J =
6.9 Hz, 1H), 1.62−1.70 (m, 2H), 1.27−1.40 (m, 4H), 0.90 (t, J = 7.0
Hz, 3H); 13C NMR (125 MHz, ppm, CDCl3) δ 167.2, 142.8, 125.1,
71.8, 52.0, 36.0, 28.1, 22.6, 14.1.
(2) Sariciftci, N. S.; Smilowitz, L.; Heeger, A. J.; Wudl, F. Science
1992, 258, 1474−1476.
(3) Reviews: (a) Imahori, H.; Sakata, Y. Adv. Mater. 1997, 9, 537−
546. (b) Gunes, S.; Neugebauer, H.; Sariciftci, N. S. Chem. Rev. 2007,
̈
107, 1324−1338.
(4) (a) Kojima, A.; Teshima, K.; Shirai, Y.; Miyasaka, T. J. Am. Chem.
Soc. 2009, 131, 6050−6051. (b) Lee, M. M.; Teuscher, J.; Miyasaka,
T.; Murakami, N.; Snaith, H. J. Science 2012, 338, 643−647.
(5) Reviews: (a) Kazim, S.; Nazeeruddin, M. K.; Gratzel, M.; Ahmad,
S. Angew. Chem., Int. Ed. 2014, 53, 2812−2824. (b) Bai, Y.; Mora-Sero,
I.; De Angelis, F. Chem. Rev. 2014, 114, 10095−10130.
S3p:25 1H NMR (500 MHz, ppm, CDCl3) δ 6.22 (d, J = 1.0 Hz,
1H), 5.79 (t, J = 1.1 Hz, 1H), 4.38 (q, J = 6.5 Hz, 1H), 3.78 (s, 3H),
2.53 (d, J = 6.8 Hz, 1H), 1.81−1.87 (m, 2H), 1.44 (br s, 1H), 1.30 (br
s, 5H), 0.88 (t, J = 6.9 Hz, 3H); 13C NMR (125 MHz, ppm, CDCl3) δ
167.1, 142.7, 124.9, 71.7, 51.9, 36.3, 31.7, 25.6, 22.7, 14.1.
S3q:24 1H NMR (500 MHz, ppm, CDCl3) δ 6.22 (s, 1H), 5.79 (d, J
= 0.8 Hz, 1H), 4.38 (q, J = 6.8 Hz, 1H), 3.78 (s, 3H), 2.53 (d, J = 6.9
Hz, 1H), 1.58−1.69 (m, 2H), 1.39−1.47 (m, 1H), 1.23−1.35 (m, 7H),
0.87 (t, J = 6.8 Hz, 3H); 13C NMR (125 MHz, ppm, CDCl3) δ 167.1,
142.7, 124.9, 71.7, 51.9, 36.4, 31.9, 29.2, 25.9, 22.7, 14.1.
(6) (a) Green, M. A.; Emery, K.; Hishikawa, Y.; Warta, W.; Warta,
W.; Dunlop, E. D. Prog. Photovoltaics 2012, 20, 12−20. (b) Bakulin, A.
A.; Rao, A.; Pavelyev, V. G.; van Loosdrecht, P. H. M.; Pshenichikov,
M. S.; Niedzialek, D.; Cornil, J.; Belijonne, D.; Friend, R. H. Science
2012, 335, 1340−1344.
(7) Hummelen, J. C.; Knight, B. W.; LePeq, F.; Wudl, F.; Yao, J.;
Wilkins, C. L. J. Org. Chem. 1995, 60, 532−538.
(8) Selected examples of OPV based on fullerene derivatives in
combination with P3HT: (a) Padinger, F.; Rittberger, R. S.; Sariciftci,
N. S. Adv. Funct. Mater. 2003, 13, 85−88. (b) Wienk, M. M.; Kroon, J.
M.; Verhees, W. J. H.; Knol, J.; Hummelen, J. C.; vanHal, P. A.;
Janssen, R. A. J. Angew. Chem., Int. Ed. 2003, 42, 3371−3375. (c) Shi,
C.; Yao, Y.; Yang, Y.; Pei, Q. J. Am. Chem. Soc. 2006, 128, 8980−8986.
(d) Camaioni, N.; Garlaschelli, L.; Geri, A.; Maggini, M.; Possamai, G.;
Ridolfi, G. J. J. Mater. Chem. 2002, 12, 2065−2070. (e) Kim, J. Y.; Lee,
K.; Coates, N. E.; Moses, D.; Nguyen, T.-Q.; Dante, M.; Hegger, A. J.
Science 2007, 317, 222−225. (f) Martijn, L.; Wetzelaer, G-J. A. H.;
Kooistra, F. B.; Veenstra, S. C.; Hummelen, J. C.; Blom, P. W. M. Adv.
Mater. 2008, 20, 2116−2119. (g) Chen, C.-P.; Chan, S.-H.; Chao, T.
C.; Ting, C.; Ko, B.-T. J. Am. Chem. Soc. 2008, 130, 12828−12833.
(h) Chan, S.-H.; Chen, C.-P.; Chao, T. C.; Ting, C.; Lin, C.-S.; Ko, B.-
T. Macromolecules 2008, 41, 5519−5526. (i) Kooistra, F. B.; Knol, J.;
Kastenberg, F.; Popescu, L. M.; Verhees, W. J. H.; Kroon, J. M.;
Hummelen, J. C. Org. Lett. 2007, 9, 551−554.
(9) (a) Troshin, P. A.; Hoppe, H.; Renz, J.; Egginger, M.; Mayorova,
J. Yu.; Goryachev, A. E.; Peregudov, A. S.; Lyubovskaya, R. N.; Gobsh,
G.; Sariciftci, N. S.; Razumov, V. F. Adv. Funct. Mater. 2009, 19, 779−
788. (b) Renz, J. A.; Troshin, P. A.; Gobsch, G.; Razumov, V. F.;
Hoppe, H. Phys. Status Solidi RRL 2008, 2, 263−265.
(10) (a) Matsuo, Y.; Iwashita, A.; Abe, Y.; Li, C.-Z.; Matsuo, K.;
Hashiguchi, M.; Nakamura, E. J. Am. Chem. Soc. 2008, 130, 15429−
15436. (b) Matsuo, Y.; Sato, Y.; Niinomi, T.; Soga, I.; Tanaka, H.;
Nakamura, E. J. Am. Chem. Soc. 2009, 131, 16048−16050. (c) Zhang,
Y.; Matsuo, Y.; Li, C.-Z.; Tanaka, H.; Nakamura, E. J. Am. Chem. Soc.
2011, 133, 8086−8089.
S3r:19 1H NMR (500 MHz, ppm, CDCl3) δ 6.21 (s, 1H), 5.80 (s,
1H), 4.45−4.47 (m, 1H), 3.78 (s, 3H), 2.51 (d, J = 6.9 Hz, 1H), 1.76−
1.84 (m, 1H), 1.55−1.61 (m, 1H), 1.40−1.46 (m, 1H), 0.94 (t, J = 6.2
Hz, 6H); 13C NMR (125 MHz, ppm, CDCl3) δ 167.2, 142.9, 125.0,
70.1, 52.0, 45.5, 24.9, 23.4, 22.0.
S3t:26 1H NMR (500 MHz, ppm, CDCl3) δ 6.23 (s, 1H), 5.77 (s,
1H), 4.32 (q, J = 7.0 Hz, 1H), 4.24 (q, J = 7.1 Hz, 2H), 2.57 (d, J = 7.0
Hz, 1H), 1.66−1.74 (m, 2H), 1.32 (t, J = 7.2 Hz, 3H), 0.95 (t, J = 7.2
Hz, 3H); 13C NMR (125 MHz, ppm, CDCl3) δ 166.7, 142.5, 124.9,
73.1, 60.9, 29.2, 14.2, 10.2.
S3u:27 1H NMR (500 MHz, ppm, CDCl3) δ 6.13 (d, J = 1.2 Hz,
1H), 5.68 (t, J = 1.1 Hz, 1H), 4.26 (q, J = 6.3 Hz, 1H), 2.69 (d, J = 6.9
Hz, 1H), 1.65−1.70 (m, 2H), 1.50 (s, 9H), 0.95 (t, J = 7.5 Hz, 3H);
13C NMR (125 MHz, ppm, CDCl3) δ 166.1, 143.6, 124.3, 81.5, 73.5,
29.3, 28.2, 10.4.
ASSOCIATED CONTENT
* Supporting Information
■
S
Additional text describing general procedures and meaterials;
one figure showing UV−visible spectra; one table listing
LUMO levels and comparison data in properties of OPVs; and
1H and 13C NMR spectra of 1a−1m, 2a−2l, and novel β-
hydroxy esters (S3g, S3i, S3j, S3k, S3l, S3s, S3v, and S3w).
This material is available free of charge via the Internet at
http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*Phone/fax +81-857-31-5259; E-mail titoh@chem.tottori-u.ac.
■
(11) Matsuo, Y.; Kawai, J.; Inada, H.; Nakagawa, T.; Ota, H.; Osyubo,
S.; Nakamura, E. Adv. Mater. 2013, 25, 6266−6269.
(12) Matsumoto, K.; Hashimoto, K.; Kamo, M.; Uetani, Y.; Hayase,
S.; Kawatsura, M.; Itoh, T. J. Mater. Chem. 2010, 20, 9226−9230.
(13) Yoshimura, K.; Matsumoto, K.; Uetani, Y.; Sakumichi, S.;
Hayase, S.; Kawatsura, K.; Itoh, T. Tetrahedron 2012, 68, 3605−3610.
jp.
Notes
The authors declare no competing financial interest.
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DOI: 10.1021/acs.joc.5b00530
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The Journal of Organic Chemistry
Article
(14) Taylor, P. G.; Lee, J.-K.; Zakhidov, A. A.; Chatzichristidi, M.;
Fong, H. H.; DeFranco, J. A.; Malliaras, G. G.; Ober, C. K. Adv. Mater.
2009, 21, 2314−2317.
(15) Yoshimura, K.; Sugawara, K.; Sakumichi, S.; Matsumoto, K.;
Uetani, Y.; Hayase, S.; Nokami, T.; Itoh, T. Chem. Lett. 2013, 42,
1209−1211.
(16) Yang, H.-T.; Ren, W.-L.; Miao, C.-B.; Dong, C.-P.; Yang, Y.; Xi,
H.-T.; Meng, Q.; Jiang, Y.; Sun, X.-Q. J. Org. Chem. 2013, 78, 1163−
1170.
(17) Kim, J. Y.; Kim, S. H.; Lee, H.-H.; Lee, K.; Ma, W.; Gong, X.;
Heeger, A. J. Adv. Mater. 2006, 18, 572−576.
(18) Wong, W.-Y.; Wang, X.-Z.; He, Z.; Djurisic, A. B.; Yip, C.-T.;
Cheung, K.-Y.; Wang, H.; Mak, C. S. K.; Chan, W.-K. Nat. Mater.
2007, 6, 521−527.
(19) Latorre, A.; Sae
Tetrahedron 2014, 70, 97−102.
́ ́
z, J. A.; Rodríguez, S.; Gonzalez, F. V.
(20) Recent reviews: (a) Basavaiah, D.; Reddy, B. S.; Badsara, S. S.
Chem. Rev. 2010, 110, 5447−5674. (b) Wei, Y.; Shi, M. Chem. Rev.
2013, 113, 6659−6690.
́
(21) Laulhe, S.; Bogdanov, B.; Johannes, L. M.; Gutierrez, O.;
Harrison, J. G.; Tantillo, D. J.; Zhang, X.; Nantz, M. H. J. Mass
Spectrom. 2012, 47, 676−686.
(22) Chanthamath, S.; Takaki, S.; Shibatomi, K.; Iwasa, S. Angew.
Chem., Int. Ed. 2013, 52, 5818−5821.
(23) Shi, M.; Li, C.-Q.; Jiang, J.-K. Molecules 2002, 7, 721−733.
(24) Giovanni, W. A.; Fernando, G. M. C. J. Braz. Chem. Soc. 2011, 8,
1568−1584.
(25) Jeong, Y.; Ryu, J. S. J. Org. Chem. 2010, 75, 4183−4191.
(26) Schmidt, Y.; Breit, B. Chem.Eur. J. 2011, 17, 11780−11788.
(27) Hoffmann, H. M. R.; Gassner, A.; Eggert, H. Chem. Ber. 1991,
124, 2475−2480.
4649
DOI: 10.1021/acs.joc.5b00530
J. Org. Chem. 2015, 80, 4638−4649