DOI: 10.1002/asia.200600026
Convergent/Divergent Synthesis and Photophysical Studies of Alternating
Benzene–Furan Oligoaryls from Substituted Propargylic Dithioacetals
Chih-Ming Chou,
[a]Wei-Qiang Chen,
[a]Jia-Hong Chen,
[a]Cheng-Lan Lin ,
[a, b]Jui-Chang Tseng,
[a]Chin-Fa Lee,
[a]and Tien-Yau Luh*
[a]Introduction
The incorporation of heteroaromatic rings into conjugated
polymers is known to modify remarkably the photophysical
and electronic properties of the polymers.
[1]For example,
polythiophenes
[2]and polypyrroles
[3]are extensively studied
and widely used in optoelectronics. There is burgeoning
in-terest in well-defined monodispersed oligomers of precise
conjugation lengths as models for polymer analogues.
[4]It is
suggested that these nanoscale conjugated oligomers may fit
nicely with the approximate size of present nanopattern
probe gaps.
[4]Various approaches are known in the synthesis
of long conjugated oligoaryls. Coupling reactions and
annu-lation protocols appear to be most commonly used in the
construction of oligomer backbones. Oligothiophenes
[5]and
oligopyrroles
[6]are conveniently synthesized by such
meth-ods. Relatively speaking, the corresponding furan analogues
have only been sporadically explored.
[7]Furan-containing
conjugated polymers are photochemically labile in the
pres-ence of air (oxygen).
[ 7a]Under inert atmosphere, however,
furan rings in oligoaryls remain intact upon irradiation.
[8]Indeed, alternating benzene–furan oligomers are used in
electroluminescence as efficient hole-transporting materials
with good charge mobility.
[8]Furthermore, the bismercaptan
derivatives of ter- and pentaaryls were shown to assemble
on the gold (111) surface with significant p–p stacking.
[9]By
adopting an annulation protocol starting from the
propargyl-icdithioacetal 1 and an aldehyde (Scheme 1),
[10]oligomers 5
and/or 6 can be formed by bidirectional iterative synthesis
from the corresponding dialdehyde and 4 (Scheme 2).
[ 10b, c]However, each annulation in Scheme 2 can only introduce
four aryl moieties, including two furan rings. A more
expedi-tious protocol would be highly desirable to enable the rapid
synthesis of higher homologues of furan-containing
oligo-ACHTUNGTRENNUNGaryls.
A range of functional groups, such as ester, ether linkage,
trifluoromethyl, cyano, hydroxyl, and even aryl bromide,
was shown to be stable under the annulation conditions in
Scheme 1.
[10]We therefore envisaged that an allenyl or
prop-argyliclithium intermediate 7, generated from 4, might
react with another molecule of aldehyde 8, which contains a
propargylicdithioacetal moiety, to give teraryl 9. Notably, 9
thus produced may contain both a propargylic dithioacetal
moiety and an ester group, and the latter may be converted
into aldehyde 10 for further transformation. Accordingly, a
similar combination of two teraryls 12 and 10 may furnish
the corresponding heptamer 13 (Scheme 3).
The strategy shown in Scheme 3 would provide an
effi-cient way to synthesize convergently a range of higher
ho-gent/divergent method from the
annu-lation of a propargylicdithioacetal and
an aldehyde with a
propargylicdithioa-cetal moiety as a substituent. These
oligomers are fairly soluble in a range
of organicsolvents and c
an be easily
purified by reprecipitation. The
sub-This route provides a useful procedure
for the synthesis of alternating
ben-region
and
are
electrochemically
active. The band gaps of these
oligom-ers appear to be less sensitive towards
changes in conjugation length than
those of oligofurans.
Keywords: annulation · band gaps ·
electrochemistry · fluorescence ·
oligomerization
[a] C.-M. Chou, Dr. W.-Q. Chen, J.-H. Chen, Dr. C.-L. Lin , Dr. J.-C. Tseng, Dr. C.-F. Lee, Prof. T.-Y. Luh
Department of Chemistry, National Taiwan University Taipei, 106 (Taiwan)
Fax: (+ 886)-2-2364-4971 E-mail: [email protected] [b] Dr. C.-L. Lin
Institute of Chemistry, Academia Sinica Nangang, Taipei, 115 (Taiwan)
Supporting information for this article is available on the WWW under http://www.chemasianj.org or from the author.
Scheme 1. Annulation protocol used as the basis for subsequent synthe-ses.
mologues of alternating benzene–furan oligoaryls in a
selec-tive manner. In this paper, we report a new iteraselec-tive
conver-gent/divergent
[ 4b, 5c]synthesis of alternating benzene–furan
oligoaryls 17 by a combination of the routes shown in
Schemes 2 and 3. A preliminary investigation of the
synthe-sis of monodispersed oligoaryls without repeated units is
also presented. As these furan-containing oligoaryls are
highly fluorescent,
[8–10]the physical properties of these
oligomers are systematically explored.
Results and Discussion
Synthesis
Propargylicdithio
ACHTUNGTRENNUNGacetal 4 was obtained in 62% yield from
the BF
3·OEt-promoted reaction of ynone 18 a with
1,2-etha-nedithiol in methanol. The ester group in 4 was reduced by
diisobutylaluminum
hydride
(DIBAL) to afford alcohol 19
in 97 % yield. Oxidation of 19
with MnO
2gave the
corre-sponding aldehyde 8 in 92 %
yield. Sequential reaction of 4
with nBuLi, 8, and
trifluoroace-tic acid (TFA) afforded the
cor-responding teraryl 9 in 56 %
overall yield. There are two
in-teresting features in this
reac-tion sequence. First,
n-butyl-lithium reacted selectively with
the sulfur moiety of the
dithio-lane functionality in 4 to give
allenyl anion 7, with the ester group remaining intact under
the reaction conditions. Second, the allenyl or propargylic
anion 7 reacted preferentially with the aldehyde group in 8
to give the corresponding annulation product 9; the
dithio-lane group in 8 was stable under these conditions.
Reduction of 9 with DIBAL gave 11, which was then
oxi-dized with MnO
2to give 10 in 90 % yield (two steps).
Meth-ylation of 11 with NaH and then MeI afforded the
corre-sponding methyl ether 12 in 94 % yield.
Attempts to annulate 9 with 10 under the conditions used
for the synthesis of 9 gave the desired heptaaryl dithioacetal
14 in trace amounts. Interestingly, a significant amount of
the ester group in 9 reacted with nBuLi under the reaction
conditions. Presumably, an extension of conjugation would
enhance the reactivity of the ester group toward nBuLi.
In-stead, treatment of 12 with nBuLi (1 equiv) followed by 10
and TFA afforded 13 in 73 % yield. Oxidation of 13 with
2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), however,
gave the corresponding aldehyde 15 in very low yield
(
5 %).
Alternatively,
treatment
of
11
with
nBuLi
(2.2 equiv) followed by 10 and TFA in usual manner
afford-ed 16 in 70 % yield. Swern oxidation of 16 (dimethyl
sulfox-Abstract in Chinese:
Scheme 2. Bidirectional iterative annulation of 4 to produce alternating benzene–furan oligoaryl 6.
Editorial Board Member
Tien-Yau Luh obtained his Ph.D. at the Univ. of Chicago (1974). After2 years of postdoctoral research at the Univ. of Min-nesota, he began independent research at the Chinese Univ. of Hong Kong (1976). He returned to his alma mater, National Taiwan Univ. (1988), where he is Profes-sor of Chemistry. He has been the recipi-ent of numerous awards. His currrecipi-ent re-search interests include OMCOS, organic synthesis of polymers, and chemistry of materials.
“Congratulations on the launching of this prestigious chemistry journal. Chemistry—An Asian Journal provides an important source for the presentation of cutting-edge re-search results to the scientific community.”
ide (DMSO), Ac
2O) gave 15 in 78 % yield. Further
annula-tion of 13 with 15 under similar condiannula-tions produced the
cor-responding 15-mer dithioacetal 20 in 73 % yield.
This protocol apparently provided a rapid convergent
syn-thesis of a range of well-defined monodispersed oligomers
that contain alternating benzene–furan rings. Furthermore,
the corresponding aldehyde functionality and propargylic
di-thioacetal groups were conveniently introduced by this
reac-tion sequence.
The oligoaryl dithioacetals thus obtained were used for
further annulations with a dialdehyde with the protocol
de-scribed in Scheme 2. For example, reaction of 13 with nBuLi
followed by terephthaldehyde (
1=
2
equiv) and the usual
treat-ment afforded 17 d in 23 % yield. Similarly, 37-mer 17 e was
obtained in 77 % yield from the annulation of 20 (2 equiv)
with 5 under typical annulation conditions. As there are
alkyl substituents on each of the furan rings, these oligomers
are fairly soluble in organicsolvents. Bec
ause the starting
materials and the products have very different molecular
weights, purification of the final products can be achieved
easily by the typical reprecipitation commonly used in
poly-mer chemistry.
As shown in Scheme 3, teraryl 9 is obtained from the
re-action of propargylic dithioacetal 4, which serves as the
pre-cursor of allenyl anion 7, and another
propargylicdithioace-tal 8, which has an electrophilic aldehyde group. We
there-fore envisaged that the substituents on the alkynyl carbons
in 4 and 8 could be different, so that the substituent on C3
of the furan rings in 9 would be different from the
substitu-ent on the alkynyl carbon atom. By employing this strategy,
synthesis of oligoaryls without repeated units would be
fea-sible. We tested this hypothesis by synthesizing teraryls 24
and 26 (Scheme 4). Thus, reaction of the allenyl anion (like
7, prepared from 21 and nBuLi) with 8 followed by
treat-ment with TFA in the same manner as that described above
afforded 24 in 53 % yield. Similarly, reaction of 7 with 23 by
the same method gave 26 in 50 % yield.
Functional-group transformation of 24 afforded the
corre-sponding aldehyde 28. In a similar manner, 26 was
convert-ed into 29, which was allowconvert-ed to annulate with 28 to form
heptaaryl 31 in 49 % overall yield. Further reaction of 31
with terephthaldehyde in the usual manner afforded the
cor-responding 17-mer 33 in 45 % yield. Dithioacetal 32 was
ob-tained similarly in 68 % yield from the annulation of 29 and
32. Further annulation of 32 with 5 under similar conditions
gave the 21-mer 34 in 66 % yield. Notably, the substituents
on the furan rings in 33 and 34 are different.
Photophysical and Electrochemical Investigations
Alternating benzene–furan oligoaryls showed strong
absorp-tion and emission in the visible region. Typical spectra for a
series of symmetrical oligoaryls 17 and 34 are shown in
Figure 1. a) Absorption and b) emission spectra of 17 a (d), 17 b (a), 17 c (b), 34 (g) and 17 e (c) in THF.
Figure 1, and their photophysical data are outlined in
Table 1. As expected, the absorption maxima showed
batho-chromic shift as the conjugation lengths increased. These
oligoaryls are also highly fluorescent with high quantum
yield. The absorption and emission reached saturation in 34
(21-mer) and little change was observed in higher
homo-logues (Table 1). As shown in Figure 1 b, the relative
intensi-ties of the emission due to 0–0 transition increased with
in-creasing chain lengths. Interestingly, the quantum yield
de-creased with increasing molecular weights of the oligomers.
The first oxidation parameters, E
p1
=2
, of 17 and 34
mea-sured by cyclic voltammetry are also listed in Table 1.
Nota-bly, the oxidation potential continually shifted to the
less-positive end as the molecular weights of the oligomers
in-creased, and there is a significant difference (119 mV) in
E
p1
=2
between the 21-mer and 37-mer compounds. Similar
be-havior was also observed in alternating
ethynylene–thio-phene oligomers.
[11]The energies of the highest occupied and lowest
unoccu-pied molecular orbitals (HOMOs and LOMOs, respectively)
of the alternating benzene–furan oligoaryls were estimated
based on the photophysical and electrochemical data in
Table 1 and are shown there. Plots of the HOMO and
LUMO energies and the band gaps of 17 and 34 against 1/n,
where n is the total number of carbon atoms in the
conju-gated oligoaryl chain, are shown in Figure 2, and compared
with those of oligothiophenes 35,
[5]oligofurans 36,
[7]and
oli-goethynylenethiophenes 37
[11]calculated from literature
data. Surprisingly, replacement of alternating furan moieties
along oligofuran chains by benzene rings may not
signifi-cantly perturb the frontier orbital energies of oligofurans
when the conjugation length is short (n < 24). However,
Scheme 4. Formation of alternating benzene–furan oligomers with different substituent groups. a) DIBAL, 98 %; b) MnO2, 92 %; c ) 1) 21, nBuLi,78 8C, 2) 5, 3) TFA; yield of 24 = 53 %; d) 1) 6, 2) TFA; yield of 26 = 50 %; e) DIBAL; yield of 25 = 93 %; f) DIBAL; yield of 27 = 90 %; g) MnO2; yield of 28 = 91 %; h) MnO2; yield of 30 = 90 %; i) NaH/MeI; yield of 29 = 93 %; j) 1) 29, nBuLi (1.1 equiv), 2) 28, 3) TFA; yield of 31 = 49 %; k) 1) 29, nBuLi (1.1 equiv), 2) 30, 3) TFA; yield of 32 = 68 %; l) 31, nBuLi (1.1 equiv), 2) terephthaldehyde, 3) TFA; yield of 33 = 45 %; m) 32, nBuLi (1.1 equiv), 2) 5, 3) TFA; yield of 34 = 66 %.
Table 1. Photophysical and electrochemical parameters of benzene–furan oligomers.[a] n[b] l max [nm] lem(Ff) [nm] E00 [eV] Ep 1= 2[c] [mV] HOMO [eV] LUMO [eV] 17 a 12 328 364, 383, 404 (0.88) 3.47 622 5.36 1.89 17 b 20 376 420, 446, 475 (0.84) 3.02 441 5.20 2.18 17 c 52 414 474, 503, 536 (0.33) 2.71 206 4.98 2.27 34 84 422 478, 509, 544 (0.29) 2.66 98 4.87 2.21 17 e 148 423 479, 509, 544 (0.23) 2.66 21 4.74 2.08
[a] Absorption and fluorescence spectra were acquired in THF. [b] Total number of carbon atoms along the conjugated oligoaryl chain. [c] The potentials reported are referenced to the ferrocene/ferrocenium couple.
when the conjugation length is increased, both the HOMO
and LUMO energies of 17 c–e and 34 started to deviate
from the linearly extrapolated values based on the smaller
analogues of oligofurans.
Interestingly, the slope from the plot of the band gaps of
17 and 34 against 1/n was smaller than that from the plot of
36. This observation indicates that the variation in band gap
may be less sensitive towards the change in conjugation
length. Similar results were also observed for 37.
[11]Conclusions
In summary, we have demonstrated a rapid
convergent/di-vergent approach for the synthesis of a range of oligoaryls
that contain alternating benzene–furan rings. These
oligom-ers are fairly soluble in a range of organicsolvents, thus
sim-plifying their purification. In particular, oligomers with
rela-tively high molecular weights can be easily purified by
re-ACHTUNGTRENNUNGprecipitation. This advantage would allow convenient
syn-thesis and isolation of the higher homologues. An extension
towards the rapid synthesis of polymers with unity dispersity
would therefore be feasible. Furthermore, since the
synthe-ses involve stepwise procedures, the substituents on the
furan rings can be varied depending on the substituents in
the starting propargylicdithioac
etals. This strategy would
provide a promising route towards polymers without
repeat-ed units (Scheme 4). Since pyrrole derivatives can also be
synthesized by this method,
[10]incorporation of such
nitro-gen heterocycles could be possible.
These alternating benzene–furan oligoaryls are highly
flu-orescent in the visible region and electrochemically active.
The band gaps of these oligomers appeared to be less
sensi-tive towards changes in conjugation length than those of
homo-oligomers such as 35 and 36.
Oligoethynylenethien-ACHTUNGTRENNUNGylenes 37 behave similarly to the oligoaryls.
[11]Our results
indicate that insertion of benzene moieties into oligofurans
may fine-tune the conjugated p-systems for further
applica-tions.
Experimental Section
Syntheses4: BF3·Et2O (66.4 mL, 0.53 mol) and 1,2-ethanedithiol (37.8 mL,
0.45 mol) was added to a solution of 18 a (107.4 g, 0.44 mol) in MeOH
(700 mL) at78 8C. The mixture was slowly warmed to room
tempera-ture and stirred for 12 h. After quenching with NaOH (10 %, 400 mL), the organiclayer was separated. The aqueous layer was extracted with CH2Cl2 (3 N 200 mL). The combined organic extracts were washed with
NaOH (10 %, 5 N 300 mL) and brine (300 mL), dried over MgSO4,
fil-tered, and evaporated in vacuo. The resulting residue was purified by flash column chromatography (silica gel, CH2Cl2/hexane 1:9) to afford 4 as a pale yellow oil. The product was dissolved in pentane and cooled in the freezer, and pure 4 crystallized as colorless needles (87.4 g, 62 %). M.p.: 46–47 8C; IR (KBr): n˜ = 2960, 2934, 2870, 1726, 1610, 1437, 1408,
1280, 1193, 1111, 1021, 966, 869, 735, 496 cm1; 1H NMR (400 MHz,
CDCl3): d = 0.92 (t,3JACHTUNGTRENNUNG(H,H) =7.3 Hz, 3H), 1.43 (sext.,3JACHTUNGTRENNUNG(H,H) =7.3 Hz, 2 H), 1.56 (tt,3JACHTUNGTRENNUNG(H,H) =7.1, 7.3 Hz, 2H), 2.35 (t,3JACHTUNGTRENNUNG(H,H) =7.1 Hz, 2 H),
3.59–3.75 (m, 4 H), 3.89 (s, 3 H), 7.98 ppm (br s, 4 H); 13C NMR
(100 MHz, CDCl3): d = 13.6, 18.9, 22.0, 30.6, 41.4, 52.1, 61.7, 81.7, 88.7, 127.7, 129.4, 129.8, 145.1, 166.6 ppm; HRMS (EI): m/z calcd for C17H20O2S2: 320.0905; found: 320.0910; elemental analysis: calcd (%) for C17H20O2S2: C 63.72, H 6.29; found: C 63.68, H 5.89.
19: DIBAL (150.0 mL, 1.0 m in hexane, 150.0 mmol) was added slowly with stirring to a solution of 4 (10.7 g, 33.5 mmol) in THF (120 mL) at 0 8C under N2 atmosphere. The reaction mixture was stirred for 2 h at room temperature, then saturated NH4Cl (150 mL) was poured in slowly to quench the reaction. The gel-like organic layer was then acidified with HCl (6 m, 200 mL) and extracted with Et2O (3 N 200 mL). The combined
organicextracts were washed with saturated NaHCO3 (2 N 150 mL) and
brine (200 mL), dried over MgSO4, filtered, and evaporated in vacuo to afford crude 19 (9.4 g, 97 %). Kugelrohr distillation (0.01 torr, 170 8C) af-forded a pure colorless oil. IR (KBr): n˜ = 3354, 2956, 2928, 2870, 1507, 1458, 1414, 1209, 1043, 1016, 852, 753 cm1;1H NMR (400 MHz, CDCl
3): d = 0.92 (t,3JACHTUNGTRENNUNG(H,H) =7.2 Hz, 3 H), 1.43 (sext.,3JACHTUNGTRENNUNG(H,H) = 7.2 Hz, 2H), 1.55 (quint., 3JACHTUNGTRENNUNG(H,H) = 7.2 Hz, 2H), 1.60–1.78 (br s, 1H), 2.35 (t, 3JACHTUNGTRENNUNG(H,H) = 7.2 Hz, 2 H), 3.58–3.74 (m, 4 H), 4.67 (s, 2 H), 7.32 (d, 3JACHTUNGTRENNUNG(H,H) =8.4 Hz, Figure 2. Plots of a) HOMO (solid) and LUMO (open) energies and
b) of 17 and 34 (circle), 35 (diamond), 36 (triangle), and 37 (square) versus 1/n.
2 H), 7.92 ppm (d,3JACHTUNGTRENNUNG(H,H) =8.4 Hz, 2H);13C NMR (100 MHz, CDCl 3): d = 13.6, 18.9, 22.0, 30.7, 41.2, 62.0, 64.9, 82.2, 88.1, 126.6, 127.8, 139.0, 140.9 ppm; elemental analysis: calcd (%) for C16H20OS2: C 65.71, H 6.89; found: C 65.33, H 6.63.
8: A solution of 19 (34.9 g, 0.12 mol) in CH2Cl2 (200 mL) was added slowly to a suspension of activated MnO2(104.3 g, 1.20 mol) in CH2Cl2 (200 mL) at room temperature. The reaction mixture was stirred for 6 h, then passed through a silica-gel bed (5 cm) and washed with EtOAc (5 N 300 mL). The combined filtrate was evaporated in vacuo to afford crude 8 as an orange oil. The crude product was purified by flash column chro-matography (silica gel, CH2Cl2/hexane 1:3) to afford 8 (32.0 g, 92 %) as a pale yellow oil. IR (KBr): n˜ = 2957, 2929, 2870, 2860, 2734, 1701, 1603,
1574, 1417, 1387, 1303, 1208, 1169, 1015, 814, 756 cm1; 1H NMR
(400 MHz, CDCl3): d = 0.92 (t, 3JACHTUNGTRENNUNG(H,H) =7.3 Hz, 3 H), 1.45 (sext., 3 J-ACHTUNGTRENNUNG(H,H) =7.3 Hz, 2H), 1.56 (tt, 3JACHTUNGTRENNUNG(H,H) =7.0, 7.3 Hz, 2 H), 2.35 (t, 3 J-ACHTUNGTRENNUNG(H,H) =7.0 Hz, 2H), 3.62–3.74 (m, 4H), 7.83 and 8.09 (AA’XX’, 3 J-ACHTUNGTRENNUNG(H,H) =8.0, 0.4, 1.9, 1.9 Hz, 4H), 10.00 ppm (s, 1H); 13C NMR (100 MHz, CDCl3): d = 13.6, 18.9, 22.1, 30.6, 41.6, 61.7, 81.5, 89.0, 128.3, 129.5, 135.9, 146.9, 191.6 ppm; HRMS (EI): m/z calcd for C16H18OS2: 290.0799; found: 290.0792; elemental analysis: calcd (%) for C16H18OS2: C 66.16, H 6.25; found: C 66.02, H 6.09.
9: Under argon, nBuLi (13.2 mL, 2.5 m in hexane, 33.0 mmol) was intro-duced dropwise to a solution of 4 (9.6 g, 30.0 mmol) in THF (200 mL) at 78 8C, and the mixture was stirred at 78 8C for 50 min. A solution of 8 (7.2 g, 25.0 mmol) in THF (40 mL) was added at78 8C, and the mixture
was stirred at78 8C for 1 h, then gradually warmed to room
tempera-ture. After further stirring for 1 h, TFA (5.5 mL, 60.0 mmol) was added, and the mixture was stirred at room temperature overnight. The reaction
was then quenched with saturated NH4Cl (150 mL), and the organic
layer was extracted with Et2O (3 N 100 mL). The combined organic
ex-tracts were washed with saturated NaHCO3 (2 N 100 mL) and brine
(100 mL), then dried over MgSO4, filtered, and evaporated in vacuo. The crude product was purified by flash column chromatography (silica gel, CH2Cl2/hexane 1:3) to give 9 (7.32 g, 56 %) as a pale yellow solid. M.p.: 98–99 8C; IR (KBr): n˜ = 2954, 2929, 2869, 1720, 1609, 1503, 1434, 1278, 1177, 1108, 933, 856, 771, 718, 700 cm1;1H NMR (400 MHz, CDCl 3): d = 0.94 (t, 3JACHTUNGTRENNUNG(H,H) =7.3 Hz, 3H), 0.95 (t,3JACHTUNGTRENNUNG(H,H) =7.3 Hz, 3H), 1.37–1.52 (m, 4 H), 1.53–1.72 (m, 4 H), 2.37 (t,3JACHTUNGTRENNUNG(H,H) =7.1 Hz, 2 H), 2.69 (t,3 J-ACHTUNGTRENNUNG(H,H) =7.8 Hz, 2 H), 3.62–3.77 (m, 4H), 3.91 (s, 3H), 6.78 (s, 1 H), 7.65 (d, 3JACHTUNGTRENNUNG(H,H) =8.2 Hz, 2H), 7.74 (d, 3JACHTUNGTRENNUNG(H,H) =8.2 Hz, 2 H), 8.00 (d, 3 J-ACHTUNGTRENNUNG(H,H) =8.2 Hz, 2H), 8.04 ppm (d, 3JACHTUNGTRENNUNG(H,H) =8.2 Hz, 2 H); 13C NMR (100 MHz, CDCl3): d = 13.6, 13.9, 18.9, 22.1, 22.6, 25.7, 30.8, 32.1, 41.3, 52.0, 62.1, 82.2, 88.3, 111.5, 123.2, 124.9, 125.3, 128.0, 128.3, 130.1, 131.1,
134.7, 138.4, 148.8, 150.9, 166.8 ppm; HRMS (FAB+): m/z calcd for
C31H35O3S2: 519.2028 [M +
+H]; found: 519.2027; elemental analysis: calcd (%) for C31H34O3S2: C 71.78, H 6.61; found: C 71.65, H 6.58. 11: As with the preparation of 19, 9 (4.0 g, 7.7 mmol) was treated with DIBAL (23.0 mL, 1.0 m in hexane, 23.0 mmol) to afford 11 (3.6 g, 97 %) as a pale yellow solid. M.p.: 60–61 8C; IR (KBr): n˜ = 3244, 2954, 2925, 2856, 1605, 1505, 1456, 1421, 1364, 1289, 1188, 1047, 1014, 933, 843, 808, 708 cm1;1H NMR (400 MHz, CDCl 3): d = 0.94 (t,3JACHTUNGTRENNUNG(H,H) = 7.2 Hz, 3H), 0.95 (t, 3JACHTUNGTRENNUNG(H,H) =7.3 Hz, 3H), 1.37–1.53 (m, 4H), 1.53–1.72 (m, 4H), 1.76–1.90 (br s, 1 H), 2.37 (t, 3JACHTUNGTRENNUNG(H,H) =7.1 Hz, 2H), 2.68 (t, 3JACHTUNGTRENNUNG(H,H) = 7.8 Hz, 2 H), 3.62–3.76 (m, 4 H), 4.68 (s, 2 H), 6.64 (s, 1 H), 7.36 (d,3 J-ACHTUNGTRENNUNG(H,H) =8.1 Hz, 2H), 7.65 (d,3JACHTUNGTRENNUNG(H,H) = 8.2 Hz, 2 H), 7.69 (d,3JACHTUNGTRENNUNG(H,H) = 8.1 Hz, 2 H), 7.99 ppm (d, 3JACHTUNGTRENNUNG(H,H) =8.2 Hz, 2 H);13C NMR (100 MHz, CDCl3): d = 13.6, 14.0, 18.9, 22.1, 22.6, 25.8, 30.7, 32.1, 41.3, 62.1, 65.1, 82.2, 88.2, 109.3, 123.8, 124.6, 125.0, 127.3, 127.9, 130.1, 131.4, 137.7,
139.8, 147.5, 151.8 ppm; HRMS (FAB+
): m/z calcd for C30H35O2S2: 491.2078 [M++H]; found: 491.2068; elemental analysis: calcd (%) for C30H34O2S2: C 73.43, H 6.98; found: C 73.42, H 6.62.
10: As with the preparation of 8, 11 (3.7 g, 7.7 mmol) was treated with ac-tivated MnO2(6.7 g, 77.1 mmol) to afford 10 (3.5 g, 93 %) as a fluores-cent yellow solid. M.p.: 68–70 8C; IR (KBr): n˜ = 2954, 2928, 2860, 2689, 1601, 1503, 1481, 1400, 1305, 1217, 1169, 931, 832, 764, 708, 669 cm1; 1H NMR (400 MHz, CDCl 3): d = 0.94 (t,3JACHTUNGTRENNUNG(H,H) =7.1 Hz, 3H), 0.96 (t, 3JACHTUNGTRENNUNG(H,H) =7.1 Hz, 3H), 1.38–1.52 (m, 4 H), 1.53–1.72 (m, 4H), 2.37 (t,3 J-ACHTUNGTRENNUNG(H,H) =7.1 Hz, 2H), 2.70 (t,3JACHTUNGTRENNUNG(H,H) =7.8 Hz, 2 H), 3.63–3.76 (m, 4H), 6.83 (s, 1 H), 7.66 (d, 3JACHTUNGTRENNUNG(H,H) =8.2 Hz, 2H), 7.82 (d, 3JACHTUNGTRENNUNG(H,H) =8.4 Hz, 2 H), 7.87 (d, 3JACHTUNGTRENNUNG(H,H) =8.4 Hz, 2H), 8.01 (d, 3JACHTUNGTRENNUNG(H,H) =8.2 Hz, 2H), 9.97 ppm (s, 1 H);13C NMR (100 MHz, CDCl 3): d = 13.6, 13.9, 18.9, 22.1, 22.6, 25.7, 30.8, 32.1, 41.3, 62.1, 82.2, 88.3, 112.4, 123.7, 125.1, 125.4, 128.0, 130.3, 131.0, 134.8, 136.0, 138.7, 149.4, 150.6, 191.4 ppm; HRMS (FAB+): m/z calcd for C30H33O2S2: 489.1922 [M + +H]; found: 489.1920; elemental analysis: calcd (%) for C30H32O2S2: C 73.73, H 6.60; found: C 73.57, H 6.53.
12: A solution of 11 (1.6 g, 3.3 mmol) in THF (30 mL) was introduced into a suspension of NaH (60 % dispersion in mineral oil, 0.20 g, 4.9 mmol prewashed with hexane) in THF (30 mL) at room temperature under N2atmosphere. After 1 h of stirring, MeI (0.4 mL, 6.6 mmol) was added, and the reaction was stirred for 3 h at room temperature. The re-action mixture was poured into saturated NH4Cl (50 mL) and the organic layer was extracted with CH2Cl2(3 N 60 mL). The combined organic ex-tracts were washed with brine (100 mL), dried over MgSO4, filtered, and evaporated in vacuo to afford the residue, which was purified by flash column chromatography (silica gel, CH2Cl2/hexane 1:3) to afford 12 (1.5 g, 94 %) as a light yellow solid. M.p.: 75–76 8C; IR (KBr): n˜ = 2954, 2922, 2855, 1604, 1504, 1487, 1456, 1376, 1199, 1103, 1060, 970, 933, 846, 811, 791, 763, 710, 667 cm1;1H NMR (400 MHz, CDCl 3): d = 0.93 (t,3 J-ACHTUNGTRENNUNG(H,H) =7.3 Hz, 3H), 0.95 (t, 3JACHTUNGTRENNUNG(H,H) =7.3 Hz, 3 H), 1.37–1.53 (m, 4H), 1.53–1.72 (m, 4 H), 2.37 (t, 3JACHTUNGTRENNUNG(H,H) =7.1 Hz, 2H), 2.68 (t, 3JACHTUNGTRENNUNG(H,H) = 7.8 Hz, 2 H), 3.38 (s, 3 H), 3.62–3.76 (m, 4 H), 4.45 (s, 2 H), 6.64 (s, 1 H), 7.34 (d,3JACHTUNGTRENNUNG(H,H) =8.2 Hz, 2 H), 7.64 (d,3JACHTUNGTRENNUNG(H,H) =8.5 Hz, 2 H), 7.68 (d,3 J-ACHTUNGTRENNUNG(H,H) =8.2 Hz, 2H), 7.98 ppm (d, 3JACHTUNGTRENNUNG(H,H) =8.5 Hz, 2 H); 13C NMR (100 MHz, CDCl3): d = 13.6, 14.0, 18.9, 22.1, 22.6, 25.8, 30.8, 32.1, 41.3, 58.1, 62.2, 74.5, 82.2, 88.2, 109.3, 123.7, 124.6, 125.1, 127.9, 128.1, 130.2,
131.5, 137.2, 137.8, 147.6, 151.9 ppm; HRMS (FAB+): m/z calcd for
C31H36O2S2: 504.2157 [M +
]; found: 504.2169; elemental analysis: calcd (%) for C31H36O2S2: C 73.77, H 7.19; found: C 73.48, H 7.09.
13: As with the preparation of 9, 12 (504 mg, 1.0 mmol) was treated with nBuLi (0.5 mL, 2.5 m in hexane, 1.1 mmol), followed by 10 (391 mg, 0.8 mmol) and then TFA (0.3 mL, 3.3 mmol) to afford 13 as an orange yellow solid (658 mg, 73 %). M.p.: 70–71 8C; IR (KBr): n˜ = 2954, 2927, 2857, 1666, 1601, 1503, 1465, 1378, 1185, 1101, 933, 839, 807, 670 cm1;
1H NMR (400 MHz, CDCl
3): d = 0.93 (t,3JACHTUNGTRENNUNG(H,H) =7.3 Hz, 3H), 0.96 (t, 3JACHTUNGTRENNUNG(H,H) =7.3 Hz, 3H), 0.97 (t,3JACHTUNGTRENNUNG(H,H) =7.3 Hz, 3H), 0.98 (t,3JACHTUNGTRENNUNG(H,H) = 7.3 Hz, 3 H), 1.38–1.54 (m, 8 H), 1.54–1.64 (m, 2 H), 1.65–1.78 (m, 6 H), 2.38 (t,3JACHTUNGTRENNUNG(H,H) =7.1 Hz, 2 H), 2.64–2.80 (m, 6H), 3.40 (s, 3 H), 3.63–3.76 (m, 4 H), 4.46 (s, 2 H), 6.66 (s, 1 H), 6.68 (s, 1 H), 6.69 (s, 1 H), 7.36 (d,3 J-ACHTUNGTRENNUNG(H,H) =8.1 Hz, 2H), 7.62–7.84 (m, 12H), 8.01 ppm (d,3JACHTUNGTRENNUNG(H,H) =8.6 Hz, 2 H); 13C NMR (100 MHz, CDCl 3): d = 13.6, 14.0, 18.9, 22.1, 22.6, 25.9, 26.0, 30.8, 32.1, 41.3, 58.1, 62.2, 74.5, 82.3, 88.2, 109.5, 109.7, 123.7, 123.8, 124.5, 124.7, 124.9, 125.1, 125.6, 127.9, 128.1, 128.9, 130.2, 130.5, 131.5, 137.2, 137.9, 147.7, 147.8, 147.9, 151.7, 151.8, 151.9 ppm; HRMS (FAB+): m/z calcd for C59H65O4S2: 901.4324 [M++H]; found: 901.4332; elemental analysis: calcd (%) for C59H64O4S2: C 78.63, H 7.16; found: C 78.33, H 6.99.
16: As with the preparation of 9, 11 (2.4 g, 5.0 mmol) was treated with nBuLi (4.1 mL, 2.5 m in hexane, 10.2 mmol), followed by 10 (2.0 g, 4.2 mmol) and then TFA (1.35 mL, 15 mmol) to afford 16 as a yellow-orange solid (2.7 g, 70 %). M.p.: 89–90 8C (Et2O/pentane); IR (KBr): n˜ = 3391, 2955, 2928, 2869, 1610, 1503, 1465, 933, 840, 808, 758, 668 cm1; 1H NMR (400 MHz, CDCl 3): d = 0.95–1.02 (m, 12 H), 1.47–1.50 (m, 8 H), 1.54–1.66 (m, 2 H), 1.70–1.73 (m, 6 H), 2.41 (t, 3JACHTUNGTRENNUNG(H,H) =7.1 Hz, 2H), 2.73–2.75 (m, 6 H), 3.71–3.75 (m, 4 H), 4.71 (s, 2 H), 6.68 (s, 1 H), 6.70 (s, 1 H), 6.71 (s, 1 H), 7.39 (d, 3JACHTUNGTRENNUNG(H,H) =8.6 Hz, 2 H), 7.68–7.80 (m, 12H), 8.02 ppm (d, 3JACHTUNGTRENNUNG(H,H) =8.6 Hz, 2H); 13C NMR (100 MHz, CDCl 3): d = 13.6, 14.0, 18.9, 22.1, 22.6, 25.8, 25.9, 30.8, 32.05, 32.09, 41.3, 62.2, 65.2, 82.2, 88.2, 109.5, 109.7, 123.8, 124.5, 124.7, 124.9, 125.1, 125.5, 127.4, 127.9, 128.9, 130.2, 130.39, 130.43, 131.5, 137.8, 139.8, 147.7, 147.8, 147.9, 151.71, 151.74, 151.9 ppm; HRMS (FAB+ ): m/z calcd for C58H62O4S2: 886.4090 [M+]; found: 886.4098.
15: A solution of 16 (786 mg, 0.89 mmol) in dry DMSO (40 mL) and acetic anhydride (5 mL) was allowed to stand for 3 days at room
temper-ature and then carefully poured into saturated NaHCO3 solution
(200 mL). The mixture was stirred for 1 h and extracted with diethyl
ether (3 N 100 mL). The combined organic extracts were washed with water (3 N 100 mL) and brine (100 mL), dried over MgSO4, and concen-trated to afford 15 as a yellow-orange solid (615 mg, 78 %). M.p.: 88– 89 8C (Et2O/pentane); IR (KBr): n˜ = 2955, 2928, 1697, 1650, 1602, 1504, 1464, 1427, 1164, 1125, 1091, 838 cm1;1H NMR (400 MHz, CDCl 3): d = 0.95–1.01 (m, 12 H), 1.44–1.52 (m, 8 H), 1.58–1.64 (m, 2 H), 1.68–1.72 (m, 6 H), 2.40 (t, 3JACHTUNGTRENNUNG(H,H) =7.1 Hz, 2 H), 2.70–2.77 (m, 6H), 3.71–3.74 (m, 4 H), 6.71 (s, 1 H), 6.73 (s, 1 H), 6.87 (s, 1 H), 7.68 (d,3JACHTUNGTRENNUNG(H,H) =8.5 Hz, 2 H), 7.74–7.82 (m, 8 H), 7.86 (d, 3JACHTUNGTRENNUNG(H,H) = 8.2 Hz, 2H), 7.91 (d, 3 J-ACHTUNGTRENNUNG(H,H) =8.2 Hz, 2H), 8.02 (d,3JACHTUNGTRENNUNG(H,H) =8.5 Hz, 2 H), 10.00 ppm (s, 1 H); 13C NMR (100 MHz, CDCl 3): d = 13.7, 13.96, 13.98, 18.9, 22.1, 22.6, 22.7, 25.7, 25.9, 26.0, 29.7, 30.8, 32.0,32.1, 41.3, 62.1, 82.2, 88.2, 109.6, 110.0, 112.4, 112.6, 123.7, 123.8, 124.7, 124.9, 125.0, 125.1, 125.6, 125.8, 127.9, 129.0, 129.5, 129.8, 130.3, 130.4, 131.5, 134.7, 136.0, 137.8, 147.7, 149.5, 150.4, 151.5, 151.8, 191.5 ppm; HRMS (FAB+): m/z calcd for C
58H60O4S2: 884.3937 [M+
]; found: 884.3933; elemental analysis: calcd (%) for C58H60O4S2: C 78.69, H 6.83; found: C 78.43, H 6.93.
20: As with the preparation of 9, 13 (458 mg, 0.5 mmol) was treated with nBuLi (0.3 mL, 2.5 m in hexane, 0.7 mmol), followed by 15 (360 mg, 0.41 mmol) and then TFA (0.18 mL, 2.0 mmol) to afford 20 as an orange yellow solid (504 mg, 73 %). M.p.: 131–133 8C; IR (KBr): n˜ = 2954, 2928, 2874, 2859, 1503, 933, 839 cm1;1H NMR (400 MHz, CDCl 3): d = 0.92– 1.05 (m, 24 H), 1.40–1.55 (m, 16 H), 1.55–1.66 (m, 2 H), 1.66–1.79 (m, 14 H), 2.40 (t,3JACHTUNGTRENNUNG(H,H) =7.2 Hz, 2H), 2.70–2.85 (m, 14 H), 3.41 (s, 3H), 3.67–3.80 (m, 4 H), 4.48 (s, 2 H), 6.65–6.78 (m, 7 H), 7.37 (d,3JACHTUNGTRENNUNG(H,H) = 8.2 Hz, 2 H), 7.63–7.85 (m, 28 H), 8.01 ppm (d, 3JACHTUNGTRENNUNG(H,H) =8.2 Hz, 2H); 13C NMR (100 MHz, CDCl 3): d = 13.6, 14.0, 18.9, 22.1, 22.7, 25.9, 26.0, 30.8, 32.1, 41.3, 58.1, 62.2, 74.5, 82.2, 88.2, 109.5, 109.7, 123.7, 123.9, 124.5, 124.7, 124.9, 125.1, 125.6, 127.9, 128.1, 128.9, 130.2, 130.4, 131.5, 137.2, 137.8, 147.8, 147.9, 151.8 ppm; HRMS (FAB+ ): m/z calcd for C115H120O8S2: 1692.8425 [M+]; found: 1692.8451.
17 a: As with the preparation of 12, 17 f[9](336 mg, 1.0 mmol) was treated with NaH (60 % dispersion in mineral oil, 121 mg, 3.0 mmol) followed by MeI (0.25 mL, 4.0 mmol) to afford 17 a (335 mg, 92 %) as a light yellow oil. IR (KBr): n˜ = 2927, 2858, 2821, 1616, 1509, 1492, 1456, 1380, 1192, 1100, 967, 934, 844, 819 cm1;1H NMR (400 MHz, CDCl
3): d = 0.94 (t,3 J-ACHTUNGTRENNUNG(H,H) =7.3 Hz, 3H), 1.43 (sext., 3JACHTUNGTRENNUNG(H,H) =7.3 Hz, 2 H), 1.66 (tt, 3 J-ACHTUNGTRENNUNG(H,H) =7.3, 7.6 Hz, 2 H), 2.68 (t,3JACHTUNGTRENNUNG(H,H) =7.6 Hz, 2H), 3.39 (s, 3H), 3.40 (s, 3 H), 4.45 (s, 2 H), 4.48 (s, 2 H), 6.64 (s, 1 H), 7.34 (d,3JACHTUNGTRENNUNG(H,H) =8.3 Hz, 2 H), 7.38 (d, 3JACHTUNGTRENNUNG(H,H) =8.3 Hz, 2H), 7.66 (d, 3JACHTUNGTRENNUNG(H,H) =8.3 Hz, 2H), 7.68 ppm (d, 3JACHTUNGTRENNUNG(H,H) =8.3 Hz, 2H); 13C NMR (100 MHz, CDCl 3): d = 13.9, 22.6, 25.7, 32.1, 58.0, 58.1, 74.5, 109.2, 123.7, 124.1, 125.5, 128.0, 128.1, 130.3, 131.2, 136.7, 137.1, 147.8, 151.8 ppm; HRMS (EI): m/z calcd for C24H28O3: 364.2038; found: 364.2030; elemental analysis: calcd (%) for C24H28O3: C 79.09, H 7.74; found: C 79.03, H 7.53.
17 b: As with the preparation of 12, 17 g[9](51.4 mg, 0.1 mmol) was treat-ed with NaH (60 % dispersion in mineral oil, 12.1 mg, 0.3 mmol) followtreat-ed by MeI (0.025 mL, 0.4 mmol) to afford 17 b (48 mg, 90 %) as a light yellow solid. M.p.: 125–126 8C; IR (KBr): n˜ = 2952, 2925, 2856, 2819, 1613, 1508, 1487, 1456, 1380, 1299, 1190, 1101, 1057, 933, 834, 811 cm1;
1H NMR (400 MHz, CDCl
3): d = 0.96 (t, 3JACHTUNGTRENNUNG(H,H) =7.3 Hz, 6 H), 1.46 (sext.,3JACHTUNGTRENNUNG(H,H) =7.3 Hz, 4H), 1.69 (tt,3JACHTUNGTRENNUNG(H,H) =7.3, 7.8 Hz, 4H), 2.73 (t, 3JACHTUNGTRENNUNG(H,H) =7.8 Hz, 4H), 3.39 (s, 6H), 4.46 (s, 4H), 6.67 (s, 2 H), 7.35 (d,3 J-ACHTUNGTRENNUNG(H,H) =8.1 Hz, 4 H), 7.71 (d,3JACHTUNGTRENNUNG(H,H) =8.1 Hz, 4H), 7.75 ppm (s, 4 H);
13C NMR (100 MHz, CDCl
3): d = 14.0, 22.7, 25.9, 32.1, 58.1, 74.5, 109.4, 123.7, 124.5, 125.4, 128.1, 129.9, 130.2, 137.1, 147.7, 151.8 ppm; HRMS (EI): m/z calcd for C38H42O4: 562.3083; found: 562.3080; elemental analy-sis: calcd (%) for C38H42O4: C 81.10, H 7.52; found: C 80.95, H 7.46. 17 c: As with the preparation of 12, 17 h[ 10b](133 mg, 0.1 mmol) was treat-ed with NaH (60 % dispersion in mineral oil, 12.1 mg, 0.3 mmol) followtreat-ed by MeI (0.025 mL, 0.4 mmol) to afford 17 c (115 mg, 85 %) as a light
yellow solid. M.p.: 141–142 8C;1H NMR (400 MHz, CDCl 3): d = 0.95–1.01 (m, 18 H), 1.44–1.48 (m, 12 H), 1.62–1.74 (m, 12 H), 2.70–2.78 (t, 12 H), 3.39 (s, 6 H), 4.46 (s, 4 H), 6.66 (s, 2 H), 6.70 (s, 2 H), 6.72 (s, 2 H), 7.35 (d, 3JACHTUNGTRENNUNG(H,H) =8.1 Hz, 4H), 7.69–7.79 ppm (m, 24H); 13C NMR (100 MHz, CDCl3): d = 14.0 (d), 22.7 (d), 25.9 (d), 32.1 (d), 58.1, 74.5, 109.5, 109.7, 123.7, 123.8, 124.5, 124.7, 125.4, 125.5, 128.1, 128.9 (d), 129.9, 130.2, 130.4, 137.1, 147.7, 147.8, 151.7 ppm.
17 d: Under an Ar atmosphere, nBuLi (0.21 mL, 2.5 m in hexane, 0.53 mmol) was added in one portion to a solution of 13 (446 mg, 0.49 mmol) in THF (100 mL) at78 8C, and the mixture was stirred for 3 h. A solution of terephthaldehyde (26.8 mg, 0.20 mmol) in THF (10 mL) was then added slowly at the same temperature. The mixture
was stirred for 30 min at 78 8C and allowed to warm to 0 8C slowly.
Then TFA (0.30 mL, 3.3 mmol) was added at 0 8C, and the resulting solu-tion was stirred at 30 8C overnight. The mixture was washed with saturat-ed NaHCO3(3 N 100 mL), dried over MgSO4, and concentrated. Further purification by silica-gel chromatography with hexane/ethyl acetate (10:1) afforded 17 d as an orange yellow solid (81 mg, 23 %). M.p.: 109– 110 8C; IR (KBr): n˜ = 2955, 2928, 2858, 1600, 1504, 1464, 1455, 1379, 1181, 1101, 933, 839, 808 cm1;1H NMR (400 MHz, CDCl 3): d = 1.00 (m, 24 H), 1.50 (m, 16 H), 1.72 (m, 16 H), 2.75 (m, 16 H), 3.41 (s, 6 H), 4.48 (s, 4 H), 6.67 (s, 1 H), 6.71 (s, 1 H), 6.73 (s, 1 H), 6.74 (s, 1 H), 7.37 (d,3JACHTUNGTRENNUNG(H,H) = 8.0 Hz, 4 H), 7.75 ppm (m, 32 H);13C NMR (100 MHz, CDCl 3): d = 14.0, 22.7, 25.9, 26.0, 32.1, 58.1, 74.5, 109.5, 109.7, 123.7, 123.9, 124.5, 124.7, 125.5, 125.6, 128.1, 128.9, 130.0, 130.2, 130.4, 137.2, 147.7, 147.9, 151.8 ppm; HRMS (FAB+ ): m/z calcd for C122H126O10: 1750.9351 [M + + H]; found: 1750.9352.
17 e: Under Ar atmosphere, nBuLi (0.2 mL, 2.5 m in hexane, 0.5 mmol) was added in one portion to a solution of 20 (507 mg, 0.3 mmol) in THF (200 mL) at65 8C, and the mixture was stirred for 90 min. A solution of 5 (53 mg, 0.1 mmol) in THF (10 mL) was then added slowly at the same temperature. The mixture was stirred for 1 h at 65 8C, and allowed to warm slowly to 0 8C. TFA (0.18 mL, 2.0 mmol) was then added at 0 8C, and the resulting solution was stirred at 30 8C overnight, washed with sa-turated NaHCO3(3 N 100 mL), dried over MgSO4, and concentrated. The
resulting residue was recrystallized from CHCl3 to afford 17 e as an
orange yellow solid (288 mg, 77 %). M.p.: 181–182 8C; IR (KBr): n˜ = 2956, 2932, 2870, 2853, 1607, 1503, 1101, 932, 837, 759, 746, 669 cm1; 1H NMR (400 MHz, CDCl 3): d = 0.94–1.07 (m, 54 H), 1.42–1.60 (m, 36 H), 1.63–1.80 (m, 36 H), 2.70–2.85 (m, 36 H), 3.41 (s, 6 H), 4.47 (s, 4 H), 6.60– 6.75 (m, 18 H), 7.36 (d,3JACHTUNGTRENNUNG(H,H) =7.9 Hz, 4 H), 7.68–7.84 ppm (m, 72H); 13C NMR (100 MHz, CDCl 3): d = 13.6, 14.0, 22.7, 26.0, 32.0, 58.0, 74.4, 109.5, 109.6, 123.6, 123.7, 124.6, 125.5, 130.3, 137.1, 147.7, 147.8, 151.7 ppm; MS (MALDI-TOF): m/z calcd for C262H266O20: 3734.9 [M
+ + H]; found: 3735.7.
21: As with the preparation of 4, 18 b (120.2 g, 0.44 mol) was treated with BF3·Et2O (66.4 mL, 0.53 mol) and 1,2-ethanedithiol (37.8 mL, 0.45 mol) to afford 21 as a white solid (62.8 g, 41 %). M.p.: 75–77 8C; IR (KBr): n˜ = 2929, 2857, 1931, 1724, 1607, 1435, 1406, 1277, 1191, 1109, 1019, , 734 cm1;1H NMR (400 MHz, CDCl 3): d = 0.90 (t,3JACHTUNGTRENNUNG(H,H) = 6.8 Hz, 3H), 1.30–1.32 (m, 4 H), 1.41–1.45 (m, 2 H), 1.55–1.60 (m, 2 H), 2.36 (t, 3 J-ACHTUNGTRENNUNG(H,H) =7.1 Hz, 2H), 3.64–3.75 (m, 4H), 3.92 (s, 3H), 8.00 ppm (s, 4H); 13C NMR (100 MHz, CDCl 3): d = 13.9, 19.1, 22.5, 28.4, 28.5, 31.2, 41.4, 52.1, 61.7, 81.7, 88.7, 127.6, 129.3, 129.7, 145.0, 166.6 ppm; HRMS (FAB+): m/z calcd for C
19H25O2S2: 349.1296 [M
++H]; found: 349.1290;
elemental analysis: calcd (%) for C19H24O2S2: C 65.48, H 6.94; found: C 65.71, H 6.77.
22: As with the preparation of 19, 21 (11.6 g, 33.5 mmol) was treated with DIBAL (150.0 mL, 1.0 m in hexane, 150 mmol) to afford 22 as color-less oil (10.5 g, 98 %). IR (KBr): n˜ = 3399, 2954, 2927, 2856, 1902, 1660, 1535, 1503, 1459, 1413, 1372, 1213, 1044, 1016, 812, 750 cm1;1H NMR (400 MHz, CDCl3): d = 0.90 (t,3JACHTUNGTRENNUNG(H,H) = 6.8 Hz, 3 H), 1.30–1.33 (m, 4 H), 1.41–1.45 (m, 2 H), 1.57–1.60 (m, 2 H), 1.65 (t,3JACHTUNGTRENNUNG(H,H) =6.0 Hz, 1H), 2.36 (t,3JACHTUNGTRENNUNG(H,H) =7.1 Hz, 2 H), 3.65–3.73 (m, 4 H), 4.69 (d,3JACHTUNGTRENNUNG(H,H) =6.0 Hz, 2 H), 7.33 (d,3JACHTUNGTRENNUNG(H,H) =8.3 Hz, 2H), 7.94 ppm (d,3JACHTUNGTRENNUNG(H,H) =8.3 Hz, 2H); 13C NMR (100 MHz, CDCl 3): d = 14.0, 19.2, 22.6, 28.6, 31.3, 41.2, 62.0, 65.0, 82.3, 88.2, 126.7, 127.9, 139.0, 140.9 ppm; HRMS (FAB+): m/z calcd for C18H25OS2: 321.1347 [M + +H]; found: 321.1352.
23: As with the preparation of 8, 22 (38.4 g, 0.12 mol) was treated with activated MnO2 (104.3 g, 1.20 mol) to afford 23 as a pale yellow oil (35.1 g, 92 %). IR (KBr): n˜ = 2961, 2927, 2856, 2732, 1702, 1603, 1574,
1463, 1416, 1389, 1301, 1208, 1168, 1017, 813, 755 cm1; 1H NMR
(400 MHz, CDCl3): d = 0.89 (t,3JACHTUNGTRENNUNG(H,H) = 7.0 Hz, 3 H), 1.29–1.32 (m, 4 H), 1.39–1.52 (m, 2 H), 1.56–1.60 (m, 2 H), 2.36 (t, 3JACHTUNGTRENNUNG(H,H) =7.0 Hz, 2H), 3.66–3.74 (m, 4 H), 7.83 (d, 3JACHTUNGTRENNUNG(H,H) = 8.4 Hz, 2 H), 8.10 (d, 3JACHTUNGTRENNUNG(H,H) =
8.3 Hz, 2 H), 10.00 ppm (s, 1 H); 13C NMR (100 MHz, CDCl 3): d = 14.0, 19.1, 22.5, 28.4, 28.6, 31.1, 41.5, 61.7, 81.5, 89.0, 128.3, 129.4, 135.9, 146.8, 191.6 ppm; HRMS (FAB+ ): m/z calcd for C16H23OS2: 319.1190 [M + +H]; found: 319.1183.
24: As with the preparation of 9, 21 (10.4 g, 30.0 mmol) was treated with nBuLi (13.2 mL, 2.5 m in hexane, 33.0 mmol), followed by 8 (7.2 g, 25.0 mmol) and then TFA (5.5 mL, 60.0 mmol) to afford 24 (7.2 g, 53 %) as a pale yellow solid. M.p.: 72–73 8C; IR (KBr): n˜ = 2959, 2932, 2846, 1722, 1611, 1434, 1282, 1110, 670.21 cm1;1H NMR (400 MHz, CDCl 3): d = 0.90 (t, 3JACHTUNGTRENNUNG(H,H) = 6.8 Hz, 3H), 0.95 (t, 3JACHTUNGTRENNUNG(H,H) =7.3 Hz, 3 H), 1.33– 1.34 (m, 4 H), 1.40–1.48 (m, 4 H), 1.57–1.68 (m, 4 H), 2.39 (t,3JACHTUNGTRENNUNG(H,H) = 7.1 Hz, 2 H), 2.70 (t,3JACHTUNGTRENNUNG(H,H) =7.7 Hz, 2 H), 3.68–3.75 (m, 4 H), 3.93 (s, 3 H), 6.80 (s, 1 H), 7.66 (d, 3JACHTUNGTRENNUNG(H,H) =8.4 Hz, 2H), 7.75 (d, 3JACHTUNGTRENNUNG(H,H) = 8.3 Hz, 2 H), 8.01 (d, 3JACHTUNGTRENNUNG(H,H) =8.4 Hz, 2H), 8.05 ppm (d, 3JACHTUNGTRENNUNG(H,H) = 8.3 Hz, 2 H);13C NMR (100 MHz, CDCl 3): d = 13.6, 14.1, 18.9, 22.1, 22.6, 26.0, 29.2, 29.9, 30.7, 31.7, 41.3, 52.0, 62.1, 82.1, 88.3, 111.5, 123.2, 125.0, 125.3, 128.0, 128.3, 130.1, 131.1, 134.7, 138.4, 148.7, 150.9, 166.8 ppm;
HRMS (FAB+): m/z calcd for C
33H39O3S2: 547.2341 [M
++H]; found:
547.2332.
25: As with the preparation of 19, 24 (4.2 g, 7.7 mmol) was treated with DIBAL (23.0 mL, 1.0 m in hexane, 23.0 mmol) to afford 25 (3.7 g, 92 %) as a pale yellow solid. M.p.: 72–73 8C; IR (KBr): n˜ = 3371, 2959, 2927, 2861, 1613, 1502, 1460, 1424, 1010, 851, 804 cm1; 1H NMR (400 MHz, CDCl3): d = 0.91 (t,3JACHTUNGTRENNUNG(H,H) = 7.3 Hz, 3H), 0.95 (t,3JACHTUNGTRENNUNG(H,H) =7.3 Hz, 3H), 1.32–1.34 (m, 4 H), 1.43–1.50 (m, 4 H), 1.56–1.70 (m, 4 H), 2.39 (t, 3 J-ACHTUNGTRENNUNG(H,H) =7.1 Hz, 2H), 2.70 (t,3JACHTUNGTRENNUNG(H,H) =7.8 Hz, 2 H), 3.69–3.75 (m, 4H), 4.71 (d, 3JACHTUNGTRENNUNG(H,H) =5.0 Hz, 2H), 6.64 (s, 1H), 7.39 (d,3JACHTUNGTRENNUNG(H,H) =7.8 Hz, 2 H), 7.65 (d, 3JACHTUNGTRENNUNG(H,H) =8.2 Hz, 2H), 7.71 (d, 3JACHTUNGTRENNUNG(H,H) =8.0 Hz, 2H), 7.99 ppm (d, 3JACHTUNGTRENNUNG(H,H) =8.4 Hz, 2H); 13C NMR (100 MHz, CDCl 3): d = 13.6, 14.0, 18.9, 22.1, 22.6, 26.1, 29.2, 29.9, 30.7, 31.7, 41.3, 62.1, 65.2, 82.2, 88.2, 109.3, 123.8, 124.7, 125.1, 127.4, 127.9, 130.2, 131.4, 137.7, 139.8,
147.5, 151.8 ppm; HRMS (FAB+): m/z calcd for C
32H39O2S2: 519.2391 [M+
+H]; found: 519.2386.
26: As with the preparation of 9, 4 (9.61 g, 30.0 mmol) was treated with nBuLi (13.2 mL, 2.5 m in hexane, 33.0 mmol), followed by 23 (7.9 g, 25.0 mmol) and then TFA (5.5 mL, 60.0 mmol) to afford 26 (6.8 g, 50 %) as a pale yellow solid. M.p.: 63–64 8C; IR (KBr): n˜ = 2955, 2928, 2857, 2734, 1698, 1604, 1308, 1213, 1166, 937, 832, 765, 712 cm1; 1H NMR (400 MHz, CDCl3): d = 0.92 (t,3JACHTUNGTRENNUNG(H,H) =6.8 Hz, 3H), 0.97 (t,3JACHTUNGTRENNUNG(H,H) = 7.3 Hz, 3 H), 1.32–1.35 (m, 4 H), 1.42–1.48 (m, 4 H), 1.59–1.68 (m, 4 H), 2.37 (t, 3JACHTUNGTRENNUNG(H,H) =7.1 Hz, 2H), 2.71 (t,3JACHTUNGTRENNUNG(H,H) =7.8 Hz, 2H), 3.70–3.74 (m, 4 H), 3.93 (s, 3 H), 6.80 (s, 1 H), 7.75 (d,3JACHTUNGTRENNUNG(H,H) =8.4 Hz, 2 H), 7.85 (d,3JACHTUNGTRENNUNG(H,H) =8.5 Hz, 2H), 8.02 (d,3JACHTUNGTRENNUNG(H,H) =8.5 Hz, 2H), 8.05 ppm (d,3 J-ACHTUNGTRENNUNG(H,H) =8.4 Hz, 2 H);13C NMR (100 MHz, CDCl 3): d = 13.9, 14.0, 19.2, 22.5, 22.6, 25.7, 28.6, 31.3, 32.0, 41.3, 52.0, 62.0, 82.1, 88.3, 111.5, 123.2, 124.9, 125.2, 128.0, 128.3, 130.1, 131.1, 134.6, 138.3, 148.7, 150.9, 166.8 ppm; HRMS (FAB+ ): calcd for C33H38O3S2): 547.2338 [M + +H]; found: 547.2341; elemental analysis: calcd (%) for C33H38O3S2: C 72.49, H 7.00; found: C 72.58, H 6.94.
27: As with the preparation of 19, 26 (4.2 g, 7.7 mmol) was treated with DIBAL (23.0 mL, 1.0 m in hexane, 23.0 mmol) to afford 27 (3.6 g, 90 %) as a pale yellow oil. IR (KBr): n˜ = 3450, 2954, 2927, 2857, 1912, 1603, 1504, 1464, 1422, 1378, 1185, 1050, 1015, 934, 844, 808 cm1; 1H NMR (400 MHz, CDCl3): d = 0.91 (t,3JACHTUNGTRENNUNG(H,H) =6.7 Hz, 3H), 0.97 (t,3JACHTUNGTRENNUNG(H,H) = 7.3 Hz, 3 H), 1.32–1.34 (m, 4 H), 1.44–1.48 (m, 4 H), 1.59–1.70 (m, 4 H), 2.38 (t, 3JACHTUNGTRENNUNG(H,H) =7.1 Hz, 2H), 2.70 (t,3JACHTUNGTRENNUNG(H,H) =7.7 Hz, 2H), 3.70–3.75 (m, 4 H), 4.72 (s, 2 H), 6.66 (s, 1 H), 7.39 (d,3JACHTUNGTRENNUNG(H,H) =8.1 Hz, 2 H), 7.66 (d,3JACHTUNGTRENNUNG(H,H) =8.5 Hz, 2H), 7.71 (d,3JACHTUNGTRENNUNG(H,H) =8.1 Hz, 2H), 8.01 ppm (d,3 J-ACHTUNGTRENNUNG(H,H) =8.4 Hz, 2 H);13C NMR (100 MHz, CDCl 3): d = 14.0, 19.2, 22.6, 25.8, 28.6, 31.3, 32.1, 41.3, 62.1, 65.2, 82.2, 88.3, 109.4, 123.9, 124.6, 125.1, 127.4, 127.9, 130.2, 131.5, 137.8, 139.8, 147.6, 151.8 ppm; HRMS (FAB+): m/z calcd for C32H39O2S2: 519.2391 [M + +H]; found: 519.2386.
28: As with the preparation of 8, 25 (3.9 g, 7.7 mmol) was treated with ac-tivated MnO2(6.7 g, 77.1 mmol) to afford 28 (3.6 g, 91 %) as a fluores-cent yellow solid. M.p.: 42–43 8C; IR (KBr): n˜ = 2959, 2932, 2860, 1700, 1606, 1429, 1415, 1168, 834 cm1;1H NMR (400 MHz, CDCl 3): d = 0.88– 0.92 (t, 3JACHTUNGTRENNUNG(H,H) =7.1 Hz, 3H), 0.96 (t,3JACHTUNGTRENNUNG(H,H) =7.1 Hz, 3H), 1.38–1.52 (m, 4 H), 1.53–1.72 (m, 4 H), 2.37 (t,3JACHTUNGTRENNUNG(H,H) =7.1 Hz, 2 H), 2.70 (t,3 J-ACHTUNGTRENNUNG(H,H) =7.8 Hz, 2 H), 3.63–3.76 (m, 4 H), 6.83 (s, 1H), 7.66 (d,3JACHTUNGTRENNUNG(H,H) = 8.2 Hz, 2 H), 7.82 (d, 3JACHTUNGTRENNUNG(H,H) =8.4 Hz, 2H), 7.87 (d, 3JACHTUNGTRENNUNG(H,H) =8.4 Hz, 2 H), 8.01 (d, 3JACHTUNGTRENNUNG(H,H) =8.2 Hz, 2H), 9.97 ppm (s, 1 H); 13C NMR (100 MHz, CDCl3): d = 13.6, 14.1, 18.9, 22.5, 26.1, 29.2, 29.9, 30.7, 31.7, 41.3, 62.0, 82.1, 88.3, 112.4, 123.7, 125.2, 125.3, 128.0, 130.4, 130.9, 134.7, 136.0, 138.5, 149.3, 150.6, 191.5 ppm; HRMS (FAB+ ): m/z calcd for C32H37O2S2: 517.2235 [M ++H]; found: 517.2227.
29: As with the preparation of 12, 27 (1.7 g, 3.2 mmol) was treated with NaH (60 % dispersion in mineral oil, 0.2 g, 4.9 mmol) followed by MeI (0.4 mL, 6.5 mmol) to afford 29 (1.6 g, 92 %) as a light yellow solid. M.p.: 57–58 8C; IR (KBr): n˜ = 2955, 2928, 2857, 2230, 1906, 1597, 1505, 1490, 1465, 1379, 1186, 1101, 930, 847, 808, 709 cm1; 1H NMR (400 MHz, CDCl3): d = 0.92 (t,3JACHTUNGTRENNUNG(H,H) = 6.9 Hz, 3H), 0.98 (t,3JACHTUNGTRENNUNG(H,H) =7.3 Hz, 3H), 1.34–1.35 (m, 4 H), 1.45–1.48 (m, 4 H), 1.60–1.68 (m, 4 H), 2.39 (t, 3 J-ACHTUNGTRENNUNG(H,H) =7.0 Hz, 2H), 2.71 (t,3JACHTUNGTRENNUNG(H,H) =7.9 Hz, 2H), 3.41 (s, 3H), 3.70– 3.75 (m, 4 H), 4.48 (s, 2 H), 6.66 (s, 1 H), 7.36 (d,3JACHTUNGTRENNUNG(H,H) =8.2 Hz, 2 H), 7.66 (d,3JACHTUNGTRENNUNG(H,H) =8.6 Hz, 2H), 7.70 (d,3JACHTUNGTRENNUNG(H,H) =8.2 Hz, 2 H), 8.01 ppm (d, 3JACHTUNGTRENNUNG(H,H) =8.6 Hz, 2 H);13C NMR (100 MHz, CDCl 3): d = 14.0, 19.2, 22.6, 25.8, 28.6, 31.3, 32.1, 41.2, 58.0, 62.1, 74.4, 82.2, 88.2, 109.3, 123.7, 124.6, 125.0, 127.9, 128.1, 130.1, 131.5, 137.2, 137.8, 147.5, 151.9 ppm;
HRMS (FAB+): m/z calcd forC
33H41O2S2: 533.2548 [M++H]; found: 533.2554; elemental analysis: calcd (%) for C33H40O2S2: C 74.39, H 7.57; found: C 74.47, H 7.69.
30: As with the preparation of 8, 27 (2.0 g, 3.9 mmol) was treated with ac-tivated MnO2(3.0 g, 34.5 mmol) to afford 30 as a fluorescent yellow solid (1.8 g, 90 %). M.p.: 62–64 8C; IR (KBr): n˜ = 2953, 2927, 2851, 1698, 1603, 1433, 1213, 1165, 833 cm1;1H NMR (400 MHz, CDCl 3): d = 0.91 (t, 3 J-ACHTUNGTRENNUNG(H,H) =6.9 Hz, 3H), 0.96 (t,3JACHTUNGTRENNUNG(H,H) =7.3 Hz, 3H), 1.34 (m, 4H), 1.47 (m, 4 H), 1.61 (m, 2 H), 1.68 (m, 2 H), 2.39 (t,3JACHTUNGTRENNUNG(H,H) =7.1 Hz, 2 H), 2.72 (t,3JACHTUNGTRENNUNG(H,H) =7.9 Hz, 2H), 3.72 (m, 4 H), 6.86 (s, 1 H), 7.68 (d,3JACHTUNGTRENNUNG(H,H) = 8.6 Hz, 2 H), 7.84 (d, 3JACHTUNGTRENNUNG(H,H) =8.2 Hz, 2H), 7.90 (d, 3JACHTUNGTRENNUNG(H,H) =8.2 Hz, 2 H), 8.03 (d, 3JACHTUNGTRENNUNG(H,H) =8.6 Hz, 2H), 9.99 ppm (s, 1 H); 13C NMR (100 MHz, CDCl3): d = 14.0 (d), 19.2, 22.6 (d), 25.7, 28.6 (d), 31.3, 32.1, 41.3, 62.1, 82.2, 88.4, 112.4, 123.7, 125.1, 125.4, 128.0, 130.4, 131.0, 134.7,
136.0, 138.6, 149.3, 150.6, 191.5 ppm; HRMS (FAB+): m/z calcd for
C32H37O2S2: 517.2235 [M +
+H]; found: 517.2227; elemental analysis: calcd (%) for C32H36O2S2: C 74.38, H 7.02; found: C 74.73, H 7.05. 31: As with the preparation of 9, 29 (532 mg, 1.00 mmol) was treated with nBuLi (0.44 mL, 2.5 m in hexane, 1.1 mmol), followed by 28 (413 mg, 0.80 mmol) and then TFA (0.30 mL, 3.3 mmol) to afford 31 as an orange yellow solid (376 mg, 49.2 %). M.p.: 63–64 8C; IR (KBr): n˜ = 2959, 2933, 2861, 2361, 1560, 1543, 1508 cm1;1H NMR (400 MHz, CDCl 3): d = 0.85– 1.03 (m, 12 H), 1.30–1.38 (m, 8 H), 1.45–1.54 (m, 8 H), 1.59–1.79 (m, 8 H), 2.40 (t,3JACHTUNGTRENNUNG(H,H) =7.2 Hz, 2 H), 2.69–2.82 (m, 6H), 3.41 (s, 3 H), 3.65–3.80 (m, 4 H), 4.49 (s, 2 H), 6.68 (s, 1 H), 6.71 (s, 1 H), 6.73 (s, 1 H), 7.37 (d,3 J-ACHTUNGTRENNUNG(H,H) =7.9 Hz, 2H), 7.67–7.84 (m, 12H), 8.02 ppm (d,3JACHTUNGTRENNUNG(H,H) =8.4 Hz, 2 H); 13C NMR (100 MHz, CDCl 3): d = 14.0, 14.1, 19.3, 22.6, 22.7, 25.9, 26.0, 26.3, 28.6, 28.7, 29.3, 29.9, 30.9, 31.3, 31.8, 32.1, 32.2, 41.3, 58.1, 62.2, 74.5, 82.3, 88.3, 109.5, 109.7, 123.7, 123.8, 124.5, 124.8, 124.9, 125.1, 125.6, 127.9, 128.1, 128.9, 130.2, 130.4, 131.5, 137.2, 137.8, 147.6, 147.7, 147.8,
151.7, 151.8, 151.9 ppm; HRMS (FAB+): m/z calcd for C
63H72O4S2: 956.4872 [M+]; found: 956.4874.
32: As with the preparation of 9, 29 (532 mg, 1 mmol) was treated with BuLi (0.44 mL, 2.5 m in hexane, 1.1 mmol), followed by 30 (413 mg, 0.80 mmol) and then TFA (0.30 mL, 3.3 mmol) to afford 32 as an orange yellow solid (522 mg, 68 %). M.p.: 107–109 8C; IR (KBr): n˜ = 2955, 2928, 2857, 1906, 1660, 1601, 1504, 1465, 1380, 1192, 1102, 930, 840, 809 cm1; 1H NMR (400 MHz, CDCl 3): d = 0.92 (t,3JACHTUNGTRENNUNG(H,H) =6.0 Hz, 6H), 0.99 (t, 3JACHTUNGTRENNUNG(H,H) =7.4 Hz, 6H), 1.35 (m, 8H), 1.45 (m, 8 H), 1.60 (m, 2H), 1.72 (m, 6 H), 2.39 (t,3JACHTUNGTRENNUNG(H,H) =7.1 Hz, 2 H), 2.75 (m, 6 H), 3.41 (s, 3H), 3.72 (m, 4 H), 4.48 (s, 2 H), 6.68 (s, 1 H), 6.70 (s, 2 H), 6.71 (ds, 2 H), 7.37 (d,3 J-ACHTUNGTRENNUNG(H,H) =8.2 Hz, 2H), 7.68–7.81 (m, 12H), 8.02 ppm (d,3JACHTUNGTRENNUNG(H,H) =8.6 Hz, 2 H);13C NMR (100 MHz, CDCl 3): d = 14.0 (d), 14.1, 19.2, 22.6 (d), 25.9 (d), 26.3, 28.6 (d), 29.3, 29.9, 31.3, 31.7, 32.1 (d), 41.3, 58.1, 62.2, 74.5, 82.3, 88.3, 109.5, 109.6, 123.7, 123.8, 124.5, 124.7, 124.8, 125.0, 125.5, 127.9, 128.1, 128.9, 130.2, 130.4, 131.5, 137.1, 137.8, 147.7 (d), 147.8, 151.7, 151.8, 151.9 ppm; HRMS (FAB+ ): m/z calcd for C563H72O4S2: 956.4872
[M+
+H]; found: 956.4863; elemental analysis: calcd (%) for C59H64O4S2: C 79.04, H 7.58; found: C 78.50, H 7.55.
33: As with the preparation of 9, 31 (287 mg, 0.30 mmol) was treated with nBuLi (0.20 mL, 2.5 m in hexane, 0.5 mmol), followed by terephthal-dehyde (13.4 mg, 0.10 mmol) and then TFA (0.18 mL, 2.0 mmol) to afford 33 as an orange yellow solid (84 mg, 45 %). M.p.: 80–81 8C; IR (KBr): n˜ = 2966, 2933, 2860, 1603, 1514, 934, 840, 811 cm1; 1H NMR (400 MHz, CDCl3): d = 0.92–1.04 (m, 24 H), 1.28–1.40 (m, 16 H), 1.40–1.54 (m, 16 H), 1.67–1.82 (m, 16 H), 2.63–2.83 (m, 16 H), 3.41 (s, 6 H), 4.48 (s, 4 H), 6.68–6.74 (m, 8 H), 7.37 (d, 3JACHTUNGTRENNUNG(H,H) =8.1 Hz, 4H), 7.71–7.87 ppm (m, 32 H);13C NMR (100 MHz, CDCl 3): d = 13.7, 14.0, 22.0, 22.7, 26.0, 26.3, 29.3, 29.9, 31.8, 32.1, 58.1, 74.5, 109.5, 109.7, 123.7, 123.9, 124.5, 124.8., 125.1, 125.6, 128.2, 128.9, 130.0, 130.2, 130.4, 137.1, 147.7, 147.9,
151.8 ppm; HRMS (FAB+): m/z calcd for C
130H142O10: 1863.0603 [M+]; found: 1863.0618.
34: As with the preparation of 9, 32 (547 mg, 0.57 mmol) was treated with nBuLi (0.25 mL, 2.5 m in hexane, 0.63 mmol), followed by 5 (106 mg, 0.20 mmol) and then TFA (0.18 mL, 2.0 mmol) to afford 34 as an orange yellow solid (300 mg, 66 %). M.p.: 165–166 8C; IR (KBr): n˜ = 2956, 2929, 2870, 1660, 1600, 1503, 1465, 1415, 1379, 1262, 1217, 1180, 1101, 933, 839, 809, 756 cm1;1H NMR (400 MHz, CDCl 3): d = 0.93 (m, 12 H), 1.00 (m, 18 H), 1.37 (m, 16 H), 1.47 (m, 20 H), 1.72 (m, 20 H), 2.75 (m, 20 H), 2.75 (m, 6 H), 3.41 (s, 6 H), 4.48 (s, 4 H), 6.70 (m, 10 H), 6.70 (s, 1 H), 6.71 (s, 1 H), 7.37 (d,3JACHTUNGTRENNUNG(H,H) =8.2 Hz, 2H), 7.68–7.81 (m, 12 H), 8.02 ppm (d,3 J-ACHTUNGTRENNUNG(H,H) =8.6 Hz, 2 H);13C NMR (100 MHz, CDCl 3): d = 14.0, 14.1, 22.7, 26.0 (d), 26.3, 29.3, 29.9, 31.7, 32.1 (d), 58.1, 74.5, 109.5, 109.7, 123.7, 123.8, 124.5, 124.7 (d), 125.4, 125.5, 128.1, 128.9, 129.9, 130.2, 130.4, 137.1, 147.7, 147.8, 151.8 ppm; HRMS (FAB+ ): m/z calcd for C158H170O12: 2259.2692 [M++H]; found: 2259.2637. Electrochemical Measurements
A conventional three-electrode system with a potentiostat/galvanostat (EG&G PAR 273 A) was employed for electrochemical experiments. The working electrode is a Pt disc with a diameter of 3 mm, the reference electrode is Ag/Ag+
(10 mm AgNO3), and a Pt wire was used as the
counter electrode. Samples were dissolved in CH2Cl2containing tetrabu-tylammonium hexafluorophosphate (0.1 m) as the electrolyte, and the sol-utions were purged with Ar for at least 15 min before electrochemical ex-periments.
Photophysical Measurements
Absorption and emission spectra were measured with a Hitachi U-3310 spectrometer and a Hitachi F-4500 fluorescence spectrometer, respective-ly. Spectrometric-grade solvents and quartz cells (1 N 1 cm2) were used.
The molar concentration of the sample solution was about 105
m. The fluorescence quantum yields were obtained by using the Parker–Reas method.[12]The quantum yield of the oligomers was calculated by Equa-tion (1), in which F is the quantum yield, I is the integrated intensity, A is the absorbance at the excitation wavelength, and n is the refractive index. The subscripts f and ref refer to the oligomers and coumarin 1 (Fref=0.99 in EtOAc), respectively.
Ff¼ Fref ðIf=IrefÞ ðAref=AfÞ ðnf=nrefÞ2 ð1Þ
Acknowledgements
This work is supported by the National Science Council of the Republic of China.
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![Table 1. Photophysical and electrochemical parameters of benzene–furan oligomers. [a] n [b] l max [nm] l em (F f )[nm] E 00 [eV] E p 1 = 2 [c][mV] HOMO[eV] LUMO[eV] 17 a 12 328 364, 383, 404 (0.88) 3.47 622 5.36 1.89 17 b 20 376 420, 446, 475 (0.84) 3.0](https://thumb-ap.123doks.com/thumbv2/9libinfo/8678411.196875/5.892.92.800.99.578/table-photophysical-electrochemical-parameters-benzene-furan-oligomers-lumo.webp)
