Novel, yellow-emitting anthracene/fluorene oligomers: synthesis and characterization

Article abstract of DOI:10.1016/j.tet.2007.05.095

A novel series of highly soluble and strongly yellow fluorescent with well-controlled, alternative anthracene, and fluorene units were successfully synthesized by a Pd/Cu-catalyzed Sonogashira coupling reaction and characterized. Their thermal stabilities

Full text of DOI:10.1016/j.tet.2007.05.095

Tetrahedron 63 (2007) 7809–7815
Novel, yellow-emitting anthracene/fluorene oligomers:
synthesis and characterization
*
Zujin Zhao, Shuqiang Yu, Lei Xu, Hongbo Wang and Ping Lu
Department of Chemistry, Zhejiang University, Hangzhou 310027, PR China
Received 5 February 2007; revised 24 May 2007; accepted 25 May 2007
Available online 2 June 2007
Abstract—A novel series of highly soluble and strongly yellow fluorescent with well-controlled, alternative anthracene, and fluorene units
were successfully synthesized by a Pd/Cu-catalyzed Sonogashira coupling reaction and characterized. Their thermal stabilities, electrochem-
ical behaviors, and photophysical properties were investigated. These oligomers might be used as models to study structure–property relation-
ship for their corresponding polymers and applied in optoelectronics devices as materials themselves.
Ó 2007 Elsevier Ltd. All rights reserved.
1. Introduction
Both fluorene and anthracene are well-known blue fluoro-
phores and their derivatives have been widely used as
emitting materials or else. Though random poly(fluorene-
co-anthracene)s have been reported,11 to the best of our
knowledge, few oligomers or polymers based on well-
controlled alternative fluorene and anthracene structures
are reported. Therefore, in this paper, we would like to report
the synthesis and characterization of a series of monodis-
perse, ethynylene-linked oligomers with well-defined, alter-
native fluorene and anthracene structures. These oligomers
could be used as models to study structure–property relation-
ship for their corresponding polymers or be applied in opto-
electronic devices as materials themselves.
Conjugated oligomers have triggered intense investigations
from both academic and industrial laboratories1 due to their
promising applications, such as light-emitting diodes
(OLEDs),2 solar cells,3 field-effect transistors (FETs),4 and
models5 to understand the structure–property relationships
of their analogous polydisperse polymers. In contrast to
polymers, monodisperse conjugated oligomers are charac-
terized by a well-defined and uniform molecular structure
as well as superior chemical purity, which would offer im-
proved stability and sharper emission bands.6 Development
of synthetic methodology makes it possible to design a vari-
ety of soluble monodisperse oligomers, which permit color
and charge injection tunable through the conjugation length
control, as well as the introduction of functional groups to
the parent p-conjugated system.7 For example, palladium-
catalyzed cross-coupling reaction of terminal alkynes with
arylhalides (the Sonogashira reaction) provides an efficient
and versatile tool to extend p–p conjugation in organic
compounds, affording simplified molecular structures com-
pared with their alkene analogues due to the lack of Z/E
isomerism of the double bonds.8 And many ethynylene-
linked oligomers of special properties have been designed
and synthesized.9 To these ethynylene-extended arenes and
heteroarenes, it has been proved to be of the function as
nanoscale ‘molecular wires’, with the extent of intramolec-
ular conjugation dependent upon the topology of the p-
system and the molecular length.10
2. Results and discussion
A Pd/Cu-catalyzed Sonogashira coupling reaction was used
as a key reaction to build ethylnylene-linked molecules.
Synthetic approach of necessary intermediates are outlined
in Scheme 1. Our strategy to the target molecules started
from 9-iodo-anthracene (1) and 9,10-diiodo-anthracene
(4). Pd/Cu-catalyzed coupling of 1 and 3-methyl-1-butyn-
3-ol provided 2, which was followed by a base-promoted de-
protection to afford 9-ethynyl-anthracene (3) in 85% total
yield. Similar procedures were performed from 4 to obtain
9,10-diethynyl-anthracene (6) in 64% total yield. Treatment
of 3 with 3 equiv of 2,7-diiodo-9,9-diheptyl-9H-fluorene
(7)12 in the presence of CuI, Pd(PPh3)2Cl2, Ph3P, and NEt3
afforded intermediate 8 in 84% yield after separation by col-
umn chromatography. Compound 8 was then converted to 10
in 78% total yield after cross-coupling and deprotection pro-
cedure. Compound 10 reacted with 3 equiv of 4 in the pres-
ence of Pd/Cu catalyst to afford 11 in 66% yield. Analogous
* Corresponding author. Tel.: +86 571 879 52543; e-mail: pinglu@zju.
edu.cn
0040–4020/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2007.05.095

7810
Z. Zhao et al. / Tetrahedron 63 (2007) 7809–7815
a
b
a
b
I
OH
I
I
HO
OH
OH
1
3
5
2
4
6
a
b
c
I
I
I
+
C7H15
C7H15
C7H15 C7H15
10
C7H15
C7H15
C7H15
C7H15
3
7
8
9
a
4
b
I
OH
c
C7H15 C7H15
13
C7H15
C7H15
C7H15
11
C7H15
12
7
c
I
C7H15
C7H15
C7H15
C7H15
14
Scheme 1. (a) 3-Methyl-1-butyn-3-ol, CuI, Pd(PPh3)2Cl2, Ph3P, NEt3, N2, reflux; (b) KOH, 2-propanol, reflux; and (c) CuI, Pd(PPh3)2Cl2, Ph3P, NEt3, N2, reflux.
procedures were performed step by step to get intermediate
14 from 11 in 28% total yield.
all of these synthesized compounds exhibited excellent sol-
ubility in common organic solvents, such as CH2Cl2, CHCl3,
THF, and toluene. This is helpful for easier preparation and
purification in the synthetic procedure leading to the suffi-
ciently long rod length as well as easier fabrication in the
procedures of optoelectronic device preparation.
In order to facilitate the synthesis of longer oligomers, we
tried to gain compound 18, which could serve as a core of
oligomers with longer molecular length after a bicoupling
with monoiodide (Scheme 2). Coupling of 9,10-diiodo-
anthracene (4) with an equal amount of 3-methyl-1-butyn-
3-ol yielded compound 15 in 72% yield, which was followed
by a further coupling with 1613 giving compound 17 in 65%
yield. Compound 18 was produced by the final base-
promoted deprotection of 17, which was indicated by thin
layer chromatography. However, it was hard to be isolated
because it was unstable when exposed to air in solid states.
It was destroyed quickly when we run column chromato-
graphy. In fact, we found that compounds 6 and 13 were
also unstable, especially for compound 6.
Thermal properties of these oligomers were examined
through differential scanning calorimetric (DSC) and ther-
mogravimetric analysis (TGA) in N2 at a heating rate of
10 ꢀC/min, and these results are listed in Table 1. The de-
composition temperatures (Tds) of these oligomers were in
the range of 386–426 ꢀC, with 5% loss of initial weight,
while their melting points were not detected. And the glass
transition temperatures (Tgs) of oligomer DAF, TADF,
TATF, and PATF were 101, 115, 119, and 122 ꢀC, respec-
tively, which gradually increased as the main chain length
increased.
The final couplings of anthracene/fluorene oligomers are il-
lustrated in Scheme 3. DAF and TATF were obtained in 89,
and 78% yields by treating 16 with 2 equiv of 1 and 11, re-
spectively, in the presence of CuI, Pd(PPh3)2Cl2, Ph3P, and
NEt3. TADF and PATF were obtained in 55 and 38% yields
by treating newly prepared 6 with 2 equiv of 8 and 14, re-
spectively, under the same conditions. Moreover, an addi-
tional oligomer TATFC was synthesized (48% yield) by
coupling intermediate 14 with 3,6-diethynyl-9-p-tolyl-9H-
carbazole (19)14 under the same conditions. The existence
of 3,6-substituted carbazole core introduced a V shape to
the molecule. All the final oligomers were characterized
by NMR and element analysis. However, their mass spectra
could not be detected by MALDI-TOF mass spectroscopy.
All of the oligomers as well as intermediates were solid.
Due to the presence of the flexible n-heptyl substituents,
Electrochemical properties of oligomers were analyzed by
cyclic voltammetry (CV) in the CH2Cl2 in the presence of
0.1 M Bu4NPF6 as supporting electrolyte. The results are
listed in Table 1. Oligomers exhibited irreversible oxidation
peaks that shift positively from 1.22 to 1.69 V with the incre-
ment of the oligomer length. On the basis of the onset poten-
tial for the oxidation and the band gap determined from the
optical absorption threshold, the HOMO and LUMO energy
levels of oligomers were calculated in the range of ꢁ5.43 to
ꢁ5.61 eV and ꢁ2.76 to ꢁ3.29 eV (Table 1), respectively,
with a steady increment as the anthracene unit accumulated.
The photophysical properties of oligomers were examined
by UV–vis and photoluminescence (PL) spectroscopy in di-
lute CH2Cl2 solutions and the results are listed in Table 1.
16
a
b
C7H15
C7H15
I
I
I
OH
HO
OH
a
C7H15 C7H15
18
C7H15
C7H15
15
4
17
Scheme 2. (a) 3-Methyl-1-butyn-3-ol, CuI, Pd(PPh3)2Cl2, Ph3P, NEt3, N2, reflux and (b) KOH, 2-propanol, reflux.

Z. Zhao et al. / Tetrahedron 63 (2007) 7809–7815
7811
1
c
DAF
C7H15
C7H15
C7H15
C7H15
C7H15 C7H15
C7H15
C7H15
C7H15
16
8
c
TADF
C7H15
C7H15
6
11
c
TATF
C7H15
C7H15
16
C7H15
C7H15
C7H15
C7H15
14
c
PATF
C7H15
C7H15
C7H15
C7H15
C7H15
C7H15
C7H15
6
N
19
C7H15
C7H15
C7H15
C7H15
14
c
C7H15
C7H15
C7H15
C7H15
N
TATFC
Scheme 3. (c) CuI, Pd(PPh3)2Cl2, Ph3P, NEt3, N2, reflux.
The UV–vis absorption and PL spectra of oligomers in solu-
tions are presented in Figure 1. DAF exhibited a maximum
absorption peak at 446 nm, while those oligomers with
9,10-diethynyl-anthracene-linked sub-structure (TADF,
TATF, PATF, and TATFC) exhibited strongly red-shifted
maximum absorption peaks in the range of 501–512 nm.
Similar phenomena were also observed for those emission
spectra. DAF emitted blue light with a main peak at
460 nm, while TADF, TATF, and PATF emitted bright yel-
low light with main peaks at 518, 524, and 528 nm, respec-
tively, with a wavelength slightly red-shifted as the
molecular size increased. However, TATFC exhibited a
main emission peak at 517 nm, which was almost identical
to that of TADF. This should be due to their similar efficient
conjugation length12,15 of both oligomers. Large red shifts in
both absorption and emission could be attributed to the intro-
duction of 9,10-diethynyl-anthracene. Moreover, relative
short Stokes’ shifts (14–17 nm) for these oligomers in
CH2Cl2 solutions were observed, which indicated little
loss of energy. The fluorescence quantum yields of these
oligomers were measured in degassed cyclohexane using
the standard 9,10-diphenylanthrecene (F¼0.95 in cyclohex-
ane)16 for DAF and 9,10-bis(phenylethynyl)anthracene
(F¼1.0 in cyclohexane)17 for the other oligomers. DAF ex-
hibited comparable higher quantum yield (0.72) than those
of the other three oligomers (0.56–0.68). Quantum yields
Table 1. Optical, thermal, and electrochemical properties of compounds
Abs.a (nm)
Em. (nm)
CH2Cl2 Film
Fb
Stokes’ shift
(nm)
fwhmc
(nm)
Eg
E
onset
HOMO/LUMOf
(eV)
Tg/Td
d
ox
e
g
CH2Cl2
Film
(eV)
(V)
(ꢀC)
DAF
446
501
507
512
502
447
502
509
513
506
460 (486)
518 (550)
524 (557)
528 (560)
517 (550)
474
0.72
0.61
0.59
0.56
0.68
14
17
17
16
15
18
25
24
22
24
2.67
2.35
2.33
2.31
2.35
1.03
1.08
1.12
1.21
1.05
ꢁ5.43/ꢁ2.76
ꢁ5.48/ꢁ3.13
ꢁ5.52/ꢁ3.19
ꢁ5.61/ꢁ3.29
ꢁ5.45/ꢁ3.10
101/386
115/410
119/421
122/426
126/424
TADF
TATF
PATF
TATFC
(525) 555
(539) 560
(543) 570
(530) 564
Maximum absorption wavelength in dilute CH2Cl2 solutions (w10ꢁ6 M).
Measured in cyclohexane solutions.
a
b
c
d
e
f
Full width at half emission maximum in dilute CH2Cl2 solutions (w10ꢁ6 M).
Determined from UV–vis absorption spectra.
ox
onset
E
¼onset oxidation potential; potentials versus Ag/AgCl, working electrode Pt, 0.1 M Bu4NPF6–CH2Cl2, scan rate 100 mV/s.
ox
onset
HOMO¼E
+4.4 eV; LUMO¼HOMOꢁEg eV.
g
Measured by DSC analysis and TGA analysis in N2 at a heating rate of 10 ꢀC/min.

7812
Z. Zhao et al. / Tetrahedron 63 (2007) 7809–7815
(a)
(b) 1.0
DAF
DAF
TADF
TATF
PATF
TATFC
1.0
0.8
0.6
0.4
0.2
0.0
TADF
0.8
TATF
PATF
0.6
TATFC
0.4
0.2
0.0
400
450
500
550
600
450
500
550
600
650
Wavelength (nm)
Wavelength (nm)
Figure 1. UV–vis absorption (a) and PL (b) spectra of oligomers in CH2Cl2 solutions.
of these oligomers became lower with the insertion of 9,10-
diethynyl-anthracene moieties.
and TATFC exhibited main emission bands in the range of
555–570 nm. Figure 2 displays the absorption and PL spec-
tra of TATF in thin neat films as an example. The emissions
in solid states were red-shifted with respect to those in solu-
tions, which was ascribed to the enhanced molecular interac-
tion in solid states. The morphological property of TATF
film was investigated by atomic force microscopy (AFM).
The one-layer film of TATF spin-coated on SiO2/Si was
measured. The large square image (2.00ꢂ2.00 mm) showed
that the film was uniform (left in Fig. 3). And the height be-
tween the highest and the deepest parts of the film was
roughly 2 nm (right in Fig. 3).
In thin neat films, absorption spectra were almost identical to
those in CH2Cl2 solutions but with a slight bathochromical
shift (1–2 nm), which indicated that these compounds ex-
hibited very similar conformations in both solution and solid
states. In the case of emission spectra in neat films, DAF ex-
hibited an emission band at 474 nm. TADF, TATF, PATF,
1.0
0.8
0.6
0.4
0.2
0.0
1.0
0.8
0.6
0.4
0.2
0.0
3. Conclusions
In summary, we had successfully synthesized and fully char-
acterized a series of novel oligomers with well-controlled,
alternative anthracene, and fluorene structure. Yellow emis-
sion as well as high quantum yields could be approached by
incorporating 9,10-diethynyl-anthracene into the molecular
backbone. These synthesized compounds might be used as
models to study structure–property relationship for their cor-
responding polymers or applied in optoelectronic devices di-
rectly. Further study will be focused on their applications in
devices.
400
450
500
550
600
650
Wavelength (nm)
Figure 2. Absorption and PL spectra of TATF in neat film.
Figure 3. Atomic force microscopy (AFM) image of TATF film spin-coated on SiO2/Si.

Z. Zhao et al. / Tetrahedron 63 (2007) 7809–7815
7813
1
4. Experimental
4.1. General information
4.1.1.3. Compound 14. Yield 52%. H NMR d CDCl3:
0.67 (br, 4H), 0.75–0.82 (m, 16H), 1.10–1.20 (m, 32H),
1.98–2.04 (m, 4H), 2.12–2.16 (m, 4H), 7.49 (d, 1H, J¼
8.0 Hz), 7.55 (t, 2H, J¼7.0 Hz), 7.65 (t, 2H, J¼7.5 Hz),
7.71–7.78 (m, 11H), 7.82 (d, 4H, J¼4.0 Hz), 8.05 (d, 2H,
J¼8.0 Hz), 8.46 (s, 1H), 8.74 (d, 2H, J¼9.0 Hz), 8.78–
8.81 (m, 4H) ppm; 13C NMR d CDCl3: 14.31, 22.84, 23.98,
24.09, 29.18, 29.22, 29.26, 30.17, 30.26, 32.03, 32.06, 40.50,
40.70, 55.80, 55.81, 87.14, 87.32, 87.37, 93.56, 104.00,
117.68, 118.78, 118.87, 120.25, 120.50, 122.03, 122.44,
122.58, 122.80, 126.00, 126.04, 126.13, 126.89, 127.13,
127.62, 127.64. 127.98, 129.02, 131.29, 131.33, 131.54,
132.44, 132.91, 136.33, 140.31, 141.15, 141.47, 151.69,
151.72, 153.73 ppm; MS (MALDI) (m/z): 1272.8 (M+).
1H and 13C NMR spectra were obtained on a Bruker
AVANCE DMX500 spectrometer operating in the FT
mode. Five percent w/v solutions in chloroform-d were
used to obtain NMR spectra. TMS was used as an internal
standard. IonSpec HiResMALDI was used to obtain mass
spectra. Fluorescence measurements were made with a
RF-5301pc spectrofluorometer (Shimadzu, Kyoto, Japan)
equipped with a xenon lamp. UV–vis absorption spectra
were recorded on Shimadzu UV-2450 spectrophotometer.
NETZSCH STA 409 PG/PC was used to measure the ther-
mal performances of the compounds. Cyclic voltammetric
measurements were performed with CHI660A electrochem-
ical workstation, using Pt working electrode, an auxiliary Pt
electrode, and an Ag/AgCl reference electrode. The solvents
were distilled before use. Commercially available reagents
were used without further purification unless otherwise.
4.1.1.4. Compound DAF. Yield 89%. 1H NMR d CDCl3:
0.75–0.80 (m, 10H), 1.12–1.20 (m, 16H), 2.12–2.15 (m, 4H),
7.54 (t, 4H, J¼7.5 Hz), 7.65 (t, 4H, J¼7.5 Hz), 7.74 (s, 2H),
7.81 (br, 4H), 8.05 (d, 4H, J¼8.5 Hz), 8.46 (s, 2H), 8.74 (d,
4H, J¼9.0 Hz) ppm; 13C NMR d CDCl3: 14.30, 22.84,
24.07, 29.25, 30.26, 32.06, 40.70, 55.78, 87.06, 102.16,
120.44, 122.69, 126.00, 126.13, 126.89, 127.12, 127.95,
129.02, 131.26, 131.55, 132.91, 141.23, 151.66 ppm. IR
(KBr): 2189.6 cmꢁ1 (C^C stretch). Anal. calcd for C59H54:
C, 92.87; H, 7.13. Found: C, 92.88; H, 7.10.
4.1.1. General procedure for the synthesis of the com-
pounds (8, 11, 14, DAF, TADF, TATF, PATF, and TATFC).
These compounds were obtained following an essentially
similar procedure. The mass spectra of DAF, TADF,
TATF, PATF, and TATFC could not be detected using
IonSpec HiResMALDI. An illustrative example was pro-
vided for 8.
4.1.1.5. Compound TADF. Yield 55%. 1H NMR d
CDCl3: 0.76–0.81 (m, 20H), 1.12–1.21 (m, 32H), 2.13–
2.16 (m, 8H), 7.55 (t, 4H, J¼7.5 Hz), 7.65 (t, 4H, J¼
7.5 Hz), 7.72–7.74 (m, 4H), 7.76 (d, 4H, J¼5.0 Hz), 7.83
(d, 8H, J¼5.0 Hz), 8.05 (d, 4H, J¼9.5 Hz), 8.46 (s, 2H),
8.74 (d, 4H, J¼9.0 Hz), 8.80–8.82 (m, 4H) ppm; 13C NMR
d CDCl3: 14.31, 22.85, 24.09, 29.26, 30.27, 32.07, 40.71,
55.79, 87.13, 87.40, 102.14, 104.00, 117.67, 118.85, 120.50,
122.46, 122.80, 126.01, 126.13, 126.15, 126.90, 127.11,
127.15, 127.16, 127.98, 129.03, 131.69, 131.34, 131.54,
132.45, 132.91, 141.15, 141.47, 151.70, 151.72 ppm. IR
(KBr): 2185.4 cmꢁ1 (C^C stretch). Anal. calcd for
C98H86: C, 93.14; H, 6.86. Found: C, 93.10; H, 6.88.
4.1.1.1. Compound 8. Compounds 3 (2 g, 0.01 mol), 7
(19 g, 0.03 mol), cuprous iodide (0.1 g, 5 mmol), dichloro-
bis(triphenylphosphine)palladium(II) (0.035 g, 0.05 mmol),
triphenylphosphine (0.05 g, 0.2 mmol), dry triethylamine
(300 mL) were placed in a 500-mL round bottle flask equip-
ped with a Teflon covered magnetic stir bar. After the solu-
tion was purged with nitrogen for half an hour, it was
refluxed under nitrogen for 4 h. The reaction mixture was fil-
tered and the filtrate was evaporated under reduced pressure.
The residue was purified through column chromatography.
1
In this way, 5.5 g (80% yield) of 8 was obtained. H NMR
d CDCl3: 0.66 (br, 4H), 0.80 (t, 6H, J¼7.0 Hz), 1.08 (br,
12H), 1.17–1.19 (m, 4H), 1.97–2.04 (m, 4H), 7.47 (d, 1H, J¼
8.0 Hz), 7.53 (t, 2H, J¼7.5 Hz), 7.63 (t, 2H, J¼7.5 Hz),
7.68–7.77 (m, 5H), 8.03 (d, 2H, J¼8.5 Hz), 8.44 (s, 1H),
8.71 (d, 2H, J¼7.5 Hz) ppm; 13C NMR d CDCl3: 14.31,
22.82, 23.96, 29.18, 30.15, 32.02, 40.49, 55.77, 86.98, 93.44,
101.98, 117.61, 120.18, 121.97, 122.77, 125.97, 126.87,
127.06, 127.95, 129.00, 131.21, 131.49, 132.38, 132.86,
136.28, 140.34, 140.83, 150.68, 153.69 ppm; MS (MALDI)
(m/z): 688.8 (M+).
4.1.1.6. Compound TATF. Yield 78%. 1H NMR d
CDCl3: 0.77–0.82 (m, 30H), 1.13–1.21 (m, 48H), 2.13–
2.17 (m, 12H), 7.54–7.57 (m, 4H), 7.64–7.67 (m, 4H),
7.72–7.77 (m, 14H), 7.82–7.85 (m, 12H), 8.05 (d, 4H,
J¼9.0 Hz), 8.47 (s, 2H), 8.74–8.75 (m, 4H), 8.81–8.83 (m,
8H) ppm; 13C NMR d CDCl3: 14.31, 22.86, 24.10, 29.26,
30.28, 32.08, 40.72, 55.82, 55.84, 87.16, 87.40, 87.48,
102.15, 103.98, 104.02, 117.70, 118.85, 118.90, 120.51,
120.57, 122.47, 122.60, 122.82, 126.01, 126.15, 126.18,
126.91, 127.16, 127.67, 127.99, 129.03, 131.31, 131.35,
131.38, 131.56, 132.48, 132.93, 141.17, 141.42, 141.50,
151.71, 151.74, 151.77 ppm. IR (KBr): 2185.4 cmꢁ1 (C^C
stretch). Anal. calcd for C149H142: C, 92.59; H, 7.41. Found:
C, 92.60; H, 7.37.
1
4.1.1.2. Compound 11. Yield 67%. H NMR d CDCl3:
0.78–0.84 (m, 10H), 1.15–1.23 (m, 16H), 2.15–2.18 (m,
4H), 7.56–7.59 (m, 2H), 7.67–7.21 (m, 6H), 7.78 (s, 2H),
7.85 (br, 4H), 8.08 (d, 2H, J¼8.5 Hz), 8.49 (s, 1H), 8.57–
8.59 (m, 1H), 8.62–8.64 (m, 1H), 8.71–8.73 (m, 4H) ppm;
13C NMR d CDCl3: 14.29, 22.83, 24.08, 29.25, 30.25,
32.05, 40.68, 55.80, 86.75, 87.14, 102.12, 103.27, 103.68,
117.67, 120.50, 122.33, 122.35, 122.83, 126.00, 126.10,
126.14, 126.90, 127.11, 127.62, 127.75, 127.83, 127.98,
128.25, 128.57, 129.03, 130.63, 131.29, 131.55, 132.92,
133.08, 133.29, 133.87, 134.35, 141.12, 141.50, 151.68,
151.73 ppm; MS (MALDI) (m/z): 889.1 (M+).
4.1.1.7. Compound PATF. Yield 38%. 1H NMR
d CDCl3: 0.76–0.82 (m, 40H), 1.14–1.20 (m, 64H), 2.15–
2.17 (m, 16H), 7.54–7.57 (m, 4H), 7.65–7.68 (m, 4H),
7.73–7.77 (m, 22H), 7.83–7.85 (m, 14H), 8.06 (d, 4H,
J¼8.0 Hz), 8.47 (s, 2H), 8.75 (d, 4H, J¼8.5 Hz), 8.81–8.83
(m, 12H) ppm; 13C NMR d CDCl3: 14.29, 14.34, 22.86,
24.13, 29.26, 30.28, 32.08, 40.71, 55.84, 55.87, 87.18,
87.42, 87.45, 87.49, 102.17, 103.99, 104.01, 104.04, 117.74,

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Z. Zhao et al. / Tetrahedron 63 (2007) 7809–7815
118.14, 118.87, 118.90, 118.93, 120.51, 120.58, 122.52,
122.63, 122.86, 126.02, 126.21, 126.91, 127.16, 127.69,
129.04, 131.31, 131.37, 131.39, 131.60, 132.51, 132.96,
141.19, 141.44, 141.52, 151.74, 151.77, 151.80 ppm. IR
(KBr): 2185.4 cmꢁ1 (C^C stretch). Anal. calcd for
C194H186: C, 92.55; H, 7.45. Found: C, 92.56; H, 7.41.
122.39, 122.79, 125.98, 126.11, 126.89, 127.03, 127.08,
127.13, 127.27, 127.33, 127.55, 127.63, 127.97, 128.45,
129.04, 131.28, 131.32, 131.51, 132.26, 132.41, 132.90,
141.12, 141.47, 151.67, 151.68 ppm; MS (MALDI) (m/z):
844.1 (M+).
4.1.3. General procedure for the synthesis of the com-
pounds (10 and 13). Both compounds were obtained follow-
ing an essentially similar procedure. An illustrative example
is provided for 10.
4.1.1.8. Compound TATFC. Yield 48%. 1H NMR
d CDCl3: 0.74 (br, 16 H), 0.78–0.83 (m, 24H), 1.12–1.22
(m, 64H), 2.09–2.16 (m, 16H), 2.52 (s, 3H), 7.38 (d, 2H,
J¼8.5 Hz), 7.44–7.48 (m, 4H), 7.53–7.56 (m, 4H), 7.62–
7.67 (m, 10H), 7.72–7.76 (m, 16H), 7.81–7.83 (m, 12H),
8.05 (d, 4H, J¼8.5 Hz), 8.41 (s, 2H), 8.47 (s, 2H), 8.74 (d,
4H, J¼9.0 Hz), 8.80–8.82 (m, 8H) ppm; 13C NMR
d CDCl3: 14.30, 21.53, 22.84, 24.08, 29.25, 29.27, 30.26,
30.30, 32.06, 32.09, 40.70, 40.73, 55.68, 55.80, 87.12,
87.7, 87.40, 89.40, 91.26, 102.14, 103.96, 104.06, 110.47,
115.23, 117.69, 118.80, 118.90, 120.37, 120.50, 122.26,
122.47, 122.78, 122.90, 123.22, 124.32, 125.99, 126.12,
126.13, 126.14, 126.20, 126.89, 127.12, 127.19, 127.96,
129.02, 130.26, 130.94, 130.98, 131.29, 131.33, 131.54,
132.44, 132.91, 134.44, 140.60, 141.16, 141.41, 141.46,
141.60, 151.48, 151.66, 151.69, 151.72 ppm. IR (KBr):
2185.4 cmꢁ1 (C^C stretch). Anal. calcd for C199H191N:
C, 92.05; H, 7.41; N, 0.54. Found: C, 92.07; H, 7.37; N, 0.51.
4.1.3.1. Compound 10. Compounds 9 (500 mg), KOH
(500 mg), and 2-propanol (100 mL) were placed in a 150-
mL round bottle flask equipped with a Teflon covered mag-
netic stir bar. After the solution was purged with nitrogen
for half an hour, it was refluxed under nitrogen for 4 h. The
solvent was then removed and the crude product was purified
by column chromatography (silica gel, hexane/methylene
chloride as eluent) to afford 10 (75% yield). 1H NMR
d CDCl3: 0.65–0.66 (m, 4H), 0.76 (t, 6H, J¼7.5 Hz), 1.08
(br 12H), 1.16–1.20 (m, 4H), 2.01–2.04 (m, 4H), 3.17 (s, 1H),
7.50–7.54 (m, 4H), 7.63 (t, 2H, J¼7.5 Hz), 7.68 (d, 1H,
J¼7.5 Hz), 7.70 (s, 1H), 7.73–7.78 (m, 2H), 8.02 (d, 2H, J¼
7.5 Hz), 8.43 (s, 1H), 8.72 (d, 2H, J¼7.5 Hz) ppm; 13C NMR
d CDCl3: 14.29, 22.81, 23.99, 29.21, 30.21, 32.04, 40.57,
55.60, 77.59, 84.87, 87.04, 102.04, 120.21, 120.44, 120.99,
122.76, 125.97, 126.07, 126.83, 126.86, 127.07, 127.96,
129.00, 131.21, 131.51, 131.54, 132.88, 140.99, 141.46,
151.34, 151.62 ppm; MS (MALDI) (m/z): 586.0 (M+).
4.1.2. General procedure for the synthesis of compounds
(9 and 12). Both compounds were obtained following an
essentially similar procedure. An illustrative example was
provided for 9.
1
4.1.3.2. Compound 13. Yield 51%. H NMR d CDCl3:
4.1.2.1. Compound 9. Compounds 8 (678 mg, 1 mmol),
3-methyl-1-butyn-3-ol (126 mg, 1.5 mmol), cuprous iodide
(10 mg, 0.05 mmol), dichlorobis(triphenylphosphine)-
palladium(II) (3.5 mg, 0.005 mmol), triphenylphosphine
(5 mg, 0.02 mmol), dry triethylamine (100 mL) were placed
in a 150-mL round bottle flask equipped with a Teflon cov-
ered magnetic stir bar. After the solution was purged with
nitrogen for half an hour, it was refluxed under nitrogen
for 8 h. The reaction mixture was filtered and the filtrate
was evaporated under reduced pressure. The residue was pu-
rified through column chromatography (silica gel, hexane/
methylene chloride as eluent) to get 9 (82% yield). 1H
NMR d CDCl3: 0.65 (br 4H), 0.80 (t, 6H, J¼7.5 Hz), 1.08
(br, 12H), 1.16–1.20 (m, 4H), 1.68 (s, 6H), 2.00–2.06 (m,
5H), 7.42–7.45 (m, 2H), 7.53 (t, 2H, J¼7.5 Hz), 7.62–7.69
(m, 4H), 7.73–7.78 (m, 2H), 8.04 (d, 2H, J¼8.0 Hz), 8.45 (s,
1H), 8.72 (d, 2H, J¼8.5 Hz) ppm; 13C NMR d CDCl3: 14.29,
22.83, 23.97, 29.22, 30.23, 31.84, 32.05, 40.62, 55.60,
66.04, 83.32, 86.96, 94.21, 102.10, 117.68, 120.15,
120.34, 121.71, 122.59, 125.98, 126.05, 126.35, 126.86,
127.09, 127.93, 128.99, 131.08, 131.18, 131.52, 132.88,
140.96, 141.14, 151.32, 151.52 ppm; MS (MALDI) (m/z):
644.2 (M+).
0.76–0.81 (m, 10H), 1.13–1.21 (m, 16H), 2.13–2.16 (m,
4H), 4.10 (s, 1H), 7.55 (t, 2H, J¼7.5 Hz), 7.65–7.71 (m,
6H), 7.76 (s, 2H), 7.82 (br, 4H), 8.05 (d, 2H, J¼8.0 Hz),
8.40 (s, 1H), 8.65 (d, 2H, J¼9.0 Hz), 8.74–8.79 (m, 4H)
ppm; 13C NMR d CDCl3: 14.30, 22.84, 24.07, 29.25,
30.25, 32.05, 40.69, 55.78, 80.71, 87.07, 87.14, 90.12,
102.11, 103.99, 117.31, 117.65, 119.56, 120.49, 122.32,
122.81, 125.92, 125.99, 126.11, 126.14, 126.89, 127.07,
127.09, 127.34, 127.35, 127.56, 127.97, 129.01, 131.28,
131.35, 131.52, 132.18, 132.89, 132.97, 141.11, 141.52,
151.67, 151.69 ppm; MS (MALDI) (m/z): 786.8 (M+).
Acknowledgements
P.L. thanks National Nature Science Foundation of China
(20374045, 20674070) and Nature Science Foundation of
Zhejiang Province (R404109) for financial support.
References and notes
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1
4.1.2.2. Compound 12. Yield 63%. H NMR d CDCl3:
0.74–0.80 (m, 10H), 1.12–1.19 (m, 16H), 1.86 (s, 6H),
2.11–2.15 (m, 4H), 2.32 (br, 1H), 7.54 (t, 2H, J¼7.5 Hz),
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24.06, 29.24, 30.24, 32.00, 32.05, 40.68, 55.78, 79.31,
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