Synthesis of oligoarylenevinylenes with fluorinated double bonds

Article abstract of DOI:10.1055/s-2008-1067033

Oligoarylenevinylenes with fluorine atoms in the vinylene units and side-chains with a range of polarities bonded to the aryl rings, have been synthesized via a methodology based on the Stille cross-coupling reaction. All compounds were stereoselectiveIy synthesized with trans double bonds. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2008-1067033

1580
PAPER
Synthesis of Oligoarylenevinylenes with Fluorinated Double Bonds
Synthesis of
O
r
ligoaryle
a
nevinylene
n
s
with Fluor
c
inate
d
D
ou
e
ble Bonds sco Babudri,a,b Antonio Cardone,b Luisa De Cola,c Gianluca M. Farinola,*a Gregg S. Kottas,c Carmela
Martinelli,a Francesco Nasoa,b
a
Dipartimento di Chimica, Università degli Studi di Bari, via Orabona 4, 70126 Bari, Italy
CNR-ICCOM Istituto di Chimica dei Composti OrganoMetallici, via Orabona 4, 70126 Bari, Italy
Physikalisches Institut, Westfälische Wilhelms-Universität Münster, Mendelstraße 7, 48149 Münster, Germany
b
c
Fax +39(080)5442924; E-mail: farinola@chimica.uniba.it
Received 14 January 2008; revised 12 February 2008
in many ways. First, similar to the behavior of the cyano
group, the electron-withdrawing character of the fluorine
atoms may lower both the HOMO and LUMO levels of
the polyconjugated systems, thus improving electron-
transport properties and conferring to these polymers
ambipolar or n-type semiconductor character. Changes in
the HOMO and LUMO levels may also result in an in-
creased band gap, which determines the blue-shift of the
emission color. Second, increased chemical stability
against photo-oxidation, one of the main reasons for the
short lifetime of PPV polymers in electronic devices, is
expected when the C–H bonds are replaced by stronger
and less reactive C–F bonds. Moreover, conjugated com-
pounds bearing fluorine-substituted units can show p-
stacked supramolecular organization in the solid state due
to the strong interactions between the electron-poor fluor-
inated and the electron-rich non-fluorinated units,12 which
may be present in the same12b,d or in different mole-
cules.12a,e–i
Abstract: Oligoarylenevinylenes with fluorine atoms in the vi-
nylene units and side-chains with a range of polarities bonded to the
aryl rings, have been synthesized via a methodology based on the
Stille cross-coupling reaction. All compounds were stereoselective-
ly synthesized with trans double bonds.
Key words: cross-coupling, fluorine, tin reagent, stereoselectivity,
Stille reaction
Oligophenylenevinylenes (OPVs) deserve special interest
because of their applications in optoelectronic devices
such as organic light-emitting diodes (OLEDs)1 and pho-
tovoltaic cells.2 OPVs have also been investigated as well-
defined models of poly(phenylenevinylene)s (PPVs) in
order to define structure–property relationships3 and to
determine the role of functionalization of the conjugated
backbone for tuning electro-optical properties.
Several methods have been reported for the stereoselec-
tive synthesis of functionalized OPVs4 and palladium-cat-
alyzed organometallic reactions, such as the Heck,5 Stille6
and Suzuki3f coupling processes, have been extensively
used. A synthetic sequence entirely based on palladium-
catalyzed cross-coupling reactions of vinylsilanes, afford-
ing stereodefined alkoxy-substituted OPVs, was devel-
oped by our group.7
We have recently presented our work on the development
of synthetic methodologies for generating fluorinated
conjugated polymeric materials, with special emphasis on
fluorinated PPVs.13
Herein, we described a general synthetic sequence leading
to functionalized oligoarylenevinylenes with fluorinated
double bonds. Functional groups with a range of polar
characteristics have been introduced onto the aromatic
ring, in order to modulate solubility in diverse solvents
and, in the case of ionic side-chains, to enable deposition
by Langmuir–Blodgett techniques.
According to theoretical calculations performed by
Brèdas et al.,8 introduction of electron-withdrawing
groups onto the phenylene rings or the vinylene units rep-
resents the method of choice for lowering the HOMO and
LUMO energy of PPVs, thus permitting the use of higher
work function metals as cathodes in electroluminescent
devices. Hence, different electron-withdrawing moieties
have been introduced onto the OPV skeleton, mainly lo-
calized on the aromatic rings, with examples of function-
alization of double bonds being mainly limited to cyano9
or trifluoromethyl10 substituents. However, to the best of
our knowledge, no general synthetic protocol has been de-
veloped for OPVs with fully fluorinated double bonds. In-
troduction of fluorine atoms as substituents on the aryl
rings of conjugated oligomers3b and polymers11 has been
reported to improve the characteristics of these materials
Our synthesis is based upon the Stille cross-coupling reac-
tion of 1-aryl-2-tributylstannyl-1,2-difluoroethylenes 1 or
2 with bis-iodoaryl derivatives 3a–d, in the presence of
Pd(0) complexes as catalyst and Cu(I) in stoichiometric
amounts (Scheme 1).14,15
All reactions were performed at room temperature in a
DMF–THF mixture as the solvent. Oligoarylenevinylenes
4a–e were obtained in fair to good yields, after simple pu-
rification by either flash chromatography or crystalliza-
tion (Table 1). All the compounds synthesized were
characterized by a trans-geometry of the double bonds.
Some of the compounds obtained were subjected to fur-
ther reactions in order to transform functional groups or to
extend the conjugated systems. Compounds 4a and 4e
were hydrolyzed with lithium hydroxide to convert the
SYNTHESIS 2008, No. 10, pp 1580–1588
Advanced online publication: 16.04.2008
DOI: 10.1055/s-2008-1067033; Art ID: Z01808SS
© Georg Thieme Verlag Stuttgart · New York
x
x.
x
x
.
2
0
0
8

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Synthesis of Oligoarylenevinylenes with Fluorinated Double Bonds
1581
R1
F
R1
Ar
F
Ar
F
Pd(PPh3)4, CuI
THF–DMF, r.t.
+
I
I
F
Ar
F
SnBu3
R2
4a–e
F
R2
3a–d
1, 2
Scheme 1 General synthetic protocol for the preparation of oligomers
Table 1 Stille Cross-Coupling Reactions for the Synthesis of Oligomers
Entry
Ar
Diiodoaryl
Yield (%)
Product
SnBu3
F
F
F
COOMe
F
COOMe
H17C8O
I
1
78
F
OC8H17
I
F
3a
OC8H17
4a
1
O(CH2)3SO3Na
I
F
O(CH2)3SO3Na
F
H17C8O
2
70
60
87
F
OC8H17
I
MeO
F
OMe
4b
3b
O(CH2)3SO3Na
I
F
O(CH2)3SO3Na
F
H17C8O
3
F
NaO3S(H2C)3O
OC8H17
I
F
O(CH2)3SO3Na
4c
3c
OTBDMS
I
F
OH
F
H17C8O
4a
F
OC8H17
I
MeO
F
OMe
4d
3d
SnBu3
F
F
COOMe
H17C8
C8H17
F
COOMe
I
F
5
71
C8H17
C8H17
F
C8H17
I
F
H17C8
3a
4e
2
a In situ hydrolysis by 40% aq KF.
carbomethoxy group into the corresponding free carboxy- Extending a protocol described in the literature for similar
lic function of oligomers 5 and 6 (Scheme 2). To explore compounds,16 the synthesis of the vinyl stannane
the possibility of a further elaboration of the conjugated building block 1 was performed as reported in Scheme 4.
system, the hydroxy functionality of compound 4d was 4-Iodooctyloxybenzene 11,17 upon treatment with butyl-
converted into the triflate group of 7 which, upon palladi- lithium, was coupled with trifluoroethenyl triethylsilane
um-catalyzed cross-coupling reaction with phenylboronic to afford the vinylsilyl derivative 13, which could be sub-
ester 8, afforded compound 9; this was subsequently hy- sequently transmetallated to the corresponding vinylstan-
drolyzed, to yield oligomer 10 (Scheme 3).
nane 1 (Bu3SnCl, KF in DMF at 70 °C). Reagent 1 was
readily purified by flash chromatography to give a color-
less dense liquid, which was stable at room temperature. 18
Synthesis 2008, No. 10, 1580–1588 © Thieme Stuttgart · New York

1582
F. Babudri et al.
PAPER
F
COOMe
F
F
COOH
H17C8O
F
H17C8O
OC8H17
F
OC8H17
F
F
F
4a
5
LiOH·H2O
H17C8
H17C8
C8H17
C8H17
THF–MeOH–H2O
F
COOMe
F
F
COOH
F
F
F
F
F
6
4e
H17C8
H17C8
C8H17
C8H17
Scheme 2 Hydrolysis of carbomethoxy groups
F
OTf
F
OH
H17C8O
F
H17C8O
F
Tf2O
F
OC8H17
F
OC8H17
pyridine, CH2Cl2
r.t.
MeO
F
MeO
F
7
4d
O
Pd(PPh3)4, LiCl
Na2CO3 (2 M)
toluene–MeOH
B
COOMe
O
8
COOH
COOMe
LiOH·H2O, r.t.
F
F
H17C8O
F
H17C8O
F
THF–MeOH–H2O
F
OC8H17
F
OC8H17
MeO
F
MeO
F
10
9
Scheme 3 Synthesis of 10
F
F
1) BuLi
KF, DMF
Bu3SnCl, 70 °C
H17C8O
H17C8O
H17C8O
I
SiEt3
SnBu3
F
F
SiEt3
F
F
F
11
2)
13
1
12
1) BuLi
2) Et3SiCl
F
F
Cl
F
Scheme 4 Synthesis of organometallic reagent 1
The protocol followed for the synthesis of 1 could not be transmetallation reaction, under the same conditions re-
extended to the preparation of vinylsilane 2, since the lith- ported for the alkene 13 (Scheme 5).
ium derivative obtained from 14 did not react with the ole-
Organometallic intermediate 15 was prepared starting
fin 12. Therefore, iodofluorene 14 was coupled with the
from the difluorovinyltriethylsilyl derivative 17,19 which
vinylstannane 15 to afford the intermediate 16, which was
was lithiated with n-butyllithium at –90 °C and then
finally converted into the tin derivative 2 by a simple
quenched with tributyltin chloride, as shown in Scheme 6.
Synthesis 2008, No. 10, 1580–1588 © Thieme Stuttgart · New York

PAPER
Synthesis of Oligoarylenevinylenes with Fluorinated Double Bonds
1583
F
F
F
SnBu3
F
Pd(PPh3)4, CuI
DMF–THF, r.t.
KF, Bu3SnCl
DMF, 70 °C
SiEt3
SnBu3
I
+
Et3Si
F
F
H17C8
C8H17
H17C8
C8H17
16
H17C8
C8H17
14
15
2
Scheme 5 Synthesis of organometallic reagent 2
[(E)-1,2-Difluoro-2-(4-octyloxyphenyl)vinyl]tributylstannane
(1)
F
SiEt3
F
F
SnBu3
1) BuLi (2.5 M), THF, –90 °C
2) Bu3SnCl
A three-neck 250 mL round-bottom flask was charged with 13 (4.8
g, 12.5 mmol), anhyd KF (1.1 g, 18.75 mmol) and anhyd DMF (100
mL), under a nitrogen atmosphere. Bu3SnCl (4.5 g, 13.75 mmol)
was added and the reaction mixture was stirred at 70 °C overnight.
The reaction mixture was extracted with hexane and washed several
times with H2O. The organic layer was dried over anhyd Na2SO4
and the solvent was distilled under reduced pressure to yield a light-
yellow liquid. The final product was isolated as a colorless liquid
after purification by column chromatography (PE, 100%); yield:
5.23 g (75%).
1H NMR (500 MHz, CDCl3): d = 7.64 (d, J = 9.0 Hz, 2 H), 6.94 (d,
J = 9.0 Hz, 2 H), 4.0 (t, J = 6.8 Hz, 2 H), 1.82 (quint, J = 6.8 Hz,
2 H), 1.63 (quint, J = 8.2 Hz, 6 H), 1.49 (quint, J = 7.4 Hz, 2 H),
1.42–1.3 (m, 8 H), 1.4 (sext, J = 7.6 Hz, 6 H), 1.17 (t, J = 8.2 Hz,
6 H), 0.95 (t, J = 7.6 Hz, 9 H), 0.93 (t, J = 7.1 Hz, 3 H).
H
Et3Si
F
17
15
Scheme 6 Synthesis of organometallic intermediate 15
The synthesis of the bifunctional olefinic building block
15, here reported for the first time as a starting material for
our sequence represents, in its own right, an interesting
and useful reactant for the synthesis of compounds bear-
ing trans-difluoroolefinic moieties.
In conclusion, we have described a general methodology
for the stereoselective synthesis of various functionalized
oligoarylenevinylene derivatives with three to five aro-
matic rings, and fluorinated double bonds with all trans-
configuration. The procedure, which is based on the Stille
cross-coupling reaction, afforded oligomers with side-
chains of differing degrees of polarity in a range of posi-
tions. Such substituents have been introduced in order to
modulate the solubility and, in the case of charged side-
groups, to make the compounds suitable for Langmuir–
Blodgett deposition techniques. We now have available
various model systems of fluorinated PPVs for photo-
physical characterization and a protocol that, in principle,
is suitable for extension to longer oligomers. Furthermore,
our work has yielded a number of useful synthetic inter-
mediates that can serve as general building blocks for
more complex molecular structures containing trans-
difluorovinylenic moieties.
MS (EI, 70 eV): m/z (%) = 558 (1) [M+], 501 (7), 445 (15), 389 (2),
333 (40), 291 (15), 253 (100), 230 (20), 177 (42), 156 (23).
Anal. Calcd for C28H48F2OSn: C, 60.34; H, 8.68. Found: C, 60.33;
H, 8.69.
[(E)-1,2-Difluoro-2-(9,9-dioctylfluoren-2-yl)vinyl]tributylstan-
nane (2)
A three-neck 50 mL round-bottom flask equipped with a cold-water
condenser and nitrogen tee was charged with 16 (1.8 g, 3.18 mmol),
anhyd KF (1.1 g, 4.77 mmol) and anhyd DMF (15 mL). Bu3SnCl
(1.04 g, 3.82 mmol) was added and the reaction mixture was stirred
at 70 °C overnight and then extracted with hexane and washed sev-
eral times with H2O. The organic layer was dried over anhyd
Na2SO4 and the solvent was distilled under reduced pressure to
yield a light-yellow liquid. The final product was isolated as a col-
orless dense liquid after purification by column chromatography
(PE, 100%); yield: 2.24 g (95%).
FTIR (KBr): 2926, 2853, 1464, 1455, 1376, 1086, 739 cm–1.
All starting materials were obtained from commercial sources.
Toluene, THF and Et2O were freshly distilled from sodium and ben-
zophenone under a nitrogen atmosphere. CH2Cl2 was distilled from
phosphorous pentoxide. DMF, pyridine and MeOH were distilled
from 4 Å molecular sieves. All solvents were freshly distilled im-
mediately prior to use. Petroleum ether (PE), where used, had a boil-
ing range of 40–60 °C. FT-IR spectra were measured on a Perkin–
1H NMR (500 MHz, CDCl3): d = 7.73–7.70 (m, 2 H), 7.68 (dd,
J = 2, 8 Hz, 1 H), 7.62 (d, J = 1 Hz, 1 H), 7.36–7.31 (m, 3 H), 1.99
(t, J = 9.9 Hz, 2 H), 1.97 (t, J = 6.7 Hz, 2 H), 1.63 (quint, J = 7.5 Hz,
6 H), 1.39 (sext, J = 7.5 Hz, 6 H), 1.23–1.05 (m, 20 H), 1.18 (t,
J = 7.5 Hz, 6 H), 0.94 (t, J = 7.5 Hz, 9 H), 0.82 (t, J = 7.1 Hz, 6 H),
0.70–0.56 (m, 4 H).
13C NMR (125 MHz, CDCl3): d = 163.30 (dd, J = 93, 294 Hz),
160.10 (dd, J = 16, 203 Hz), 151.20, 150.66 (d, J = 3 Hz), 141.48
(d, J = 3 Hz), 140.50, 128.40 (dd, J = 3, 28 Hz), 127.33, 126.75,
124.14 (dd, J = 8, 10 Hz), 122.89, 119.89, 119.48 (d, J = 2 Hz),
119.44 (t, J = 9 Hz), 55.17, 40.21, 31.75, 29.95, 29.16, 29.13, 28.87,
27.19, 23.65, 22.57, 14.03, 13.66, 10.12.
1
Elmer 1710 spectrophotometer using dry KBr pellets. H and 13C
NMR spectra were recorded in CDCl3 or DMSO-d6 on a Bruker AM
500 spectrometer at 500 MHz and 125 MHz, respectively. 19F NMR
spectra were recorded in CDCl3 or DMSO-d6 on a Varian Inova 400
spectrometer at 376 MHz. The residual CHCl3 (or DMSO) signal at
d = 7.24 (or 2.49) ppm and the CDCl3 (or DMSO-d6) signal at
d = 77.0 (or 39.5) ppm were used as standards for 1H NMR and 13
C
19F NMR (376 MHz, CDCl3): d = –153.48 (d, J = 112, 1 F), –154.15
(d, J = 112, 1 F).
NMR spectra, respectively. CFCl3 was used as internal standard for
19F NMR spectra. MS spectra were recorded on a Shimadzu GCMS-
QP 5000 spectrometer. Elemental analyses were performed on a
Carlo Erba CHNS-O EA1108-Elemental Analyzer. A Büchi GKR-
51 apparatus was used to purify the liquid products by distillation.
Flash chromatography was performed using silica gel 60 (particle
size 0.040–0.063 mm) as stationary phase.
MS (EI, 70 eV): m/z (%) = 685 (2), 630 (18), 627 (13), 571 (4), 414
(3), 253 (37), 234 (8), 207 (31), 177 (29), 139 (7), 119 (4), 57 (100).
Anal. Calcd for C43H68F2Sn: C, 69.63; H, 9.24. Found: C, 69.70; H,
9.25.
Synthesis 2008, No. 10, 1580–1588 © Thieme Stuttgart · New York

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F. Babudri et al.
PAPER
Sodium 3-(2,5-Diiodo-4-methoxyphenoxy)propane-1-sulfonate
(3b)
Sodium 3-{2,5-Bis[(E)-1,2-difluoro-2-(4-octyloxyphenyl)vinyl]-
4-methoxyphenoxy}propane-1-sulfonate (4b)
Purified by column chromatography (EtOAc–MeOH, 9:1). Yield:
70%; thick orange oil.
A 100 mL round-bottom flask was charged with sodium 3-(4-meth-
oxyphenoxy)propane-1-sulfonate20 (2 g, 7.46 mmol), I2 (1.7 g, 6.7
mmol), HIO3 (0.8 g, 4.55 mmol), H2SO4 (aq 30%, 3 mL), CCl4
(3mL) and AcOH (12 mL). The resulting mixture was heated at
75 °C overnight and then cooled to 25 °C. The precipitate obtained
was filtered and the solid was crystallized twice from DMF–acetone
to yield 3b. Yield: 3.26 g (84%); colorless powder; mp 293 °C
(dec).
FTIR (KBr): 3447, 2926, 2854, 1608, 1514, 1466, 1392, 1255,
1216, 1181, 1107, 1033, 832, 804 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.7–7.4 (br m, 4 H), 7.23 (br, 2 H),
7.1–6.6 (br m, 4 H), 4.0–3.3 (br m, 9 H), 2.9–2.4 (br s, 2 H), 2.1–1.8
(br s, 2 H), 1.8–1.5 (br m, 4 H), 1.5–1.1 (br m, 20 H), 1.0–0.75 (m,
6 H).
13C NMR (125 MHz, CDCl3): d = 159.49 (d, J = 2 Hz), 159.45 (d,
J = 2 Hz), 150.89, 150.33, 147.90 (dd, J = 47, 233 Hz), 147.82 (d,
J = 47, 232 Hz), 145.37 (dd, J = 55, 240 Hz), 145.15 (dd, J = 56,
240 Hz), 132.29, 131.98 (d, J = 10 Hz), 128.55 (d, J = 12 Hz),
127.21 (t, J = 8 Hz), 122.07 (dd, J = 7, 55 Hz), 122.06 (t, J = 6 Hz),
121.5–120.8 (m), 114.34, 114.23, 67.92, 56.24, 47.81, 31.82, 29.40,
29.24, 29.22, 29.18, 26.01, 25.97, 22.63, 22.62, 14.04.
FTIR (KBr): 3438, 2928, 2870, 1485, 1350, 1269, 1210, 1061,
1025, 839, 809 cm–1.
1H NMR (500 MHz, DMSO-d6): d = 7.32 (s, 1 H), 7.31 (s, 1 H),
4.04 (t, J = 7.5 Hz, 2 H), 3.77 (s, 3 H), 2.58 (t, J = 7.5 Hz, 2 H), 1.97
(t, J = 7.5 Hz, 2 H).
13C NMR (125 MHz, DMSO-d6): d = 152.80, 152.17, 122.44,
121.13, 86.91, 86.03, 68.82, 57.00, 47.95, 25.24.
Anal. Calcd for C10H11I2NaO5S: C, 23.10; H, 2.13; S, 15.38. Found:
C, 23.02; H, 2.40; S, 15.20.
19F NMR (376 MHz, CDCl3): d = –143.51 (d, J = 130 Hz, 1 F),
–144.19 (d, J = 128 Hz, 1 F), –149.55 (d, J = 128 Hz, 1 F), –150.10
(d, J = 130 Hz, 1 F).
(2,5-Diiodo-4-methoxyphenoxy)-(tert-butyl)dimethylsilane (3d)
2,5-diiodo-4-methoxyphenol21 (9.7 g, 25.8 mmol), TBSCl (10 g,
28.4 mmol) and imidazole (1.85 g, 27.2 mmol) were dissolved in
anhyd CH2Cl2 (40 mL) under a nitrogen atmosphere. After stirring
vigorously overnight, the reaction mixture was diluted with CH2Cl2
(40 mL) and washed with aq HCl (5%, 2 × 30 mL) and H2O (40
mL). The organic layer was dried over anhyd Na2SO4 and the sol-
vent was removed under reduced pressure to yield a dense brown
liquid. The final product was isolated as a colorless dense liquid af-
ter column chromatography (PE–CH2Cl2, 9:1); yield: 9.5 g (75%).
Anal. Calcd for C42H53F4NaO7S: C, 62.98; H, 6.67; S, 4.00. Found:
C, 63.02; H, 6.88; S, 4.12.
Disodium 3-{2,5-Bis[(E)-1,2-difluoro-2-(4-octyloxyphenyl)vi-
nyl]-4-(3-sulfonatepropoxy)phenoxy}propane-1-sulfonate (4c)
Crystallized (×2) from DMF–acetone. Yield: 60%; grey solid; mp
194–196 °C.
FTIR (KBr): 3460, 2955, 2924, 2856, 1607, 1514, 1465, 1385,
1254, 1215, 1182, 1109, 1038 cm–1.
1H NMR (500 MHz, DMSO-d6): d = 7.62 (br s, 4 H), 7.22 (br s,
2 H), 7.06 (br s, 4 H), 4.12 (br s, 4 H), 4.02 (br s, 4 H), 2.7 (br s,
4 H), 2.03 (br s, 4 H), 1.77–1.5 (br m, 4 H), 1.48–1.05 (br s, 20 H),
0.86 (br s, 6 H).
FTIR (KBr): 2928, 2855, 1480, 1434, 1351, 1254, 1214, 1056, 939,
847, 780 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.21 (s, 1 H), 7.14 (s, 1 H), 3.79
(s, 3 H), 1.04 (s, 9 H), 0.26 (s, 6 H).
13C NMR (125 MHz, CDCl3): d = 153.02, 149.83, 128.05, 120.62,
89.63, 85.17, 56.84, 25.74, 18.11, –4.14.
MS (EI, 70 eV): m/z (%) = 490 (5) [M+], 433 (40), 306 (100), 291
(25).
19F NMR (376 MHz, CDCl3): d = –141.67 (d, J = 124 Hz, 2 F),
–147.68 (d, J = 124 Hz, 2 F).
Anal. Calcd for C44H56F4Na2O10S2: C, 56.76; H, 6.06; S, 6.89.
Found: C, 56.80; H, 6.08; S, 6.95.
Anal. Calcd for C13H20I2O2Si: C, 31.85; H, 4.11. Found: C, 31.90;
H, 4.10.
2,5-Bis[(E)-1,2-difluoro-2-(4-octyloxyphenyl)vinyl]-4-methoxy-
phenol (4d)
Purified by column chromatography (PE–EtOAc, 9:1). Yield: 87%;
pale-yellow solid; mp 68–69 °C.
Methyl 2,5-Bis[(E)-1,2-difluoro-2-(4-octyloxyphenyl)vinyl]ben-
zoate (4a); Typical Procedure
FTIR (KBr): 2922, 2852, 1608, 1514, 1467, 1304, 1254, 1219,
1182, 1108, 1042, 831 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.7 (d, J = 9.0 Hz, 4 H), 7.13 (s,
1 H), 7.05 (s, 1 H), 7.0 (s, 1 H), 6.99 –6.95 (m, 4 H), 4.04–3.98 (m,
4 H), 3.86 (s, 3 H), 1.85–1.77 (m, 4 H), 1.51–1.43 (m, 4 H), 1.41–
1.25 (m, 16 H), 0.90 (t, J = 6.7 Hz, 6 H).
13C NMR (125 MHz, CDCl3): d = 160.38 (d, J = 3 Hz), 159.99 (d,
J = 3 Hz), 156.42, 149.57 (dd, J = 42, 236 Hz), 148.83 (dd, J = 45,
234 Hz), 143.49 (dd, J = 54, 238 Hz), 142.35 (dd, J = 53, 236 Hz),
139.21, 127.81 (d, J = 9 Hz), 127.74 (d, J = 8 Hz), 127.55 (d, J = 9
Hz), 127.49 (d, J = 8 Hz), 126.08 (dd, J = 4, 23 Hz), 124.35 (m),
121.66 (dd, J = 4, 24 Hz), 121.59 (dd, J = 7, 25 Hz), 121.00 (dd,
J = 6, 25 Hz), 114.60 (d, J = 2 Hz), 114.50 (d, J = 2 Hz), 112.68
(m), 68.15, 68.12, 56.40, 31.82, 29.34, 29.24, 29.18, 29.16, 26.02,
22.66, 14.09.
A three-neck, 50 mL round-bottom flask equipped with a nitrogen
tee, was charged with 3a (0.3 g, 0.77 mmol), 1 (0.86 g, 1.55 mmol),
CuI (0.295 g, 1.55 mmol), Pd(Ph3P)4 (0.09 g, 0.08 mmol), anhyd
THF (12 mL) and anhyd DMF (12 mL). The resulting mixture was
stirred at 25 °C for 12 h, then quenched with H2O (50 mL) and ex-
tracted with CH2Cl2 (3 × 70 mL). The organic phase was dried over
anhyd Na2SO4, filtered and the solvent was evaporated at reduced
pressure. The crude product was purified by column chromatogra-
phy (PE–EtOAc, 9:1) to give 4a as a pale-yellow solid; yield: 0.41
g (78%); mp 64–65 °C.
1H NMR (500 MHz, CDCl3): d = 8.24 (app d, J = ~2 Hz, 1 H), 7.87
(app d, J = ~8 Hz, 1 H), 7.69–7.64 (m, 5 H), 6.95 (m, 4 H), 3.97 (m,
J = 6.6 Hz, 2 H), 3.94 (t, J = 6.9 Hz, 2 H), 3.89 (s, 3 H), 1.82–1.75
(m, 4 H), 1.48–1.20 (br s, 20 H), 0.92–0 84 (br s, 6 H).
Anal. Calcd for C40H48F4O4: C, 71.83; H, 7.23. Found: C, 71.85; H,
7.25.
19F NMR (376 MHz, CDCl3): d = –146.30 (d, J = 129 Hz, 1 F),
–146.56 (d, J = 129 Hz, 1 F), –148.01 (d, J = 129 Hz, 1 F), –148.60
(d, J = 129 Hz, 1 F).
Anal. Calcd for C39H48F4O4: C, 71.32; H, 7.37. Found: C, 71.50; H,
7.41.
Synthesis 2008, No. 10, 1580–1588 © Thieme Stuttgart · New York

PAPER
Synthesis of Oligoarylenevinylenes with Fluorinated Double Bonds
1585
Methyl 2,5-Bis[(E)-2-(9,9-dioctylfluoren-2-yl)-1,2-difluoro-
vinyl]benzoate (4e)
Purified by column chromatography (PE–EtOAc, 8:2). Yield: 71%;
pale-yellow solid; mp 69–70 °C.
2,5-Bis[(E)-2-(9,9-dioctylfluoren-2-yl)-1,2-difluorovinyl]benzo-
ic Acid (6)
Purified by column chromatography (PE–EtOAc, 3:7). Yield: 92%;
pale-yellow solid; mp 122–123 °C.
FTIR (KBr): 2925, 2852, 1729, 1465, 1454, 1295, 1246, 1166,
1125, 834, 738 cm–1.
FTIR (KBr): 3436, 2925, 2852, 1703, 1601, 1501, 1465, 1454,
1376, 1254, 1120, 835 cm–1.
1H NMR (500 MHz, CDCl3): d = 8.34 (d, J = 2.0 Hz, 1 H), 8.02 (d,
J = 7.5 Hz, 1 H), 7.85–7.72 (m, 9 H), 7.40–7.34 (m, 6 H), 2.07–1.97
(m, 8 H), 1.26–1.02 (m, 44 H), 0.83 (t, J = 7.0 Hz, 6 H), 0.82 (t,
J = 7.0 Hz, 6 H), 0.78–0.60 (m, 8 H).
1H NMR (500 MHz, CDCl3): d = 8.51 (d, J = 1.9 Hz, 1 H), 8.07 (d,
J = 8.3 Hz, 1 H), 7.87–7.7 (m, 10 H), 7.4–7.32 (m, 6 H), 2.05–1.95
(m, 8 H), 1.23–1.0 (m, 40 H), 0.82 (t, J = 7.2 Hz, 6 H), 0.8 (t, J = 7.2
Hz, 6 H), 0.72–0.59 (m, 8 H).
13C NMR (125 MHz, CDCl3): d = 167.33, 151.35, 151.29, 150.90
(d, J = 2 Hz), 150.84 (d, J = 2 Hz), 150.55 (dd, J = 47, 240 Hz),
148.64 (dd, J = 45, 231 Hz), 147.38 (dd, J = 54, 240 Hz), 146.67
(dd, J = 48, 235 Hz), 142.65 (d, J = 2 Hz), 142.31 (d, J = 2 Hz),
140.26, 140.15, 131.73 (dd, J = 7, 25 Hz), 130.76–130.6 (br s),
130.40–130.20 (m), 129.80–129.65 (m), 129.60–129.48 (m),
128.18 (t, J = 7 Hz), 127.99 (t, J = 8 Hz), 127.97 (t, J = 4 Hz),
127.82, 127.66, 127.24 (t, J = 8 Hz), 126.92, 126.87, 125.02 (dd,
J = 9, 21 Hz), 124.96 (dd, J = 9, 20 Hz), 122.95, 120.31 (t, J = 9
Hz), 120.19, 120.10, 119.95 (t, J = 9 Hz), 119.75 (dd, J = 2, 9 Hz),
55.27, 55.25, 52.64, 40.24, 31.76, 29.99, 29.95, 29.20, 29.18, 29.15,
23.73, 23.70, 22.57, 14.05.
13C NMR (125 MHz, CDCl3): d = 171.38, 151.42, 151.37, 150.91
(d, J = 2 Hz), 150.86 (d, J = 2 Hz), 150.66 (dd, J = 47, 239 Hz),
147.77 (dd, J = 45, 233 Hz), 147.10 (dd, J = 55, 241 Hz), 146.54
(dd, J = 48, 235 Hz), 142.69 (d, J = 2 Hz), 142.33 (d, J = 2 Hz),
140.28, 140.17, 131.85 (dd, J = 7, 25 Hz), 130.76–130.6 (br s),
130.15 (dd, J = 6, 23 Hz), 129.60–129.40 (br s), 128.90–128.60
(m), 128.16 (dd, J = 2, 7 Hz), 128.09–127.8 (m), 127.82, 127.61,
126.92, 126.85, 125.17–124.99 (m), 122.96, 122.94, 120.33 (t,
J = 9 Hz), 120.18, 120.12, 120.03 (t, J = 8 Hz), 119.78 (d, J = 2 Hz),
119.73 (d, J = 2 Hz), 55.29, 55.25, 40.24, 40.19, 31.76, 31.74,
29.94, 29.18, 29.16, 29.15, 23.70, 22.57, 14.03.
19F NMR (376 MHz, CDCl3): d = –138.82 (d, J = 127 Hz, 1 F),
–147.16 (d, J = 119 Hz, 1 F), –150.11 (d, J = 127 Hz, 1 F), –153.94
(d, J = 119 Hz, 1 F).
19F NMR (376 MHz, CDCl3): d = –139.47 (d, J = 127 Hz, 1 F),
–147.33 (d, J = 120 Hz, 1 F), –150.79 (d, J = 127 Hz, 1 F), –153.82
(d, J = 120 Hz, 1 F).
Anal. Calcd for C69H86F4O2: C, 80.98; H, 8.47. Found: C, 80.92; H,
8.50.
Anal. Calcd for C70H88F4O2: C, 81.04; H, 8.55. Found: C, 81.02; H,
8.60.
2,5-Bis[(E)-1,2-difluoro-2-(4-octyloxyphenyl)vinyl]-4-methoxy-
phenyltrifluoromethanesulfonate (7)
2,5-Bis{(E)-1,2-difluoro-2-[4-(octyloxyphenyl)vinyl]}benzoic
Acid (5); Typical Procedure
A three-neck 50 mL round-bottom flask equipped with a nitrogen
tee, was charged with 4d (0.42 g, 0.6 mmol), pyridine (0.11 mL, 1.2
mmol) and anhyd CH2Cl2 (15 mL). To the reaction mixture, cooled
to 0 °C, Tf2O (0.13 mL, 0.72 mmol) was added dropwise and the re-
sulting mixture was stirred at 25 °C for 1 h. The mixture was
quenched with aq HCl (10%) and extracted with CH2Cl2 (3 × 20
mL). The organic layer was washed with aq NaHCO3 (2 M, 30 mL),
dried over Na2SO4 and the solvent was evaporated under reduced
pressure. The crude product was purified by column chromatogra-
phy (PE–EtOAc, 9:1). Yield: 0.43 g (85%); pale-yellow solid; mp
76–77 °C.
A 50 mL round bottom-flask was charged with 4a (0.7 g, 1.03
mmol), THF (12 mL), MeOH (4 mL), water (4 mL) and LiOH (0.43
g, 10.3 mmol). The resulting mixture was stirred at 25 °C for 30
min. The reaction mixture was diluted with H2O (20 mL), extracted
with CH2Cl2 (3 × 30 mL) and dried over anhyd Na2SO4. The solvent
was removed under reduced pressure and the residue was purified
by column chromatography (PE–EtOAc, 3:7) to give 5. Yield: 0.64
g (95%); pale-yellow solid; mp 152–153 °C.
FTIR (KBr): 2922, 2854, 1709, 1606, 1513, 1469, 1393, 1252,
1184, 1114, 832 cm–1.
FTIR (KBr): 2935, 2918, 2852, 1609, 1516, 1467, 1400, 1310,
1255, 1217, 1184, 1150, 1113, 1043, 979, 896, 872, 853, 830 cm–1.
1H NMR (500 MHz, CDCl3 + D2O): d = 8.38 (app d, J = ~2 Hz,
1 H), 7.96 (app d, J = ~9.0 Hz, 1 H), 7.74–7.68 (m, 5 H), 6.99–6.94
(m, 4 H), 4.02 (t, J = 6.6 Hz, 2 H), 4.0 (t, J = 6.6 Hz, 2 H), 1.82
(quint, J = 6.6 Hz, 2 H), 1.80 (quint, J = 6.6 Hz, 2 H), 1.52–1.20 (br
s, 24 H), 0.90 (t, J = 5.1 Hz, 3 H), 0.89 (t, J = 5.8 Hz, 3 H).
13C NMR (125 MHz, CDCl3): d = 170.51 (d, J = 5 Hz), 160.09 (d,
J = 3 Hz), 159.83 (d, J = 2 Hz), 150.12 (dd, J = 47, 240 Hz), 148.24
(dd, J = 44, 233 Hz), 146.21 (dd, J = 54, 238 Hz), 145.73 (dd,
J = 47, 233 Hz), 131.77 (dd, J = 6, 26 Hz), 130.68–130.40 (br s),
129.91 (dd, J = 5, 24 Hz), 129.40–129.24 (br s), 128.48 (dd, J = 8,
11 Hz), 127.72 (d, J = 9 Hz), 127.65 (d, J = 8 Hz), 127.49 (d, J = 8
Hz), 127.43 (d, J = 9 Hz), 121.88 (dd, J = 7, 25 Hz), 118.62, 115.95,
114.59, 114.50, 68.14, 68.09, 31.81, 29.35, 29.23, 29.16, 26.01,
22.65, 14.09.
1H NMR (500 MHz, CDCl3): d = 7.70 (app d, J = ~9.0 Hz, 2 H),
7.69 (app d, J = ~9 Hz, 2 H), 7.48 (s, 1 H), 7.19 (s, 1 H), 6.99 (app
d, J = ~9.0 Hz, 2 H), 6.97 (app d, J = ~9.0 Hz, 2 H), 4.02 (t, J = 6.9
Hz, 2 H), 4.01 (t, J = 6.6 Hz, 2 H), 3.94 (s, 3 H), 1.82 (quint, J = 6.6
Hz, 2 H), 1.81 (quint, J = 6.9 Hz, 2 H), 1.48 (quint, J = 7.4 Hz, 4 H),
1.41–1.22 (m, 16 H), 0.90 (t, J = 7.0 Hz, 6 H).
13C NMR (125 MHz, CDCl3): d = 160.35 (d, J = 2 Hz), 159.96 (d,
J = 2 Hz), 156.39, 149.54 (dd, J = 42, 235 Hz), 148.81 (dd, J = 44,
234 Hz), 143.47 (dd, J = 54, 238 Hz), 142.32 (dd, J = 53, 237 Hz),
139.18, 127.79 (d, J = 9 Hz), 127.72 (d, J = 8 Hz), 127.53 (d, J = 9
Hz), 127.46 (d, J = 8 Hz), 126.04 (dd, J = 5, 20 Hz), 124.32 (t, J = 5
Hz), 121.63 (dd, J = 4, 24 Hz), 121.55 (dd, J = 6, 25 Hz), 120.97
(dd, J = 6, 25 Hz), 118.60 (q, J = 320 Hz), 114.58 (d, J = 2 Hz),
114.48 (d, J = 2 Hz), 112.69–112.63 (m), 68.12, 68.11, 56.39,
31.79, 29.32, 29.22, 29.16, 29.14, 26.00, 22.64, 14.07.
19F NMR (376 MHz, CDCl3): d = –141.60 (d, J = 128 Hz, 1 F),
–147.91 (d, J = 120 Hz, 1 F), –150.97 (d, J = 128 Hz, 1 F), –156.74
(d, J = 120 Hz, 1 F).
19F NMR (376 MHz, CDCl3): d = –73.98 (s, 3 F), –146.29 (d,
J = 129 Hz, 1 F), –146.56 (d, J = 130 Hz, 1 F), –148.01 (d, J = 130
Hz, 1 F), –148.60 (d, J = 129 Hz, 1 F).
Anal. Calcd for C39H46F4O4: C, 71.54; H, 7.08. Found: C, 71.33; H,
7.11.
Anal. Calcd for C40H47F7O6S: C, 60.90; H, 6.01; S, 4.06. Found: C,
60.91; H, 6.00; S, 4.07.
Synthesis 2008, No. 10, 1580–1588 © Thieme Stuttgart · New York

1586
F. Babudri et al.
PAPER
Methyl 2¢,5¢-Bis[(E)-1,2-difluoro-2-(4-octyloxyphenyl)vinyl]-4¢-
methoxybiphenyl-4-carboxylate (9)
Anal. Calcd for C46H52F4O5: C, 72.61; H, 6.89. Found: C, 72.60; H,
6.86.
A three-neck, 100 mL round-bottom flask equipped with a nitrogen
tee, was charged with 7 (1.17 g 1.48 mmol), methyl-4-(4,4,5,5-tet-
ramethyl-1,3,2-dioxaborolan-2-yl)benzoate (8; 0.58 g, 1.5 mmol),
Pd(Ph3P)4 (0.09 g, 0.07 mmol), toluene (30 mL) and MeOH (8 mL).
To the stirred solution, LiCl (0.19 g, 4.43 mmol) and Na2CO3 (2M,
2.34 mL) were added and the resulting mixture was refluxed over-
night. The reaction mixture was quenched with H2O (50 mL), ex-
tracted with CH2Cl2 (3 × 70 mL) and the organic layer was dried
over anhyd Na2SO4, filtered and the solvent was evaporated at re-
duced pressure. The residue was purified by column chromatogra-
phy (PE–EtOAc, 8:2). Yield: 0.8 g (70%); pale-yellow solid; mp
93–94 °C.
(E)-[1,2-Difluoro-2-(4-octyloxyphenyl)vinyl]-1-triethylsilane
(13)
A three-neck, 50 mL round-bottom flask equipped with a low tem-
perature thermometer, a magnetic stirrer bar, two 10 mL dropping
funnels and a nitrogen tee, was charged with 1-octyloxy-4-iodoben-
zene (11; 3.4 g, 10.2 mmol) and anhyd THF (30 mL). The resulting
mixture was cooled to –90 °C and n-BuLi (2.5 M, 4.1 mL, 10.2
mmol) was slowly added dropwise over 20 min. After the addition
was complete, the solution was stirred at –90 °C for 1 h and then
1,1,2-trifluorotriethylsilylethylene (2.0 g, 10.2 mmol) was added
dropwise. The reaction mixture was stirred at –80 °C for 2 h and
then warmed to 25 °C overnight. Sat. aq NH4Cl (25 mL) was added
slowly and the reaction mixture was extracted with Et2O (3 × 30
mL). The organic layer was dried over Na2SO4 and, after evapora-
tion of the solvent, the residue was purified by column chromatog-
raphy (PE, 100%). Yield: 3.11 g (80%); colorless dense liquid.
1H NMR (500 MHz, CDCl3): d = 7.65 (app d, J = ~9 Hz, 2 H), 6.93
(app d, J = ~9 Hz, 2 H), 3.99 (t, J = 6.7 Hz, 2 H), 1.80 (quint, J = 7.2
Hz, 2 H), 1.48 (quint, J = 7.5 Hz, 2 H), 1.40–1.26 (m, 8 H), 1.05 (t,
J = 7.9 Hz, 9 H), 0.91 (t, J = 6.7 Hz, 3 H), 0.82 (q, J = 7.9 Hz, 6 H).
13C NMR (125 MHz, CDCl3): d = 160.38 (dd, J = 34, 222 Hz),
159.55 (d, J = 3 Hz), 156.09 (dd, J = 84, 266 Hz), 127.20 (dd, J = 8,
10 Hz), 122.51 (dd, J = 4, 28 Hz), 114.26 (d, J = 3 Hz), 68.03,
31.82, 29.36, 29.25, 29.20, 26.02, 22.66, 14.07, 7.16, 2.59.
FTIR (KBr): 2917, 2850, 1719, 1609, 1516, 1475, 1464, 1309,
1280, 1257, 1223, 1183, 1107, 1038, 841 cm–1.
1H NMR (500 MHz, CDCl3): d = 8.04 (app d, J = ~8 Hz, 2 H), 7.71
(app d, J = ~9 Hz, 2 H), 7.56 (s, 1 H), 7.54 (app d, J = ~8 Hz, 2 H),
7.53 (app d, J = ~9 Hz, 2 H), 7.25 (s, 1 H), 6.97 (app d, J = ~9 Hz,
2 H), 6.92 (app d, J = ~8.6 Hz, 2 H), 4.01 (t, J = 6.8 Hz, 2 H), 3.98
(t, J = 6.8 Hz, 2 H), 3.97 (s, 3 H), 3.91 (s, 3 H), 1.81 (quint, J = 6.8
Hz, 2 H), 1.80 (quint, J = 8.3 Hz, 2 H), 1.48 (quint, J = 7.4 Hz, 2 H),
1.46 (quint, J = 7.8 Hz, 2 H), 1.41–1.3 (m, 16 H), 0.91 (t, J = 6.7
Hz, 3 H), 0.90 (t, J = 6.7 Hz, 3 H).
13C NMR (125 MHz, CDCl3): d = 166.94, 159.77 (d, J = 2 Hz),
159.63 (d, J = 3 Hz), 156.70, 148.09 (dd, J = 47, 266 Hz), 148.08
(dd, J = 46, 198 Hz), 146.74 (dd, J = 55, 212 Hz), 144.89, 144.83
(dd, J = 55, 211 Hz), 132.70, 132.57 (t, J = 4 Hz), 130.81 (dd, J = 4,
23 Hz), 129.58, 128.69, 128.30, 127.30 (t, J = 8 Hz), 127.26 (t, J = 9
Hz), 122.02 (dd, J = 7, 25 Hz), 121.52 (dd, J = 7, 25 Hz), 120.71
(dd, J = 4, 25 Hz), 114.40, 114.38, 113.14–112.96 (br m), 68.03,
56.07, 52.03, 31.78, 29.32, 29.30, 29.20, 29.15, 29.11, 25.98, 25.97,
22.63, 14.07.
MS (EI, 70 eV): m/z (%) = 382 (23) [M+], 185 (55), 128 (85), 101
(51), 77 (100), 57 (80).
Anal. Calcd for C22H36F2OSi: C, 69.06; H, 9.48. Found: C, 69.07;
H, 9.49.
(E)-(1,2-Difluoro-2-tributylstannylvinyl)-1-triethylsilane (15)
A three-neck, 250 ml round-bottom flask equipped with a low tem-
perature thermometer, 25 mL dropping funnel and nitrogen tee, was
charged with (Z)-1,2-difluorotriethylsilylethylene (17; 9.63 g, 5.4
mmol) and anhyd THF (140 mL). To the resulting solution, cooled
to –90 °C, n-BuLi (2.5M, 21.6 mL, 5.4 mmol) was added dropwise
over 2 h. After the addition was complete, Bu3SnCl (15.4 mL, 5.4
mmol) was added dropwise. The reaction mixture was stirred at
–90 °C for 2 h and then warmed to r.t. overnight. The reaction mix-
ture was quenched with H2O (100 mL) and extracted with Et2O
(3 × 30 mL). The organic layer was dried over anhyd Na2SO4, fil-
tered and the solvent was removed under reduced pressure. The res-
idue was distilled using a Kughelrohr apparatus (8 × 10–4 mbar,
120 °C). Yield: 22 g (87%); colorless liquid.
19F NMR (376 MHz, CDCl3): d = –140.31 (d, J = 131 Hz, 1 F),
–144.32 (d, J = 129 Hz, 1 F), –150.23 (d, J = 129 Hz, 1 F), –150.36
(d, J = 131 Hz, 1 F).
Anal. Calcd for C47H54F4O5: C, 72.85; H, 7.02. Found: C, 72.91; H,
6.98.
2¢,5¢-Bis[(E)-1,2-difluoro-2-(4-octyloxyphenyl)-vinyl]-4¢-meth-
oxybiphenyl-4-carboxylic Acid (10)
See the typical procedure given for compound 5 (hydrolysis of car-
bomethoxy groups). Purified by column chromatography (PE–
EtOAc, 2:8). Yield: 80%; pale-yellow solid; mp 129–130 °C.
FTIR (KBr): 2924, 2852, 1689, 1608, 1513, 1466, 1419, 1392,
1289, 1254, 1218, 1181, 1106, 1036, 833 cm–1.
FTIR (KBr): 2956, 2921, 2874, 1463, 1416, 1377, 1239, 1047,
1019, 1005, 742, 725 cm–1.
1H NMR (500 MHz, CDCl3): d = 1.55 (quint, J = 8.0 Hz, 6 H), 1.33
(sext, J = 7.4 Hz, 6 H), 1.06 (t, J = 8.0 Hz, 6 H), 0.98 (t, J = 7.4 Hz,
9 H), 0.9 (t, J = 7.9 Hz, 9 H), 0.72 (q, J = 7.9 Hz, 6 H).
13C NMR (125 MHz, CDCl3): d = 177.20 (dd, J = 113, 376 Hz),
169.96 (dd, J = 69, 311 Hz), 28.90, 27.09, 13.64, 10.00, 7.13, 2.51.
1H NMR (500 MHz, CDCl3 + D2O): d = 8.10 (app d, J = ~9 Hz,
2 H), 7.71 (d, J = ~9 Hz, 2 H), 7.57 (app d, J = ~9 Hz, 2 H), 7.56 (s,
1 H), 7.53 (app d, J = ~9 Hz, 2 H), 7.25 (s, 1 H), 6.97 (app d, J = ~9
Hz, 2 H), 6.92 (app d, J = ~9 Hz, 2 H), 4.01 (t, J = 6.8 Hz, 2 H), 3.98
(t, J = 6.8 Hz, 2 H), 3.97 (s, 3 H), 1.81 (quint, J = 6.8 Hz, 2 H), 1.79
(quint, J = 6.8 Hz, 2 H), 1.50–1.40 (m, 4 H), 1.40–1.24 (m, 16 H),
0.90 (t, J = 6.5 Hz, 3 H), 0.89 (t, J = 7.4 Hz, 3 H).
13C NMR (125 MHz, CDCl3): d = 171.57, 159.82 (d, J = 3 Hz),
159.65 (d, J = 2 Hz), 156.80, 148.16 (dd, J = 47, 259 Hz), 148.15
(dd, J = 46, 204 Hz), 146.70 (dd, J = 56, 206 Hz), 145.84, 144.80
(dd, J = 56, 208 Hz), 132.70–132.48 (m), 130.86 (dd, J = 2, 20 Hz),
130.25, 128.44, 127.77, 127.34 (t, J = 8 Hz), 127.29 (t, J = 9 Hz),
122.03 (dd, J = 7, 26 Hz), 121.50 (dd, J = 7, 25 Hz), 120.76 (dd,
J = 4, 25 Hz), 114.46, 114.41, 113.20–113.00 (br m), 68.07, 56.12,
31.79, 29.34, 29.31, 29.21, 29.17, 29.12, 26.00, 25.98, 22.63, 14.09.
19F NMR (376 MHz, CDCl3): d = –155.60 (d, J = 106 Hz, 1 F),
–166.21 (d, J = 106 Hz, 1 F).
Anal. Calcd for C20H42F2SiSn: C, 51.40; H, 9.06. Found: C, 51.40;
H, 9.08.
[(E)-1,2-Difluoro-2-(9,9-dioctylfluoren-2-yl)vinyl]triethylsilane
(16)
A three-neck, 50 mL round-bottom flask equipped with a nitrogen
tee, was charged with 2-iodo-9,9-dioctylfluorene (14; 2.6 g, 4.03
mmol), 15 (1.88 g, 4.03 mmol), CuI (0.77 g, 4.03 mmol), Pd(Ph3P)4
(0.23 g, 0.2 mmol), anhyd THF (15 mL) and anhyd DMF (15 mL).
19F NMR (376 MHz, CDCl3): d = –140.40 (d, J = 131 Hz, 1 F),
–144.39 (d, J = 131 Hz, 1 F), –150.22 (d, J = 130 Hz, 1 F), –150.28
(d, J = 130 Hz, 1 F).
Synthesis 2008, No. 10, 1580–1588 © Thieme Stuttgart · New York

PAPER
Synthesis of Oligoarylenevinylenes with Fluorinated Double Bonds
1587
The resulting mixture was stirred at r.t. for 12 h and then quenched
with H2O (50 mL) and extracted with CH2Cl2 (3 × 70 mL). The or-
ganic layer was dried over anhyd Na2SO4, filtered and the solvent
was evaporated at reduced pressure. The crude product was purified
by column chromatography (PE–CH2Cl2, 9:1). Yield: 1.8 g (95%);
colorless dense liquid.
(4) (a) Electronic Materials: The Oligomer Approach; Müllen,
K.; Wegner, G., Eds.; Wiley-VCH: New York, 1998.
(b) Drefahl, G.; Kühmsted, R.; Ostwald, H.; Hörhold, H.-H.
Makromol. Chem. 1970, 131, 89. (c) Shenk, R.; Gregorius,
H.; Meerholz, K.; Heinze, J.; Müllen, K. J. Am. Chem. Soc.
1991, 113, 2635. (d) Gregorius, M.; Baumgarten, M.;
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FTIR (KBr): 2955, 2927, 2854, 1633, 1465, 1455, 1416, 1377,
1240, 1081, 1004, 832, 739 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.77–7.75 (m, 3 H), 7.71 (app d,
J = 1 Hz, 1 H), 7.41–7.34 (m, 3 H), 2.06–2.00 (m, 4 H), 1.25 (quint,
J = 7.0 Hz, 4 H), 1.20–1.06 (m, 16 H), 1.13 (t, J = 7.9 Hz, 9 H), 0.91
(q, J = 7.9 Hz, 6 H), 0.87 (t, J = 7.1 Hz, 6 H), 0.75–0.62 (br m, 4 H).
13C NMR (125 MHz, CDCl3): d = 160.80 (dd, J = 34, 224 Hz),
157.46 (dd, J = 86, 272 Hz), 151.27, 150.68 (d, J = 2 Hz), 142.03
(d, J = 2 Hz), 140.43, 128.61 (dd, J = 5, 27 Hz), 127.51, 126.83,
124.72 (dd, J = 8, 10 Hz), 122.92, 120.03, 119.91 (t, J = 9 Hz),
119.51 (d, J = 2 Hz), 55.23, 40.24, 31.80, 29.97, 29.19, 29.16,
23.66, 22.61, 14.05, 7.24, 2.65.
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19F NMR (376 MHz, CDCl3): d = –151.97 (d, J = 122 Hz, 1 F),
–164.35 (d, J = 122 Hz, 1 F).
MS (EI, 70 eV): m/z (%) = 566 (100) [M+], 453 (58), 355 (25), 341
(62), 313 (13), 217 (17), 203 (14).
Anal. Calcd for C37H56F2Si: C, 78.39; H, 9.96. Found: C, 78.49; H,
9.95.
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Acknowledgment
This work was financially supported by the Ministero dell’Univer-
sità e della Ricerca (MIUR ‘Progetto FIRB 2003 SYNERGY
RBNE03S7XZ’), by the Università degli Studi di Bari and by Pro-
getto Vigoni 2006 and 2007: ‘Self-assembling of Polymers and Me-
tal Complexes for (Electro)luminescent Materials’.
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