A convenient one-pot synthesis of bis[(E)-4-halostyryl]arene derivatives

Article abstract of DOI:10.1055/s-2008-1067253

A new convenient synthetic protocol for the one-pot stereoselective synthesis of bis[(E)-4-bromo(or chloro)styryl]arene derivatives via the sequential reaction of silylative-coupling of 4-halostyrenes with vinylsilanes followed by palladium-catalyzed cross-coupling 4-halostyrylsilanes with diiodoarenes, is described. The reaction leads to symmetrical bis[(E)-4-halostyryl]arene derivatives obtained in a stereocontrolled manner with high efficiency. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2008-1067253

PAPER
3047
A Convenient One-Pot Synthesis of Bis[(E)-4-halostyryl]arene Derivatives
S
ynthesis of Bis[(
E
)-4-h
i
alostyr
e
yl]arene
D
e
s
rivativesław Prukała, Mariusz Majchrzak, Krystian Posała, Bogdan Marciniec*
Department of Organometallic Chemistry, Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznan, Poland
Fax +48(61)8291508; E-mail: marcinb@amu.edu.pl
Received 17 March 2008; revised 13 June 2008
nyl organosilicon compounds occurs by cleavage of
Abstract: A new convenient synthetic protocol for the one-pot ste-
the =C–Si bond of the vinylsilane and the activation of
the =C–H bond of the styrene molecule. Thus obtained
styrylsilanes can be easily transformed into the desired
reoselective synthesis of bis[(E)-4-bromo(or chloro)styryl]arene
derivatives via the sequential reaction of silylative-coupling of 4-
halostyrenes with vinylsilanes followed by palladium-catalyzed
cross-coupling 4-halostyrylsilanes with diiodoarenes, is described. styryl-arenes in desilylative coupling reaction with ha-
loarenes (Hiyama coupling, HC)10 in the presence of a
palladium catalyst and TBAF (Bu4NF) as an activator.
The reaction leads to symmetrical bis[(E)-4-halostyryl]arene deriv-
atives obtained in a stereocontrolled manner with high efficiency.
Key words: vinylsilanes, transition metals catalysis, silylative
cross-coupling
This sequence of highly-stereoselective reactions allows
the use of the vinyl group in vinylsilanes as a synthon for
C=C double bond in the obtained arylene-vinylene deriv-
atives.
Organic molecules with extended p-conjugated double
bond systems have found wide application in optoelec-
tronic devices including light-emitting diodes (LED),
nonlinear optics (NLO), photovoltaic cells, plastic lasers,
and field-effect transistors.1 The search for novel electro-
phores and chromophores is still of fundamental and prac-
tical interest. Stilbenoid compounds with extended p-
systems show interesting photophysical and photochemi-
cal properties and are therefore suited for various applica-
tions in material science.2 Due to similar basic structure
and interesting photophysical properties of bis(halostyr-
yl)arenes to those of poly(phenylene vinylene), they have
gained significant attention as potential unsaturated mo-
nomeric building blocks in polymer synthesis.3
We have recently reported a new and efficient protocol for
the synthesis of unsymmetrical (E)-4-chlorostilbene and
its derivatives via Hiyama coupling (HC) of 1-aryl-2-si-
lylethenes with aryl iodides in the presence of
[Pd2(dba)3]10c and a one-pot palladium-catalyzed Hiyama-
type strategy for the stereoselective synthesis of (E)-
poly(arylene vinylene)s using aryl dihalides and isomeric
bis(silyl)ethenes as new double bond equivalents.10d
Herein, we present the results of our synthetic studies of
halo-substituted symmetrical bis[(E)-styryl]arenes. The
desired products were obtained via the sequential reaction
of silylative coupling (SC) of divinyltetramethyldisilox-
ane with 4-halostyrenes, followed by desilylative cou-
pling of bis(4-halostyryl)tetramethyldisiloxane in the
presence of a palladium catalyst. This one-pot reaction
leads to a wide range of symmetrical bis[(E)-4-halostyr-
yl]arenes in high yield and with stereoselectivity. In an
initial experiment, we synthesized (E)-[1-(4-bromophe-
nyl)-2-(pentamethyldisiloxane)]ethene (1) via silylative
cross-coupling between vinylpentamethyldisiloxane and
4-bromostyrene using ruthenium complex [Ru-
Symmetrical derivatives of 1,4-distyrylbenzene belong to
disperse optical brightening agents4 and can be used as a
core of stilbenoid dendrimers.5 Despite their importance,
only few methods of their synthesis have been proposed.
Conventional approaches to the synthesis of bis(styr-
yl)arenes are: Wittig–Horner-type condensation,3g,5b,6
Heck,3c,7 Suzuki–Miyaura,3c,f,8 or Hiyama8 reaction.
On the other hand, in the series of our studies we have de- HCl(CO)(PPh3)3] as a catalyst (Scheme 1).
veloped in the last two decades, the silylative coupling re-
This reaction was examined in an open system under a
action of vinylsilane with styrene derivatives in the
presence of transition-metal complexes (e.g., ruthenium
and rhodium) initially containing or generating M–H and
M–Si bonds.9 The silylative coupling reaction of monovi-
gentle stream of argon. The reaction was effectively cata-
lyzed by ruthenium catalyst (0.1 mol%) in toluene at
110 °C for 7 hours. Such a small amount of catalyst needs
CuCl as a co-catalyst (0.4 mol%). The exclusive forma-
Me
Me
Si
O SiMe3
[Ru], CuCl
+
Si
O SiMe3
Br
Br
Me
toluene
Ar, 110 °C, 7 h
Me
1
[Ru] = RuH(Cl)(CO)(PPh3)3
Scheme 1 Synthesis of (E)-(1-(4-bromophenyl)-2-(pentamethyldisiloxane))ethene (1)
SYNTHESIS 2008, No. 19, pp 3047–3052
x
x.
x
x
.
2
0
0
8
Advanced online publication: 04.09.2008
DOI: 10.1055/s-2008-1067253; Art ID: T04308SS
© Georg Thieme Verlag Stuttgart · New York

3048
W. Prukała et al.
PAPER
Me
Si
Br
O
SiMe3
Pd2(dba)3
Br
Me
I-Ar-I
TBAF, dioxane
30 °C
Br
1
2
Scheme 2 Palladium-catalyzed cross-coupling of (E)-[1-(4-bromophenyl)-2-(pentamethyldisiloxane)]ethene (1) with 1,4-diiodobenzene
[Ru], CuCl
tion of the E-isomer of [1-(4-bromophenyl)-2-(penta-
methyldisiloxane)]ethene (1) was confirmed by 1H NMR
spectroscopy. The expected product 1 was isolated as a
colorless liquid by column chromatography and further
purified by distillation under low pressure (89%).
+
R
Si O Si
2
dioxane
100 °C, 24 h
R = Br, Cl;
[Ru] = RuHCl(CO)(PPh3)3
The synthesized 1 was used for a catalytic examination in
the synthesis of 1,4-bis[(E)-4-bromostyryl]benzene (2)
(Scheme 2). Compound 1 underwent desilylative cou-
pling reaction (HC) with 1,4-diiodobenzene catalyzed by
palladium catalyst [Pd2(dba)3] in the presence of TBAF as
an activator.
R
Ar
Pd2(dba)3
R
I-Ar-I
TBAF, dioxane
30 °C
The reaction was performed in an open system under a
gentle flow of argon at 30 °C for 72 hours (Table 1). Con-
version of substrates, selectivity, and yield of the process
were determined using a GC method with an internal stan-
dard. The results clearly showed that the best catalytic
system contains at least 0.2% of [Pd2(dba)3] relative to the
silyl compound. However, the reduction of the catalyst
amount to 0.2 mol% required longer reaction time (24 h).
The use of the catalyst in a lower amount (0.1%) gave a
low yield of desired product 2. On the other hand, the use
of higher amount of palladium catalyst (0.5%) reduced the
reaction time to 8 hours (Table 1).
F
F
F
Ar =
;
;
;
;
F
;
S
Scheme 3 One-pot silylative coupling of 4-halostyrenes with divi-
nyltetramethyldisiloxane and Hiyama coupling reaction of bis[(E)-4-
halostyryl]tetramethyldisiloxane with diiodobenzene
Table 1 Synthesis of 1,4-Bis[(E)-4-bromostyryl]benzene (2)
benzene, toluene, and DMSO. Due to solubility of sub-
strates and favorable properties, dioxane appeared the best
one for both steps of ‘one-pot’ reaction.
Entry [Pd]:[Si]
Time (h) Conv. (IArI) (%) Yield (%)a
1
2
3
4
1:10000
1:1000
1:500
72
24
24
8
0
23
–
The first step (SC) of the one-pot reaction was the synthe-
sis of bis[(E)-4-bromo(or chloro)styryl]tetramethyldisi-
loxane in a mini-reactor. The use of dioxane as a solvent
entailed the lower temperature (100 °C), higher excess of
catalyst (1 mol%), co-catalyst (1 mol%), and a longer time
(16 h) of the reaction. These reaction conditions were also
necessary to totally transform vinyl groups in divinyltet-
ramethyldisiloxane, because in the second step of the one-
pot synthesis they can produce some by-products. Two-
fold excess of 4-bromo(or chloro)styrene relative to di-
vinyltetramethyldisiloxane was enough to complete silyl-
ative coupling reaction of both vinyl groups, and still
homopolymerization of halostyrene was not observed.
Conversion of substrates (>99%), selectivity (>99%) and
the yield of the process were determined using the GC
method with an internal standard. Then, the components
for the Hiyama coupling (additional amount of dioxane,
IArI, TBAF, and catalyst) were introduced. The dilution
was necessary for dissolving the diiodoarene. The second
step of the one-pot reaction was performed at a lower tem-
perature (30 °C) for 8–48 hours (Table 2).
–
~99
100
96
98
1:200
a Isolated yield of chromatographically pure product.
The results of the catalytic study prompted us to perform
experiments aiming at an elaboration of the one-pot reac-
tion system [without isolation of (E)-4-halostyryldisilox-
ane (1)]. However, instead of vinylpentamethyldisiloxane
substrate, commercially available divinyl substituted di-
siloxane was initially used as a substrate in the silylative
coupling reaction to get bis[(E)-4-halostyryl]tetramethyl-
disiloxane as a ‘product-substrate’ and followed without
isolation by Hiyama coupling, according to Scheme 3.
The silylative coupling reaction of divinyltetramethyldi-
siloxane with 4-bromostyrene and desilylative coupling
‘product-substrate’ with 1,4-diiodobenzene were tested in
some common solvents such as: THF, dioxane, DMF,
Synthesis 2008, No. 19, 3047–3052 © Thieme Stuttgart · New York

PAPER
Synthesis of Bis[(E)-4-halostyryl]arene Derivatives
3049
Table 2 One-Pot Synthesis of Bis[(E)-4-bromo(or chloro)styr-
group. Because of the lack of polar substituents, com-
pounds 2, 3, and 11 were found to be only poorly soluble
in common deuterated solvents (C6D6, CDCl3, DMSO-d6,
THF-d8) and their 13C NMR spectra could not be record-
ed. The molecular weights of obtained bis[(E)-4-bro-
mo(or chlorostyryl)]arenes 2–13 were confirmed by EI-
MS and high-resolution mass spectroscopic analyses.
yl]arenesa
Entry Aryl diiodide
R
Time
(h)
Product Yield
(%)b
1
2
1,4-I2C6H4
Br
Cl
Br
Cl
Br
Cl
Br
Cl
Br
Cl
Br
Cl
8
8
2
3
97
98
91
90
82
86
43
51
98
94
89
95
1,4-I2C6H4
In conclusion, we have developed a new efficient, highly
stereoselective, one-pot synthetic methodology for the
construction of bis[(E)-4-bromo(or chloro)styryl]arenes
based on ruthenium catalyzed silylative cross-coupling of
divinyltetramethyldisiloxane with 4-bromo(or chloro)sty-
renes followed by palladium-catalyzed desilylative
coupling of the intermediate bis[(E)-4-halostyryl]tetra-
methyldisiloxane with diiodoarenes. The availability of
the starting materials, simplicity of the experimental tech-
nique and the possibility of mild reaction conditions are
favorable features of this new catalytic approach to syn-
thesis of bis[(E)-4-halostyryl]arenes.
3
1,3-I2C6H4
24
24
24
24
48
48
16
16
24
24
4
4
1,3-I2C6H4
5
5
1,2-I2C6H4
6
6
1,2-I2C6H4
7
7
1,4-I2C6F4
8
8
1,4-I2C6F4
9
9
4-IC6H4–C6H4-4¢-I
4-IC6H4–C6H4-4¢-I
2,5-I2C4H2S
2,5-I2C4H2S
10
11
12
13
10
11
12
1H NMR (300 MHz), 13C NMR (75 MHz), and 29Si NMR were re-
corded on Varian XL 300 MHz spectrometer in CDCl3 (or DMSO-
d6, THF-d8) solution. IR spectra (KBr pellets) were recorded on a
Bruker ITS 113v spectrometer. Analytical gas chromatographic
(GC) analyses were performed on a Varian Star 3400CX with a DB-
5 fused silica capillary column (30 m × 0.15 mm) and TCD. Mass
spectra of the monomers and products were obtained by GCMS
analysis (Varian Saturn 2100T, equipped with a BD-5 capillary col-
umn (30 m) and an ion trap detector. High-resolution mass spectro-
scopic (HRMS) analyses were performed on an AMD-402 mass
spectrometer. TLC was performed on plates coated with 250 mm
thick silica gel (Merck), and column chromatography was per-
formed with silica gel 60 (70–230 mesh, Fluka). Toluene and hex-
ane were dried by distillation from NaH; THF and dioxane were
distilled from Na under argon. All liquid substrates were also dried
and degassed by bulb-to-bulb distillation. All the reactions were
carried out under dry argon. Melting points are uncorrected and
were determined by using Boetius melting point apparatus.
a SC conditions: [Si–O–Si]:[RuHCl(CO)(PPh3)3]:[CuCl] =
1:0.02:0.02; dioxane (1 M), 100 °C. HC conditions: [Si–O–Si]:
[XArX]:[TBAF]:[Pd2(dba)3] = 1:0.8:2.4:0.02, dioxane, 30 °C.
b Isolated yields of products.
The desilylative coupling reaction required a small excess
of silyl compounds (10% per one iodo substituent) and
TBAF (20% per one silyl group). This reaction needs at
least 1 mol% catalyst loading ([Pd2(dba)3]) per one silyl
group for exclusive formation of the products expected. In
the above specified reaction conditions, the desired
bis[(E)-4-bromo(or chloro)styryl]arenes 2–13 were ob-
tained with perfect stereoselectivity (Table 2). With 1,4-
diiobenzene and 4,4¢-diiodobiphenyl as substrates, this
one-pot procedure provided almost quantitative yields
(97–99%) of the expected products (Table 2, entries 1, 2,
9, and 10). These compounds 2, 3, 10, and 11 were almost
insoluble in dioxane and they could be easily separated
The chemicals were obtained from the following sources: toluene,
THF, dioxane, EtOAc, decane, and hexane were purchased from
Fluka; CDCl3 from Dr. Glaser A.G. Basel; vinylpentamethyldisi-
loxane and 1,3-divinyltetramethyldisiloxane were purchased from
ABCR company; 1,4-diodobenzene, 1,3-diodobenzene, 1,2-diodo-
from the reaction mixture by filtration. Only when 1,4-di- benzene, 4,4¢-diiodobiphenyl, 4,4¢-diiodobiphenyl, 2,5-diiodo-
thiophene, Bu4NF and pentane, were bought from Aldrich. The
iodotetrafluorobenzene was used, low transformation
(43% for 8 and 51% for 9) was observed (Table 2, entries
ruthenium and palladium complexes – [RuHCl(CO)(PPh3)3]11 and
[Pd2(dba)3]12 – were prepared according to procedures described in
7 and 8). The extended reaction time (48 h) did not cause
literature.
a significant increase in the yield of products 8 and 9
(Table 2). Compounds 4–9 and 12,13 were separated on a
silica gel chromatographic column (EtOAc–THF).
Catalytic Examination of Hiyama Coupling Reaction
In a typical catalytic test, the reagents (0.5 mmol) and decane as an
internal standard (5% by volume of all components) were dissolved
in dioxane (5 mL) and placed in a glass ampoule under argon (usu-
ally used in the molar ratio: [Si]:[XArX]:[TBAF] = 1:0.8:2.4). Then
the palladium catalyst (0.1–1.0 mol%) was added and the ampoule
was heated at 30 °C for 16–48 h. The conversion of the substrates
The structures of the obtained products 2–13 were con-
1
firmed by FT-IR, H NMR, 13C NMR, and EI-MS spec-
troscopy. The presence of E-vinylene functionality was
unambiguously confirmed by the appearance of FT-IR
bands attributable to CH bending of trans-vinylene at was calculated using the internal standard method. The composition
929–998 cm–1. Unfortunately, the corresponding 1H NMR
of the reaction mixture was analyzed by GC, GCMS, or TLC.
signals (J = 14.8–16.2 Hz) fell in the region of aromatic
(E)-[1-(4-Bromophenyl)-2-(pentamethyldisiloxane)]ethene (1)
protons and could not be assigned for 4,4¢-bis[(E)-4-chlo-
A toluene solution (1 M) of the reagents, vinylpentamethyldisilox-
rostyryl]biphenyl (11). In two compounds 6 and 10 only
ane (10.0 mL, 45.13 mmol) and 4-bromostyrene (11.8 mL, 90.26
mmol) was placed in a two-necked glass flask equipped with a mag-
one signal was assigned to CH in the trans-vinylene
Synthesis 2008, No. 19, 3047–3052 © Thieme Stuttgart · New York

3050
W. Prukała et al.
PAPER
The analytical data were in accord with the literature values.
netic stirring bar and a condenser connected to a bubbler. Then the
mixture was stirred and heated at 110 °C under a flow of argon. Af-
ter 5 min, the ruthenium complex [RuHCl(CO)(PPh3)3] (43 mg, 0.1
mol%) was added and then, after 10 min CuCl (17.8 mg, 0.4 mol%)
was added as a co-catalyst. The color of the solution changed from
yellow through green to yellow again. The synthesis process was
carried out for the next 7 h. After cooling, the resulting mixture was
flushed through a short column chromatography with hexane elu-
tion in order to separate the final mixture from the remains of com-
plex. The product was further purified by distillation under low
pressure (72 °C/0.8 mmHg) to give 13.23 g (89%) of a colorless liq-
uid.
1,3-Bis[(E)-4-bromostyryl]benzene (4)
Yellow powder; yield: 0.16 g (91%); mp 192–195 °C.
IR (KBr): 3012.0, 2970.7, 1605.5, 1486.3, 1251.9, 1109.3, 1022.9,
987.4, 883.0, 846.0, 791.2 cm–1.
1H NMR (CDCl3): d = 7.63 (s, 1 H, C6H4), 7.48 (d, J = 16.0 Hz, 2
H, C6H4CH), 7.01 (d, J = 16.2 Hz, 2 H, BrC6H4CH), 7.50–7.10 (m,
11 H, Ar).
13C NMR (CDCl3): d = 137.4, 136.1, 131.8, 131.4, 130.5, 129.1,
128.0, 127.8, 126.0, 125.5.
1H NMR (CDCl3): d = 7.46 (d, J = 8.4 Hz, 2 H, C6H4Br), 7.31 (d,
J = 8.7 Hz, 2 H, C6H4Br), 6.85 (d, J = 19.2 Hz, 1 H, SiHC=CH),
6.41 (d, J = 19.5 Hz, 1 H, SiHC=CH), 0.23 [s, 6 H, Si(CH3)2], 0.12
[s, 9 H, OSi(CH3)3].
13C NMR (CDCl3): d = 142.6, 137.0, 131.5, 129.7, 127.9, 121.9,
2.1, 0.9.
MS (EI): m/z (%) = 440 (9), 438 (12), 286 (57), 205 (100), 202 (62),
178 (69), 103 (41).
HRMS (EI): m/z calcd for C22H1679Br81Br: 439.9598; found:
439.9584.
Anal. Calcd for C22H16Br2: C, 60.03; H, 3.66; Br, 36.31. Found: C,
59.79; H, 3.74; Br, 36.09.
29Si NMR (CDCl3): d = –2.53, 9.29.
1,3-Bis[(E)-4-chlorostyryl]benzene (5)
Yellow crystals; yield: 0.126 g (90%); mp 178–182 °C.
MS (EI): m/z (%) = 328 (5), 313 (82), 249 (38), 233 (100), 193 (31),
149 (48), 133 (33).
HRMS (EI): m/z calcd for C13H2179Br81BrOSi2: 328.03143; found:
328.03138.
IR (KBr): 3434.6, 3013.3, 2924.3, 1909.7, 1645.4, 1587.6, 1575.8,
1490.2, 1420.9, 1400.1, 1092.2, 1011.8, 970.2, 855.1, 820.4, 691.4,
514.1 cm–1.
1H NMR (THF-d8): d = 7.72 (s, 1 H, C6H4), 7.54 (d, J = 16.0 Hz, 2
H, C6H4CH), 7.10 (d, J = 16.0 Hz, 2 H, ClC6H4CH), 7.50–7.10 (m,
11 H, Ar).
Anal. Calcd for C13H21BrOSi2: C, 47.40; H, 6.43. Found: C, 47.38;
H, 6.42.
One-Pot Synthesis of Bis[(E)-4-halostyryl]tetramethyldisilox-
anes 2–13; General Procedure
13C NMR (CDCl3): d = 138.6, 137.3, 133.8, 130.1, 129.7, 129.6,
128.7, 128.4, 126.8, 125.6.
The glass mini-reactor (15 mL, equipped with a magnetic stirring
bar, argon bubbling tube, and thermostated heating oil bath) was
evacuated and flushed with argon. [RuHCl(CO)(PPh3)3] (9.52 mg,
0.01 mmol), CuCl (0.99 mg, 0.01 mmol), 1,3-divinyltetramethyl-
disiloxane (0.1 g, 0.5 mmol), 4-bromo(or chloro)styrene (2.0
mmol), and anhydrous dioxane (1.0 mL) were added to the reactor.
The mixture was heated at 100 °C for 16 h under an argon flow. Af-
ter completion of the reaction (GCMS and 1H NMR analyses con-
firmed the formation of bis[(E)-4-halostyryltetramethyldisilox-
ane]), palladium catalyst [Pd2(dba)3] (9.16 mg, 0.01 mmol), TBAF
(320 mg, 1.2 mmol), dioxane (4.0 mL or 9 mL in the case of reaction
with 4,4¢-diiodobiphenyl and 1,4-diiodotetrafluorobenzene) and the
respective dihaloarene (0.4 mmol) were added and the mixture was
heated at 30 °C for 8–48 h under argon. The degree of conversion
of the substrates was estimated by GC and TLC analyses. Then the
mixture was cooled and the precipitated solid (2, 3, 10–11) was fil-
tered and washed extensively with dioxane or chromatographed on
a silica gel column (4–9, 12, 13) (EtOAc–THF).
MS (EI): m/z (%) = 352 (84), 350 (100), 280 (30), 278 (38), 276
(29), 202 (55), 178 (25).
HRMS (EI): m/z calcd for C22H1635Cl2: 350.0629; found: 350.0618.
Anal. Calcd for C22H16Cl2: C, 75.22; H, 4.59; Cl, 20.19. Found: C,
74.97; H, 4.72; Cl, 20.01.
1,2-Bis[(E)-4-bromostyryl]benzene (6)
Yellow oil; yield: 0.144 g (82%).
IR (KBr): 3058.2, 2957.4, 1669.0, 1591.7, 1437.6, 1182.4, 1120.1,
1028.1, 998.0, 754.3, 722.1, 694.5, 541.7 cm–1.
1H NMR (CDCl3): d = 7.50–7.10 (m, 14 H, Ar), 7.01 (d, J = 16.2
Hz, 2 H, BrC6H4CH).
13C NMR (CDCl3): d = 139.3, 131.7, 131.3, 130.2, 129.0, 128.9,
127.9, 125.4, 119.7.
MS (EI): m/z (%) = 440 (21), 438 (21), 286 (14), 219 (88), 205
(100), 203 (65), 169 (69).
1,4-Bis[(E)-4-bromostyryl]benzene (2)
HRMS (EI): m/z calcd for C22H1679Br81Br: 439.9598; found:
Yellow powder; yield: 0.17 g (97%); mp 345–348 °C.
439.9606.
IR (KBr): 3016.9, 2957.9, 2873.2, 1907.8, 1701.3, 1636.3, 1583.2,
1484.4, 1419.9, 1076.7, 1009.1, 971.2, 830.2 cm–1.
1H NMR (DMSO-d6): d = 7.92 (d, J = 8.5 Hz, 4 H, BrC6H4), 7.85
(m, 4 H, C6H4), 7.58 (m, 4 H, BrC6H4), 7.60 (d, J = 16.0 Hz, 2 H,
C6H4CH), 7.32 (d, J = 16.1 Hz, 2 H, BrC6H4CH).
Anal. Calcd for C22H16Br2: C, 60.03; H, 3.66; Br, 36.31. Found: C,
59.75; H, 3.41; Br, 36.03.
1,2-Bis[(E)-4-chlorostyryl]benzene (7)
Pale yellow powder; yield: 0.12 g (86%); mp 58–63 °C.
MS (EI): m/z (%) = 440 (100), 438 (61), 279 (35), 278 (32), 202
IR (KBr): 3025.2, 2955.8, 1685.7, 1591.1, 1489.2, 1449.9, 1402.9,
1259.6, 1176.7, 1088.4, 1011.0, 958.1, 855.8, 804.6, 747.1, 701.3,
523.4 cm–1.
1H NMR (CDCl3): d = 7.57 (d, J = 16.2 Hz, 2 H, C6H4CH), 7.50–
7.25 (m, 12 H, Ar), 6.94 (d, J = 16.2 Hz, 2 H, ClC6H4CH).
13C NMR (CDCl3): d = 135.9, 133.4, 130.3, 130.2, 128.9, 128.0,
127.8, 127.0, 126.7.
(29), 178 (37), 132 (22).
HRMS (EI): m/z calcd for C22H1679Br81Br: 439.9598; found:
439.9572.
Anal. Calcd for C22H16Br2: C, 60.03; H, 3.66; Br, 36.31. Found: C,
60.05; H, 3.78; Br, 36.17.
1,4-Bis[(E)-4-chlorostyryl]benzene (3)6c
Yellow powder; yield: 0.137 g (98%); mp 299–302 °C.
Synthesis 2008, No. 19, 3047–3052 © Thieme Stuttgart · New York

PAPER
Synthesis of Bis[(E)-4-halostyryl]arene Derivatives
1H NMR (DMSO-d6): d = 7.80–7.30 (m, Ar).
3051
MS (EI): m/z (%) = 352 (25), 350 (36), 278 (13), 276 (16), 225
(100), 204 (44), 178 (31).
HRMS (EI): m/z calcd for C22H1635Cl2: 350.0629; found: 350.0642.
MS (EI): m/z (%) = 428 (78), 426 (100), 265 (20), 253 (31), 213
(25), 178 (31), 126 (18).
Anal. Calcd for C22H16Cl2: C, 75.22; H, 4.59; Cl, 20.19. Found: C,
74.90; H, 4.35; Cl, 19.88.
HRMS (EI): m/z calcd for C28H2035Cl2: 426.0942; found: 426.0932.
Anal. Calcd for C28H20Cl2: C, 78.69; H, 4.72; Cl, 16.59. Found: C,
78.64; H, 4.57; Cl, 16.41.
1,4-Bis[(E)-4-bromostyryl]-2,3,5,6-tetrafluorobenzene (8)
Yellow powder; yield: 0.088 g (43%); mp 154–158 °C.
2,5-Bis[(E)-4-bromostyryl]thiophene (12)
IR (KBr): 2988.0, 2958.1, 2873.4, 1628.1, 1585.7, 1472.7, 1396.9,
1242.1, 1109.2, 1070.9, 1029.9, 1008.2, 969.2, 922.0, 880.6, 808.2,
736.0 cm–1.
1H NMR (DMSO-d6): d = 7.55 (d, J = 8.5 Hz, 4 H, BrC6H4), 7.48
(d, J = 8.7 Hz, 4 H, BrC6H4), 7.12 (d, J = 14.8 Hz, 2 H,
BrC6H4CH), 6.76 (d, J = 14.8 Hz, 2 H, C6F4CH).
Brown powder; yield: 0.158 g (89%); mp 188–191 °C.
IR (KBr): 3636.3, 3027.0, 2958.8, 2924.5, 2855.3, 1615.1, 1599.0,
1484.1, 1072.8, 1007.4, 960.7, 947.6, 854.7, 808.5, 540.8 cm–1.
1H NMR (CDCl3): d = 7.46 (d, J = 8.5 Hz, 4 H, BrC6H4), 7.32 (d,
J = 8.5 Hz, 4 H, BrC6H4), 7.16 (d, J = 16.2 Hz, 2 H, C4H2SCH),
6.96 (s, 2 H, C4H2S), 6.83 (d, J = 16.2 Hz, 2 H, BrC6H4CH).
13C NMR (CDCl3): d = 141.7, 135.7, 131.8, 128.9, 127.7, 127.3,
122.3, 121.3.
13C NMR (DMSO-d6): d = 142.9, 139.3, 136.3, 134.2, 132.0, 131.7,
130.2, 128.4, 120.6.
MS (EI): m/z (%) = 512 (11), 364 (34), 219 (100), 185 (47), 171
(49), 169 (53), 131 (72).
HRMS (EI): m/z calcd for C22H1279Br81BrF4: 511.9221; found:
511.9214.
MS (EI): m/z (%) = 448 (15), 446 (12), 184 (61), 142 (100), 100
(72), 57 (90).
HRMS (EI): m/z calcd for C20H14S79Br81Br: 445.9163; found:
445.9182.
Anal. Calcd for C22H12Br2F4: C, 51.60; H, 2.36; Br, 31.20. Found:
C, 51.26; H, 2.63; Br, 30.98.
Anal. Calcd for C20H14Br2S: C, 53.84; H, 3.16; Br, 35.82. Found: C,
53.59; H, 3.24; Br, 35.67.
1,4-Bis[(E)-4-chlorostyryl]-2,3,5,6-tetrafluorobenzene (9)
Yellow crystals; yield: 0.086 g (51%); mp 162–166 °C.
2,5-Bis[(E)-4-chlorostyryl]thiophene (13)
Brown powder; yield: 0.135 g (95%); mp 208–211 °C.
IR (KBr): 3027.9, 3009.6, 2923.0, 1620.1, 1589.7, 1486.9, 1401.1,
1245.3, 1089.5, 1011.0, 994.3, 967.4, 929.6, 852.6, 800.9 cm–1.
1H NMR (DMSO-d6): d = 7.55 (d, J = 8.5 Hz, 4 H, ClC6H4), 7.41
(d, J = 8.5 Hz, 4 H, ClC6H4), 7.17 (d, J = 15.2 Hz, 2 H, ClC6H4CH),
6.76 (d, J = 14.9 Hz, 2 H, C6F4CH).
13C NMR (DMSO-d6): d = 169.2, 142.7, 135.7, 134.8, 133.4, 128.6,
127.9, 114.2, 105.2.
IR (KBr): 3028.2, 2923.6, 2852.3, 1731.6, 1650.3, 1615.5, 1587.4,
1487.0, 1403.8, 1092.0, 1010.7, 961.8, 948.1, 855.6, 811.9, 542.0
cm–1.
1H NMR (CDCl3): d = 7.39 (d, J = 8.5 Hz, 4 H, ClC6H4), 7.30 (d,
J = 8.5 Hz, 4 H, ClC6H4), 7.15 (d, J = 16.2 Hz, 2 H, C4H2SCH),
6.96 (s, 2 H, C4H2S), 6.84 (d, J = 16.0 Hz, 2 H, ClC6H4CH).
13C NMR (CDCl3): d = 141.7, 135.3, 133.2, 128.8, 127.4, 127.3,
127.2, 122.3.
MS (EI): m/z (%) = 422 (32), 286 (55), 276 (58), 239 (70), 225 (57),
204 (100), 125 (66).
HRMS (EI): m/z calcd for C22H1235Cl2F4: 422.0252; found:
MS (EI): m/z (%) = 358 (74), 356 (100), 320 (10), 284 (13), 252
(21), 142 (21), 126 (18).
422.0252.
HRMS (EI): m/z calcd for C20H1435Cl2S: 356.0193; found:
Anal. Calcd for C22H12Cl2F4: C, 62.43; H, 2.86; Cl, 16.75. Found:
C, 62.19; H, 2.99; Cl, 16.51.
356.0201.
Anal. Calcd for C20H14Cl2S: C, 67.23; H, 3.95; Cl, 19.85. Found: C,
67.01; H, 4.07; Cl, 19.59.
4,4¢-Bis[(E)-4-bromostyryl]biphenyl (10)
Yellow powder; yield: 0.202 g (98%); mp >340 °C.
Acknowledgment
IR (KBr): 3440.8, 3016.7, 2923.7, 2852.3, 1904.0, 1632.2, 1580.8,
1495.5, 1484.6, 1403.4, 1073.9, 1007.6, 969.7, 828.4, 819.9, 720.4,
529.0 cm–1.
1H NMR (THF-d8): d = 7.77 (d, J = 8.6 Hz, 4 H, BrC6H4), 7.62–
7.20 (m, 14 H, Ar), 7.18 (d, J = 14.8 Hz, 2 H, BrC6H4CH).
13C NMR (THF-d8): d = 140.9, 138.8, 137.7, 132.6, 129.7, 129.4,
129.0, 128.0, 127.7, 121.9.
This work was made possible by a grant PBZ-KBN 118/T09/17
from Ministry of Education and Science (Poland).
References
(1) (a) Special issue: Molecular Materials in Electronic and
Optoelectronic Devices; Sheats, J. R.; Barbara, P. F., Eds.;
Acc. Chem. Res. 1999, 32, 191–276. (b) Videlot-
MS (EI): m/z (%) = 516 (8), 462 (100), 253 (88), 178 (17), 152 (17),
126 (29), 102 (15).
HRMS (EI): m/z calcd for C28H2079Br81Br: 515.9911; found:
515.9906.
Ackermann, C.; Ackermann, J.; Brisset, H.; Kawamura, K.;
Yoshimoto, N.; Raynal, P.; El Kassmi, A.; Fages, F. J. Am.
Chem. Soc. 2005, 127, 16346. (c) Wilson, J. N.; Bunz, U. H.
F. J. Am. Chem. Soc. 2005, 127, 4124. (d) Takeshi, T.;
Takaaki, I. European Patent EP 1 843 211, 2007.
Anal. Calcd for C28H20Br2: C, 65.14; H, 3.90; Br, 30.95. Found: C,
64.97; H, 3.96; Br, 30.71.
(2) Meier, H. Angew. Chem., Int. Ed. Engl. 1992, 31, 1399.
(3) (a) Weitzel, H. P.; Müllen, K. Makromol. Chem. 1990, 13,
563. (b) Suzuki, M.; Lim, J. C.; Saegusa, T. Macromolecules
1990, 23, 1574. (c) Scherf, U.; Mullen, K. Synthesis 1992,
23; and literature cited therein. (d) Katayama, H.; Nagao,
M.; Nishimura, T.; Matsui, Y.; Umeda, K.; Akamatsu, K.;
4,4¢-Bis[(E)-4-chlorostyryl]biphenyl (11)
Yellow powder; yield: 0.16 g (94%); mp 303–307 °C.
IR (KBr): 3018.2, 2921.1, 1904.8, 1668.9, 1585.6, 1496.0, 1487.5,
1405.6, 1098.7, 1010.7, 999.5, 969.9, 829.4, 721.0, 530.8 cm–1.
Synthesis 2008, No. 19, 3047–3052 © Thieme Stuttgart · New York

3052
W. Prukała et al.
PAPER
(7) (a) Sengupta, S.; Sadhukhan, S. K.; Singh, R. S.; Pal, N.
Tsuruoka, T.; Nawafune, H.; Ozawa, F. J. Am. Chem. Soc.
2005, 127, 4350. (e) Katayama, H.; Nagao, M.; Ozawa, F.;
Ikegami, M.; Arai, T. J. Org. Chem. 2006, 71, 2699.
(f) Leclerc, N.; Sanaur, S.; Galmiche, L.; Mathevet, F.;
Attias, A.-J.; Fave, J.-L.; Roussel, J.; Hapiot, P.; Lemaitre,
N.; Geffroy, B. Chem. Mater. 2005, 17, 502. (g) Egbe, D.
A. M.; Tekin, E.; Berckner, E.; Pivrikas, A.; Sariciftci, N. S.;
Schubert, U. S. Macromolecules 2007, 40, 7786.
Tetrahedron Lett. 2002, 43, 1117. (b) Itami, K.; Tonogaki,
K.; Nokami, T.; Ohashi, Y.; Yoshida, J. Angew. Chem. Int.
Ed. 2006, 45, 2404.
(8) (a) Katayama, H.; Nagao, M.; Nishimura, T.; Matsui, Y.;
Fukuse, Y.; Wakioka, M.; Ozawa, F. Macromolecules 2006,
39, 2039. (b) Katayama, H.; Nagao, M.; Ozawa, F.; Ikegami,
M.; Arai, T. J. Org. Chem. 2006, 71, 2699.
(4) (a) Quintini, M. US Patent 5 250 223, 1993. (b) Reinehr,
D.; Sauter, H.; Kramer, J.; Weigmann, R.; Eckhardt, C.;
Meyer, H. R. European Patent EP 0900784, 1999.
(c) Hhoaf, G. L.; Ollis, G. W.; Stockl, R. R.; Munjal, R. C.
US Patent 0249764, 2007.
(5) (a) Frechet, J. M.; Hawker, C. J.; Gitsov, I.; Leon, J. W. J.
Macromol. Sci., Part A: Pure Appl. Chem. 1996, A33, 1399.
(b) Meier, H.; Lehmann, M. Angew. Chem. Int. Ed. 1998, 37,
643. (c) Lo, S.-C.; Burn, P. L. Chem. Rev. 2007, 107, 1097;
and literature cited therein.
(6) (a) Friedrich, K.; Henning, H.-G. Chem. Ber. 1959, 92,
2944. (b) Bontagy, J.; Thomas, R. Chem. Rev. 1974, 74, 87.
(c) Arient, J. Collect. Czech. Chem. Commun. 1981, 46,
101. (d) Deb, S. K.; Maddux, T. M.; Yu, L. J. Am. Chem.
Soc. 1997, 119, 9079. (e) Pillow, J. N. G.; Halim, M.;
Lupton, J. M.; Burn, P. L.; Samuel, I. D. W. Macromolecules
1999, 32, 5985. (f) Segura, J. L.; Gomez, R.; Martin, N.;
Guldi, D. M. Org. Lett. 2001, 3, 2645. (g) Palsson, L.-O.;
Beavington, R.; Frampton, M. J.; Lupon, J. M.; Magennis, S.
W.; Markham, J. P. J.; Pillow, J. N. G.; Burn, P. L.; Samuel,
I. D. W. Macromolecules 2002, 35, 7891. (h) Cano-Marin,
A. R.; Diez-Barra, E.; Rodriguez-Lopez, J. Tetrahedron
2005, 61, 395.
(9) (a) Marciniec, B.; Pietraszuk, C. Handbook of Metathesis,
Vol. 2; Grubbs, R., Ed.; Wiley-VCH: Weinheim, 2003.
(b) Marciniec, B.; Zaidlewicz, M.; Pietraszuk, C.;
Kownacki, I. In Comprehensive Organic Functional Group
Transformations II, Vol. 2; Katritzky, A. R.; Taylor, R. J. K.,
Eds.; Elsevier Science: Amsterdam, 2005, 941–1024.
(c) Marciniec, B. Coord. Chem. Rev. 2005, 249, 2374.
(d) Marciniec, B. Acc. Chem. Res. 2007, 40, 943.
(10) (a) Hiyama, T. In Handbook of Organopalladium Chemistry
for Organic Synthesis, Vol. 1; Negishi, E., Ed.; Wiley-
Interscience: New York, 2002, 285. (b) Hiyama, T. In
Metal-Catalyzed Cross-Coupling Reactions; Diederich, F.;
Stang, P. J., Eds.; Wiley-VCH: Weinheim, 1998.
(c) Prukała, W.; Majchrzak, M.; Pietraszuk, C.; Marciniec,
B. J. Mol. Catal. A: Chem. 2006, 254, 58. (d) Prukała, W.;
Pawluć, P.; Posała, K.; Marciniec, B. Synlett 2008, 41.
(11) (a) Levison, J. J.; Robinson, S. D. J. Chem. Soc. A 1970,
2947. (b) Ahmad, N.; Levison, J. J.; Robinson, S. D.; Uttley,
M. F. Inorg. Synth. 1974, 15, 45.
(12) Ukai, T.; Kawazura, H.; Ishii, Y. J. Organomet. Chem. 1974,
65, 253.
Synthesis 2008, No. 19, 3047–3052 © Thieme Stuttgart · New York