Utilization of industrially available 2,3-dichloro-1,3-butadiene for direct synthesis of 2,3-diaryl-1,3-butadienes

Article abstract of DOI:10.1246/bcsj.79.498

It is shown that industrially available 2,3-dichloro-1,3-butadiene is a useful starting material for the synthesis of 2,3-diaryl-1,3-butadienes. Ni(II)-catalyzed cross-coupling reaction of 2,3-dichloro-1,3-butadiene with ArMgBr (Ar = 2-thienyl, phenyl, 4-dodecyloxyphenyl, and 4-fluorophenyl) gives the corresponding 2,3-diaryl-1,3-butadienes in good yields.

Full text of DOI:10.1246/bcsj.79.498

498 Short Articles
Bull. Chem. Soc. Jpn. Vol. 79, No. 3, 498–500 (2006)
with aryl Grignard reagents is considered to provide a new
industrially profitable route to 2,3-diaryl-1,3-butadienes.
However, the usability of this route has not been examined.
The high tendency of 2,3-dichloro-1,3-butadiene to be poly-
merized and synthetic chemists being unaware of this route
seem to be the reasons. We now report that 2,3-dichloro-1,3-
butadiene containing inhibitors of radical polymerization (e.g.,
4-t-butylcatechol) can be handled normally as the starting
material of 2,3-diaryl-1,3-butadienes.
The coupling reactions of 2,3-dichloro-1,3-butadiene were
carried out with ArMgBr, where Ar = 2-thienyl, phenyl, 4-
dodecyloxyphenyl, or 4-fluorophenyl, by using [NiCl2(dppp)]
(dppp = 1,3-bis(diphenylphosphino)propane) as the catalyst
(Eq. 1). Details of the synthetic procedure are described in
the Experimental section.
Utilization of Industrially Available
2,3-Dichloro-1,3-butadiene for
Direct Synthesis of 2,3-Diaryl-
1,3-butadienes
ꢀ1
Takakazu Yamamoto, Takuma Yasuda,1
Kazuaki Kobayashi,1 Isao Yamaguchi,1
Take-aki Koizumi,1 Daisuke Ishii,1
Masaru Nakagawa,1 Yoshihiro Mashiko,2
and Norihiro Shimizu3
Cl
Ar
1Chemical Resources Laboratory, Tokyo Institute
of Technology, 4259 Nagatsuta, Midori-ku,
Yokohama 226-8503
[NiCl2(dppp)]
+
2 Ar-MgBr
ð1Þ
Cl
Ar
2Organic Materials Research Center, Denki Kagaku
Kogyo K. K., 2209 Omi, Itoigawa, Niigata 949-0393
Ar = 2-thienyl
phenyl
(1)
(2)
4-dodecyloxyphenyl (3)
4-fluorophenyl (4)
3Electronic Materials Research Center, Denki Kagaku
Table 1 shows the results of the coupling reactions. As
shown in Table 1, the reaction gave the expected products in
good yields. In this reaction, electron-withdrawing group-
Kogyo K. K., 1135 Nakamura, Shibukawa, Gunma 377-8520
Received August 17, 2005; E-mail: tyamamot@res.titech.ac.jp
Table 1. Synthesis of 2,3-Diaryl-1,3-butadienes
Entry
Ar
Product
Yield/%
It is shown that industrially available 2,3-dichloro-1,3-
butadiene is a useful starting material for the synthesis of 2,3-
diaryl-1,3-butadienes. Ni(II)-catalyzed cross-coupling reac-
tion of 2,3-dichloro-1,3-butadiene with ArMgBr (Ar = 2-thi-
enyl, phenyl, 4-dodecyloxyphenyl, and 4-fluorophenyl) gives
the corresponding 2,3-diaryl-1,3-butadienes in good yields.
S
1
65
S
S
1
2
1,3-Butadiene derivatives are useful materials for organic
synthesis as monomers for poly(butadiene)s and as building
blocks for natural product syntheses.1 Especially, 2,3-diaryl-
1,3-butadienes have a so-called cross-conjugated system, and
much attention has been paid to their molecular structures
and electronic properties.2 There have been several reports
on synthetic methods for 2,3-diaryl-1,3-butadienes. For exam-
ple, dehydration of pinacol derivatives,3 1,4-debromination of
1,4-dibromo-2-olefins,4 coupling of alkenyl halides catalyzed
by Pd–C in the presence of LiCl,5 Pd-catalyzed coupling of
propynyl carbonates with organoborons and -tins,6 Pd-cata-
lyzed reaction of 2,3-bis(boryl)-1,3-butadiene with aryl hal-
ides,7 Zr-mediated coupling of alkynes with vinyl bromide
with skeletal rearrangement,8 conversion of ꢀ,ꢀ0-diketo sul-
fides,9 and Cu-catalyzed coupling reaction of 1,4-dimethoxy-
2-butyne with aryl Grignard reagents10 have been developed.
However, these synthetic methods have problems such as low
yields, necessity of multistep routes to synthesize the precur-
sor, and complicated synthetic conditions. Incidentally, 2,3-di-
chloro-1,3-butadiene has been used industrially as a comono-
mer of chloroprene to produce chloroprene rubber.11 Because
nickel(II)-catalyzed coupling of vinyl halides with Grignard
reagents12,13 is useful to produce C–C coupling products, direct
reaction of industrially produced 2,3-dichloro-1,3-butadiene
2
52
OC12H25
OC12H25
3
64
C12H25
O
3
F
F
4
56
F
4
Published on the web March 8, 2006; DOI 10.1246/bcsj.79.498

Bull. Chem. Soc. Jpn. Vol. 79, No. 3 (2006)
Ó 2006 The Chemical Society of Japan
499
obtained in 52% yield as a white solid after purification. Identifi-
cation of the compound was performed by comparing its 1H NMR
data with those of commercially available 2. Use of a smaller
amount of the Grignard reagent (PhMgBr/2,3-dichloro-1,3-buta-
diene = 1:1) gave 2 in 23% yield, and the intermediate 2-phen-
yl-3-chloro-1,3-butadiene was not detected in the H NMR spec-
trum of the reaction product. This indicated that the intermediate
species had high reactivity toward PhMgBr.
Preparation of 2,3-Bis(4-dodecyloxyphenyl)-1,3-butadiene
(3). Preparation was carried out analogously by using activated
Mg (2.78 g, 115 mmol), 1-bromo-4-dodecyloxybenzene (36.0 g,
106 mmol), and a 1:1 (v/v) solution of 2,3-dichloro-1,3-butadiene
(40.0 mmol) in THF. 3 was obtained in 64% yield as a pale yellow
solid after purification. Found: C, 83.38; H, 10.66; O, 5.79%.
Calcd for C40H62O2: C, 83.56; H, 10.87; O, 5.57%. 1H NMR
(CDCl3) ꢂ 7.30 (d, 4H, J ¼ 8:8 Hz), 6.77 (d, 4H, J ¼ 8:8 Hz), 5.45
(d, 2H, J ¼ 1:6 Hz), 5.21 (d, 2H, J ¼ 1:6 Hz), 3.90 (t, 4H, J ¼ 6:4
Hz), 1.74 (m, 4H), 1.42 (m, 4H), 1.38–1.29 (m, 32H), 0.87 (t, 6H,
J ¼ 6:8 Hz); 13C{1H} NMR (CDCl3) ꢂ 158.6, 149.4, 132.4, 128.4,
114.1, 67.9, 32.0, 29.7, 29.7, 29.6, 29.6, 29.4, 29.4, 29.3, 26.1,
22.8, 14.2; IR (KBr disk, cmꢁ1) 2953, 2920, 2851, 1607, 1511,
1469, 1293, 1249, 1177, 1031, 902, 832, 720, 506.
and electron-donating group-substituted aromatic rings can be
introduced to the 2,3-position of 1,3-butadiene. 1, 2, and 4
have been prepared via different routes, whereas 3 is a new
compound. The electronic spectrum of 3 in CHCl3 showed
one absorption band at ꢁmax ¼ 262 nm (" ¼ 17900), which
is shifted to a longer wavelength by 17 nm from that of 2
(ꢁmax ¼ 245 nm in CHCl3) due to the substitution of the long
alkoxyl chain on the phenyl group. 3 exhibited photolumines-
cence at ꢁmax ¼ 363 nm (ꢁmaxðExÞ ¼ 260 nm), though the in-
tensity was very weak (quantum yield = 1.75%).
Long alkyl- and alkoxyl-group substituted aromatic com-
pounds often display interesting chemical properties and reac-
tivities,14 and 3 is expected to be the building block for such
materials. Compound 3 is the first example of 2,3-diaryl-1,3-
butadienes having a long alkoxyl chain, and the convenient
one-step synthesis of 3 will expand the scope of such kinds
of compounds.
1
As described above, it has been shown that industrially
available 2,3-dichloro-1,3-butadiene can be an important and
key compound for the synthesis of 2,3-diaryl-1,3-butadienes.
Experimental
Preparation of 2,3-Bis(4-fluorophenyl)-1,3-butadiene (4).
Preparation was carried out analogously by using activated
Mg (0.70 g, 28.8 mmol), 1-bromo-4-fluorobenzene (3.0 mL, 27.3
mmol), and a 1:1 (v/v) solution of 2,3-dichloro-1,3-butadiene
(10.4 mmol) in THF. 4 was obtained in 56% yield as a colorless
solid after purification. 4 had been previously prepared by other
method.10,16 1H NMR (CDCl3) ꢂ 7.31 (m, 4H), 6.94 (m, 4H), 5.48
(d, 2H, J ¼ 1:2 Hz), 5.29 (d, 2H, J ¼ 1:2 Hz); 13C{1H} NMR
(CDCl3) ꢂ 162.3 (JðC{FÞ ¼ 247 Hz), 148.6, 135.9 (JðC{FÞ ¼
2:7 Hz), 128.5 (JðC{FÞ ¼ 8:0 Hz), 115.1 (JðC{FÞ ¼ 21 Hz); IR
(KBr disk, cmꢁ1) 3051, 1601, 1506, 1227, 1161, 1106, 1013,
905, 842, 751, 541, 502, 492.
General and Materials.
1H NMR spectra were recorded
on a JEOL EX-400 spectrometer. IR spectra were recorded on a
JASCO IR 810 spectrophotometer. UV–vis and photolumines-
cence spectra were measured with a Shimadzu UV-2550 UV–visi-
ble spectrophotometer and a Hitachi F-4500 fluorescence spectro-
photometer, respectively. Thermal analysis was performed with a
Shimadzu TA-50 WS thermal analyzer equipped with a Shimadzu
DSC-50 differential scanning calorimeter and a Shimadzu TGA-
50 thermogravimetric analyzer. An optical microscopy observa-
tion of the morphology of 3 was carried out using a BX-60 optical
microscope (Olympus). 2,3-Dichloro-1,3-butadiene15 produced
industrially by Denki Kagaku Kogyo K. K. was obtained from a
production line for chloroprene rubber, and 4-t-butylcatechol
(TBC, 200 ppm by wt/wt) was added to 2,3-dichloro-1,3-buta-
diene. With TBC, 2,3-dichloro-1,3-butadiene was able to be kept
for 7 days without apparent polymerization at low temperature
(at about ꢁ30 ꢂC). 4-Dodecyloxyphenyl bromide was prepared
from 4-bromophenol and dodecyl bromide. [NiCl2(dppp)] was
purchased from Aldrich and other reagents were purchased from
Tokyo Kasei Kogyo Co., Ltd.
Preparation of 2,3-Di(2-thienyl)-1,3-butadiene (1). To a
suspension of activated Mg (2.78 g, 115 mmol) in dry THF (20
cm3) was added slowly a solution of 2-bromothiophene (17.2 g,
106 mmol) in dry THF (50 cm3) under N2 at 60 ꢂC for 12 h. The
resulting solution was transferred slowly to a 1:1 (v/v) solution
of 2,3-dichloro-1,3-butadiene (40.0 mmol) in THF under N2 at
0 ꢂC. [NiCl2(dppp)] (0.51 g, 1.00 mmol) was added to the mixture
and the mixture was stirred for 30 min at room temperature. After
additional stirring at 50 ꢂC for 24 h, the mixture was added to
water, and the product was then extracted with hexane. The
extract was washed with water and dried with Na2SO4. Evapora-
tion of the solvent and purification by column chromatography
(SiO2, hexane) afforded 1 in 65% yield as a light yellow oil.
The identification of the compound was performed according to
the literature.9
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