Synthesis and photophysical properties of novel biphenyl derivatives containing furan and thiophene groups

Article abstract of DOI:10.3184/030823410X12887880118791

(Z)-2-(4-Bromophenyl)-3-(furan-2-yl)acrylonitrile and (Z)-2-(4-bromophenyl) -3-(thiophen-2-yl)acrylonitrile were prepared by condensation of furan-2-carbaldehyde and thiophene-2-carbaldehyde with (4-bromophenyl) acetonitrile in the presence of catalytic a

Full text of DOI:10.3184/030823410X12887880118791

JOURNAL OF CHEMICAL RESEARCH 2010
RESEARCH PAPER 653
NOVEMBER, 653–655
Synthesis and photophysical properties of novel biphenyl derivatives
containing furan and thiophene groups
Bao Li, Bin Liu, Qian Li, Haiyan Fang and Mingxin Yu*
Department of Chemistry, Zhejiang University, Hangzhou, 310027, P. R. China
(Z)-2-(4-Bromophenyl)-3-(furan-2-yl)acrylonitrile and (Z)-2-(4-bromophenyl)-3- (thiophen-2-yl)acrylonitrile were pre-
pared by condensation of furan-2-carbaldehyde and thiophene-2-carbaldehyde with (4-bromophenyl)acetonitrile in
the presence of catalytic amount of NaOCH3 at room temperature. A series of novel biphenyl derivatives containing
furan and thiophene groups was synthesised from (Z)-2-(4-bromophenyl)-3-(furan-2-yl)acrylonitrile and (Z)-2-(4-
bromophenyl)-3- (thiophen-2-yl)acrylonitrile via Suzuki coupling to arylboronic acids. The structures of these com-
pounds were characterised by FT-IR, 1H NMR, 13C NMR, and HRMS. The UV-Vis absorption and photoluminescence
spectra of the novel compounds in CH2Cl2 solution were investigated.
Keywords: furan, thiophene, Suzuki reaction, Pd-catalysed coupling, acrylonitrile
Furan and thiophene chemistry has been studied for a long
time.1,2 Furan can be used for conducting polymers because of
its superior electrochromic effect and good redox ability.3,4
While thiophene-based heterocycles are key intermediates and
relevant targets in the fields of synthetic, medicinal, and mate-
rials chemistry.5,6 Furthermore, aromatic compounds based on
biphenyls also play an important role in OLEDs as well as in
dyes and pigments because of their easy synthesis and highly
polarisable π-electron systems.7,8
Based on our extensive studies in the field of organic light-
emitting device materials as well as in palladium-catalysed
coupling reactions,9–11 we became interested in the preparation
of new functional biphenyl derivatives containing furan and
thiophene groups. We now report the design and synthesis of
a series of novel biphenyl derivatives containing furan and
thiophene rings and studied their photophysical properties as
potential OLED materials.
reactions which are widely used to form C–C bonds are impor-
tant reactions in organic synthesis.14 In this work, we used the
catalytic system of Pd(PPh3)4 to prepare compounds 2a–j. The
synthesis of (Z)-2-(4-bromophenyl)-3-(thiophen-2-yl) acrylo-
nitrile and (Z)-2-(4-bromophenyl)-3-(furan-2-yl)acrylonitrile
(1a,1b) were based on the previously reported literature.15 For
the second step, various substituted arylboronic acids were
reacted with 1a and 1b to afford a series of novel biphenyl
derivatives containing furan and thiophene rings by Suzuki
reaction in the presence of the catalyst Pd(PPh3)4. The reaction
times and yields are shown in Table 1.
In order to investigate their photophysical properties, the
UV and PL spectra in dilute dichloromethane solution were
recorded. All compounds yield blue emissions in solution at
room temperature.
As indicated by the absorption spectra (Table 1), the absorp-
tion behaviour of 2a–j were quite similar to each other, and
most of them displayed two absorption peaks at about 255–268
nm and 357–363 nm which were ascribed to π–π* transitions.
For the emission spectra in dilute dichloromethane solu-
tions, all of the compounds yield blue emission at room
The target compounds (2a–j) were obtained by a two-step
procedure (Scheme 1). To the best of our knowledge, aryl C–C
bond construction can be induced either by palladium catalysts
or nickel catalysts.12,13 Palladium-catalysed cross coupling
Scheme 1 Synthesis of target compounds 2a–j.
* Correspondent: E-mail:mingxinyu@zju.edu.cn

654 JOURNAL OF CHEMICAL RESEARCH 2010
Table 1 Reaction conditions, yields and photophysical properties of compounds 2a–j
Entry
X
Time/h
Yield/%
aλmaxabs/nm
bλmaxem/nm
εc/mol·L−1·cm−1
2a
2b
2c
2d
2e
2f
S
O
S
O
S
O
S
O
S
O
4
4
4
4
4
4
6
6
8
8
93
95
90
94
91
94
87
92
82
89
266, 358
255, 357
268, 360
257, 359
259, 359
255, 357
268, 360
255, 358
260, 363
258, 362
436
420
433
432
431
431
444
441
445
442
13504, 19232
12314, 18199
13655, 19748
12887, 18201
14102, 19983
13251, 18793
13656, 19786
12784, 18910
14256, 21053
13470, 19483
2g
2h
2i
2j
a Maximum absorption wavelength in CH2Cl2.
b Maximum emission wavelength in CH2Cl2.
c Extinction coefficients determined in CH2Cl2 solutions when the concentration of each compound is 1.0 × 10−5 M.
(0.8 mL), 1,2-dimethoxyethane (2.5 mL), the arylboronic acid
(1.2 mmol), and Pd(PPh3)4 (0.01 mmol) was heated at reflux for the
requisite time (Table 1). The reaction mixture was allowed to cool to
room temperature, and the inorganic material was filtered off. The
filtrate was concentrated under reduced pressure, and the resulting
crude oil was chromatographed on silica gel to afford the target
compounds 2a–j [eluent: ethyl acetate-hexane (1:8)].
temperature. The emission peaks of compounds are located at
about 420–445 nm (Table 1).
Conclusion
In conclusion, several novel biphenyl derivatives containing
furan and thiophene groups have been synthesised via the
Suzuki reaction under mild conditions and in high yields.
The absorption and photoluminescence spectra of the products
in CH2Cl2 were investigated. These compounds exhibit
similar absorption and emission behaviour and emit strongly
in solution, with the emission maxima in the range of
420–445 nm.
(Z)-2-(Biphenyl-4-yl)-3- (thiophen-2-yl)acrylonitrile (2a): Yellow
solid. Yield: 93%. M.p. 139 °C. FTIR (KBr pellet, cm−1): 3113, 3032,
1
2209, 1578, 1485, 1418, 1363, 1201, 1054, 839, 765,719. H NMR
(400 MHz, CDCl3) δH: 7.74–7.72 (m, 3H), 7.70–7.66 (m, 3H), 7.62 (d,
J = 7.2 Hz, 2H), 7.56 (d, J = 5.2 Hz, 1H), 7.47 (dd, J = 7.2 Hz,
J = 8.0 Hz, 2H), 7.39 (dd, J = 7.2 Hz, J = 7.6 Hz, 1H), 7.17(dd,
J = 3.6 Hz, J = 3.2 Hz, 1H). 13C NMR (100 MHz, CDCl3) δc: 141.7,
139.9, 138.0, 133.8, 132.8, 132.4, 130.0, 128.9, 127.8, 127.8, 127.6,
127.0, 126.0, 118.1, 107.9. HRMS (EI): Calcd for C19H13NS: 287.0769.
Found: 287.0762.
Experimental
Boronic acid derivatives and tetrakis(triphenylphosphine)palladium
(0) were purchased from Aldrich Chemical Co. Sodium carbonate was
purchased from Alfa-Aesar and stored in a Vacuum Atmospheres
glove box under nitrogen. All chemicals were used as supplied. All
melting points were determined with a WRS-1A melting point appa-
ratus and were uncorrected. Proton NMR (1H NMR and l3C NMR)
spectra were run on a Bruker AV-400 NMR spectrometer in CDCl3
and chemical shifts are expressed as δ (ppm) values with TMS as an
internal standard. IR spectra were recorded in KBr on a Nicolet
NEXUS 470 FT-IR spectrophotometer. Vibrational transition frequen-
cies are reported in wave numbers (cm−1). Mass spectra were obtained
on a Jeol JMS-SX102 A HRGC/LC/MS instrument operating in an
electron-impact (EI) mode at 70 eV. UV-Vis spectra were recorded on
a Hitachi U-3300 model while PL spectra were taken using a Hitachi
F-4500 fluorescence spectrophotometer.
(Z)-2-(Biphenyl-4-yl)-3- (furan-2-yl)acrylonitrile (2b): Yellow
solid Yield: 95%. M.p. 171 °C. FTIR (KBr pellet, cm−1): 3125, 3023,
2215, 1610, 1588, 1487, 1463, 1403, 1330, 1083, 1025, 929, 885, 838,
1
764, 721, 691, 585, 475. H NMR (400 MHz, CDCl3) δH: 7.73 (d,
J = 8.4 Hz, 2H), 7.67 (d, J = 8.4 Hz, 2H), 7.63 (d,J = 7.2 Hz, 3H),
7.47 (m, 3H), 7.39 (dd, J = 7.2 Hz, J = 7.2 Hz, 1H), 7.24 (d, J = 3.6 Hz,
1H), 6.60 (dd, J = 1.6 Hz, J = 2.0Hz, 1H). 13C NMR (100 MHz,
CDCl3) δc: 150.0, 144.6, 141.6, 139.6, 132.3, 128.6, 127.5, 127.4,
127.3, 126.7, 125.7, 117.4, 115.0, 112.6, 107.0. HRMS (EI): Calcd for
C13H8NO: 271.0997. Found: 271.0998.
(Z)-2-(4-Methylbiphenyl-4-yl)-3-(thiophen-2-yl)acrylonitrile (2c):
Yellow solid.Yield: 90%. M.p. 186 °C. FTIR (KBr pellet, cm−1): 3089,
1
2209, 1604, 1583, 1493, 1417, 1205, 1053, 809, 718. H NMR (400
MHz, CDCl3) δH: 7.70 (d, J = 6.8 Hz, 2H), 7.68 (d, J = 6.4 Hz, 2H),
7.64 (d, J = 8.0 Hz, 2H), 7.55 (d, J = 4.8 Hz, 1H), 7.51 (d, J = 8.0 Hz,
2H), 7.26 (d, J = 2.0 Hz, 2H), 7.16 (dd, J = 4.4 Hz, J = 4.0 Hz, 1H),
2.41 (s, 3H). 13C NMR (100 MHz, CDCl3) δc: 141.7, 138.0, 137.7,
137.0, 133.6, 132.4, 132.3, 129.9, 129.6, 127.8, 127.4, 126.8, 126.0,
118.1, 107.9, 21.1. HRMS (EI): Calcd for C20H15NS: 301.0925.
Found: 301.0934.
Synthesis of (1a, 1b); general procedure
A solution of the thiophene-2-carbaldehyde or furan-2-carbaldehyde
(1 mmol) and (4-bromophenyl)acetonitrile (1 mmol) in absolute
EtOH (10 mL) was treated with NaOMe (0.1 mmol) portionwise,
stirred at room temperature for 2–3 h, cooled to 0 °C, and filtered. The
precipitate was washed with EtOH.
(Z)-2-(4-Methylbiphenyl-4-yl)-3-(furan-2-yl)acrylonitrile (2d):
Yellow solid.Yield: 94%. M.p. 182 °C. FTIR (KBr pellet, cm−1): 3141,
3017, 2949, 2362, 2213, 1612, 1498, 1466, 1398, 1329, 1026, 887,
809, 746, 586, 475. 1H NMR (400 MHz, CDCl3) δH: 7.71 (d, J = 8.4 Hz,
2H), 7.65 (d, J = 8.4 Hz, 2H), 7.61 (d, J = 1.2Hz, 1H), 7.52 (d,
J = 8.0 Hz, 2H), 7.43 (s, 1H), 7.29 (d, J = 8.0 Hz, 2H), 7.22 (d,
J = 3.6 Hz, 1H), 6.60 (dd, J = 1.6 Hz, J = 2.0 Hz, 1H), 2.41 (s, 3H).
13C NMR (100 MHz, CDCl3) δc: 150.0, 144.6, 141.5, 137.5, 136.7,
132.0, 129.4, 127.2, 126.5, 125.7, 117.5, 114.9, 112.6, 107.1, 20.9.
HRMS (EI): Calcd for C20H15NO: 285.1154. Found: 285.1155.
(Z)-2-(4-Methoxybiphenyl-4-yl)-3-(thiophen-2-yl)acrylonitrile
(2e):Yellow solid.Yield: 91 %. M.p. 178 °C. FTIR (KBr pellet, cm−1):
3069, 2980, 2970, 2209, 1600, 1586, 1492, 1417, 1210, 1205, 1051,
(Z)-2-(4-Bromophenyl)-3-(thiophen-2-yl)acrylonitrile16 (1a): Yel-
low solid. Yield: 96%. M.p. 115–116 °C. (lit.16 118 °C) FTIR (KBr
pellet, cm−1): 3034, 2207, 1593, 1487, 1417, 1369, 1077, 824, 696.
1H NMR (400 MHz, CDCl3) δH: 7.67 (d, J = 3.6 Hz, 1H), 7.65 (s, 1H),
7.56 (d, J = 8.8 Hz, 1H), 7.55 (s, 1H), 7.50 (d, J = 8.8Hz, 2H), 7.15–
7.17 (m, 1H).
(Z)-2-(4-Bromophenyl)-3-(furan-2-yl)acrylonitrile (1b): Yellow
solid.Yield: 90%. M.p. 63–65 °C FTIR(KBr pellet, cm−1): 3148, 3045,
2214, 1596, 1486, 1464, 1406, 1334, 1141, 1090, 1078, 1026, 1003,
1
931, 894, 822, 745, 591, 488. H NMR (400 MHz, CDCl3) δH: 7.62
(d, J = 1.2 Hz, 1H), 7.55 (d, J = 8.8 Hz, 2H), 7.50 (d, J = 8.8 Hz, 2H),
7.37 (s, 1H), 7.21 (d, J = 3.2 Hz, 1H), 6.60 (dd, J = 1.6 Hz, J = 2.0 Hz,
1H). 13C NMR (100 MHz, CDCl3) δc: 149.9, 145.2, 132.6, 132.2,
128.2, 127.0, 123.2, 117.4, 115.9, 113.0, 106.3. HRMS (EI): Calcd for
C13H8BrNO: 272.9789. Found: 272.9787.
1
801, 713. H NMR (400 MHz, CDCl3) δH: 7.71 (d, J = 4.8 Hz, 2H),
7.69 (d, J = 3.2 Hz, 2H), 7.65 (d, J = 8.8 Hz, 2H), 7.59 (s, 1H), 7.50
(d, J = 5.2 Hz, 2H), 7.18 (dd, J = 3.6 Hz, J=3.2 Hz, 1H), 7.01 (d,
J = 8.8 Hz, 2H), 3.88 (s, 3H). 13C NMR (100 MHz, CDCl3) δc: 160.1,
140.2, 138.0, 137.6, 135.8, 134.2, 133.5, 132.8, 132.4, 130.1, 128.3,
127.9, 118.3, 114.4, 107.2, 55.3. HRMS (EI): Calcd for C20H16NOS:
317.0874. Found: 317.0875.
Synthesis of 2a–j; general procedure
A
degassed mixture of (Z)-2-(4-bromophenyl)-3-(furan-2-yl)
acrylonitrile (1.0 mmol), Na2CO3 (2.2 mmol), water(1.1 mL), EtOH

JOURNAL OF CHEMICAL RESEARCH 2010 655
(Z)-2-(4-Methoxybiphenyl-4-yl)-3-(furan-2-yl)acrylonitrile (2f):
Yellow solid.Yield: 94%. M.p. 150 °C. FTIR (KBr pellet, cm−1): 3125,
3034, 2940, 2215, 1611, 1588, 1464, 1402, 1330, 1087, 1026, 1003,
932, 886, 839, 764, 722, 692, 589, 474. 1H NMR (400 MHz, CDCl3)
δH: 7.69 (d, J = 7.6 Hz, 2H), 7.62 (d, J = 7.2 Hz, 3H), 7.57 (d,
J = 8.4 Hz, 2H), 7.42 (s, 1H), 7.22 (d, J = 3.6 Hz, 1H), 7.00 (d,
J = 8.8 Hz, 2H), 6.60 (dd, J = 1.2 Hz, J = 1.6 Hz, 1H), 3.87 (s, 3H).
13C NMR (100 MHz, CDCl3) δc: 159.6, 150.2, 144.8, 141.4, 132.4,
131.9, 128.0, 127.3, 127.1,125.9, 117.7, 115.0, 114.3, 112.8, 107.2,
55.3. HRMS (EI): Calcd for C20H15NO2: 301.1103. Found: 301.1105.
(Z)-2-(3,5-Dimethylbiphenyl-4-yl)-3-(thiophen-2-yl)acrylonitrile
(2g):Yellow solid.Yield: 87 %. M.p. 103 °C. FTIR (KBr pellet, cm−1):
3088, 3049, 2914, 2210, 1602, 1585, 1417, 1401, 1384, 1204, 1054,
832, 808, 717, 702. 1H NMR (400 MHz, CDCl3) δH: 7.69 (d, J = 7.6 Hz,
3H), 7.63 (d, J = 8.0 Hz, 2H),7.55 (d, J = 5.2 Hz, 1H), 7.24 (d,
J = 8.8 Hz, 3H), 7.16 (dd, J = 4.4 Hz, J = 4.8 Hz, 1H), 7.03 (s, 1H),
2.39 (s, 6H). 13C NMR (100 MHz, CDCl3) δc:141.2, 141.0, 138.5,
137.6, 135.8, 134.2, 132.2, 130.0, 129.9, 128.8, 127.7, 125.8, 125.2,
118.2, 105.2, 21.3. HRMS (EI): Calcd for C21H17NS: 315.1082.
Found: 315.1085.
(dd, J = 8.4 Hz, J = 8.0 Hz, 2H), 7.89 (d, J = 6.8 Hz, 1H), 7.82–7.58
(m, 5H), 7.64 (d, J = 1.2 Hz, 1H), 7.55–7.52 (m, 2H), 7.47 (s, 1H),
7.26 (d, J = 3.6 Hz, 1H), 6.62 (dd, J = 1.6 Hz, J = 2.0 Hz, 1H). 13C
NMR (100 MHz, CDCl3) δc: 150.2, 144.9, 141.6, 137.1, 133.6, 132.8,
132.6, 128.6, 128.2, 127.9, 127.6, 127.6, 126.5, 126.2, 126.0, 125.8,
125.1, 117.7, 115.3, 112.9, 107.2. HRMS (EI): Calcd for C23H15NO
321.1154. Found: 321.1158.
The project is sponsored by the Natural Science Foundation
(Y200908302) for the Education Ministry of Zhejiang
Province.
Received 17 May 2010;accepted 27 September 2010
Paper 1000141 doi: 10.3184/030823410X12887880118791
Published online: 24 November 2010
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7.21 (s ,3H), 7.01 (s, 1H), 6.57 (dd, J = 1.6Hz, J = 2.0 Hz, 1H), 2.38
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753, 589, 487. H NMR (400, MHz CDCl3) δH: 8.09 (s, 1H), 7.94
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