A novel colorimetric and fluorescent sensor for cyanide anions detection based on triphenylamine and benzothiadiazole

Article abstract of DOI:10.1016/j.tet.2016.01.019

A chemical sensor containing triphenylamine and benzothiadiazole for cyanide anions detection was designed and synthesized, whose structural feature is a donor-acceptor-donor (D-A-D) molecular configuration, which is substituted with a dicyanovinyl group

Full text of DOI:10.1016/j.tet.2016.01.019

Accepted Manuscript
A novel colorimetric and fluorescent sensor for cyanide anions detection based on
triphenylamine and benzothiadiazole
Qisong Zhang, Jian Zhang, Hujin Zuo, Chengyun Wang, Yongjia Shen
PII:
S0040-4020(16)30019-9
10.1016/j.tet.2016.01.019
TET 27426
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 19 November 2015
Revised Date: 11 January 2016
Accepted Date: 13 January 2016
Please cite this article as: Zhang Q, Zhang J, Zuo H, Wang C, Shen Y, A novel colorimetric and
fluorescent sensor for cyanide anions detection based on triphenylamine and benzothiadiazole,
Tetrahedron (2016), doi: 10.1016/j.tet.2016.01.019.
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT
Graphical Abstract
A novel colorimetric and fluorescent sensor
for cyanide anions detection based on
triphenylamine and benzothiadiazole
Qisong Zhang, Jian Zhang, Hujin Zuo, Chengyun
∗
Wang, Yongjia Shen
Key Laboratory for Advanced Materials and Institute of Fine Chemicals, East China University of Science &
Technology, Shanghai 200237, P. R. China.

1
ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
A novel colorimetric and fluorescent sensor for cyanide anions detection based on
triphenylamine and benzothiadiazole
∗
Qisong Zhang, Jian Zhang, Hujin Zuo, Chengyun Wang,Yongjia Shen
Key Laboratory for Advanced Materials and Institute of Fine Chemicals, East China University of Science & Technology, Shanghai 200237, P. R. China.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
A chemical sensor containing triphenylamine and benzothiadiazole for cyanide anions detection
was designed and synthesized, whose structural feature is a donor-acceptor-donor (D-A-D)
molecular configuration, which is substituted with a dicyanovinyl group served as a sensing unit.
The nucleophilic addition of cyanide ion to the dicyanovinyl moiety was activated in the
principle of Michael addition, which broken the electron-withdrawing interaction of
dicyanovinyl moiety. The obstruction in the intramolecular charge transfer (ICT) induced
remarkable changes in the absorption and emission spectra. The sensor exhibited splendid
Available online
Keywords:
-
-
-
-
-
-
triphenylamine
benzothiadiazole
colorimetric
selectivity and anti-interference performance towards CN over other anions (F , Cl , Br , I , NO
2
- - - - - - - 2- 2- 2- 2-
, NO
3 3 2 4 3 3 4 4 3
, HCO , H PO , HS , HSO , NCO , SCN , SO , SO , HPO , CO ). The mechanism
1
was investigated by absorption and emission spectra together with H-NMR titration.
fluorescent
cyanide-sensing
2
015 Elsevier Ltd. All rights reserved.
detecting, because it can be modulated easily and variously.
Moreover this sensor has a large stokes shift, as a result, the
fluorescence wavelength of DTPA-BT is near infrared, which is
helpful for biosensing. In our strategy, the dicyanovinyl group
was utilized as the sensing unit to realize the nucleophilic -
1
.
Introduction
In the past decades, the studies on designing and synthesizing
new chemical sensors for detecting anions had been an
remarkable topic because of their key functions in biological,
chemical and environmental systems . Cyanide (CN ), a highly
toxic anion, has drawn special interest due to its affection to
many biological functions and widely applications in numerous
chemical processes, such as electroplating, plastic
manufacturing, gold extraction, tanning and metallurgy . Many
solutions have been proposed to detect cyanide, for example,
titrimetric, electrochemical, and chromatography . Among
these solutions, optical sensors have drawn much attention, as
their higher selectivity, sensitivity and low cost . Hence, several
-
1
,2
-
addition reaction. The CN (nucleophilic ion) can be bonded with
dicyanovinyl group resulting from the electron-withdrawing
feature, which breaks conjugation through nucleophilic addition
-
reaction. Upon the addition of CN , the spectra changed rapidly,
3
and showed high sensitivity. Furthermore, we investigated the
-
-
-
-
-
-
response towards CN over other anions F , Cl , Br , I , NO ,
2
-
-
-
-
-
-
-
2-
2-
4
-7
NO , HCO , H PO , HS , HSO , NCO , SCN , SO , SO ,
3 3 2 4 3 3 4
2- 2-
HPO , CO and found that it performances well both in
4
3
8.9
selectivity and anti-interference.
-
chemosensor systems for CN detection have been developed,
including nucleophilic addition reaction , hydrogen bonding
interaction
2
.
Results and discussion
10-12
1
3,14
15,16
,
supramolecular
self-assembly
,
2.1 Design and synthesis of sensor DTPA-BT
1
7
deprotonation , and so on. Among these strategies, sensors
based on nucleophilic addition reaction showed both specific
selectivity and high sensitivity, due to the selective reaction with
cyanide anion.
The structure of DTPA-BT contained both triphenylamine
and benzothiadiazole moieties, in which a dicyanovinyl group
was attached to act as a sensing unit (Scheme 1). Moreover, the
electrophilic nature of the dicyanovinyl substituent can be
-
18
In this work, we synthesized a new highly selective ‘turn-on’
fluorescent and colorimetric chemosensor, 2-((4,7-bis(4-
modulated by CN , which interrupts the π-conjugation .
DTPA-BT was prepared by Knoevenagel condensation
(diphenylamino)phenyl)benzo[c][1,2,5]thiadiazol-5-
19
reaction , in 92% yield. The synthetic routes of DTPA-BT were
shown in Scheme 1. Detailed synthetic procedures and product
characterizations are provided in the Experimental section and
yl)methylene)malononitrile (DTPA-BT), for cyanide detection
which was based on triphenylamine and benzothiadiazole. In the
molecular structure, the triphenylamine-benzothiadiazole unit
displays excellent potential to be an optical platform for
Supplementary
data
(Fig.S1-S18).
—
——
∗
Corresponding author. Tel./fax: +086-21-64252967; e-mail address: yjshen@ecust.edu.cn (Y.-J. Shen)

2
Tetrahedron
ACCEPTED MANUSCRIPT
(
i) CH
2
Cl
2
/TEA, reflux, 5h, 82%. (ii) HBr (47%), reflux, 6h, 71%. (iii) CCl
4
2 2 3
, reflux, 17h, 80%. (iv) reflux, 0.5h, 76%. (v) THF/H O/K CO , reflux, 12h,
5
6%. (vi) AcOH/AcONH
4
, reflux, 8h, 92%.
Scheme 1. Synthetic route of compound DTPA-BT
2
.2 Absorption spectral response to cyanide ions
and a new band centered at 450 nm was generated. The color of
the solution changed from purple to yellow, which was easily
observed by the naked eyes (Fig. 5(a)). A gradual spectral
change was also shown in Fig. 2, where a clear isosbestic point
can be observed at 487 nm, indicating a clear transformation to a
new species. The Fluorescence quantum yield of DTPA-BT with
-
CN (2 equiv.) is 0.23.
-5
Fig.1. Absorption spectra of DTPA-BT (1×10 M) in a THF/H2O (99:1
[
v/v]) solution upon addition of 2.0 equiv. of various anions.
The sensing properties of DTPA-BT were examined in
THF/H O solutions (99:1 [v/v]) through the addition of sodium
2
-
-
-
-
-
-
salt of various anions, including F , Cl , Br , I , NO , NO ,
HCO , H PO , HS , HSO , NCO , SCN , SO , SO , HPO ,
CO . Upon the addition of 2.0 equivalent (equiv.) of various
anions (except for the CN ion), the absorption spectra of DTPA-
2
3
-
-
-
-
-
-
2-
2-
2-
3
2
4
3
3
4
4
2
-
3
-5
-
Fig.2. Absorption spectra of DTPA-BT (1×10 M) in a THF/H
v/v]) solution upon gradual addition of increasing amounts of cyanide
anions (from 0 to 2.0 equiv.).
2
O (99:1
[
BT did not show any substantial change (Fig. 1). However, upon
-
the gradual addition of CN ion, the absorption band centered at
5
21 nm was apparently decreased, which was attributed to the
intramolecular charge transfer (ICT) transition in the molecule,

3
ACCEPTED MANUSCRIPT
2
.3 Anions-induced fluorescence spectral response to cyanide
ions
The excitation of the sensor DTPA-BT at 480 nm produced
an emission peak at 627 nm, showing a marvelous stokes shift
nearly 150 nm, and gave an orange-red emission. Upon the
-
-
-
-
-
-
-
-
-
addition of F , Cl , Br , I , NO , NO , HCO , H PO , HS ,
2
3
3
2
4
-
-
-
2-
2-
2-
2-
HSO , NCO , SCN , SO , SO , HPO , CO no significant
3
3
4
4
3
change was observed in the emission spectra of DTPA-BT (Fig.
-
3
). The only substantial response appeared when CN was added,
and the band at 627 nm remarkably increased. This color change
of the solution was easily observed by the naked eyes under the
irradiation of a UV-lamp, which was shown in Fig. 5(b). After
-
the addition of 1.2 equiv. of CN , the peak at 627 nm was
increased completely (Fig. 4). The fluorescent intensity (627 nm)
-
increased linearly as a function of concentration of CN , and thus
-
can be potentially used for quantification of CN (Fig. S19). The
detection limit of the fluorescent spectrum changes calculated on
-
the basis of 3σ/K is 0.014 ꢀM for CN , which is comparable or
12,20
slightly lower than other dicanovinyl-based chemosensors
.
-5
Fig.5(a). Naked-eye visible images of DTPA-BT (1×10 M) upon the
-
2
addition of 2.0 equiv. of CN and other interfering anions in a THF/H O
(
99:1 [v/v]) solution at 25°C.
-
5
(
b). Naked-eye fluorescent (λex=480 nm) images of DTPA-BT (1×10
-
M) upon the addition of 2.0 equiv. of CN and other interfering anions in
a THF/H O (99:1 [v/v]) solution at 25°C.
2
2
.4 Selectivity and competivity investigation
The spectra of both absorption (Fig. 1) and emission (Fig. 3),
mentioned above, showed that the sensor DTPA-BT was not
substantially influenced by the subsequent addition of competing
anions. To evaluate the anti-interference performance of DTPA-
BT, competitive experiments (Fig. 6) were conducted with
-
-
-
-
-
5
addition of 2.0 equiv. of various other anions (F , Cl , Br , I ,
Fig.3. Emission spectra (λex=480 nm) of DTPA-BT (1×10 M) in a
THF/H
anions.
- - - - - - - - 2-
NO , NO , HCO , H PO , HS , HSO , NCO , SCN , SO ,
2
3
3
2
4
3
3
2
O (99:1 [v/v]) solution upon addition of 2.0 equiv. of various
2-
2-
2-
SO , HPO , CO ) in a solution of THF/H O (99:1 [v/v]). As
4
4
3
2
shown in Fig.6, the fluorescence was changed prominently upon
-
the following addition of CN when other anions were in
presence. This result confirmed the excellent selectivity and anti-
-
interference of the dicyanovinyl-based sensor DTPA-BT for CN
.
-5
Fig.4. Emission spectra of DTPA-BT (1×10 M) in a THF/H
v/v]) solution upon gradual addition of increasing amounts of cyanide
anions (from 0 to 2.0 equiv.).
2
O (99:1
[
-5
Fig.6. The fluorescence responses of DTPA-BT (1×10 M) upon the
-
addition of 2.0 equiv. of CN and other interfering anions in a THF/H
2
O
(
99:1 [v/v]) solution at 25°C (DTPA-BT + other anions, black bar;
-
DTPA-BT + other anions + CN , red bar).

4
Tetrahedron
ACCEPTED MANUSCRIPT
All chemical reagents and solvents were purchased from
2
.5 Sensing mechanism of sensor DTPA-BT to cyanide
commercial suppliers and were used without further purification
unless it is noted by other way. Tetrahydrofuran was dried with
metal sodium and distilled immediately prior to use. All
moisture-sensitive and air-sensitive reactions were carried out
under argon atmosphere.
-
The mechanism of DTPA-BT for CN sensing was further
1
analyzed accordingly with H-NMR spectroscopy. Fig. 7 shows
H-NMR of DTPA-BT upon the addition of
tetrabutylammonium cyanide in a solution (CDCl /DMSO-d6
9:1 [v/v]). The addition of cyanide resulted in a slow reduction
of the vinylic proton signal at 8.38 ppm (H ), which was
disappeared finally with the addition of 1.0 equiv. of CN , while
a new signal increased at 4.70 ppm (H ’), corresponding to the β-
proton of dicyanovinyl. Also the original aromatic protons
showed a downfield shift, which was in accordance with
previous studies that CN links up the β-conjugated position of
1
the
3
9
1
13
H-NMR and C-NMR spectra were measured on a Bruker
c
-
AM-400 spectrometer using d-chloroform as a solvent and
tetramethylsilane (TMS, δ = 0 ppm) as an internal standard. The
UV-vis spectra were recorded on a Varian CARY 100
spectrophotometer at room temperature. Fluorescence-emission
was detected on Varian Cary Eclipse spectrophotometer at room
temperature in acetonitrile.
c
-
12,18,21
dicyanovinyl moiety
.
CN-
4.2 Synthesis
N
N
1
22
N
N
Synthesis of 5-methylbenzo[c][1,2,5]thiadiazole (1)
c
N b'
c'
b
a
a'
N
N
N
N
To a 250 mL three-neck flask were added commercial 4-
methylbenzene-1,2-diamine (3.75 g, 0.03 mol), 60 mL of CH Cl
2
2
N
N
N
N
S
S
and, trimethylamine (13.14 g, 0.13 mol). The solution was stirred
until total dissolution of the diamine .Sulfurous dichloride (11.47
g, 0.10 mol) was added dropwise very slowly and the mixture
refluxed for 5 h. After quenching the reaction with 1mol/L
sodium hydroxide solution, the solvent was extracted 3 times
with dichloromethane (30 mL) and removed by rotary
evaporation. The residue was purified by silica gel column
chromatography using pure petroleum ether as eluant to collect a
1
brown needle solid, yield 3.69 g (82%). m.p. 33-34 °C; H-NMR
(
7
CDCl , 400 MHz, TMS) : δ 7.88 (d, 1H, J =9 Hz), 7.76 (s, 1H),
3
13
.43 (d, 1H, J = 9 Hz), 2.55 (s, 3H); C-NMR (CDCl , 100
3
MHz, TMS) : δ 155.31, 153.54, 139.94, 132.41, 120.66, 119.76,
+
2
1.91; EI-MS [M ] Calcd. 150.0252, Found 150.0251.
Synthesis of 4,7-dibromo-5-
23
methylbenzo[c][1,2,5]thiadiazole (2)
To a 250 mL three-neck flask was added 5-methyl-
benzothiadiazole (6.0 g, 0.04 mol) and HBr (75 mL, 47%). A
solution containing Br (22.21 g, 0.12 mol) in HBr (10 mL) was
2
added dropwise very slowly. After addition was complete,
solution was stirred and heated under reflux for 6 h. Precipitation
of a lot of solid was noted. After the reaction was cooled to room
temperature, sufficient saturated solution of sodium bisulfite was
added to consume excess liquid bromine. The mixture was
filtrated and washed with water. The solid was then washed once
1
Fig. 7. H-NMR spectra changes of DTPA-BT in
(
a
solution
-
3 6
CDCl /DMSO-d 99:1 [v/v]), upon the addition of CN anion.
with cold Et O and dried and the residue purified by silica gel
column chromatography using pure petroleum ether as eluent to
2
3
.
Conclusions
In summary, a colorimetric and fluorescent dual channel CN
-
collect a pale yellow powder, yield 0.612 g (71%); m.p. 150-151
1
°
3
C; H-NMR (CDCl , 400 MHz, TMS) : δ 7.78 (s, 1H ), 2.62 (s,
3
probe (DTPA-BT), containing triphenylamine donor and
benzothiadiazole acceptor was designed and synthesized. DTPA-
BT could react, in principle, with 1.2 equiv. of CN . The
interaction of cyanide with the probe inhibited the intramolecular
charge transfer and resulted in the disappearance of the
corresponding absorption peak (521 nm), and generated a new
13
H); C-NMR (CDCl , 100 MHz, TMS) : δ 153.41, 151.53,
3
+
-
140.43, 135.14, 114.22, 112.60, 22.67; EI-MS [M ] Calcd.
05.8462, Found 305.8461.
3
Synthesis
of
4,7-dibromo-5-
23
(bromomethyl)benzo[c][1,2,5]thiadiazole (3)
-
one (450 nm). Furthermore, the nucleophilic attack of CN to the
A mixture of 4,7-dibromo-5-methylbenzo[c][1,2,5]thiadiazole
1.5 g, 4.8 mmol), N-bromosuccinimide (NBS; 0.9 g, 4.8 mmol)
dicyanovinyl moiety induces a conspicuous emission spectra
change (band centered at 627 nm increased prominently), which
means it has a large stokes shift and the fluorescence wavelength
is near infrared. So it has advantages to be a colorimetric and
fluorescent dual channel probe. Comparing to the competitive
experiments, DTPA-BT showed fast response, good selectivity
and outstanding anti-interference performance.
(
and benzoyl peroxide (BPO; 30 mg, 0.13 mmol) was added to a
00 mL three-neck flask, which was dissolved in carbon
1
tetrachloride (30 mL). The mixture was heated at reflux for 17 h
under argon atmosphere. The solution was filtered and the
filtrate concentrated by rotary evaporation. The residues were
purified by silica gel column chromatography using petroleum
ether-CH Cl (4:1 (v/v)) as eluent to give a pale-yellow solid,
4
.
Experimental section
2
2
1
yield 1.26 g (80%); m.p. 159-160 °C; H-NMR (CDCl , 400
MHz, TMS): δ 7.93 (s, 1H), 2.62 (s, 2H ); C-NMR (CDCl , 100
3
4
.1 Materials and Instrumentation
13
3

5
ACCEPTED MANUSCRIPT
1.26; EI-MS [M ] Calcd. 383.7567, Found 383.7570.
MHz, TMS) : δ 153.33, 152.36, 139.29, 133.97, 115.32, 113.89,
3
Acknowledgments
+
The project was supported by National Natural Science
Foundation of China (No. 21576087，21076078)
Synthesis
carbaldehyde (4)
of
4,25
4,7-dibromobenzo[c][1,2,5]thiadiazole-5-
Supplementary data
2
1
13
H-NMR, C-NMR, and MS of DTPA-BT are available, and
4
,7-dibromo-5-(bromomethyl)benzo[c][1,2,5]thiadiazole
additional graphs for calculation of detection limit can be found
in ESI.
(
1.161 g, 3 mmol) and DMSO (30mL) was added to a 100 mL
three-neck flask. After refluxed for 30 min, the mixture was
extracted with water and dichloromethane. The solvent was
removed by rotary evaporation, and the residue was purified by
References
1 Z. Xu, S. K. Kim, J. Yoon, Chem. Soc. Rev., 2010, 39, 1457–
1466.
silica gel column chromatography using petroleum ether-CH Cl2
2
(
3:1 (v/v)) as eluent to give a yellow powder, yield 0.73 g (76%);
2 S. W. Thomas, G. D. Joly, T. M. Swager, Chem. Rev., 2007,
107, 1339–1386.
3 K. Matsubara, A. Akane, C. Maseda, H. Shiono, Forensic Sci.
Int., 1990, 46, 203–208.
1
m.p. > 200 °C; H-NMR (CDCl , 400 MHz, TMS): δ 10.54 (s,
1
1
3
13
H), 8.34 (s, 1H); C-NMR (CDCl , 100 MHz, TMS) : δ
3
89.68, 154.84, 153.59, 134.08, 130.35, 121.84, 114.84. EI-MS
+
[
M ] Calcd. 319.8255, Found 319.8258.
4 T. Suzuki, A. Hiolki, M. Kurahashi, Anal. Chim. Acta, 2003,
4
76, 159–165.
A. Safavi, N. Maleki, H. R. Shahbaazi, Anal. Chim. Acta, 2004,
03, 213–221.
Synthesis
diphenylamino)phenyl)benzo[c][1,2,5]thiadiazole-5-
carbaldehyde (5)
of
4,7-bis(4-
5
6
(
5
D. Shan, C. Mousty, S. Cosnier, Anal. Chem., 2004, 76, 178–
183.
7 T. T. Christison, J. S. Rohrer, J. Chromatogr. A, 2007, 1155,
31–39.
8 Y. Sun, G. F. Wang, W. Guo, Tetrahedron, 2009, 65, 3480–3485.
9 J. Shao, H. Lin, M. Yu, Z. S. Cai, H. K. Lin, Talanta, 2008, 75,
551–555.
10 X. H. Cheng, R. L. Tang, H. Z. Jia, J. Feng, J. G. Qin, Z. Li,
Appl. Mater. Interfaces, 2012, 4, 4387–4392.
11 L. Yang, X. Li, J. B. Yang, Y. Qu, J. L. Hua, Appl. Mater.
Interfaces, 2013, 5, 1317–1326.12 Y. D. Lin, Y. S. Peng, W. T.
Su, C. H. Tu, C. H. Sun, T. J. Chow, Tetrahedron, 2012, 68,
2523–2526.
13 S. S. Sun, A. J. Lees, Chem. Commun. 2000, 1687–1688.
14 H. Miyaji, J. L. Sessler, Angew. Chem., 2001, 113, 154–157.
15 L. Yao, J. Zhou, J. Liu, W. Feng, F. Li, Adv. Funct. Mater.
2012, 22, 2667–2672.
16 B. B. Shi, P. Zhang, T. B. Wei, H. Yao, Q. Lin, Y. M. Zhang,
Chem. Commun., 2013, 49 7812–7814.
To a mixture of 4,7-dibromobenzo[c][1,2,5]thiadiazole-5-
carbaldehyde (0.22 g, 0.68 mmol) in THF (20 mL) and aqueous
2
M potassium carbonate solution (25 mL) was added 4-
diphenylaminophenylboronic acid (0.8 g, 2.72 mmol) in THF
20 mL) under an argon atmosphere. Subsequently,
(
tetrakis(triphenylphosphine)palladium (0) (78.58 mg, 0.068
mmol) was added to the mixture. After the mixture was refluxed
for 12 h, the reaction mixture was poured into water and
extracted with dichloromethane. The organic layer was dried
over anhydrous sodium sulfate and evaporated to dryness. The
residue was purified by silica gel column chromatography using
petroleum ether-CH Cl (4:1 (v/v)) as eluent to give a red
2
2
1
powder, yield 0.25g (56%); m.p. > 200 °C; H-NMR (CDCl ,
3
4
00 MHz, TMS): δ 10.23 (s, 1H), 8.29 (s, 1H), 7.91 (d, 2H, J = 8
Hz), 7.50 (d, 2H, J = 8 Hz), 7.36-7.29 (m, 8H), 7.24-7.19 (m,
1
3
1
1
1
1
6
2H), 7.14-7.06 (m, 4H); C-NMR (CDCl , 100 MHz, TMS): δ
3
92.30, 155.84, 155.64, 149.17, 148.47, 147.38, 147.04, 138.68,
33.07, 132.77, 130.00, 129.57, 129.42, 125.57, 125.05, 124.50,
24.06, 123.49, 122.65, 121.13; ESI-MS [M+Na ] Calcd.
+
17 N. Gimeno, X. Li, J. R. Durrant, R. Vilar, Chem. Eur. J., 2008,
14, 3006–3012.
73.2033, Found 673.2042.
1
8 Y. D. Lin, Y. S. Pen, W. Su, K. L. Liau, Y. S. Wen, C. H. Sun,
C. H. Tu, T. J. Chow, Chem. Asian J., 2012, 7, 2864-2871.
9 X. Dong, Y. Hui, S. Xie, P. Zhang, G. Zhou, Z. Xie, RSC Adv.,
Synthesis
of
2-((4,7-bis(4-
(diphenylamino)phenyl)benzo[c][1,2,5]thiadiazol-5-
1
yl)methylene)malononitrile (DTPA-BT)
2
013, 3, 3222–3226.
A
mixture
of
4,7-bis(4-
20 X. Cheng, Y. Zhou, J. Qin, Z. Li, Appl. Mater. Interfaces,
2012, 4, 2133-2138.
(
diphenylamino)phenyl)benzo[c][1,2,5]thiadiazole-5-
carbaldehyde (0.065 g, 0.1 mmol), ammonium acetate (0.154 g,
21 Q. Li, Y. Cai, H. Yao, Q. Lin, Y. R. Zhu, H. Li, Spectrochim.
Acta. A. 2015, 136, 1047-1051.
22 B. A. D. S. Neto, A. S. A. Lopes, G. Ebeling, R. Goncalves, V.
E. U. Costa, F. H. Quina, J. Dupont, Tetrahedron, 2005, 61,
10975–10982.
2
1
mmol), glacial acetic acid (80 mL) and malononitrile (0.066 g,
mmol) was refluxed under an argon atmosphere for 8 h. After
cooling to room temperature, the mixture was poured into water
300 mL), and then extracted with dichloromethane (50 mL×3).
(
The organic layer was concentrated and residue was purified by
23 Q. Peng, S. L. Lim, I. H. K. Wong, J. Xu, Z. K. Chen, Chem.
Eur. J., 2012, 18, 12140 – 12151
silica gel column chromatography using petroleum ether-CH Cl2
2
(
1:1 (v/v)) as eluent to give a black purple powder, yield 0.064 g
24 N. Kornblum, J. W. Powers, G. J. Anderson, W. J. Jones, H. O.
Larson, O. Levand, W. M. Weaver, J. Am. Chem. Soc., 1957,
79, 6562.
25 N. Kornblum, J. W. Powers, G. J. Anderson, W. J. Jones, J.
Am. Chem. Soc. 1959, 81, 4113–4114.
1
(92%); m.p. > 200 °C; H-NMR (THF-d , 400 MHz, TMS): δ
8
8
8
4
1
1
1
.44 (s, 1H), 8.22 (s, 1H), 8.03 (d, 2H, J = 8 Hz), 7.50 (d, 2H, J =
Hz), 7.35-7.28 (m, 8H), 7.23-7.16 (m, 12H), 7.13-7.01 (m,
13
H); C-NMR( CDCl , 100 MHz, TMS): δ 158.28, 154.05,
3
53.87, 148.75, 147.81, 146.19, 145.58, 138.20, 132.17, 131.81,
29.06, 128.66, 128.41, 125.07, 124.23, 123.58, 122.66, 121.34,
+
19.08, 113.05; EI-MS [M ] Calcd. 698.2253 , Found 698.2252