Click synthesis and dye extraction properties of novel thiacalix[4]arene derivatives with triazolyl and hydrogen bonding groups

Article abstract of DOI:10.1016/j.cclet.2013.04.003

Using a click reaction between alkynylthiacalix[4]arene and ethyl 2-azidoacetate followed by an ammonolysis with ethanolamine, leucinol and hydrazine hydrate, respectively, three novel thiacalix[4]arene derivatives 4, 5 and 6 with triazolyl and hydrogen bonding groups (NH and OH) were synthesized in high yields. They exhibited excellent extraction capability for six anionic and cationic dyes. The flexible cavity, π-triazole rings and hydrogen bonding groups all play crucial roles in dye complexation.

Full text of DOI:10.1016/j.cclet.2013.04.003

G Model
CCLET-2544; No. of Pages 3
Chinese Chemical Letters xxx (2013) xxx–xxx
Contents lists available at SciVerse ScienceDirect
Chinese Chemical Letters
journal homepage: www.elsevier.com/locate/cclet
Original article
Click synthesis and dye extraction properties of novel thiacalix[4]arene
derivatives with triazolyl and hydrogen bonding groups
a
a,b,
b
a
Hong-Yu Guo , Fa-Fu Yang *, Zi-Yu Jiao , Jian-Rong Lin
a
College of Chemistry and Chemical Engineering, Fujian Normal University, Fuzhou 350007, China
b
Fujian Key Laboratory of Polymer Materials, Fujian Normal University, Fuzhou 350007, China
A R T I C L E I N F O
A B S T R A C T
Article history:
Using a click reaction between alkynylthiacalix[4]arene and ethyl 2-azidoacetate followed by an
ammonolysis with ethanolamine, leucinol and hydrazine hydrate, respectively, three novel thiaca-
lix[4]arene derivatives 4, 5 and 6 with triazolyl and hydrogen bonding groups (NH and OH) were
synthesized in high yields. They exhibited excellent extraction capability for six anionic and cationic
Received 23 February 2013
Received in revised form 19 March 2013
Accepted 22 March 2013
Available online xxx
dyes. The flexible cavity,
complexation.
p-triazole rings and hydrogen bonding groups all play crucial roles in dye
Keywords:
ß 2013 Fa-Fu Yang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
Thiacalix[4]arene
Synthesis
Click chemistry
Dye extraction
1
. Introduction
Dyes are widely used in various industries including textiles,
important for the inclusion of dyes, and the cavity of calix[4]arene
was not favorable for the inclusion of commonly used dyes [11–
16]. Compared to calix[4]arenes, thiacalix[4]arenes possess a more
flexible cavity, which might be more amicable for size adjustment
to match the dimension of the dyes of interest. However, no
thiacalix[4]arene derivatives were reported to bind dyes up until
now. In this paper, several novel thiacalix[4]arene derivatives with
triazolyl and hydrogen bonding groups were designed and
synthesized by a click reaction and their dye complexation
properties were studied for the first time. The extraction
experiments indicated they exhibited excellent extraction capa-
bility for all kinds of dyes, which might be attributed to the flexible
leather, dyestuffs, papers, etc. Unfortunately, the wastewater from
these industries represents a serious source of pollution [1,2]. In
order to remove the dyes from wastewater, various types of
conventional treatment processes including chemical coagulation,
precipitation, extraction, adsorption, membrane filtration, photo-
degradation etc., had been developed [3–7]. Among them, liquid–
liquid extractions can provide a selective separation and recovery
of dyes from the effluent mixtures. In the processes of liquid–liquid
extraction, the extractants or carriers played the crucial roles.
Recently, supramolecular chemistry has provided a much im-
proved solution to search for molecular structures that could serve
as building blocks for the production of sophisticated molecules by
anchoring functional groups oriented in such a way that they
provided a suitable binding site for the dyes of interest [8–10]. In
particular, calixarene-based derivatives were paid much attention
to as potential extractants owing to their highly efficient
complexation for dyes lately. Calixarene-based derivatives and
resins with highly removal ability of dyes were reported by Yilmaz
cavity of thiacalix[4]arene, the
p–p interactions between the
triazole ring and the dyes, and the hydrogen bonding interactions
between the NH or OH groups and the dyes.
2. Experimental
1
3
H NMR spectra were recorded in CDCl on a Bruker-ARX 600
instrument at room temperature, using TMS as an internal
standard. ESI-MS spectra were obtained from DECAX-30000 LCQ
Deca XP mass spectrometer. Elemental analyses were performed
using a Carlo-Erba 1106 Elemental Analyzer. IR spectra were
recorded on a Perkin-Elmer 1605 FTIR spectrometer as KBr pellets.
UV–vis measurements were performed on a Varian UV–vis
[
11–13], Memnon [14,15] and Diao [16], respectively. Data from
previous research indicated that the size of cavity, the and
hydrogen bond interactions with the dye molecules were
p–p
instrument. Alkynylthiacalix[4]arene
2 and 25, 26, 27, 28-
tetra(ethylacetyl-1H-1,2,3-triazolyl-methyloxy)thiacalix[4]arene
3 were prepared using literature methods [17,18]. The liquid–
liquid extraction studies were performed following the classic
*
Corresponding author at: Fujian Key Laboratory of Polymer Materials, Fujian
Normal University, Fuzhou 350007, China.
E-mail address: yangfafu@fjnu.edu.cn (F.-F. Yang).
1
001-8417/$ – see front matter ß 2013 Fa-Fu Yang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
http://dx.doi.org/10.1016/j.cclet.2013.04.003
Please cite this article in press as: H.-Y. Guo, et al., Click synthesis and dye extraction properties of novel thiacalix[4]arene derivatives
with triazolyl and hydrogen bonding groups, Chin. Chem. Lett. (2013), http://dx.doi.org/10.1016/j.cclet.2013.04.003

G Model
CCLET-2544; No. of Pages 3
2
H.-Y. Guo et al. / Chinese Chemical Letters xxx (2013) xxx–xxx
O
O
NaN3
Cl
N3
O
O
DMF
NHNH2
O
O
1
N
O
N
N
N
N
N
OH
O
O
*
S
Br *
K CO3
S
NH NH
O
1
2
2
*
*
*
S
*
*
S
4
4
*
2
4
93%
8
2%
4
86%
2
3
H N
6
2
H
N
H N
OH
2
OH
9
1%
HO
H
O
81%
N
NH OH
O
N
O
N
N
H
N
O
N
*
S
*
*
S
4
*
4
4
5
Scheme 1. The synthetic routes for title compounds.
À5
Pedersen’s procedure [19]. A 10 mL of 2.0 Â 10 mol/L aqueous
84 120 16 12 4
C H N O S : C 60.27, H 7.23, N 13.39; found C 60.21, H 7.28, N
À3
1
solution of dye and 10 mL of 1.0 Â 10 mol/L solution of carrier in
13.33. 6: Mp: 225–228 8C; H NMR (400 MHz, CDCl
36H, CH ), 2.25 (bs, 8H, NH ), 4.99 (s, 8H, NCH CO), 5.07 (s, 8H,
OCH ), 7.41 (s, 8H, ArH), 8.11 (s, 4H, CH 55 N), 8.26 (s, 4H, NH); IR
(KBr, cm ):
100). Anal. Calcd. for C60
3
): d 1.01 (s,
CH
2
Cl
2
were vigorously agitated in a stoppered glass tube with a
3
2
2
mechanical shaker for 2 min. Then the mixture was stirred
magnetically in a thermostated water-bath at 25 8C for 1 h, and
was finally left standing for an additional 30 min. The concentra-
tion of the dyes remaining in the aqueous phase was subsequently
determined by UV–vis analyses. Blank experiments showed that
dye extraction were less than 2% in the absence of extractants. The
2
À1
+
n
3407 (NH), 1668 (C 55 O); MS m/z (%): 1355.2(M+Na ,
: C 54.04, H 5.73, N 21.02;
76 20 8 4
H N O S
found C 54.09, H 5.78, N 21.08.
3. Results and discussion
percent extraction (E%) was calculated as: E% = 100 (A
0
À A)/A
0
.
Where A and A are initial and final concentrations of the dyes
0
The synthetic route is shown in Scheme 1. Alkynylthiacalix[4]-
arene 2 and its triazolyl derivative 3 were prepared by a click
reaction according to the literature procedures [17,18]. Then by
ammonolysis of compound 3 with ethanolamine, leucinol and
hydrazine hydrate, the target novel thiacalix[4]arene derivatives 4,
5 and 6 were obtained in yields of 80%–93%, respectively. The
structures of compounds 4, 5 and 6 were characterized by
elemental analysis, IR, ESI-MS, and NMR spectroscopy. Their IR
spectra showed the corresponding amide groups (NHC 55 O) instead
of ester groups (OC 55 O). Their ESI-MS spectra exhibited the
before and after the extraction, respectively. Each experiment was
repeated three times. The dye concentration in the receiving phase
was reported as the mean of the determination and the relative
standard deviation from the mean was less than 5%.
Synthesis of novel thiacalix[4]arene derivatives with triazolyl
and hydrogen bonding groups 4, 5 and 6: Under nitrogen
atmosphere, a mixture of compound 3 (0.21 g, 0.15 mmol) and
ethanolamine (0.2 g, 3.3 mmol) was refluxed in a 20 mL of EtOH/
CHCl
distilled under reduced pressure. The residue was recrystallized in
MeOH/H O (v:v = 1:1) to afford 4 as a white solid (0.22 g, 91%). 4:
Mp: 208–211 8C; H NMR (400 MHz, DMSO-d d 0.98 (s, 36H,
3
(v:v = 1:1) solution for 10 h. After cooling, the solution was
+
1
corresponding molecular base peaks (M+Na ). In their H NMR
spectra, one singlet for the tert-butyl groups, one singlet for the
aromatic protons, indicated 4, 5 and 6 were in the cone or 1,3-
alternate conformation. The analysis of structures of compounds
2
1
6
):
), 3.32 (s, 4H, 4 Â OH),
CO), 5.08 (s,
1
3
8
4
1
6
2 Â CH
3
), 3.19 (d, 8H, J = 5.6 Hz, 4 Â CH
2
.46 (d, 8H, J = 5.6 Hz, 4 Â CH
2
), 4.97 (s, 8H, 4 Â NCH
2
4–6 suggested they possessed a flexible cavity, four p-triazole
H, 4 Â OCH
2
), 7.47(s, 8H, 8 Â ArH), 8.14 (s, 4H, 4 Â CH 55 N), 8.33 (s,
rings and several NH and OH groups, which were favorable for
binding dyes. Thus, six normal dyes were chosen to test their
extraction ability by liquid–liquid extraction. The results are
shown in Table 1.
Previously, it was reported that the cavity of calix[4]arene was
not favorable for inclusion of dyes [11–16]. However, from Table 1,
it could be seen that compound 2 showed a certain level of
extraction ability for dyes, which could be attributed to its flexible
cavity for dye complexation as expected. Moreover, the extraction
percentage of compound 3 was higher than that of compound 2,
À1
H, 4 Â NH); IR (KBr, cm ):
n 3412 (NH), 1680 (C 55 O); MS m/z (%):
+
471.7 (M+Na , 100). Anal. Calcd. for C68
.12, N 15.46; found C 56.38, H 6.16, N 15.41.
Using a similar procedure, compounds 5 and 6 were obtained by
88 16 12 4
H N O S : C 56.34, H
ammonolysis with leucinol and hydrazine hydrate in yields of 81%
1
and 93%, respectively. 5: Mp: 201–203 8C; H NMR (400 MHz,
CDCl
1
3
):
.35–1.38 (m, 8H, 4 Â CH
), 4.04 (s, 4H, 4 Â OH), 5.14 (s, 8H, 4 Â NCH
.18 (s, 8H, 4 Â OCH ), 6.82 (d, 4H, J = 8.4 Hz, 4 Â NH), 7.0 (s, 8H,
 CH 55 N), 7.16 (s, 4H, 4  ArH); IR (KBr, cm ):
d
0.92 (d, 24H, J = 6.8 Hz, 8 Â CH
), 1.51–1.69 (m, 4H, 4 Â CH), 3.52–3.77
CO),
3
), 1.04 (s, 36H, 12 Â CH
3
),
2
(
5
8
m, 12H, 6 Â CH
2
2
2
increased from 30% to 60%. These results suggested the p-triazole
rings in compound 3 produced more favorable interactions for dye
complexation. Further, after bridging with NH and OH groups, the
À1
n
3380 (NH and
+
OH), 1675 (C 55 O); MS m/z (%): 1696.8 (M+Na , 100). Anal. Calcd. for
Please cite this article in press as: H.-Y. Guo, et al., Click synthesis and dye extraction properties of novel thiacalix[4]arene derivatives
with triazolyl and hydrogen bonding groups, Chin. Chem. Lett. (2013), http://dx.doi.org/10.1016/j.cclet.2013.04.003

G Model
CCLET-2544; No. of Pages 3
H.-Y. Guo et al. / Chinese Chemical Letters xxx (2013) xxx–xxx
3
Table 1
Researchers in University of Fujian Province (No. JA10056) were
greatly acknowledged.
a
Extraction percentages of six dyes with compounds 2, 3, 4, 5 and 6.
Compound
OG
BP
VB
CV
NR
MB
2
3
4
5
6
26.8
56.2
91.4
93.8
91.3
19.7
49.8
90.6
88.1
86.5
21.7
38.9
74.7
79.7
82.6
16.6
44.6
88.6
84.3
88.8
25.6
50.1
88.7
80.1
82.9
23.4
43.6
86.3
88.3
79.8
References
[1] Y. Wong, J. Yu, Laccase-catalyzed decolorization of synthetic dyes, Water Res. 33
(1999) 3512–3519.
[2] G. Crini, Recent developments in polysaccharide-based materials used as adsor-
a
The pH 7 in aqueous solution were adjusted by HAc or ammonia. OG, BP, VB, CV,
NR and MB were the abbreviation of Orange G sodium salt, Brilliant ponceau 5R,
Victoria blue B, Crystal violet, Neutral red and Methylene blue, respectively.
bents in wastewater treatment, Prog. Polym. Sci. 30 (2005) 38–46.
[3] I.T. Peternel, N. Koprivanac, A.M.L. Bozic, et al., Comparative study of UV/TiO , UV/
2
ZnO and photo-Fenton processes for the organic reactive dye degradation in
aqueous solution, J. Hazard. Mater. 148 (2007) 477–484.
[
4] G. Crini, P.M. Badot, Application of chitosan, a natural aminopolysaccharide, for
dye removal from aqueous solutions by adsorption processes using bath studies: a
review of recent literature, Prog. Polym. Sci. 33 (2008) 399–447.
extraction percentages of compounds 4, 5 and 6 were greatly
improved to 80% and some were as high as 90%. By comparing the
structures of compounds 2, 3 and 4–6, it could be deduced that the
hydrogen bonding groups (NH and OH) in compounds 4–6
improved the extraction ability greatly. On the other hand, the
different structures of dyes, such as anionic dyes and cationic dyes,
had little influence on extraction percentages. All these results
[
5] M.K. Purkait, S. DasGupta, S. De, Resistance in series model for micellar enhanced
ultrafiltration of eosin dye, J. Colloid Interface Sci. 270 (2004) 496–506.
6] S. Chakraborty, M.K. Purkait, S. DasGupta, et al., Nanofiltration of textile plant
effluent for color removal and reduction in COD, Sep. Purif. Technol. 31 (2003)
[
141–151.
[7] D. Ghosh, K.G. Bhattacharyya, Adsorption of metheylene blue on kaolinite, Appl.
Clay Sci. 20 (2002) 295–300.
[
8] Y. Al-Degs, M.A.M. Khraisheh, S.J. Allen, et al., Sorption behavior of cationic and
anionic dyes from aqueous solution on different types of activated carbons, Sep.
Sci. Technol. 36 (2001) 91–102.
suggested the flexible cavity of thiacalix[4]arene,
p-triazole rings
and hydrogen bonding groups all played crucial roles in binding
dyes.
[9] P.R. Jana, S. De, J.K. Basu, A generalized shrinking core model applied to batch
adsorption, Chem. Eng. J. 95 (2003) 143–154.
[10] F.C. Wu, R.L. Tseng, R.S. Juang, Comparative adsorption of metal and dye on flake-
and bead-types of chitosan prepared from fishery wastes, J. Hazard. Mater. 73
4
. Conclusion
(2000) 63–75.
[
11] E. Akceylan, M. Bahadir, M. Yilmaz, Removal efficiency of a calix[4]arene-based
polymer for water-soluble carcinogenic direct azo dyes and aromatic amines, J.
Hazard. Mater. 162 (2009) 960–966.
In summary, using a click reaction between alkynylthiaca-
lix[4]arene and ethyl 2-azidoacetate followed by an ammonolysis
with ethanolamine, leucinol and hydrazine hydrate, respectively,
three novel thiacalix[4]arene derivatives 4, 5 and 6 with triazolyl
groups and hydrogen bonding groups (NH and OH) were
synthesized in high yields. They exhibited excellent extraction
[12] E.O. Yilmaz, A. Sirit, M. Yilmaz, A calix[4]arene oligomer and two betacyclodextrin
polymers: synthesis and sorption studies of azo dyes, J. Macromol. Sci. A: Pure
Appl. Chem. 44 (2007) 167–174.
[
[
[
13] A. Yilmaz, E. Yilmaz, M. Yilmaz, et al., Removal of azo dyes from aqueous solutions
using calix[4]arene and cyclodextrin, Dyes Pigm. 74 (2007) 54–60.
14] M.A. Kamboh, I.B. Solangi, S.T.H. Sherazi, et al., A highly efficient calix[4]arene
based resin for the removal of azo dyes, Desalination 268 (2011) 83–89.
15] M.A. Kamboh, I.B. Solangi, S. Memon, Synthesis and application of p-tert-butyl-
calix[8]arene immobilized material for the removal of azo dyes, J. Hazard. Mater.
capability for six anionic and cationic dyes. The flexible cavity,
p-
triazole rings and hydrogen bonding groups all play crucial roles in
dye complexation. The in-depth studies for binding dyes by liquid
membrane transportion and adsorption, which are important for
practical applications, will be reported in future work.
186 (2011) 651–656.
[
16] M. Chen, T. Shang, W. Fang, G. Diao, Study on adsorption and desorption
properties of the starch grafted p-tert-butyl-calix[n]arene for butyl Rhodamine
B solution, J. Hazard. Mater. 185 (2011) 914–920.
[
[
[
17] E.H. Ryu, Y. Zhao, Efficient synthesis of water-soluble calixarenes using click
chemistry, Org. Lett. 7 (2005) 1035–1037.
18] S.P. Bew, R.A. Brimage, N.L. Hermite, et al., Upper rim appended hybrid calixarenes
via click chemistry, Org. Lett. 9 (2007) 3713–3717.
19] O. Gungor, A. Yilmaz, S. Memon, et al., Evaluation of the performance of calix[8]-
arene derivatives as liquid phase extraction material for the removal of azo dyes, J.
Hazard. Mater. 158 (2008) 202–210.
Acknowledgments
Financial support from the National Natural Science Foundation
of China (No. 20402002), Fujian Natural Science Foundation of
China (No. 2011J01031), Project of Fujian Provincial Department of
Education (No. JA11044) and Program for Excellent Young
Please cite this article in press as: H.-Y. Guo, et al., Click synthesis and dye extraction properties of novel thiacalix[4]arene derivatives
with triazolyl and hydrogen bonding groups, Chin. Chem. Lett. (2013), http://dx.doi.org/10.1016/j.cclet.2013.04.003