Synthesis and structure of a novel thiacalix[4]arene based triazine derivative

Article abstract of DOI:10.14233/ajchem.2013.13373

Using thiacalix[4]arene and 1,3-bis-(dichloro-s-triazinyloxy)benzene as a starting materials, a novel thiacalix[4]arene based triazine derivative has been designed and synthesized. This nucleophilic displacement reaction occurred in mild condition. The co

Full text of DOI:10.14233/ajchem.2013.13373

Asian Journal of Chemistry; Vol. 25, No. 1 (2013), 512-514
http://dx.doi.org/10.14233/ajchem.2013.13373
Synthesis and Structure of a Novel Thiacalix[4]arene based Triazine Derivative
1
1
1,*
1
1
2
MIN DENG , LAN MU , XI ZENG , XUE-KAI JIANG , YUN-QIAN ZHANG and TAKEHIKO YAMATO
1
2
Key Laboratory of Macrocyclic and Supramolecular Chemistry of Guizhou Province, Guizhou University, Guiyang 550025, P.R. China
Department of Applied Chemistry, Faculty of Science and Engineering, Saga University, Honjo-machi 1, Saga-shi, Saga 840-8502, Japan
*
Corresponding author: E-mail: zengxi1962@163.com
Received: 2 January 2012;
(
Accepted: 2 August 2012)
AJC-11913
Using thiacalix[4]arene and 1,3-bis-(dichloro-s-triazinyloxy)benzene as a starting materials, a novel thiacalix[4]arene based triazine
derivative has been designed and synthesized. This nucleophilic displacement reaction occurred in mild condition. The conformation of
1
,3-alternate was confirmed by NMR spectra and X-ray crystal structure analyses. Moreover, it formed a unique π-electron-deficient
cavity has the potential to recognize cations and anions.
Key Words: Thiacalix[4]arene, Triazine, Synthesis, Structure.
were determined on a XT-4 binocular microscope (Beijing
INTRODUCTION
1
13
Tech Instrument Co. China) and were uncorrected. H and C
NMR spectra were measured on a Varian Nova-400 NMR
spectrometer at room temperature. ESI-MS spectra were
recorded on an Agilent HPLC-MSD-Trap-VL spectrometer.
Crystal X-ray diffraction was conducted on a Bruker Smart
ApexII CCD diffractometer. The X-ray datas were collected
Thiacalix[4]arene, as a kind of thiacalixarenes, has
attracted considerable attention in the fast-growing field of
supramolecular chemistry. Four sulfur atoms instead of the
methylene bridges make it has many novel features comparing
with classical calixarenes, such as larger cavity, more flexibility,
considerably different conformational behaviour, chemical
1
with graphite-Monochro-mated MoK radiation (λ = 0.071073
α
modification of bridges and excellent coordination abilities .
Å) in φ and ω scan modes. The structure solution was solved
by direct methods using SHELX-97 software packages.
Hydrogen atoms were not refined and were placed either
theoretically or found in the Fourier difference maps. 7 Water
molecules in the unit cell have been taken into account to
SQUEEZE option of the PLATON program. The crystallo-
graphic data in this paper have been deposited with the
Cambridge crystallographic data centre as supplementary
publication number CCDC(857542).
We have reported some fluorescent sensors based on
thiacalix[4]arene modified with different functional groups .
2
Much effort have been done to develop of new functional
thiacalix[4]arenes and worthwhile to continue devote to do.
Triazine-based derivatives are valuable in molecular
recognition and self-assembly research, because of it providing
both hydrogen bond donor and acceptor sites for the selective
3
binding of guest molecules . Recent research indicated that a
potential application of triazine act as an electron-deficient
π-aromatic component to interact with anion species. In view
of the high reactivity of a cyanuric halide toward nucleophilic
reagents in a controlled fashion, we utilized the synthetic
advantage of it to linking desired moiety with thiacalix[4]arene.
Yielding a cleft formed by π-electron deficient triazine rings,
we envisioned that this π-electron-deficient cavity would act
as a receptor to interact with anions through π-anion interactions.
Herein, we report the synthesis of the novel thiacalix[4]arene
linked with triazine.
Synthesis: Compound (2), (3), (4) and (5) were sythesized
3,4
following the literature procedures .
Synthesis of compound 1: At room temperature, solu-
tions of 2 (461.5 mg, 0.5 mmol) in acetone (50 mL) and 3
(
202 mg, 0.5 mmol) in acetone (50 mL) were added dropwise
at the same time and the same rate to a solution of DIPEA
387 mg, 3 mmol) in 150 mL acetone during 6 h. After
(
addition of two reactants, took about 24 h until the starting
materials were consumed (Scheme-I). The solvents were
removed and the residue was chromatographed with mixture
of petroleum ether/ethyl acetate (6:1, v/v) as the mobile phase
EXPERIMENTAL
All the reagents used in the study were dried or purified
according to standard procedures prior to use. Melting points
to give pure product 1 220 mg, yielding 37 %. m.p. > 300 ºC;
1
H NMR (CDCl
3
, 400 MHz), δ (ppm): 1.14 (s, 18H, C(CH )),
3

Vol. 25, No. 1 (2013)
Synthesis and Structure of a Novel Thiacalix[4]arene based Triazine Derivative 513
O
O
O
O
NH2
O
O
O
O
H N
2
N
N
O
N
N
O
O
O
OH
OH
s
Cs CO CH CN
2
NH NH .H O
2
s
3
3
2
2
s
O
O
s
s
s
s
s
s
s
s s EtOH reflux
O
O
O
O
O
TsO
O
O
O
O
4
2
3
Cl
H N
NH
N
N
THF
N
N
N
N
N
+
Cl
N
Cl
H2N
NH2
DIPE A
Cl
N
Cl
Cl
Cl
5
HN
N
NH
N
N
N
N
NH2
H 2N
Cl
Cl
N
O
O
NH
HN
N
NH
N
HN
s
N
N
s
s
N
Cl
N
acetone
s
+
Cl
O
O
O
O
O
DIPEA
s
s
s
Cl
Cl
s
O
O
O
O
O
5
4
1
Scheme-I: Synthesis of compound 1
1
6
7
.32 (s, 18H, C(CH
H, CH ), 3.63-3.71 (m, 4H, OCH
.16 (br, 1H, NH), 7.23 (br, 1H, NH), 7.31 (t, J = 8.0 Hz, 1H,
3
)), 3.16 (t, J = 6.8 Hz, 4H, OCH
2
), 3.31 (s,
a selection of bond distances/angles and crystallographic data
can be found in Tables 1 and 2. X-ray diffraction studies reveal
that the thiacalix[4]arene adopted a 1,3-alternate conformation,
which was also confirmed by NMR spectra. For every two
opposite benzene rings of thiacalix[4]arene framework, the
dihedral angle and centroid distance are 32.14(16)º, 6.08 Å
and 41.37(16)º, 6.83 Å, respectively. The four bridging sulfur
atoms on thiacalix[4]arene skeleton lie in the same plane. The
average distance between two neighbouring sulfur atoms in 1
is 5.57 Å. Triazine rings are twisted out of plane with the
inclined angles exist between the two triazine ring planes and
the benzene ring is 13.69(19)º, 27.02(18)º respectively. In the
center of the cavity, there is a water molecule, the Intra-
molecular hydrogen-bond N(9)…H(9)…O(1W) were formed
between water oxygen and the hydrogen amino group with
the very short distance of 2.20 Å. The average bond lengths
and bond angles of the bridging nitrogen atoms indicated that
four linking nitrogen atoms adopted an sp2 configuration.
3
2
), 4.05-4.12 (m, 8H, OCH
2
),
Ar-H), 7.37 (s, 4H, Ar-H), 7.42-7.46 (m, 2H, Ar-H), 7.51 (s,
13
4
H, Ar-H), 7.61 (s, 1H, Ar-H); C NMR (CDCl
δ (ppm): 30.98 (CH ), 31.15 (CH ), 31.20 (CH
4.28 (C), 58.82 (NCH ), 67.27 (OCH ), 69.98 (OCH
OCH ), 127.91 (Ar-C), 128.05 (Ar-C), 128.59 (Ar-C), 128.98
3
, 400 MHz),
), 34.17 (C),
), 70.63
3
3
3
3
(
2
2
2
2
(
(
(
Ar-C), 129.16 (Ar-C), 129.61 (Ar-C), 130.90 (Ar-C), 138.33
Ar-C), 139.33(Ar-C), 145.99 (Ar-C), 146.08 (Ar-C), 146.76
Ar-C), 165.40 (Ar-C), 165.74 (Ar-C), 169.00 (Ar-C); IR (KBr,
-1
ν
1
max, cm ): 3413, 3283, 2962, 2873, 1573, 1541, 1437, 1240,
+
087, 1033, 805; ESI-MS: m/z 1277 [M+Na] .
RESULTS AND DISCUSSION
The single crystal of compound 1 was obtained by slow
crystallization from its ethyl acetate/n-hexane (80:1 v/v)
solution. The molecular structure for 1 is presented in Fig. 1,

514 Deng et al.
Asian J. Chem.
TABLE-1
X-RAY CRYSTALLOGRAPHIC DATA OF COMPOUND 1
-
3
Formula
Formula weight
Temperature (K)
Wavelength, Å
Crystal system
Space group
a (Å)
b (Å)
c (Å)
α,º
C H N O Cl S ·8H O
1398.56
293(2)
0.71073
Monoclinic
P 21/n
15.6034(7)
24.9078(11)
19.4826(9)
90.00
D (calcd.) g cm
µ, mm
F(000)
θ range, º
h, k, l range
1.124
0.261
2960
1.55 to 25.00
-18 < h < 18
-29 < k < 29
-23 < l < 20
4
62
90 10 14
2
4
2
-1
Z
Reflection collected
Independent reflection
13178
8354
β,º
γ,º
V, Å
97.318(2)
90.00
7510.2(6)
R
int
0.0509
0.0652, 0.1928
0.0980, 0.2107
R1,wR2 [I> 2σ(I)]
R1,wR2 (all data)
3
TABLE-2
SELECTED BOND DISTANCES (Å) AND ANGLES (º)
N6-C50
N6-C54
N7-C48
N7-C51
N9-C56
N9-C62
N10-C53
N10-C58
1.462(4)
1.326(4)
1.456(5)
1.330(4)
1.346(4)
1.429(4)
1.347(5)
1.395(4)
N6-H6
N7-H7
N9-H9
N9-H9
C50-N6-H6
C54-N6-H6
C50-N6-C54
C48-N7-H7
0.86
0.86
0.86
0.86
119
119
121.9(3)
116
C51-N7-H7
C48-N7-C51
C56-N9-H9
116
127.9(3)
115
115
129.6(3)
113
C62-N9-H9
C56-N9-C62
C53-N10-H10
C58-N10-H10
C53-N10-C58
113
133.5(3)
characterized by IR, NMR, MS spectrometry and X-ray diffra-
ction. The spectrascopy and X-ray single crystallography data
showed that the new thiacalix[4]arene derivative adopted a
1
,3-alternate conformation. The thiacalix[4]arene platform
with the segment of N,N'-bis-(dichloro-s-triazinyl)-m-
phenylenediamine formed a unique π-electron-deficient cavity.
It was envisioned that the introduction of ether groups on to
the benzene rings would give rise to a functionalized cavity.
In addition, the macrocyclic framework contains multiple
triazine and secondary amine moieties, which are potential
hydrogen bond acceptors and donors, respectively. Most
noticeably, the cavity such as 1 is composed of all two electron-
deficient triazine walls. It might be useful in complexation
with highly electron-rich species. The study of the molecular
recognition property of the functionalized thiacalix[4]arene
is in progress and will be reported in due course.
ACKNOWLEDGEMENTS
The authors are grateful for the financial support from
the Fund of the International cooperation projects of Guizhou
Province (No. 20107002), "Chun-Hui" Fund of Chinese of
Education (No. Z2009-1-52001), Natural Science Foundation
of China (No. 21165006).
Fig. 1. Molecular structure of compound 1
REFERENCES
Conclusion
1
2
.
.
N. Morohashi, F. Narumi, N. Iki, T. Hattoriand and S. Miyano, Chem.
Rev., 106, 5291 (2006).
X.Y. Zheng, W.J. Zhang, L. Mu, X. Zeng, S.F. Xue, Z. Tao and T.
Yamato, J. Incl. Phenom. Macrocycl. Chem., 68, 139 (2010).
In summary, a novel 1,3-alternate-25,27-[(N,N'-bis-
chloro-s-triazinyl)-m-phenyl-enediamine)minoethoxy]-
(
26,28-bis-(2-methoxyethyl)-thiacalix[4]arene had been first
3. M.X. Wangand and H.B. Yang, J. Am. Chem. Soc., 126, 15413 (2004).
4. M. Kumar, A. Dhir and V. Bhalla, Eur. J. Org. Chem., 4535 (2009).
synthesized under very mild conditions. It's structure was