Macrocyclic compounds from benzenedithiols and triazine: Modification of tetrathiacalix[4]arene

Article abstract of DOI:10.1002/jhet.5570450225

(Chemical Equation Presented) Synthesis of macrocyclic compounds having benzenedithionate and triazine moieties was achieved by an efficient fragment coupling approach. In the solid state, they adopted 1,3-alternate conformations. Combination of two pairs

Full text of DOI:10.1002/jhet.5570450225

Mar-Apr 2008
461
Macrocyclic Compounds from Benzenedithiols and Triazine:
Modification of Tetrathiacalix[4]arene
Ashraful Alam, Miharu Yamaguchi, Tatsuya Yamamoto, Shiduko Nakajo,
Satoshi Ogawa and Ryu Sato*
Department of Chemical Engineering, Faculty of Engineering,
Iwate University, Morioka 020-8551, Japan
E-mail: rsato@iwate-u.ac.jp
Received June 8, 2007
S
S
N
S
S
N
N
N
N
N
N
N
N
R
N
R
N
R
R
N
S
S
S
S
R = Cl, Ph
Synthesis of macrocyclic compounds having benzenedithionate and triazine moieties was achieved by
an efficient fragment coupling approach. In the solid state, they adopted 1,3-alternate conformations.
Combination of two pairs of electron rich and electron poor units, and ortho-ortho and/or ortho-meta
connections of sulfur atoms with aromatic carbons were novel features of the macrocycles.
J. Heterocyclic Chem., 45, 461 (2008).
RESULTS AND DISCUSSION
INTRODUCTION
building blocks
Cyanuric chlorides have high reactivity towards
nucleophilic reagents. Therefore, 1,2-benzenedithiol was
allowed to react with 2.0 equiv of cyanuric chloride in
THF at 0 °C in the presence of diisopropylethylamine
(DIPEA) as an acid scavenger (Scheme 1). Linear
trimer, 1,2-bis(dichloro-s-triazynylthio)benzene (3), was
generated in slow reactions. The results of controlled
experiments are reported in Table 1 (entries 1-6). Isolated
yields were surprisingly improved after lengthening of
both mixing time of reactants and reaction time under
more dilute conditions. The best yield (95%) of linear
trimer 3 was observed in the reaction for 45 h.
Macrocyclic
have
attracted
considerable interest in supramolecular chemistry [1]. The
methylene bridge of calix[4]arene has been replaced by
various heteroatoms such as sulfur, nitrogen, oxygen,
boron, silicon, germanium, and phosphorous [2,3].
Some intriguing macrocycles having heterocycles
such as calixpyrroles [4], calixpyridines [5], and other
heteroaromatics [6] have emerged as powerful tools for
binding ions and/or even neutral molecules. Recent
results concerning anion recognitions have also shown
that triazine is an electron deficient π-aromatic
component which can interact with anionic species
[7,8]. The triazine [9] skeleton has already been
incorporated by many authors for the synthesis of
hetroatom-bridged calixarenes the same as pyridine and
pyrimidine [10]. Tetrathiacalix[4]arenes have also
some unique structural advantages [3,11]. Classical
calix[n]arene or [In]metacyclophanes are meta-meta
connected macrocycles, whereas cyclophanes having
ortho-ortho or ortho-meta connected with methylene or
other heteroatoms have not appeared in the literature
[12]. Here, 1,2-benzenedithionate seems to decrease
the cavity size and simultaneously increase the
structural rigidity [13,14].
The macrocyclizative coupling reaction between 1 and
3 was also carried out in acetone at room temperature in
dilute condition in the presence of DIPEA as a base.
Typical isolated yields of tetrathia[2]arene[2]triazine (4)
are summarized in Table 1(entries 7-11). The yield of 4
was increased up to 40%. A similar coupling reaction was
also carried out between 3 and 1,3-benzenedithiol and
ortho-meta derivative (6) was isolated in 14% yield.
Cyclophanes 4 and 6 have each two chloride functional
groups and thus open the opportunity to convert them into
other derivatives with appropriate nucleophiles.
For instance, chlorine atoms of 4 and 6 were
successfully replaced by PhMgBr/THF in THF at 50°C
for 10 h. Isolation of corresponding benzo analogues, 5
(64%) and 7 (41%), revealed that the nucleophilic
replacement afforded corresponding phenyl derivatives.
We report herein, the first synthesis of macrocyclic
compounds having benzenedithionate and triazine
moieties.

462
A. Alam, M. Yamaguchi, T. Yamamoto, S. Nakajo, S. Ogawa and R. Sato
Vol 45
Scheme 1
Cl
N
Cl
SH
SH
a
+
N
N
Cl
1
2
N
Cl
Cl
N
S
S
N
N
N
N
Cl
Cl
3 (95%)
c
b
a
S
S
S
S
N
N
N
N
N
N
N
N
N
R
N
N
R
R
N
R
S
S
S
S
4 (R = Cl, 40%)
5 (R = Ph, 64%)
6 (R = Cl, 17%)
7 (R = Ph, 41%)
Reagents and conditions: a. THF, DIPEA, 0°C; b. (i) DIPEA, acetone,
1,2-benzenedithiol, rt, (ii) PhMgBr/THF; c. (i) DIPEA, acetone, 1,3-
benzenedithiol, rt, (ii) PhMgBr/THF.
The structures of all products were unambiguously
characterized by spectroscopic data. In H and 13C NMR,
the compounds 3, 4 and 5 showed symmetric signals
1
b
while unsymmetrical peaks appeared for remaining
compounds. Recrystallization of
5
and
7
from
hexane/CH2Cl2 gave some single crystals suitable for X-
ray crystallographic analysis.
Table 1. Synthesis of 3 and 4 by fragment coupling strategy
entrya
1
timeb
3c
timeb
entryd
7
4c
1 + 8 h
3
7 + 6 h
24
2
3
4 + 0 h
16 + 8 h
30
78
5 + 14 h
8+ 18 h
8
9
30
24
4
5
6
20 + 20 h
23 + 18 h
25+ 20 h
91
82
95
7 + 25 h
6+ 50 h
10
11
40
21
c
Figure 1. ORTEP structures of compound 5 demonstrating the 1,3-
alternate conformation in the solid state; for clarity all hydrogen atoms
a A reaction between 1 and 2, b Period of the mixing of reactants +
reaction time, c Isolated yields in %,d A reaction between 3 and 1.
are omitted. (a) Top view, where bond lengths
Å (sulfur to
heteroaromatic carbon) S1-C1 1.745(2), S2-C3 1.731(2), S3-C16
1.7603(19), S4-C17 1.727(2); (sulfur to aromatic carbon) S1-C10
1.769(2), S2-C35 1.7879(19), S3-C15 1.7785(19), S4-C30 1.7919(17)
(b) Side view shows π−π stacking where the distance between plane 1
and plane 2 is 4.663 Å and plane 3 and plane 4 is 9.131 Å (c) Side view
shows clip like conformation.
The compounds adopted the expected 1,3-alternate
conformation in the solid state [15,16]. The pair of central
benzene rings framed themselves in
a
clip-like
conformation, while the remaining two triazine rings are

Mar-Apr 2008
Macrocyclic Compounds from Benzenedithiols and Triazine
463
roughly coplanar and edge-to-edge oriented and well
separated. Conformational structures appeared more
clearly due to the attachment of two phenyl groups with
the outer s-triazine moiety. The four bridging sulfur atoms
of both compounds are located nearly at the same plane
although they were ortho-ortho or ortho-meta connected
with aromatic units.
For introduction of 1,2-benzodithionate elements in the
calixes, the comparative flexibility of the four bridges
(sulfur atoms) are reduced while corresponding stresses of
the two parallel benzene ring towards the center of cavity
are increased. Therefore, π−π stacking interaction of the
two central benzene rings, the position of bridging sulfur
in the conformational structures and observable cavities
were different than meta-meta connected tetrathia-
calix[4]arene.
a
The average bond lengths for S-C (heteroaromatic
carbon) and S-C (aromatic carbon) are 1.740 and 1.781 Å
for 5, while these values are 1.755 and 1.773 Å for
compound 7. The bond distance from sulfur to the
aromatic carbon is larger than that of sulfur to the
heteroaromatic carbon (Fig. 1a and 2a). Therefore, the
sulfur atom is more conjugated with the triazine units than
with the phenyl ring. The same results were also reflected
for similar oxa and azacalixerenes [9a].
The dihedral angles between the triazine ring and the
outer phenyl ring are 18.839° and 5.406° for compound 5.
Almost the same angles were observed for compound 7. It
seems that the outer phenyl rings and triazines stay in
completely different planes due to different electrostatic
interactions among various units. The cavity of the
macrocycles is an important criterion to hold the various
guest species. No solvent molecule was found to bind
within cavities, and therefore, the cavities were too small
to allow small solvent molecules [11b].
b
The distances between two triazine rings at the upper
rim are 4.663 and 6.292 Å for 5 and 7 respectively (Fig.
1b and 2b). The greater separation of the outer phenyl
rings of 7 suggests that its comparative cavity size is
larger than that of 5. This result is also expected from
bonding arrangements of the sulfur atoms. The cavities
are viewed as resulting from a cyclic array of two isolated
phenyl rings and triazine units in a 1,3-alternate fashion.
Hence, tuning of the isomeric position of the bridging
sulfur can control the cavity size of macrocycle.
c
The rings are almost perpendicular to the plane formed
by the four bridging sulfur with inclined angles near 90°.
The average distances of the face-to-face paralleled
phenyl rings are 4.002 and 4.127 Å for compounds 5 and
7, respectively, suggesting a weak π−π stacking
interaction in the solid state. For a similar type of
oxacalixarene the average distance of face-to-face the
phenyl rings is 4.726 Å [9a]. The parent calixarene has
intramolecular hydrogen bonding that forces it into a cone
conformation, but macrocycles 5 and 7 lack such bonds.
Moreover, to avoid possible steric hindrance from the
Figure 2. ORTEP structure of compound 7 demonstrating the 1,3-
alternate conformation in the solid state. (a) Top view, where bond
lengths Å (sulfur to heteroaromatic carbon) S1-C18 1.7519 (17), S2-C16
1.7532(18), S3-C1 1.7569(18), S4-C3 1.7584(16); (sulfur to aromatic
carbon) S1-C14 1.7718(18), S2-C25 1.774(2), S3-C30 1.7748(19), S4-
C10 1.7739(18) (b) Side view shows π−π stacking where the distance
between plane 1 and plane 2 is 6.292 Å and plane 3 and plane 4 is
12.143 Å (c) Side view
cone conformation, these molecules adopt a 1,3-alternate
conformation. The crystal structures of these macrocylcles

464
A. Alam, M. Yamaguchi, T. Yamamoto, S. Nakajo, S. Ogawa and R. Sato
Vol 45
(1:1) as an eluent to give product 3 (8.30 g, 95%) as a colorless
solid. mp 128.0-129.2°C; ir (KBr): 1510, 1478, 1243, 845 cm-1;
1H NMR (400 MHz, CDCl3): δ 7.50 (dd, J = 6.0, 3.2Hz, 2H,
ArH), 7.75 (dd, J = 6.0, 3.3Hz, 2H, ArH); 13C NMR (101 MHz,
CDCl3): δ 131.72, 132.08, 137.59, 170.47, 184.98; FAB MS:
m/z = 439 [M+1]+. Anal calcd. for C26H4N6S2: C 32.90; H 0.92;
N 19.18. Found: C 32.90; H 1.08; N 18.85.
result from the combination of electronic and steric
factors of bridging sulfur, triazine as well as phenyl rings.
The same conformation was also observed for azacalix-
[2]arene[2]pyridine [9b], which also adopted a 1,3-
alternate as the most energetically stable conformation.
The electron withdrawing nature of triazine is very strong
and the steric repulsion between triazinyl and bridging
moieties are weak. Therefore, the sulfur atom may favor
triazine ring to be conjugated rather than the phenyl ring.
Tetrathiacalix[2]ortho-ortho arene[2]triazine (4). A solution
of DIPEA (0.84 ml, 4.8 mmol) in acetone (140 ml) was stirred
under N2 in a 500 ml three neck flask fitted with two dropping
funnels. 1,2-Benzenedithiol (0.28 g, 2 mmol) was dissolved in
acetone (60 ml) and the solution was taken in one dropping
funnel. In another dropping funnel, a solution of compound 3
(0.87 g, 2 mmol) in acetone (60 ml) was taken at the same time.
The two reactants were simultaneously dropped into the DIPEA
solution under constant stirring over 7 h at room temperature.
The reaction mixture was stirred for 25 h at room temperature.
Acetone was evaporated and crude product was separated by
column chromatography on silica gel using CHCl3/ n-hexane
(2:1) as an eluent to yield product 4 (40%) as a colorless solid.
mp. >300.0 °C; ir (KBr): 1502, 1460, 1249, 843, 759, 561 cm-
1;1H NMR (400 MHz, CDCl3): δ 7.25 (dd, J = 5.5, 3.6 Hz, 4H,
ArH), 7.41 (dd, J =5.5, 3.6 Hz, 4H, ArH); 13C NMR (101 MHz,
CDCl3) δ 131.35, 132.49, 137.77, 168.02, 183.04; FAB MS: m/z
= 507 [M+1]+. Anal calcd. for C18H8N6S4Cl2: C 42.60; H 1.59; N
16.56. Found: C 42.52; H 1.80; N 16.22.
Compound 5. Macrocycle 4 (0.10 g, 0.2 mmol) was
dissolved in THF (20 ml) and the solution was placed in an ice-
bath under N2. PhMgBr in THF (5 equiv.) was added and the
reaction mixture was refluxed for 10 h at 50 °C. The reaction
mixture was quenched with ice water, acidified with HCl and
extracted with CH2Cl2. The organic product was dried over
MgSO4. After evaporation of the solvent, the crude product was
purified by column chromatography by using CHCl3/n-hexane
(2:1) as an eluent to afford 5 in 64% yield. Colorless solid, mp.
>300.0 °C; ir (KBr): 1495, 1442, 1249, 763 cm-1; 1H NMR (400
MHz, CDCl3): δ 7.23 (dd, J = 3.4, 6.0 Hz, 4H, ArH), 7.43 (t, J =
8.0 Hz, 2H, ArH), 7.46 (dd, J =3.4, 6.0Hz, 4H, ArH), 7.52 (t, J =
7.2Hz, 4H, ArH), 8.40 (d, J = 8.4Hz, 4H, ArH); 13C NMR (101
MHz, CDCl3): δ 128.54, 129.23, 130.62, 132.80, 133.50,
134.32, 137.71, 168.77, 181.79; FAB MS: m/z = 591[M+1]+.
Anal calcd. for C30H18N6S4: C 60.99; H 3.07; N 14.23. Found: C
60.90; H 3.15; N 14.23.
CONCLUSION
Triazine is regarded as a π-deficient aromatic ring with
a little positive charge [8], and thus two opposite triazine
rings in the macrocycles adopted roughly coplanar and are
kept apart from each other. In contrast, however, the two
opposite the phenyl rings tend to align in parallel due to
weak π−π stacking interaction that might bring an extra
stabilization to the molecules.
In conclusion, two novel modified tetrathiacalix[4]-
arenes have been developed by stepwise fragment
coupling approach. The cavity size of the calixarenes was
varied for binding positions of sulfur atoms. Ortho-ortho
and/or ortho-meta connections of sulfur atom with
aromatic carbon offered some novel structural features in
the solid state. Combination of two pairs of electron rich
and electron deficient π-aromatics indicates a good design
for construction of 1,3-alternate macrocycles. Syntheses
of macrocyclic compounds having more structural
flexibility by using aromatic dithiols are underway.
EXPERIMENTAL
Melting points were measured with a MEL-TEMP capillary
melting point apparatus and are uncorrected. 1H-(400 MHz) and
13C-(101MHz) NMR spectra are recorded on a Bruker AC-400P
instrument with CDCl3 as a solvent. 1H NMR chemical shifts are
given ppm from internal TMS. 13C NMR chemical shifts are
given in relative ppm from internal CDCl3 δ Acetone, CH2Cl2
and THF were freshly distilled according to standard laboratory
procedures prior to use. 1,2- And 1,3-benzenedithiols were
synthesized according to the standard literature methods [17].
Diisopropylethylamine (DIPEA) and cyanuric chloride were
purchased from Aldrich and these were used without further
purification. FAB MS was measured by using matrix of
nitrobenzylalcohol/dithiothreitol (NBA/DTT). C-200 was used
for silica gel column chromatography. Elemental analyses were
recorded using Yanaco MT-5 apparatus at the elemental analysis
division of Iwate University.
1,3-Bis(dichloro-s-triazinylthio)benzene (3). In a typical run
(run 6, Table 1), a solution of cyanuric chloride (14.75 g, 80
mmol) in THF (200 ml) was taken in a 500 ml three neck reactor
under air. Diisopropylethylamine (DIPEA, 4.2 ml, 24 mmol)
was poured into the reactor and the mixture was cooled to 0°C.
A solution of 1,2-benzenedithiol (2.76 g, 20 mmol) in THF (200
ml) was added dropwise into the reactor over 25 h. The reaction
mixture was stirred for 20 h at room temperature. After
evaporation of the solvent, the crude product was purified by
column chromatography on silica gel using CHCl3/n-hexane
Tetrathiacalix[2] ortho-ortho and ortho-para arene[2]-
triazine (6). The experimental procedure for compound 6 was
the same as that of compound 4. In both cases a single
macrocyle was isolated. Generation of macrocyles larger than 4
or 6 was not observed at all. Colorless solid, mp. 300.0 °C; ir
(KBr): 1493, 1441, 1375, 1315, 1275, 124, 840, 762, 693, cm-1;
1H NMR (400 MHz, CDCl3): δ 7.19 (t, J = 8.4 Hz, 1H, ArH),
7.29-7.40 (m, 6H, ArH), 7.43 (t, J =1.7 Hz, 1H, ArH); 13C NMR
(101 MHz, CDCl3): δ 127.69, 130.49, 131.01, 132.20, 137.30,
137.61, 143.90, 168.04, 182.82, 184.02; FAB MS: m/z = 507
[M+1]+. Anal calcd. for C18H8N6S4Cl2: C 42.60; H 1.59; N 16.56.
Found: C 42.54; H 1.81; N 16.29.
Compound 7. The experimental procedure for compound 7
was as same as that of compound 5. Colorless solid, mp. >300.0
°C; ir (KBr): 1492, 1441, 1375, 1316, 1275, 1248, 837, 763, 694
1
cm-1; H NMR (400 MHz, CDCl3): δ 7.16-7.20 (m 1H, ArH),
7.26-7.30 (m, 2H, ArH), 7.37-7.39 (m 2H, ArH), 7.42-7.46 (m,
2H, ArH), 7.48-7.51 (m, 5H, ArH), 7.53-7.58 (m, 2H, ArH),
8.43-8.45 (m, 4H, ArH); 13C NMR (101 MHz, CDCl3): δ 127.01,

Mar-Apr 2008
Macrocyclic Compounds from Benzenedithiols and Triazine
465
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127.69, 128.00, 129.00, 130.49, 131.01, 132.20, 132.40, 136.53,
137.30, 137.61, 143.90, 168.04, 169.10, 182.82, 184.50; FAB
MS: m/z = 591 [M+1]+. Anal calcd. for C30H18N6S4: C 60.99; H
3.07; N 14.23. Found: C 60.70; H 3.35; N 14.20.
Crystallographic information. X-ray crystal data for
compounds 5 and 7 have been deposited in the Cambridge
Crystallographic Data Centre as supplementary publication
number CCDC 640621 and CCDC 640622, respectively. Copies
of the data can be obtained, free of charge, on application to
CCDC, 12 Union Road, Cambridge, CB2 IEZ, UK [fax: 44 1223
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monoclinic, space group P21/n (#14), a = 9.304(5) Å, b = 20.734(3) Å, c
= 14.224 (3) Å, β = 90.6696(16)° V= 2743.6(16)Å3, Z = 4, Dcalc= 1.430g
cm-3, T = 123 K, Radiation M0Kα (λ=71075 Å). A colorless prism
crystal of approximate dimensions of 0.20 x 0.20 x 0.10 mm was used
for the measurement. The structure was solved by the direct methods and
expanded using Fourier technique (DIRDIF-99). All the calculations
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measurement. The structure was solved by the direct methods and
expanded using Fourier technique (DIRDIF-99). All the calculations
based on 6045 observed reflections (I >2.00σ (I)) and 361 variables
parameters with R1= 0.0399 and wR2= 0.0497(all data).
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Mezailles, N.; Richard, L.; Le Floch, P.; Mathey, F. Science, 1998, 280,
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Lex, J.; Gross, M.; Gisselbrecht, J. P. Angew. Chem. Int. Ed. Engl. 1996,
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[16] Crystal data for compound 7: M = 590.74, C30H18N6S4,
orthorhombic, space group P212121/n (#19), a = 10.0499(6) Å, b =
14.1979(10) Å, c = 19.0802(14) Å, V= 2722.5(3) Å3, Z = 4, Dcalc
=
1.441g cm-3, T = 123 K, Radiation M0Kα (λ= 0.7107A). A colorless
block crystal of approximate dimensions of 0.40 x 0.20 x 0.20 mm was
used for the measurement. The structure was solved by the direct
methods and expanded using Fourier technique (DIRDIF-99). All the
calculations were performed using crystal structure 3.5.1 crystal
structure analysis package of Rigaku and Rigaku/MSC. The final cycle
of full matrix least squares refinement was based on 6223 observed
reflections (I >2.00σ (I)) and 380 variables parameters with R1= 0.0296
and wR2= 0.0557(all data).
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3617-3627. [c] Bielejewska, G.; Marjo, C. E.; Prins, L. J.;
Timmerman,P.; De Jong, F.; Reinhoudt, D. N. J. Am. Chem. Soc. 2001,
123, 7518-7533. [d] Seto, T.; Whitesides, G. M. J. Am. Chem. Soc. 1993,
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451-452. [b] Maiolo, F.; Testaferri, L.; Teicco, M.; Tingoli, M. J. Org.
Chem. 1981, 46, 307-30730.