Syntheses, reactions and crystal structures of 1,3-alternate p-tert-butylthiacalix[4]arene esters and amides

Article abstract of DOI:10.1007/s10847-009-9652-4

p-tert-Butylthiacalix[4]arene was efficiently alkylated in the system of K₂CO₃/KI/acetone to give several thiacalixarene derivatives in 1,3-alternate conformation with functional ester, chloro, cyano and amide groups. Thiacalixarene tetraacateate can be converted to bicyclic amides by ammonolysis with alkylenediamine, and to sulfonylcalixarene by oxidation with hydrogen peroxide in acetic acid. Single crystal X-ray diffraction analysis reveals that thiacalixarene and sulfonylcalixarene exist mainly in 1,3-alternate conformation.

Full text of DOI:10.1007/s10847-009-9652-4

J Incl Phenom Macrocycl Chem (2010) 66:349–355
DOI 10.1007/s10847-009-9652-4
ORIGINAL ARTICLE
Syntheses, reactions and crystal structures of 1,3-alternate
p-tert-butylthiacalix[4]arene esters and amides
Li Liu Æ Kun Huang Æ Chao Guo Yan
Received: 28 March 2009 / Accepted: 18 July 2009 / Published online: 2 August 2009
ꢀ Springer Science+Business Media B.V. 2009
Abstract p-tert-Butylthiacalix[4]arene was efficiently
alkylated in the system of K2CO3/KI/acetone to give sev-
eral thiacalixarene derivatives in 1,3-alternate conforma-
tion with functional ester, chloro, cyano and amide groups.
Thiacalixarene tetraacateate can be converted to bicyclic
amides by ammonolysis with alkylenediamine, and to
sulfonylcalixarene by oxidation with hydrogen peroxide in
acetic acid. Single crystal X-ray diffraction analysis reveals
that thiacalixarene and sulfonylcalixarene exist mainly in
1,3-alternate conformation.
prepared for versatile potential uses [6–11]. During our
on-going research on thiacalix[4]arene derivatisation we
noted that the presence of four sulphur atoms implicates
many novel features of the conformational behavior and
the solid-state preferences. In this paper we wish to report
syntheses, reactions and crystal structures of a series of
p-tert-butylthiacalix[4]arene functional esters and amides.
Results and discussion
Keywords Calixarene ꢀ Thiacalixarene ꢀ Alkylation ꢀ
Conformation ꢀ Crystal structure
Tetrtraalkylation of the phenolic hydroxyl groups in lower
rim of thiacalixarene is a standard method by which to
modify the calix[4]arene skeleton [12, 13]. Accordingly,
several groups have studied the alkylation of thiacalixa-
renes with ethyl a-bromoacetate using the M2CO3/acetone/
reaction system (M = Li, Na, K, and Cs) [14–16]. This
reaction exhibits a surprisingly pronounced template effect,
and leads to high yields of the corresponding tetraacetates
in various con-formations (cone, partial cone, 1,3-alternate)
[17]. By using ethyl a-chloroacetate as alkylating reagent,
we carried out the alkylation reaction of thiacalixarene 1 in
the system of K2CO3/KI/acetone. The desired ethyl thi-
acalixarylacetate 2a was prepared in satisfied yield (62%),
which is pure enough for analysis without chromatographic
Introduction
During the past decades, thiacalixarenes, in which sulfur
atoms instead of methylene bridge of calixarenes, have
attracted much attention as examples of simple or novel
receptors in supramolecular chemistry [1, 2]. As with the
calix[4]arenes, thiacalix[4]arenes have larger cavity, can be
easily functionalized at the upper and lower rim of the
macrocycle as well as on the sulfur atoms, show stronger
affinity towards transition metal ions. These stimulated a
lot of chemist to design versatile supramolecular receptors
and other chemical engineering using thiacalix[4]arenes as
platform [3–5]. A variety of thiacalixarene derivatives
having functional groups on lower and upper rim have been
1
purification. The H NMR spectrum is extremely simple
and shows the presence of one conformer. The singlet at
7.66 ppm observed for the aromatic hydrogen atoms, one
singlet at 4.92 ppm for OCH2CO groups and singlet at
1.32 ppm for the t-butyl groups together with the singlet set
of signals OCH2CH3 groups indicate the high symmetry of
the product. According to the different deshielding zone of
the adjacent phenyl units and tert-butyl groups, Nobuhiko
Iki [14] has indicated that the isomer which exhibited butyl
and OCH2CO protons at 1.09 and 5.18 ppm, respectively,
L. Liu ꢀ K. Huang ꢀ C. G. Yan (&)
College of Chemistry and Chemical Engineering, Yangzhou
University, Yangzhou 225002, China
e-mail: cgyan@yzu.edu.cn
123

350
J Incl Phenom Macrocycl Chem (2010) 66:349–355
was assigned to cone 2a, while that which exhibited pro-
tons at 1.25 and 4.60 ppm was assigned to 1,3-alternate 2a.
Thus we could conclude that our product 2a exists mainly
in 1,3-alternate configuration (Scheme 1).
Under the similar reaction condition p-tert-thiaca-
lix[4]arene 1 was alkylated in the system of K2CO3/acetone
with 1-bromo-3-chloropropane to give O-(3-chloropro-
pyl)thiacalixarene 2b in 86% yield. In such reaction con-
dition 3-chloro group remained unreactive and very higher
yield of thiacalixarene with functional chloroalkyl group
can be conveniently prepared. When 4-chlorobutyronitrile
and N,N-dipropyl a-chloroacetamide were used as alkyl-
ating reagents, p-tert-thiacalix[4]arene 1 was alkylated in
K2CO3/KI/acetone system for five days. After workup the
tetrasubstituted thiacalix[4]arenes having functional cyano
groups 2c and amido groups 2d were prepared in 70% and
54% yields, respectively. In such case pure products could
be gotten by merely crystallization from ethanol and no
need further purification with LC. IR spectra of products 2c
and 2d clearly displays a stronger absorption at 2,230 cm-1
for cyano groups and 1,644 cm-1 for amide carbonyl
Fig. 1 Molecular structure of compound 2c
with the two standing upside and other two pointing
downside. Intramolecular hydrogen bond C(53)-
H(53A)…N(4) were formed between cyano groups and
tert-butyl groups with the distance of 3.33 (Table 2). The
intermolecular hydrogen bonds are also formed between
cyano groups and tert-butyl groups C(27)-H(27A)…N(1)A,
C(57)-H(57A)…N(3), and another hydrogen bond between
sulfur atom and tert-butyl group C(24)-H(24C)…S(3)B is
also formed. Through the intermolecular hydrogen bonds
the molecule 2c form a 2D networks in solid state.
1
group. H NMR spectra shows that thiacalixarene 2b–2d
all exist in 1,3-alternate configuration. As for an example
the 1H NMR spectrum of 2c showed one singlet at
7.38 ppm for phenolic protons and one singlet at 1.32 ppm
for tert-butyl groups.
Single crystal of 2c was determined by X-ray diffraction
analysis. The perspective view with the some atomic
numbering scheme is shown in Fig. 1. The crystal data and
refinement details are given in Table 1. It is clearly seen that
thiacalix[4]arene 2c adopted an 1,3-alternate conformation.
The four cyanopropyl groups are divided into two groups
The sulfonylation reaction of p-tert-butylthiacalixarene
is very interesting. The mixture of thiacalixarene 1 and
excess p-toluenesulfonyl chloride with triethylamine as
acid-capture reagent in chloroform was heated at 50–60 ꢁC
for 12 h. After workup we are surprised to find that
1,3-ditosylthiacarlixarene 2e was produced in 92% yield.
Prolonging the reaction time or adding more p-toluene-
sulfonyl chloride in the reaction still gave 1,3-ditosylthia-
C4H9
C4H9
1
carlixarene 2e as main compound. H NMR spectra shows
that thiacalixarene 2e displays sign of two phenolic
hydroxyl groups at 7.24 ppm, two singlets at 7.37,
6.99 ppm for protons at phenolic ring and two singlets at
1.27 and 0.82 ppm for tert-butyl groups, which indicates
there two kinds of phenolic ring in the molecule. The
molecular structure is shown in Fig. 2. It is clearly seen
that the 1,3-phenolic hydroxyl groups were O-tolylated.
The two phenolic ring bearing toluenesulfonyl groups stand
more perpendicularly than the other two phenolic rings.
The remained two pheolic hydroxyl groups provided good
chance for further chemical modification of thiacalixarene
(Scheme 2).
S
S
4
OCH2CH2CH2Cl
4
OCH2COOEt
2a
2b
ClCH2COOEt
BrCH2CH2CH2Cl
K2CO3/KI
K2CO3
C4H9
C4H9
ClCH2CONPr2
K2CO3/KI
S
S
4
4
OCH2CONPr2
OH
1
2d
ClCH2CH2CH2CN
TsCl
Et3N
K2CO3/KI
C4H9
C4H9
C4H9
OH
Thiacalixarene tetraacetate 2a, which have precisely
defined three-dimensional structures, is valuable building
block for the construction of more sophisticated thiacalix-
arene systems. The reactions of tetraacetate 2 with an
excess of ethylenediamine, or propylenediamine were
S
4
S
S
2
OCH2CH2CH2CN
OTs
2c
2e
Scheme 1 Synthesis of thiacalix[4]arenes 2a–2e
123

J Incl Phenom Macrocycl Chem (2010) 66:349–355
351
Table 1 Crystal data and structure refinement details of thiacalixarene
Phase
2c
2e
3a
4a (partial cone)
4a (1,3-alternate)
Empirical formula
Formula weight
Temperature (K)
C56H68N4O4S4.CHCl3 C54H60O8S6.2CHCl3 C55H66Cl2N4O9S4
C56H72O20S4.CHCl3 C56H72O20S4
1108.75
293(2)
1268.12
296(2)
1126.26
1312.74
273(2)
1193.38
273(2)
193(2)
˚
Wavelength (A)
0.71073
0.71073
0.71073
0.71073
Triclinic
0.71073
Crystal system, space
group
Monoclinic, P2(1)/c Monoclinic,C2/c
Monoclinic, P2(1)/c
Monoclinic, C 2/c
˚
a (A)
12.7934(17
90
27.747(6)
90.00
15.5068(19)
90
11.683(3)
76.051(4)
15.575(4)
82.672(4)
19.961(5)
69.836(4)
3304.8(15)
2, 1.319
24.18(1)
90
a
˚
b (A)
15.078(2)
99.044(2)
30.941(2)
90
12.513(2)
103.025(5)
18.047(3)
90.00
13.7553(17)
91.538(3)
28.088(4)
90
13.712(6)
123.35
21.990(9)
90
b
˚
c (A)
c
3
˚
Volume (A )
5928.1(14)
4, 1.242
6105(2)
4, 1.380
5989.0(13)
4, 1.249
6090(4)
4, 1.302
Z, Calculated density
)
(gꢀcm-3
Absorption coefficient 0.342
0.537
0.302
0.334
0.228
(mm-1
F(000)
)
2,344
2,640
1,636
1,380
2,456
h range for data
collection
0.993–25.01
1.52–28.35
0.993–25.35
0.981–25.00
2.20–25.00
h, k, l ranges
-15 B hB15,
-17 B kB17,
-35 B lB36
-36 B hB35,
-16 B kB16,
-23 B lB23
-17 B hB18,
-16 B kB16,
-33 B lB30
-13 B hB12,
-18 B kB10,
-23 B 20
-28 B hB24,
-16 B kB11,
-26 B lB25
Reflections collected/
unique
41868/10373
[R(int) = 0.1902]
28011/7548
[R(int) = 0.1766]
56287/ 17091/11411
10886[R(int) = 0.1533] [R(int) = 0.0628]
11345/4202
[R(int) = 0.057]
Completeness to
theta = 27.50
99.3%
98.8
99.3%
98.1%
78.2%
Data/restraints/
parameters
Goodness-of-fit on F2
10373/0/649
0.925
7548/0/343
0.938
10886/0/795
0.979
11411/8/774
1.045
4202/4/339
0.99
Final R indices [I [ 2r R1 = 0.0850,
R1 = 0.0795,
wR2 = 0.1831
R1 = 0.0986,
wR2 = 0.2622
R1 = 0.1161,
wR2 = 0.2912
R1 = 0.1004,
wR2 = 0.2926
(I)]
wR2 = 0.1950
R indices (all data)
R1 = 0.2329,
wR2 = 0.2383
R1 = 0.2024,
wR2 = 0.2184
R1 = 0.1422,
wR2 = 0.3006
R1 = 0.2256,
wR2 = 0.3484
R1 = 0.1607,
wR2 = 0.3219
Largest diff. peak and 0.401 and –0.510
-3
2.065 and -0.962
0.989 and -0.892
0.928 and -0.615
0.91and -0.55
˚
hole(eꢀA
)
Table 2 Hydrogen bonding parameters in crystal structure of 2c
D–H…A
D–H
H…A
D…A
D–H…A
C(53)-H(53A)…N(4)
C(27)-H(27A)…N(1)a
C(24)-H(24C)…S(3)b
C(57)-H(57A)…N(3)
0.97
0.97
0.96
0.98
2.61
2.32
2.83
2.04
3.33
3.21
3.68
2.95
131
154
147
154
a
-1?x, y, z
b
1-x, 1/2 ? y, 1/2-z
carried out by refluxing the reactants in ethanol for about
24 h. We wish to let only one amino group of ethylene-
diamine to attack the ester group to give the thiacalixarene
Fig. 2 Molecular structure of compound 2e
123

352
J Incl Phenom Macrocycl Chem (2010) 66:349–355
Scheme 2 Synthesis of
thiacalixarene bicyclic amides
3a–3b
Z
HN
O
NH
O
C4H9
C4H9
O
O
NH2ZNH2
EtOH
H2O2/HAc
S
O
S
S
S
S
O
O
S
4
4
O
OCH2COOEt
O
OCH2COOEt
O
HN
NH
Z
3a: Z = CH2CH2; 3b: Z = CH2CH2CH2
2a
4a
amide derivative with four free terminal amino groups. But
the 1H NMR and single crystal analysis show that the
prepared product is thiacalixarene bicyclic amide 3a–3b.
changed in the ammonolysis process. Ethylenediamine
reacted with two ester groups respectively on upper rim
and lower rim to form two diamide cycles. Due to this
cyclic diamide bridge the opposing pairs of phenyl rings
significantly inclined to each other. The whole molecule
looks like as a carcerand compound. It is pity no solvent
molecule was found trapped in its cavity. As shown by the
packing diagram intramolecular hydrogen bonds between
N2-H3A…O2 exist in the molecule. But no intermolecular
hydrogen bonds exist among the molecules to form inter-
esting supramolecular structures. It should be pointed that
the similar types of (lower rim) proximally bridged p-tert-
butylthiacalix[4]arenes bicyclic diamides have been pre-
pared by direct aminolysis of the starting cone tetraacetates
with aliphatic a,x-diamines. The structures of the corre-
sponding products were also proved by X-ray analysis [18].
The presence of sulfur atoms in the thiacalixarene
skeleton offers another pathway for derivatization of the
molecule: reactions on the bridging moieties [19, 20].
Oxidation of the prepared thiacalixarene tetraacetate 2a
and tetraamide 2d were carried out by using aqueous H2O2
as oxidant in refluxing chloroform/acetic acid for two days.
After work up the sulfone bridging calixarenes 4a and 4b
were obtained in high yields (85%). IR spectrum of prod-
1
Similarly to that of tetraacetate 2a, H NMR spectrum of
3a show one singlet at 7.66 ppm for the aromatic hydrogen
atoms and one singlet at 1.32 ppm for the t-butyl groups.
The one singlet at 4.40 ppm for OCH2CO groups and
another singlet at 3.05 ppm for the four NCH2 units clearly
show that the product has high symmetry and the two
amino groups of ethylenediamine all reacted with ester
groups.
The single crystal of 3a suitable for X-ray diffraction
was obtained by slow evaporation of compound 3a in
mixed solution of chloroform and methanol. The molecular
structure of thiacalixarene 3a is shown in Fig. 3. There are
three chloroform molecules and two methanol molecules in
the crystal. There are some disorders of t-butyl groups
including C30(C300), C31(C310), C32(C320), C51(C510),
C52(C520) atoms and bridging ethylenediamine unit
including O8(O80), N3(N30), N4(N40), C11(C110),
C12(C120) atoms. From Fig. 3 it can be seen that the thi-
acalix[4]arene adopts 1,3-alternate configuration, which
also indicated that precursor 2a is also in 1,3-alternate
configuration because the configuration of 2a could not be
ucts 4a clearly displays
a stronger absorption at
1,767 cm-1 for carbonyl groups and another absorption at
1,025 cm-1 for S=O bonds. 1H NMR spectra of 4a showed
a mixed peak at 8.57–7.74 ppm for phenolic protons, one
singlet at 4.84 ppm for OCH2CO group and one singlet at
1.44 ppm for tert-butyl groups.
The single crystal structure of 4a was determined by
X-ray diffraction analysis, which was obtained from
CHCl3/ethanol (Fig. 4). Form the molecular picture it was
clearly found to be in the 1,3-alternate configuration with
oxygen atoms of the sulfones pointing outward. The S=O
bond distances were in the range of 1.421(5)–1.441(5). The
four phenolic ring stands more parallel comparing with
thiacalixarene such as 2c, which might attribute to the push
of S=O bonds. In another attempt of crystallization we also
obtained the single crystal of sulfone bridging calixarene
4a in partial cone configuration, which was drawn in
Fig. 3 Molecular structure of compound 3a
123

J Incl Phenom Macrocycl Chem (2010) 66:349–355
353
Experimental
Reaction of p-tert-butylthiacalix[4]arene with ethyl
a-chloroacetate
A suspension of p-tert-butylthiacalix[4]arene 1 (6.94 mmol,
5.0 g) and anhydrous potassium carbonate (43.4 mmol,
6.0 g), potassium iodide (3.0 mmol, 0.45 g) in dry acetone
(100 mL) was heated to refluxing under nitrogen for at least
0.5 h. Then ethyl a-chloroacetate (5.3 mL, 50 mmol) was
added. The reaction mixture was refluxed 5 days. After
removal of acetone, the residue was dissolved in water and
acidified with hydrochloride acid, then extracted with
CHCl3. The yellow organic layers were separated and dried
with MgSO4. Evaporation of the solvent yields red oil, which
was titrated with alcohol to give yellow crude products,
recrystallized from absolute ethanol to give the white solid
of 2a: Yield: 62%, mp: [ 250 ꢁC. IR (KBr) t: 1,759
(C=O) cm-1. 1H NMR (CDCl3) d: 7.66 (s, 8H, ArH), 4.92
(s, 8H, COCH2O), 4.40 (q, J = 7.1 Hz, 8H, OCH2), 1.37 (t,
J = 7.1 Hz, 12H, CH3), 1.32 (s, 36H, CH3) ppm; Anal Calcd
for C56H72O12S4: C 63.31, H 6.81; Found: C 63.58, H 7.03.
Fig. 4 Molecular structure of p1,3-alternate isomer of 4a
Reaction of p-tert-butylthiacalix[4]arene
with 1-bromo-3-chloropropane
A suspension of p-tert-butylthiacalix[4]arene 1 (4.17 mmol,
3.0 g) and anhydrous potassium carbonate (21.7 mmol,
3.0 g) in dry acetone (100 mL) was heated to refluxing under
nitrogen for at least 0.5 h. Then 1-bromo-3-chloropropane
(4.0 mL) was added. The reaction mixture was refluxed
5 days. Afterremovalofacetone, theresiduewasdissolvedin
water and acidified with hydrochloride acid, then extracted
with CHCl3. The yellow organic layers were separated and
dried with MgSO4. Evaporation of the solvent yields red oil,
whichwastitratedwithalcoholtogiveyellowcrudeproducts,
recrystallized from absolute ethanol to give the white solid of
2b: Yield: 86%, mp:[250 ꢁC. IR(KBr)t: 2985(w), 2936(w),
1548(m), 1379(m), 1309(m), 1203(vs), 1161(m), 1112(m),
Fig. 5 Molecular structure of partial cone isomer of 4a
Fig. 5. We could not detect its presence in the product
sample by 1H NMR spectrum. From the Fig. 5 it is clearly
seen that on phenolic ring stands opposite to the other three
phenolic rings with the oxyacetate group pointing to
downside.
1076(m), 1027(m), 929(m), 858(m), 823(m), 731(m) cm-1
.
In conclusion a series of thiacalixarene derivatives in
1,3-alternate conformation with functional ester, chloro,
cyano, amide and toluenesulfonyl groups were efficiently
prepared by the peralkylation of in p-tert-butylthiaca-
lix[4]arene in K2CO3/KI/acetone system. Thiacalixarene
bicyclic amides and sulfonylcalixarenes were also synthe-
sized by convenient procedure. Single crystal X-ray dif-
fraction analysis confirmed that these kinds of functional
thiacalixarene and sulfonylcalixarenes exist mainly in
1,3-alternate conformation. The reaction procedure is
convenient, involving simple experimental procedure and
product isolation. Thus our present protocol provides
practical methods for the regioselective synthesis of func-
tional thiacalixrene compounds.
1H NMR (CDCl3) d: 7.36 (s, 8H, ArH), 3.99 (t, J = 6.6 Hz,
8H, OCH2), 3.73 (t, J = 7.2 Hz, 8H, CH2Cl), 3.20 (br, 8H,
CH2), 1.30 (s, 36H, CH3) ppm; Anal Calcd for C52
H68Cl4O4S4: C 60.08, H 6.67; Found: C 59.76, H 6.43.
Reaction of p-tert-butylthiacalix[4]arene
with 4-chlorobutyronitrile
A
suspension of p-tert-butylthiacalix[4]arene (2.0 g,
2.8 mmol) and anhydrous potassium carbonate (3.0 g,
21.7 mmol), potassium iodide (0.45 g,3.0 mmol) in dry
acetone (50 mL) was heated to refluxing under nitrogen for
2 h. Then 4-chlorobutyronitrile (1.4 g, 13.5 mmol) was
123

354
J Incl Phenom Macrocycl Chem (2010) 66:349–355
added. The reaction mixture was refluxed for five days. The
solid was filtrated off. The solution was concentrated to
nearly dry and ethanol was added to give crude product.
Then recrystallization from chloroform and ethanol gives
pure white solid of 2c: Yield: 70%; mp: 235–237 ꢁC,
was refluxed for 24 h. The volatile material was removed by
evaporation. The residue was washed with larger quantity of
water and recrystallizated from methanol and chloroform to
give grey solid 3a: Yield: 80%; mp: [250 ꢁC; IR(KBr) t:
3,416 (NH), 1,682 (C=O) cm-1
;
1H NMR (CDCl3,
IR(KBr) t: 2,230 (C:N) cm-1
;
1H NMR(CDCl3,
600 MHz) d: 7.41 (s, 8H, ArH), 5.45 (s, 4H, CONH), 4.40 (s,
8H, OCH2), 3.05 (s, 8H, NHCH2CH2NH), 1.28 (s, 36H,
C(CH3)3); Anal Calcd for C52H64N4O8S4: C 62.37, H 6.44, N
5.59; Found: C 62.69, H 6.71, N 5.33.
600 MHz) d: 7.38 (s, 8H, ArH), 3.96 (t, J = 7.2 Hz, 8H,
OCH2), 1.98–1.94 (m, 8H, CH2CN), 1.32 (s, 36H,
C(CH3)3), 1.25–1.23 (m, 8H, CH2CH2); Anal Calcd for
C56H68N4O4S4: C 67.98, H 6.93, N 5.66; Found: C 68.31,
H 7.28, N 5.42.
The same procedure was used by using propylene dia-
mine to substitute ethylene dimine to give the product 3b:
grey solid, 72%; mp: [250 ꢁC; IR(KBr) t: 3,415 (NH),
1,668 (C=O) cm-1; 1H NMR(CDCl3, 600 MHz) d: 7.40 (s,
8H, ArH), 5.47 (s, 4H, CONH), 4.32 (s, 8H, OCH2), 3.12
(br, 8H, NHCH2CH2NH), 1.67 (br, 4H, CH2), 1.28 (s, 36H,
C(CH3)3); Anal Calcd for C54H68N4O8S4: C 63.01, H 6.66,
N 5.44; Found: C 63.29, H 6.75, N 5.17.
Reaction of p-tert-butylthiacalix[4]arene with N,
N-dialkyl a-chloroacetamide
p-tert-Buthylthiacalix[4]arene (2.0 g, 2.8 mmol), K2CO3
(3.0 g, 21.7 mmol) in dry acetone (100 mL) were stirred at
room temperature for 2 h. Then ClCH2CON(i-Pr)2 (4.0 g,
22.4 mmol) and KI (0.45 g, 3.0 mmol) were added and the
resulting mixture was refluxing for 3 days. The solid was
filtrated off. The solution was concentrated to nearly dry
and ethanol was added to give crude product. Then
recrystallization from ethanol gives pure white solid of 2d:
Yield: 54%; mp: 206–208 ꢁC; IR(KBr) t: 1,644 (C=O)
Reaction of p-tert-butylthiacalix[4]arene with hydrogen
peroxide
To a solution of 2a (1.000 g, 0.94 mmol) in chloroform
(10 mL) were added acetic acid (20 mL) and hydrogen
peroxide (30%, 10 mL). The mixture had been stirred at
60 ꢁC for 2 days. 100 mL of water was added. The organic
layer was separated and the water layer was extracted with
chloroform (15 mL). Then the organic layer washed with a
solution of NaHSO3. After evaporation of the solvent, a
white powder was obtained and washed with petroleum
ether to give 4a: Yield: 85%; mp: [ 250 ꢁC. IR (KBr) t:
1
cm-1; H NMR (CDCl3, 600 MHz) d: 7.64 (s, 8H, ArH),
5.07 (s, 8H, OCH2CO), 3.38–3.24 (m, 16H,
N(CH2CH2CH3)2), 1.68–1.77 (m, 16H, NCH2CH2CH3),
1.36 (s, 36H, C(CH3)3), 0.99–1.06 (m, 24H,
NCH2CH2CH3). 13C NMR (CDCl3, 150 MHz) d: 164.8,
152.0, 147.5, 131.6, 129.2, 67.9, 46.7, 45.3, 33.1, 29.0,
19.8, 19.0, 9.8, 9.3; Anal Calcd for C72H108N4O8S4: C
67.25, H 8.46, N 4.36; Found: C 67.18, H 8.25, N 4.11.
1,767 (C=O), 1,025 (S=O) cm-1
;
1H NMR (CDCl3,
600 MHz) d: 8.57–7.74 (m, 8H, ArH), 4.83 (s, 8H,
OCH2CO), 4.25 (s, 8H, OCH2,) 1.44 (s, 36H, C(CH3)3),
1.11 (12H, CH3); Anal Calcd for C56H72O20S4: C 56.36, H
6.08; Found: C 56.51, H 6.37.
Reaction of p-tert-butylthiacalix[4]arene with p-
toluenesulfonyl chloride
The same procedure was used by using 2d to substitute
2a to give the product 4b: white solid, 85%; mp: 238–
p-tert-Buthylthiacalix[4]arene (2.0 g, 2.8 mmol), p-tolu-
enesulfonyl chloride and triethylamine (1.0 mL) in dry
chloroform (10 mL) were heated to 50–60 ꢁC for 12 h.
Then the mixture was washed with water. The chloroform
was concentrated to nearly dry and ethanol was added to
give crude product. Then recrystallization from ethanol and
chloroform gave pure white solid of 2e: Yield: 92%. Mp:
[250 ꢁC 1H NMR(CDCl3, 600 MHz) d: 7.85 (s, 4H, ArH),
7.58 (s, 4H, ArH), 7.37 (s, 4H, ArH), 7.24 (s, 2H, ArOH),
6.99 (s, 4H, ArH), 2.48 (s, 6H, CH3), 1.27 (s, 18H,
C(CH3)3), 0.82 (s, 18H, C(CH3)3); Anal Calcd for
C54H60O8S6: C 63.00, H 5.87; Found: C 62.65, H 6.13.
1
340 ꢁC; IR (KBr) t: 1,677 (C=O), 1,026 (S=O) cm-1; H
NMR (CDCl3, 600 MHz) d: 8.18 (s, 8H, ArH), 4.90 (s, 8H,
OCH2), 3.26–2.92 (m, 16H, NCH2), 1.53–1.50 (m, 16H,
CH2), 1.29 (s, 36H, C(CH3)3), 0.82–0.80 (m, 24H, CH3);
13C NMR (CDCl3, 600 MHz) d: 163.1, 151.0, 146.6, 134.0,
132.5, 72.6, 46.1, 45.1, 33.3, 28.7, 20.2, 19.4, 9.7, 9.3; Anal
Calcd for C72H108N4O16S4: C 61.16, H 7.70, N 3.96;
Found: C 60.87, H 7.54, N 3.62.
Supplementary material
Reaction of p-tert-butylthiacalix[4]arene with diamine
Crystallographic data can be obtained from the Cambridge
Crystallographic Data Center, by quoting the reference
number CCDC-714942 for 2c, CCDC-714943 for 2e,
CCDC 715766 for 3a, CCDC 724339 for 1,3-alternate
A solution of ethyl p-butylthiacalix[4]arylacetate 2a (1.1 g,
1.0 mmol) and ethylenediamine (10 mL) in ethanol (20 mL)
123

J Incl Phenom Macrocycl Chem (2010) 66:349–355
355
´
ˇ´ˇ
´
10. Lhotak, P., Himl, M., Stibor, I., Petrıckova, H.: Alkylation of
thiacalix[4]arenes. Tetrahedron Lett. 43, 9621–9624 (2002)
11. Desroches, C., Kessler, V., Parola, S.: The formylation of the
upper-rims of thiacalixarenes: synthesis of the first tetra-formy-
lated and the first meta-substituted thiacalix[4]arenes. Tetrahe-
dron Lett. 45, 6329–6331 (2004)
isomer of 4a, and CCDC 724056 for partial cone isomer of
4a.
Acknowledgements This work was financially supported by the
National Natural Science Foundation of China (Grant No. 20672091)
12. Duta, M., Asfri, Z., Kruchinina, N., Thurey, P., Hagege, A.,
Leroy, M.: Thiacrowncalix[4]arene derivatives: synthesis and
complexing properties. Supramol. Chem. 17, 221–226 (2005)
13. Bhalla, V., Kumar, M., Hattori, M.S.: Stereoselective synthesis of
all stereoisomers of vicinal and distal bis(O-2-aminoethyl)-p-tert-
butylthiacalix[4]arene. Tetrahedron 60, 5881–5887 (2004)
14. van Leeuwen, F.W.B., Beijleveld, H., Kooijman, H., Spek, A.L.,
Verboom, W., Reihoudt, D.N.: Synthesis and conformational
evuation of p-tert-butylthiacalix[4]arene-crowns. J. Org. Chem.
69, 3928–3936 (2004)
15. Iki, N., Narumi, F., Fujimoto, T., Morohashi, N., Miyano, S.:
Selective synthesis of three conformational isomers of tetra-
kis[(ethoxycarbonyl)methoxy]thiacalix[4]arene and their com-
plexation properties towards alkali metal ions. J. Chem. Soc.
Perkin Trans. 2, 2745–2750 (1998)
References
´
1. Lhotak, P.: Chemistry of thiacalixarenes. Eur. J. Org. Chem.
1671–1692 (2004)
2. Morohashi, N., Narumi Iki, N., Hattori, T., Miyano, S.: Thiaca-
lixarenes. Chem. Rev. 106, 5291–5316 (2006)
3. Liu, L., Han, J., Yan, C.G.: Progress in study of novel supra-
molecular host-thiacalixarene. Chin. J. Org. Chem. 27, 907–917
(2007)
4. Iki, N., Miyano, S.: Can thiacalixarene surpass calixarene. J. Incl.
Phenom. Macrocycl. Chem. 41, 99–105 (2001)
5. Dhir, A., Bhalla, V., Kumar, M.: Ratiometry of monomer/exci-
mer emissions of dipyrenyl thiacalix[4]arene for Cu2? detection:
a potential Cu2? and K? switched INHIBIT logic gate with NOT
and YES logic functions. Tetrahedron Lett. 49, 4227–4230 (2008)
6. Stoikov, I.I., Yushkova, E.A., Zhukov, A.Y., Zharov, H., Antipin,
I.S., Konovalov, A.I.: The synthesis of p-tert-butyl thiaca-
lix[4]arenes functionalized with secondary amide groups at the
lower rim and their extraction properties and self-assembly into
nanoscale aggregates. Tetrahedron 64, 7112–7121 (2008)
7. Li, X., Gong, S.L., Yang, W.P., Chen, Y.Y., Meng, X.G.: The
influence of isomerism on the self-assembly behavior and com-
plexation property of 1,3-alternate tetraaminopyridyl-thiaca-
lix[4]arene derivatives. Tetrahedron 64, 6230–6237 (2008)
16. Singh, S.P., Chakrabarti, A., Chawla, H.M., Pant, N.: Aminolysis
of p-tert-butyltetrathiacalix[4]arene tetraethylacetates in cone,
partial cone and 1, 3-alternate conformation: synthesis of amide
based receptors for oxyanions. Tetrahedron 64, 1983–1987
(2008)
17. Akdas, H., Mislin, G., Graf, E., Hosseini, M.W., Cian, A.D.,
Fischer, J.: Synthesis and solid state structural analysis of con-
formers
lix[4]arene. Tetrahedron Lett. 40, 2113–2116 (1999)
of
tetrakis((ethoxycarbonyl)methoxy)tetrathiaca-
ˇ
´
´
´
18. St’astny, V., Stibor, I., Petrickova, H., Sykora, J., Lhotak, P.H.:
Thiacalix[4]arene derivatives with proximally bridged lower rim.
Tetrahedron 61, 9990–9995 (2005)
ˇ
´
´
ˇ´
´
´
´
8. Simanova, M., Dvorakova, H., Stibor, I., Pojarova, M., Lhotak,
P.: Synthesis and conformational behaviour of lower-rim tetra-
acetylated thiacalix[4]arenes. Tetrahedron Lett. 49, 1026–1029
(2008)
´
19. Lhotak, P.: Regioselective and stereoselective oxidation of thi-
acalix[4]arene tetraacetate: synthesis of all possible sulfinylca-
lix[4]arenes. Tetrahedron 57, 4775–4779 (2001)
20. Mislin, G., Graf, E., Hosseini, M.W., Cian, A.D., Fischer, J.:
Sulfone-calixarenes: a new class of molecular building block,
Chem. Commun. 134, 5–1346 (1998)
ˇ
´
ˇ´
´
´
9. Stastny, V., Stibor, I., Dvorakova, H., Lhotak, P.: Synthesis of
(thia)calix[4]arene oligomers: towards calixarene-based dendri-
mers. Tetrahedron 60, 3383–3391 (2004)
123