Synthesis, spectral characterisation and thermal behaviours of some new p-tert-butylcalix[4]arene and calix[4]arene-esters containing acryloyl groups

Article abstract of DOI:10.1016/j.molstruc.2012.06.061

The mono-, di-, tri-, and tetra-acryloyl esters of p-tert-butylcalix [4]arene and calix[4]arene were synthesised by reacting acryloyl chloride with sodium salts of p-tert-butylcalix[4]arene and calix[4]arene in THF. The structures of these compounds were characterised by IR, UV-VIS, ¹H NMR, and ¹³C NMR. Thermal behaviour of the compounds were also examined by means of differential thermal analysis (DTA), thermogravimetry (TG), and derivative thermogravimetry (DTG).

Full text of DOI:10.1016/j.molstruc.2012.06.061

Journal of Molecular Structure 1031 (2013) 70–78
Contents lists available at SciVerse ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Synthesis, spectral characterisation and thermal behaviours of some new
p-tert-butylcalix[4]arene and calix[4]arene-esters containing acryloyl groups
b
Sevil Özkınalı a, , Hasan Kocaokutgen
⇑
a Department of Chemistry, Faculty of Science and Arts, Hitit University, 19030 Çorum, Turkey
b Department of Chemistry, Faculty of Science and Arts, OndokuzMayıs University, 55139 Samsun, Turkey
h i g h l i g h t s
"
"
In this work, some interesting data on newly synthesised novel/calixarene-esters have been presented.
These compounds may have of significance in synthesising new, novel organic materials.
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 28 April 2012
Received in revised form 29 June 2012
Accepted 29 June 2012
Available online 25 July 2012
The mono-, di-, tri-, and tetra-acryloyl esters of p-tert-butylcalix [4]arene and calix[4]arene were synthes-
ised by reacting acryloyl chloride with sodium salts of p-tert-butylcalix[4]arene and calix[4]arene in THF.
The structures of these compounds were characterised by IR, UV–VIS, 1H NMR, and 13C NMR. Thermal
behaviour of the compounds were also examined by means of differential thermal analysis (DTA), ther-
mogravimetry (TG), and derivative thermogravimetry (DTG).
Ó 2012 Elsevier B.V. All rights reserved.
Keywords:
Acryloyl esters of calixarene
Spectral analysis
Thermal analysis
1. Introduction
try, because they can form typical host–guest complexes with
many neutral molecules and ions, such as cyclodextrins and crown
Calixarene are macrocyclic molecules made up of p-substituted
phenolic units linked by methylene bridges ortho to the OH groups
[1–5]. They are known to be useful building blocks for hollow
molecular scaffolds with easily functionalisable hydrophilic and
hydrophobic lower and upper rims, respectively [6–8]. Also when
appropriately designed, they perform a large variety of functions,
e.g., as inclusion compounds, selective complexing agents for metal
ions and catalysts [7–10]. Calixarene molecules represent them-
selves as macrocycles with cavities of sufficient size and hydroxyl
groups capable of forming intramolecular- and intermolecular-
hydrogen bonds. These properties of the calixarene structure and
their capabilities of self-organisation and molecular recognition
have made them subjects of supramolecular studies. Calixarenes
are studied not only for the purely scientific interest evoked in
the unusual complex structure and rich conformational possibili-
ties of their molecules, but also for the wide practical applications
of this class of compounds [8–12] .
ethers [13]. Owing to their non-planar structure, calix[4]arenes can
exist in one of four conformations designated as cone, partial cone,
1,2-alternate and 1,3-alternate [14–18]. Conformations can be
locked by placing substituents of hydroxyl hydrogen with groups
larger than the methyl group. Very often cone and partial cone con-
formers were synthesised by alkylation [19] and acylation [20]
reactions at the lower rim of calix[4]arene. The ester compounds
obtained from calixarenes have been investigated by a variety of
spectroscopic techniques to identify their structures and spectral
properties, but the literature so far report that calixarene-ester
compounds containing unsaturated groups like acryloyloxy moiety
are scarce [19,20,21]. The thermal behaviour of calix[4]arene-
esters having acryloyl groups have not been reported previously.
We have previously reported the synthesis, characterisation and
dyeing properties of the acryloyloxy derivatives of o,o0-dihydroxya-
zo [22] and hydroxazo [23] dyes that have polymerisable, and later
of the crystal structures of the diacryloyloxy derivatives of p-tert-
butylcalix[4]arene and calix[4]arene [24,25]. The mono-, di-,
tri-, and tetra-acryloyl esters of p-tert-butylcalix[4]arene and ca-
lix[4]arene compounds can be important in preparing calixarenes
containing unsaturated groups in their molecules and undergo
The cavity-shaped macrocycles of calixarene have attracted
much attention mainly in supramolecular and analytical chemis-
⇑
Corresponding author. Fax: +90 0364 219 19 80.
E-mail address: sevilozkinali@hitit.edu.tr (S. Özkınalı).
0022-2860/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.molstruc.2012.06.061

S. Özkınalı, H. Kocaokutgen / Journal of Molecular Structure 1031 (2013) 70–78
71
Fig. 1. Synthesis and structures of p-tert-calix[4]arene and calix[4]arene having acryloyl groups.
copolymerisation with different vinyl monomers (Fig. 1) [23–26],
their antioxidant properties and in other experiments.
As a part of an on going research project, we are interested in
exploring the antioxidant properties of acryloyloxy calix[4]arene
derivatives with the other our research group. In this study, we
report the synthesis and spectroscopic properties of new mixed
calix[4]arene-esters with acryloyloxy groups that have polymeri-
sable and probably antioxidant properties. The characterisation
of the compounds were determined by IR, UV–VIS, 1H, and 13C
NMR techniques and also thermal analysis (DTA TG and DTG)
techniques.
measurement was obtained using a flowing nitrogen atmosphere.
-Al2O3 was used as the reference material. Elemental analyses
were performed at the Instrumental Analysis Laboratory of ODTÜ
Research Center. Purities of the p-tert-butylcalix[4]arene deriva-
tives were examined in a mixture of chloroform/methanol (1:3)
and those of the other compounds in a mixture of acetone/toluene
a
(1:1) by TLC with Kieselgel 60 HF254
.
2.2. General procedure for synthesis of acryloyl derivatives of p-tert-
butylcalix[4]arene and calix[4]arene 3–10
In first step, p-tert-butylcalix[4]arene 1 and calix[4]arene 2
were prepared as described in the literature [27,28]. Acryloyl
derivatives of p-tert-butylcalix[4]arene and calix[4]arene were
synthesised by reacting p-tert-butylcalix[4]arene and calix[4]arene
with metallic sodium and later with acryloyl chloride in N2 atmo-
sphere in the order of molar ratios 1:1, 1:2, 1:3, and 1:4. The route
of synthesis of the compounds is presented in Fig. 1. A typical pro-
cedure used for preparation of the compounds 3–10 is described
below.
p-tert-Butylcalix[4]arene (0.77 mmol) and fresh metallic so-
dium (0.77 mmol) in dry THF (40 mL) were stirred together in N2
atmosphere for 24 h. Acryloyl chloride (molar ratios 1:1, 1:2, 1:3,
and 1:4 according to p-tert-butylcalix[4]arene and calix[4]arene)
was then directly added drop wise to this stirred solution in an
atmosphere of dry nitrogen. After stirring the resulting mixture
for 4 h, it was filtered and the desired product precipitated out
2. Experimental
2.1. Materials and methods
Melting points were taken with a digital melting apparatus and
were uncorrected. The IR spectra were recorded on a MATTSON
1000 FTIR spectrophotometer using the KBr disc. Absorption
spectra in ethanol, chloroform, and DMF were determined on a
UNICAM UV2 UV–VIS spectrophotometer. The 1H NMR and 13C
NMR spectra were observed and recorded on a Bruker AC 200
Fourier Transform Spectrometer operated at 200 MHz in CDCl3.
Thermal analysis was carried out with a Shimadzu DTG-GOH
simultaneous thermal analyser combined with a TAS 100 thermo-
gravimetric analyser using ca. 3.5 mg samples, which were heated
at the rate of 10°/min from ambient temperature to 1000 °C. The

72
S. Özkınalı, H. Kocaokutgen / Journal of Molecular Structure 1031 (2013) 70–78
by adding water. The product was filtered and washed several
times with water and dried. After, the acrylate derivatives of p-
tert-butylcalix[4]arene 3–6 were recrystallised from THF–water
mixture, ethyl alchol–water from the other compounds 7–10.
All acryloyloxy derivatives 3–10 were synthesised in a manner
similar to that described above.
2.2.7. Triacryloyloxy derivative of calix[4]arene [25,26,27-
triacryloyloxy-28-hydroxycalix[4]arene] 9
Yield: 30%, Mp: 180–183 °C, TLC (Acetone/Toluene (1:1)):
Rf:0.68, IR (KBr pellet, cmꢀ1): 3537 (OH), 2967, 2942, 2863
(CH3A, ACH2A), 1733 (C@O), 1629 (AC@CA), 1259, 1251o, 1152–
1132 (CAC(@O)AO), and (ArAO). Analysis by calculation for
C37H30O7.C, 75.76; H, 5.11%. Found: C, 75.08; H, 5.08%. Crystal Col-
our: S02O02Y20
.
2.2.1. Monoacryloyloxy derivative of p-tert-butylcalix[4]arene
[5,11,17,23-Tetra-tert-butyl-25-acryloyloxy-26,27,28-trihydroxycalix
[4]arene] 3
Yield: 33%, Mp: 275–278 °C, TLC (Chloroform/Methanol
(1:3)):Rf:0.51, IR (KBr pellet, cmꢀ1): 3550 (OH), 3600–3200 (OH),
2967, 2880, 2840 (CH3A, ACH2A), 1732 (C@O), 1624 (AC@CA),
1278, 1205, 1178 (CAC(@O) AO), and (ArAO). Analysis by calcula-
tion for C47H58O5. H2O: C, 78.33; H, 8.26%. Found: C, 78.69; H,
2.2.8. Tetraacryloyloxy derivative of calix[4]arene [25,26,27,28-
tetraacryloyloxycalix[4]arene] 10
Yield: 63%, Mp: 240–245 °C, TLC (Acetone/Toluene (1:1)):
Rf:0.79, IR (KBr pellet, cmꢀ1): 2942, 2874 (CH3A, ACH2A), 1738
(C@O), 1634 (AC@CA), 1253, 1164 (CAC(@O)AO), and (ArAO).
Analysis by calculation for C40H32O8.0.5 Toluene.C, 76.09; H,
5.24%. Found: C, 76.41; H, 5.44%. Crystal Colour: S02O00Y15
.
8.03%. Crystal Colour: S02O00Y07
.
2.2.2. Diacryloyloxy derivative of p-tert-butylcalix[4]arene
[5,11,17,23-Tetra-tert-butyl-25,27-diacryloyloxy-26,28-dihydroxy
calix[4]arene] 4
3. Results and discussion
3.1. Synthesis
Yield: 27%, Mp: 289–291 °C, TLC (Chloroform/Methanol (1:3)):
Rf:0.83, IR (KBr pellet, cmꢀ1): 3540 (OH), 3140s (OH), 2967, 2901,
2835 (CH3A, ACH2A), 1733 (C@O), 1624 (AC@CA), 1290, 1208,
1178 (CAC(@O) AO), and (ArAO). Analysis by calculation for
p-tert-Butylcalix[4]arene [27] and calix[4]arene [20] were
prepared as described by a previously reported method. The acry-
loyl-ester derivatives of p-tert-butylcalix[4]arene and calix[4]arene
3–10 were synthesised by the reactions of p-tert-butylcalix[4]arene
and calix[4]arene with metallic sodium and then with acryloyl
chloride in N2 atmosphere in molar ratios in the order 1:1, 1:2,
1:3, and 1:4. Fig. 1 shows the synthesis and structures of the p-
tert-calix[4]arene and calix[4]arene having acryloyl groups 1–10
and the experimental conditions employed.
C50H60O6. C, 79.36; H, 7.93%. Found: C, 79.28; H, 8.05%. Crystal Col-
our: S02O00Y20
.
2.2.3. Triacryloyloxy derivative of p-tert-butylcalix[4]arene
[5,11,17,23-Tetra-tert-butyl-25,26,27-triacryloyloxy-28-hydroxycalix
[4]arene] 5
Yield: 34%, Mp: 293–297 °C, TLC (Chloroform/Methanol (1:3)):
Rf:0.48, IR (KBr pellet, cmꢀ1): 3575 (OH), 2967, 2901, 2835
(CH3A, ACH2A), 1733 (C@O), 1600 (AC@CA), 1301, 1208, 1172
(CAC(@O) AO), and (ArAO). Analysis by calculation for
The characterisation of the synthesised compounds 3–10 were
based on the IR, UV–VIS, 1H NMR, and 13C NMR data. Spectroscopic
and analytical data of these compounds are givenin Tables 1–4.
C53H62O7.C, 78.51; H, 7.65%. Found: C, 78.30; H, 7.68%. Crystal Col-
3.2. IR spectral analysis of the compounds
our: S02O00Y20
.
The FT-IR data of the p-tert-butylcalix[4]arene and calix[4]ar-
ene-ester derivatives 3–10 (the structures of these compounds
are illustrated in Fig. 1) were given in Section 2. The characteristic
stretches of the carbonyl groups of acryloyl moiety of the synthes-
ised compounds were identified as a very strong singlet absorption
at 1749–1732 cmꢀ1 [24–26]. The OH group stretching vibration of
p-tert-butylcalix[4]arene and calix[4]arene 1, 2 was observed at ca.
3170 cmꢀ1 due to very strong intramolecular hydrogen bonds as
reported in the literatures [11,28]. After esterification in molar ra-
tios in the order 1:1, 1:2, and 1:3, two kinds of hydroxyl peaks ap-
peared; the first, at 3600–3104 cmꢀ1 for the compounds
containing intramolecular hydrogen bond and the second, as nar-
row peak at 3575–3537 cmꢀ1 for these with non-intramolecular
hydrogen bonds. The intramolecular hydrogen bonds among the
OH groups and free forms of OAH bonds showed conformational
changes in the molecules. The hydroxyl group in the tetraacryloyl-
oxy derivative of calix[4]arene 10 was not observed because of the
esterification between the hydroxyl groups and the acryloyl chlo-
rides, but in tetraacryloyloxy derivative of p-tert-butylca-
lix[4]arene 6, the hydroxyl group appeared due to the presence
of 0.5 mol H2O. The esterification in all the synthesised compounds
was confirmed by the appearance of the intensive absorption
bands between 1732 and 1749 cmꢀ1 which are attributed to the
carbonyl groups of the acryloyl moiety. When in the acryloyl deriv-
atives of p-tert-butylcalix[4]arene 3–6, three aliphatic CAH
stretching bands were observed in the range 2980–2835 cmꢀ1, in
the acryloyl derivatives of calix[4]arene 7–10, two CAH stretching
appeared at ca. 2940 and 2863 cmꢀ1 as given in Section 2. The
other characteristic features coming at 1635–1593 cmꢀ1 and
2.2.4. Tetraacryloyloxy derivative of p-tert-butylcalix[4]arene
[5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetraacryloyloxycalix
[4]arene] 6
Yield: 54%, Mp:>300 °C, TLC (Chloroform/Methanol (1:3)):
Rf:0.61, IR (KBr pellet, cmꢀ1): 3540 (OH), 2978, 2952, 2876
(CH3A, ACH2A), 1749 (C@O), 1635 (AC@CA), 1306, 1172
(CAC(@O) AO), and (ArAO). Analysis by calculation for
C
56H64O8.0.5 THF. 0.5ꢁH2O C, 76.78; H, 7.74%. Found: C, 76.56; H,
7.59%. Crystal Colour: S02O00Y04
.
2.2.5. Monoacryloyloxy derivative of calix[4]arene [25-acryloyloxy-
26,27,28-trihydroxycalix[4]arene] 7
Yield: 30%, Mp: 214–218 °C, TLC (Acetone/Toluene (1:1)):
Rf:0.40, IR (KBr pellet, cmꢀ1): 3537 (OH), 3343–3104 (OH), 2939,
2863 (CH3A, ACH2A), 1747 (C@O), 1626 (AC@CA), 1244, 1251s,
1145 (CAC(@O) AO), and (ArAO). Analysis by calculation for
C31H26O5. 0.5H2O: C, 76.38; H, 5.54%. Found: C, 76.20; H, 5.35%.
Crystal Colour: S02O00Y07
.
2.2.6. Diacryloyloxy derivative of calix[4]arene [25,27-diacryloyloxy-
26,28-dihydroxycalix[4]arene] 8
Yield: 33%, Mp: 208–212 °C, TLC (Acetone/Toluene (1:1)):
Rf:0.67, IR (KBr pellet, cmꢀ1): 3537 (OH), 2942, 2863 (CH3A,
ACH2A), 1733 (C@O), 1626 (AC@CA), 1259, 1251s, 1152–1132
(CAC(@O) AO), and (ArAO). Analysis by calculation for
C34H28O6.C, 76.69; H, 5.26%. Found: C, 75.92; H, 5.26%. Crystal Col-
our: S00O00Y07
.

S. Özkınalı, H. Kocaokutgen / Journal of Molecular Structure 1031 (2013) 70–78
73
Table 1
UV–VIS data of the related compounds.
Compounds
Wavelength [kmax (nm)][log
e
(L/mol cm)]
CHCl3
EtOH
DMF
pH 1–2 (DMF)
282 (3.66)
pH 12 (DMF)
1
2
280 (4.47)
279 (3.08)
290 (4.16)
311a (3.68)
286 (4.12)
308a (3.66)
291 (4.04)
311a (3.59)
290 (4.07)
311a (3.61)
287 (3.95)
311a (3.33)
288 (4.12)
314a (3.48)
286 (4.18)
308a (3.78)
285 (4.20)
305a (3.80)
285 (3.87)
308a (3.45)
285 (3.85)
308a (3.41)
290 (4.19)
311a (3.95)
287 (4.17)
302a (4.07)
290 (4.14)
311a (3.88)
290 (4.15)
311a (3.89)
288 (3.93)
311a (3.38)
288 (4.13)
314a (3.55)
288 (4.24)
305a (4.09)
285 (4.17)
305a (3.80)
286 (4.16)
308a (3.95)
285 (3.82)
308a (3.40)
275 (4.81)
281 (4.69)
281 (3.76)
278 (3.71)
277 (4.38)
276 (4.73)
277 (3.75)
276 (3.75)
273 (4.44)
275 (3.99)
282 (3.72)
281 (3.88)
274 (3.63)
275 (3.62)
275 (3.83)
275 (3.73)
275 (4.48)
271 (3.74)
278 (3.83)
283 (3.42)
283 (3.79)
279 (3.56)
278 (3.81)
279 (3.58)
280 (3.21)
280 (3.55)
279 (3.20)
3
4
5
6
7
8
9
10
a
Shoulder.
1306–1132 cmꢀ1 are attributed to the ethenyl (CH2@CHA) and the
aromatics AC@CA, AC(O) AOA and ArAO, respectively. These find-
ings indicates that the synthesised compounds exist in calixarene-
esters forms as proved by studies in the literature [24,25–32].
calix[4]arene 7 containing one acryloyl group, was shown in Fig. 3
as a typical example. The esterification in the compounds 3–10 was
confirmed by the existence of the resonance peaks between 6.50
and 5.00 ppm which are attributed to the ethenyl group of the
acryloyl moiety. In addition, the attaching of acryloyl groups was
observed by displacement and disappearence of the hydroxyl sig-
nals. After esterification in molar ratios in the order 1:1, 1:2, and
1:3, the hydroxyl peaks were generally appeared as two kinds of
peaks; the first, at ca. 10.2 ppm for the compounds containing
intramolecular hydrogen bonds and the second peaks at 4.44–
5.41 ppm for those with non-intramolecular hydrogen bonds (see
Table 2 and Fig. 3).
In the p-tert-butylcalix[4]arene derivatives 3, 4 containing one
and two acryloyl group, respectively, the hydroxyl protons reso-
nated at 10.20 and 10.30 ppm as weak intramolecular hydrogen
bonds as reported in the literature [1] and at 4.53 and 4.58 ppm
without hydrogen bonds. The other p-tert-butylcalix[4]arene
derivative 5 having three acryloyl groups does not represent intra-
molecular hydrogen bond because of one structural hydroxyl
group. In the compound 6 containing four acryloyloxy groups,
the hydroxyl resonance peak cannot be observed due to the ester-
ification with acryloyl chlorides of all hydroxyl groups in the
structure.
In examining hydroxyl peaks of the calix[4]arene derivatives
not containing p-tert-butyl groups, the hydroxyl groups of the
compound 7 containing one acryloyl group was defined by the
10.19 ppm peak origination from weak intramolecular hydrogen
band and the peak at 5.41 ppm without hydrogen bond. The intra-
molecular hydrogen bonding in compound 8 having two acryloyl
group was not observed because of the absence of intramolecular
hydrogen bond but two hydroxyl groups gave rise to peaks at
5.41 and 5.07 ppm. In the other calix[4]arene derivative 9 having
three acryloyl groups, intramolecular hydrogen bond was not ob-
served as expected because of one hydroxyl group in the structure.
In the last compound 10, the hydroxyl resonance was not there due
to the lack of hydroxyl groups (Table 2). The proton signals of hy-
droxyl groups in all the calix[4]arene derivatives 3–10 were deter-
mined by making exchange with D2O.
3.3. UV–VIS spectral analysis of the compounds
The UV–VIS absorption bands of the related compounds 1–10
were given in Table 1. The absorption behaviours of the p-tert-
butylcalix[4]arene and calix[4]arene-ester derivatives 3–10 were
investigated in a different solvents such as absolute ethyl alcohol,
chloroform, and DMF depending on their solubility and also in
DMF of pH = 2 and 12. As can be seen from Table 1, the absorption
maxima (kmax.) for the compounds 1–10 were observed at 271–
282 nm in ethyl alcohol, at 273–281 nm in choloroform, at 285–
291 nm with a shoulder at 305–314 nm in DMF, at 278–283 nm
in DMF of pH = 2, at 285–290 nm with a shoulder at 302–314 nm
of pH = 12. While the synthesised compounds represent one
absorption band in ethyl alcohol and chloroform, they show two
absorption band in DMF, one of which is a shoulder as pointed
out above. The above given bands with high extinction coefficient
are attributed to the aromatic
p ?
pꢂ transitions of the related
compounds. Comparing the UV–VIS spectral data for different val-
ues of pH in DMF, the absorption maxima of the compounds
showed a hypsochromic shift up to ca. 8 nm at pH = 2 depending
on the hydrogenation of probably azo and oxygene of acryloyl
groups. However, there were no shift at pH = 12, indicating that
aqueous sodium hydroxide at pH = 12 does not hydrolyse the com-
pounds 3–10 containing acryloyl groups. As a result, the acryloyl
derivatives of calixarenes 3–10 give similar absorption bands in
the UV region resembling that of the p-tert-butylcalix[4]arene
and calix[4]arene 1–2 because of the electronic effects of the acry-
loyloxy moiety instead of the hydroxyl groups. The UV–VIS elec-
tronic spectra of the compounds 1, 3, 6 and 2, 7, 10, in CHCl3 (as
1 ꢃ 10ꢀ4 M) are shown as two parts in Fig. 2a and b. Examining
the UV–VIS spectra of the compounds 4, 5, 8 and 9, it was found
that their spectra in the same region are similar to each other.
The resonance peaks of ethenyl hydrogen atoms in acryloyl
groups of the compounds 3–10 were identified as three different
groups (H13, H14, H15) at 6.50–4.50 ppm in agreement with the
literature [26,32,33]. When the acryloyl proton peaks of the
3.4. NMR spectral analysis of the compounds
The 1H NMR chemical shift values of the related compounds re-
corded in CDCl3, are given in Table 2. The 1H NMR spectrum of the

Table 2
1H NMR data of the related compounds.
2 n=0, 7 n=1, 8 n=2, 9 n=3, 10 n=4
1 n=0, 3 n=1, 4 n=2, 5 n=3, 6 n=4
AOH Phenyl groups
Compounds
Acryloyl group
ACH2A
t-Bu
H16
H7
H9, H11
H10
H2, H4
H3
H13
H14
H15
H6
1
2
3
4
5
6
7
8
9
9.74 (bs)
10.20 (s)
10.20 (s); 4.53 (s)
10.30 (s); 4.58 (s)
4.44 (s)
6.73 (s)
7.02 (d)
3.81 (s)
1.17 (s)
–
1.46–0.93 (m)
1.41–0.87 (m)
1.65–1.02 (m)
1.77–0.77 (m)
–
–
–
–
–
–
–
–
–
6.72 (t)
–
–
–
–
–
–
4.21 (bs); 3.54 (bs)
3.73–3.48 (m)
3.79–3.54(m)
3.89–3.26 (m)
3.94–3.20 (m)
3.88–3.49 (m)
3.89–3.50 (m)
3.88–3.49 (m)
3.88–3.27 (m)
7.18–6.94 (m)
7.30–7.10 (m)
7.41–6.80 (m)
7.18–6.68 (m)
7.08–7.06 (m)
7.08 (s)
6.92–6.88 (m)
7.08–6.90 (m)
6.80–6.61 (m)
–
6.94–6.89 (m)
6.99–6.84 (m)
6.98–6.81 (m)
–
6.09–5.89 (m)
6.06–5.90 (m)
6.13–5.96 (m)
6.20–5.10 (m)
6.15–6.10 (d)
6.15–6.10 (dd)
5.96–5.86 (dd)
5.99–5.83 (m)
5.44–5.04 (m)
5.25–5.00 (m)
5.96–5.30 (m)
5.40–4.50 (m)
5.40–5.25 (m)
5.69–5.50 (m)
5.67–5.43 (m)
5.72–5.40 (m)
6.46–6.33 (dd)
6.48–6.39 (dd)
6.47–6.31 (m)
6.50–6.10 (m)
6.38–6.25 (dd)
6.39–6.20 (m)
6.38–6.08 (m)
6.38–6.09 (m)
–
–
–
10.19 (s); 5.41 (s)
5.41 (s); 5.07 (s)
5.39 (s)
7.04–7.02 (m)
7.04 (s)
7.05–7.01 (m)
6.98–6.56 (m)
6.85–6.65 (m)
6.81–6.65 (m)
6.80–6.63 (m)
–
7.18–7.06 (m)
7.28–7.03 (m)
10
–

S. Özkınalı, H. Kocaokutgen / Journal of Molecular Structure 1031 (2013) 70–78
75
Table 3
The 13C NMR data of the compounds.
1 n=0, 3 n=1, 4 n=2, 5 n=3, 6 n=4
2 n=0, 7 n=1,8 n=2, 9 n=3, 10 n=4
Compounds
>C@O
Phenol group
Acryloyl group
>CH2
C17
tert-Butyl
C14
C7
C10
C13
C8, C12
C1, C5
C2, C4
C3
C9, C11
C16
C15
C6
C18
1
2
3
–
–
149.8
148.7
149.0
–
–
–
–
–
–
129.7
128.9
127.0
125.0
128.2
126.5
143.6
122.2
141.8
–
–
–
–
–
–
32.4
31.6
33.9
41.3
–
35.1
31.4
–
163.6
146.6
144.0
132.2
125.8
131.9
127.6
31.6
31.1
31.6
31.4
31.0
31.8
30.9
31.8
31.0
–
4
163.6
150.5
148.9
144.0
132.2
126.9
126.5
141.8
125.8
132.9
127.6
33.8
35.1
5
6
7
8
166.0
165.0
164.9-
163.2
163.6
151.5
–
148.0
146.6
126.8
126.7
143.5
144.0
145.2
132.5
133.0
132.2
132.3
127.6
–
126.0
–
141.8
–
125.4
127.1
127.6
127.2
134.3
134.1
133.4
133.0
128.2
129.1
127.2
130.2
34.1
34.0
36.6
35.1
38.8
35.8
–
152.6
148.7
152.6
129.2
129.2
128.9
127.6
119.8
32.9
31.6
37.3
33.7
32.9
37.3
33.7
32.9
37.2-
29.6
163.5
163.1
146.6
145.2
119.8
119.6
–
–
–
–
–
–
9
163.5
163.1
162.9
164.7
163.1
152.6
–
127.1
126.9
126.7
125.8
147.8
146.6
145.2
148.9
146.6
133.0
132.3
130.2
130.1
125.8
–
119.8
119.6
127.6
127.2
133.4
132.9
129.5
129.2
129.0
130.2
129.3
10
133.0
–
–
127.1
compounds 3–6 which have the p-tert-butyl groups, were seen at
6,50–4.50 ppm, in the other calix[4]arenes 7–10 without p-tert-bu-
tyl groups, these peaks were observed between 6.39–5.25 ppm
depending on the increase in the number of acryloyl group. The
resonance intervals above, belong to the protons H13, H14 and
H15 (Table 2). For example, the peaks of the H15 in Z configuration
according to carbonyl group in an acryloyl moiety were came at
6.50–6.08 ppm as doublet of doublets and multiplets. On the other
hand, the peaks of the H14 in E configuration according to carbonyl
group were seen at 5.96–5.00 ppm as generally multiplets. For the
geminal H13, the related peaks resonate at 6.20–5.10 ppm. As a re-
sult, with increasing the number of the acryloylgroups in the com-
pounds 3–10, the resonance peaks of ethenyl hydrogen atoms were
observed as mixed multi-peaks in the above internal.
The aromatic = CAH resonance signals of the compound 1 were
observed as singlet at 6.73 ppm and for compound 2, as doublet
and triplet at 7.02 and 6.72 ppm, respectively (Table 2). The aro-
matic = CAH resonance peaks in the compounds 3–10 resonated
between 7.41 and 6.61 ppm as multipletsas a result of attachment
of the acryloyl groups to hydroxyl groups in the compounds 1, 2. In
parallel with the numberof the acryloyl groups in the synthesised
compounds 3–10, the aromatic = CAH resonance signals were
determined as mixed multi-peaks. In the tetraacryloyl derivatives
of p-tert-butylcalix[4]arene 6, the proton peaks H2 and H4 were
not observed as expected because of the absence of the hydroxyl
group in the aromatic structure and also the protons H2, H3, and
H4 of compound 10 does not have hydroxyl group. The protons
of ACH2A groups of all calix[4]arenes 3–10 were shifted both
up-field and low field with increasing the number of the acryloyl
groups. The related values can be seen in Table 2. These findings
indicate that the compounds 3–10 exist in calixarene-ester forms
[24–32].
The 13C NMR chemical shift values of the compounds 1–10 were
summarised in Table 3. It is clearly seen from >C@O group signals be-
tween 166.0 and 163.1 ppm in the 13C NMR data of the compounds
3–10 that acryloyl group was attached to the oxygen of hydroxyl
group in comparison with p-tert-butylcalix[4]arene and calix[4]ar-
ene 1, 2 without acryloyl group. The peaks of C15 atom of CH moiety
found in acryloyl group resonated at 130.2–127.2 ppm and also at
134.4–131.9 ppm for C16 atom of CH2 as expected [25,26,33,34].
Close similarities among all these values are clearly seen in Table 3.
When the phenyl groups of p-tert-calix[4]arene compounds reso-
nated at 151.5–125.4 ppm, the same signals were observed at
152.6–119.6 ppm in the calix[4]arene derivatives without tert-butyl
groups. The C8 and C12 atoms of the phenyl groups of the p-tert-
butylcalix[4]arene-esters 3 (Fig. 4), 4 and 5 shifted to low field at
5.2–2.2 ppm according to C1 and C5 atoms, at 3.1–0.3 ppm in the ca-
lix[4]arene-esters 7, 8, and 9 under the electronic attraction effect of
the acryloyl groups. When the ACH2A groups of the calix[4]arene
compounds 7–10 with out tert-butyl groups resonated at 37.3–
29,6 ppm, in the calix[4]arene derivatives 3–6 having tert-butyl
groups, the same signals were observed at 34.1–33.8 ppm as
mixed-peaks with the C17 and C18 peaks of tert-butyl groups be-
cause of the resonance in the same regious (Table 3).
As given in Section 2, the colour codes of the related compounds
3–10 are from Farbenatlas [35].

76
S. Özkınalı, H. Kocaokutgen / Journal of Molecular Structure 1031 (2013) 70–78
Table 4
Thermoanalytical results of the compounds.
Compounds
Decomposition
DTGmax (°C)
% Mass loss
% Total mass loss
Stage
Temperature range (°C)
C
44H56O4 (1)
1
2
3
4
111–301
301–435
435–748
748–1392
203 (ꢀ)
385 (+)
489 (+)
1157 (+)
9.78
62.98
17.37
7.39
97.52
77.61
C
C
28H24O4 (2)
1
2
3
93–247
247–454
454–1393
203 (ꢀ)
378 (+)
522 (+)
4.63
49.82
23.16
47H58O5 (3)
1
2
3
109–214
214–699
699–1345
140 (ꢀ)
414 (+)
1145 (ꢀ)
2.22
79.38
12.04
93.64
85.36
91.18
C
C
C
50H60O6 (4)
53H62O7 (5)
56H64O8 (6)
1
2
133–356
356–872
333 (ꢀ)
8.31
77.05
413 (+)
1
90–190
250–620
144 (+)
432 (+)
3.28
80.45
1
2
3
90–275
275–495
495–1382
200 (ꢀ)
434 (+)
525 (+)
4.37
74.65
17.72
96.74
86.09
C
C
31H26O5 (7)
1
2
3
229–358
358–511
511–1393
335 (+)
403 (+)
526 (+)
9.48
50.53
24.79
34H28O6 (8)
1
2
3
100–301
361–511
511–890
276 (ꢀ)
422 (+)
542 (+)
2.66
53.70
10.45
66.81
69.80
77.27
C
C
37H30O7 (9)
1
105–600
425 (+)
58.96
40H32O8 (10)
1
2
220–849
849–1395
631 (+)
1371 (+)
66.95
10.32
(a)
(b)
n
4-n
O
O
H
n
O
4-n
O
OH
O
Fig. 2. UV–VIS spectra of p-tert-butylcalix[4]arene and calix[4]arene derivatives in CHCl3.

S. Özkınalı, H. Kocaokutgen / Journal of Molecular Structure 1031 (2013) 70–78
77
3
10
2
1
4
5
9
8
11
12
3
6
O
O
H
O
7
H
13
H
H
14
15
Fig. 3. 1H NMR spectrum of the calix[4]arene derivative 7.
18
18
17
17
3
10
2
1
4
5
9
8
11
12
7
13
3
6
O
14
15
16
O
H
O
Fig. 4. 13C NMR spectrum of the p-tert-butylcalix[4]arene derivative 3.
3.5. Thermal analysis
the second stage mass loss of these compounds becomes sharp
as shown by the DTGmax at 414–434 °C but the compound 10, at
631 °C. In the second stage, the thermal mass losses of the synthes-
ised compounds occur between 214 and 361 °C and completed in
the interval 422–872 °C together with the mass losses between
49.82% and 79.38%. The second thermal mass loss stage of these
compounds is the basic decomposition stage but the first stage in
the compound 10 being four acryloyl groups, at 220–849 °C with
the mass loss of 66.95%.
Considering the TG curve of the compound IV (Fig. 5) containing
two acryloyl groups, it is seen that the mass losses in the first and
second stages appear at 133–356 °C and 356–872 °C, respectively,
the mass losses of this compound were determined as 8.31% and
77.05%, respectively. As can be seen from DTG and DTA curves in
Fig. 5, the DTG values of the given compound were about 333 °C
The thermoanalytical results obtained from TG, DTA and DTG
curves of the compounds 1–10, were summarised in Table 4. All
these values were taken from ambient temperature to 1000 °C in
flowing nitrogen atmosphere. The TG, DTG and DTA curves of the
compound 4 containing two acryloyl groups were illustrated in
Fig. 5 as the typical example.
The TG, DTG and DTA curves of all calixarene compounds con-
taining acryloyl groups clearly show that the mass losses of the
compounds which contain tert-butyl groups and non-tert-butyl
groups, are similar to each other by exothermic change but the first
mass losses of all compounds, during endothermic/exothermic
processes as can be seen from Table 4. The first and final mass
losses of the investigated compounds takes place slowly, whereas

78
S. Özkınalı, H. Kocaokutgen / Journal of Molecular Structure 1031 (2013) 70–78
110
-2.69
0
3
2
100
90
80
70
60
50
40
30
20
TG
5
0
10
15
DTG
-2
-4
-6
-8
20
25
30
35
40
DTA
-10
10
0
45
47.25
-11.8
37 100
200
300
400
500
600
700
800
Temperature (°C )
Fig. 5. TG, DTG and DTA curves of the p-tert-butylcalix[4]arene derivative 4.
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University Press, New York, 1991.
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by endothermic process and 413°Cby exothermic process,
respectively.
Although the decomposition mechanism of the p-tert-butylca-
lix[4]arene and calix[4]arene-ester derivatives 3–10 is complex,
it probably consists of a splitting of the calixarene bonds similar
the most of the calixarenes and the acryloyl groups. In all the com-
pounds, the total mass loss occuring in two or three stages but one
stage in the compound 9, during heating changes from 66.81% to
97.52% as depending on the number of the acryloyl groups in the
structure as can be seen from Table 4.
4. Conclusion
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379–381.
The structural properties of the newly synthesised the mono-,
di-, tri-, and tetraacrylate derivatives of p-tert-butylcalix [4]arene
and calix[4]arene were characterised and discussied by IR, UV–
VIS, 1H NMR, and 13C NMR. The esterification in these compounds
was confirmed by both the appearance of the vibrational bands
between 1732 and 1749 cmꢀ1 due to the carbonyl groups of the
acryloyl moiety and 1H NMR data between 6.5 and 5.00 ppm orig-
inating from the resonance peaks of ethenyl hydrogen atoms in
acryloyl groups which were also confirmed by the presence of
mixed multi-peaks in relation with the increase in the number of
acryloyl group. The basic mass loss stage of all calixarene com-
pounds containing acryloyl groups clearly took place between
214 and 361 °C and except the compounds 9,10.
[18] C. Fischer, G. Lin, W. Seichter, E. Weber, Tetrahedron 67 (2011) 5656–5662.
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_
_
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