Spectroscopic and thermal properties of newly mixed azocalix[4]arene ester derivatives

Article abstract of DOI:10.1016/j.dyepig.2014.03.028

The mono-, di-, tri-, and tetra-acryloyl esters of p-chloroazocalix[4]arene which include the first examples of mixed azo ester dyes were synthesized by reacting acryloyl chloride with sodium salts of p-chloroazocalix[4]arene in tetrahydrofuran with inert atmosphere. Diazonium salt of p-chloroaniline was synthesized by using n-amlynitrite and coupled with calix[4]arene in anhydrous condition. This is the diazo coupling reactions used for the first time for synthesized azocalix[4]arene. The characterization of synthesized compounds by spectroscopic methods revealed that azocalix[4]arenes adopt a cone conformation if they contain at least one free phenolic group. The structures of these compounds have been characterized by infrared (IR), ultraviolet-visible (UV-VIS), proton nuclear magnetic resonance (¹H NMR) and carbon nuclear magnetic resonance (¹³C NMR). Differential thermal analysis (DTA), thermogravimetry (TG) and derivative thermogravimetry (DTG) were used to determine the thermal behaviors of the compounds.

Full text of DOI:10.1016/j.dyepig.2014.03.028

Accepted Manuscript
Spectroscopic and Thermal Properties of Newly Mixed Azocalix[4]Arene Ester
Derivatives
S. Özkınalı
PII:
S0143-7208(14)00108-9
10.1016/j.dyepig.2014.03.028
DYPI 4316
DOI:
Reference:
To appear in: Dyes and Pigments
Received Date: 10 November 2013
Revised Date: 7 March 2014
Accepted Date: 20 March 2014
Please cite this article as: Özkınalı S, Spectroscopic and Thermal Properties of Newly Mixed
Azocalix[4]Arene Ester Derivatives, Dyes and Pigments (2014), doi: 10.1016/j.dyepig.2014.03.028.
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ACCEPTED MANUSCRIPT
Graphical Abstract
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ACCEPTED MANUSCRIPT
Spectroscopic and Thermal Properties of Newly Mixed Azocalix[4]Arene Ester
Derivatives
S.Özkınalı*
Department of Chemistry, Faculty of Arts and Sciences, Hitit University, 19030, Çorum,
TURKEY
ABSTRACT
The mono-, di-, tri-, and tetra-acryloyl esters of p-chloroazocalix[4]arene which include the
first examples of mixed azo ester dyes were synthesized by reacting acryloyl chloride with
sodium salts of p-chloroazocalix[4]arene in tetrahydrofuran with inert atmosphere. Diazonium
salt of p-chloroaniline was synthesized by using n-amlynitrite and coupled with calix[4]arene in
anhydrous condition. This is the diazo coupling reactions used for the first time for synthesized
azocalix[4]arene. The characterization of synthesized compounds by spectroscopic methods
revealed that azocalix[4]arenes adopt a cone conformation if they contain at least one free
phenolic group. The structures of these compounds have been characterized by infrared (IR),
ultraviolet-visible (UV-VIS), proton nuclear magnetic resonance (1H-NMR) and carbon nuclear
magnetic resonance (13C-NMR). Differential thermal analysis (DTA), thermogravimetry (TG)
and derivative thermogravimetry (DTG) were used to determine the thermal behaviours of the
compounds.
Keywords:
Calix[4]arene, Azocalix[4]arene, Azocalix[4]arene-ester, Acryloyl chloride, Acryloyl ester of
azocalix[4]arene, Spectral properties, Thermal analysis

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1. Introduction
Calixarene are well known macrocyclic molecules of defined size promising for
versatile supramolecular and biological applications due to their multiple availability for
chemical modification within a concentrated space [1-3]. Calixarene are ideal host compounds
with their unique cavity shaped structure and modifiable lower and upper rims. Compared with
other host compounds, the conformations of calixarenes which result from the free rotation
about the σ bonds of the Ar-CH2-Ar groups are flexible [4]. By changing the chemical groups
of the upper and/or lower rim, it is possible to prepare different derivatives with differing
selectivities for various guest ions and molecules [5-6]. Furthermore, they are appropriately
designed, and they exhibit a large variety of functions; e.g. as inclusion compounds, selective
complexing agents for metal ions, and catalysts [7-10]. The purpose of studying calixarenes
properties can be explained by not only pure scientific interest in the unusual complex structure
and rich conformational possibilities of their molecules but also by wide practical applications
of this class of compounds [8-11].
The cavity-shaped macrocycles have attracted much attention mainly in supramolecular
and analytical chemistry because they can form typical host-guest complexes with many neutral
molecules and ions like cyclodextrins and crown ethers [12]. Owing to their non-planar
structure, calix[4]arenes can exist in one of the four conformations, and have been designated
as cone, partial cone, 1,2- alternate and 1,3- alternate [13-16]. Conformation can be locked by
placing the substituents at OH groups larger than methyl. The cone and partial cone conformers
were usually synthesized by the alkylation and acylation reaction at the lower rim of calix[4]
arene. However, 1,2-alternate and 1,3-alternate conformers were observed only under certain
reaction conditions [17-20].

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Thermal analysis play an important role in the study of the structure and the stability of
the calixarenes. Heat resistance is one of the main properties of dyes used in high temperature
processes such as the dyeing of textile fibers, ink-jet printing and photocopying. It is also a
crucial property in the high technology devices such as lasers and electro optical devices [21].
The thermal behaviour of azocalix[4]arene esters with acryloyl groups have not been reported
previously.
Synthesis of calixarenes which include an azo group can be created by a useful method
for the development of molecular diagnostics. These chromogenic calixarenes can be used as
sensor materials for metal ions and organic molecules. For example, various researchers have
recenlty studied the typically substituted azocalix [n] arenes for their use in ionic and molecular
recognition [22]. Although the monomeric [23] and tetrameric azocalix[4]arene [24]
derivatives were present in the literature, monomeric and dimeric p-chloroazocalix [4] arene
and mono, di-, tri- and tetra- esters of azocalix[4]arene were synthesized for the first time in
this study. The calix[4]arene compounds containing azo groups have been prepared by the
reaction of diazotized p-chloroaniline with calix[4]arene in dry condition in the order of molar
ratios 1:1 and 1:2. First p-chloroazocalix[4]arene reacts with metallic sodium and then with
acryloyl chloride in N2 atmosphere in the order of 1:1; 1:2; 1:3 and 1:4, and therefore it
becomes a acryloyl derivatives of azocalix[4]arene.
The azo-ester compounds that contain unsaturated group like acryloyloxy moiety is
scarce in the literature [20]. During this study, the first attempt was to understand the
diazocoupling reaction of calix[4]arenes in order to rationally obtain chromogenic molecular
filters that may be selective for metal ions and organic substrates. Afterwards, it’s reported the
synthesis of the newly synthesized mixed azocalix[4]arene-ester compounds which have
polymerizable acryloyloxy group [25-28]. The spectroscopic properties of the compounds were

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determined by IR, Uv-vis, 1H and 13C-NMR techniques. Thermal studies decomposition points
and amounts of volatile prolysis products were determined in nitrogen using TG, DTA and
DTG curves.
2. Experimental
The uncorrected melting points were taken with a digital melting apparatus. The
spectrum was recorded on a MATTSON 1000 FTIR spectrophotometer with the use of a KBr
disc. Absorption spectra in ethanol, chloroform and DMF were determined on a UNICAM
1
13
UV2 UV-vis spectrophotometer. The H-NMR and C-NMR spectra were taken on a Bruker
AC 200 Fourier Transform Spectrometer that operates at 200 MHz in CDCl3. The crystal data
were collected on Bruker AXS SMART CCD diffractometer. Thermal analysis was carried out
with a Shimadzu DTG-GOH simultaneous thermal analyzer combined with a TAS 100
thermogravimetric analyzer using CA. 3.5 mg samples which were heated at a rate of 10
deg/min from ambient temperature to 1400 ºC. The measurement was obtained using a flowing
nitrogen atmosphere. α-Al2O3 was used as a reference material. Elemental analyses were
performed by the Instrumental Analysis Laboratory of METU Research Center.
2.1. General procedure for the synthesis of azo and acryloyl derivatives of calix[4]arene.
In the first step, p-tert-butylcalix[4]arene was prepared by reacting p-tert-butylphenol
with formaldehyde as described in the literature [29-30]. In the second step, calix[4]arene has
been prepared by removing the tert-butyl group by the reaction of p-tert-butylcalix[4]arene
with AlCl3 according to reverse Friedel-Crafts reaction. In the third step, the azo derivatives of
calix[4]arene have been synthesised by the reaction of 4-chlorophenyl diazenyl salt with calix
[4]arene in dry DMF in the order of 1:1 and 1:2 molar ratio. In the fourth step, azocalix[4]
arene reacts with metallic sodium in N2 atmosphere in the order of 1:1, 1:2, 1:3 and 1:4 molar
ratio. In the fifth step, the acryloyl derivatives of azocalix[4]arene have been synthesised by the
reaction of sodium salts of azocalix[4]arene with acryloyl chloride in N2 atmosphere in the

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order of to 1:1, 1:2, 1:3 and 1:4 molar ratio. The structure of the compounds which were
synthesized by the esterfication reactions is shown in Fig. 1.
2.1.1. Synthesis of p-tert-butylcalix[4]arene [5,11,17,23-Tetra-tert-butyl-25,26,27,28-
tetrahydroxycalix[4]arene] and calix[4]arene [25,26,27,28-tetrahydroxycalix[4]arene], 1
The p-tert-Butylcalix[4]arene was prepared by reacting p-tert-butylphenol with
formaldehyde as described in the literature [29]. Afterwards, calix[4]arene was prepared by
removing the tert-butyl group by the reaction of p-tert-butylcalix[4]arene with AlCl3 according
to reverse Friedel-Crafts reaction [30].
2.1.2. Synthesis of n-amyl nitrite
(24 g; 0.347 mol) NaNO2 was dissolved in 94 mL water. When the temperature falls to
0°C (or slightly below), a mixture of 6 ml of water, 8 mL of concentrated sulfuric acid and 27.5
mL (0.25 mol) of pentan-1-ol, which had previously been cooled to 0°C, are slowly introduced
from the separatory funnel to the mixture. The rate of the addition must be controlled so that
the temperature can be maintained at +/- 1°C. This addition takes 45 – 60 minutes. Afterwards,
let the mixture stand for 1.5 hours and then filter from the precipitated sodium sulphate.
Separate the upper yellow pentyl nitrite layer (22.52 g; 76%), wash it with a solution containing
0.25 g of sodium hydrogen carbonate and 3.0 g of sodium chloride in 12.5 mL of water, and
lastly dry it with 3.0 g of magnesium sulfate.
2.1.3. Synthesis of 4-chlorophenyldiazonium salt {p-Chlorophyneldiazenyl salt}
4-Chloroaniline (1.5 g; 11.76 mmol) was dissolved in 14 mL absolute ethyl alcohol with
1.20 mL H2SO4 in an ice bath at 0 °C. Following this, 6.82 mL of n-amyl nitrite (1.47 g; 12.56
mmol) solution was added dropwise to produce a diazonium salt. After stirring 30 minute,

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diazonium salt was precipitated by adding diethyl ether. The precipitated salt was filtered and
washed with cold ether. And than, was dried in a vacuum. It must be remembered that solid
diazonium salts are very sensitive to shock when they are perfectly dry.
2.1.4. Synthesis of the monodiazenyl derivative of calix[4]arene [5-(4 (-Chlorophenylazo) -
25, 26, 27, 28-tetrahydroxycalix[4]arene] {E-5-((4-chlorophenyl) diazenyl) -25,26,27,28-
tetra-hydroxycalix[4]arene}, 2.
Diazonium salt (98 mg; 0.707 mmol) was dissolved in 0-5 °C in dry DMF (5 mL) and
within half an hour it was added dropwise to a stirred mixture of calix[4]arene (300 mg; 0.707)
in dry DMF (20 mL) at 0-5 °C. Cold pyridine was added dropwise to the ultimate solution until
that pH became 7-8 under ice cooling. After stirred for 4 hours at 0-5 °C, the ultimate solution
was acidified to pH~1-2 with 0.1 N cold HCl. Afterwards, a large quantity of orange
precipitated was formed and then it was filtered and washed with cold ether and water. The
product was purified from acetonitrile/water to give a present compound of m.p. 305-306 °C.
Yield %62. TLC (Chloroform/Hexane (4:3)): Rf :0.32, IR (KBr pellet, cm-1): 3510-2981 (OH),
2948, 2895 (-CH2-), 1601 (-C=C-), 1266, 1247,1110 (C-O), 1095 (-C-Cl). 1H-NMR (200 MHz,
CDCl3, ppm): δ 10.20 (4H, s, ArOH (H7)), 7.44-7.40 (2H,m, ArazoH (H3′,H5′)),7.78-7.72 (2H,
m, ArazoH (H2′,H6′)), 7.68 (2H,s, ArcalxH(H9,H11)), 7.20-7.06 (6H, m, ArcalxH(H2,H4)), 6,82-
6.68 (3H, m, ArcalxH(H3)), 4.28 (4H,s, ArCH2Ar (H6)), 3,58 (4H, s, ArCH2Ar (H6)). 13C NMR
(200 MHz, CDCl3, ppm): δ 148.5 (C1′), 136.1 (C4′), 124.1 (C2′,C6′), 127.5 (C3′,C5′) (ArazoC);
151.0 (C7), 152.0 (C10), 147.2 (C13), 128.9 (C8,C12), 129,2 (C1, C5), 128.3 (C2,C4), 122.4
(C3), 123.8 (C9, C11) (ArcalxC); 31.7 (C6, Ar-CH2-Ar),

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2.1.5. Synthesis of bisdiazenyl derivative of calix[4]arene [5,17-Bis (4 (-Chlorophenylazo) -
25,26,27,28-tetrahydroxycalix[4]arene] {E-5, 17-Bis ((4-chlorophenyl) diazenyl) -25,26,27,
28-tetrahydroxycalix[4]arene}, 3.
The procedure used in 2 was used in 3, too. Therefore, 3 was synthesized by using calix
[4] arene (0.30g; 0.707 mmol) and 4-chlorophenyldiazonium salt (0.212 g; 1.4 mmol) in dry
DMF (20 mL) at 0-5 °C and purified by using acetonitrile-water. M.p. >300 °C. Yield %25.
TLC (Chloroform/Hexane (4:3)): Rf :0.63, IR (KBr pellet, cm-1): 3528-2981 (OH), 2948, 2895
1
(-CH2-), 1594 (-C=C-), 1254, 1244 (C-O), 1089 (C-Cl). H-NMR (200 MHz, CDCl3, ppm): δ
10.30 (4H, s, ArOH (H7)), 7.44-7.40 (4H,m, ArazoH (H3′,H5′)), 7.76-7.70 (4H, m, ArazoH
(H2′,H6′)), 7.68 (4H,s, ArcalxH(H9,H11)), 7.25-7.01 (4H, m, ArcalxH(H2,H4)), 6.76-6.71 (2H,
13
m, ArcalxH(H3)), 4.26 (4H,bs, ArCH2Ar (H6)), 3.57 (4H, bs, ArCH2Ar (H6)). C NMR (200
MHz, CDCl3, ppm): δ 148.7 (C1′), 136.0 (C4′), 124.2 (C2′,C6′), 127.6 (C3′,C5′) (ArazoC);
151.1 (C7), 152.1 (C10), 147.1 (C13), 132.2 (C8,C12), 128,9 (C1, C5), 128.2 (C2,C4), 122.3
(C3), 123.8 (C9, C11) (ArcalxC); 31.7 (C6, Ar-CH2-Ar).
2.1.6. Synthesis of monoacryloyloxy derivative of monodiazenylcalix[4]arene [5-(4′-
Chlorophenylazo)-28-acryloyloxy-25,26,27-trihydroxycalix[4]arene]
phenyl)diazenyl)-28-acryloyloxy-25,26,27-trihydroxycalix[4]arene }, 4.
{E-5-((4-chloro-
Derivatives of calix[4]arene (3) (0.67 g; 1.19 mmol) and fresh metallic sodium (27.0
mg; 1.19 mmol) in dry THF (30 mL) were stirred in N2 atmosphere for 24 hours. Then,
acryloyl chloride (0.10 mL; 1.19 mmol) was directly added and stirred dropwise to a THF
solution of sodium salt of azocalix[4]arene in an atmosphere of dry nitrogen. After stirred for 4
hours, the mixture was filtered and the desired product was precipitated out by drying the THF.

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Thereafter, an orange solid was recrystallized from THF-water. Yield: 53%, mp: 148-149 ºC,
TLC (Acetone/Toluene (1:1)): Rf :0.34, IR (KBr pellet, cm-1): 3514 (OH), 3387-3095 (OH),
2953, 2876 (-CH2-) 1749 (C=O), 1635, 1594 (-C=C-), 1265, 1151 (C-C(=O)-O), 1089 (C-Cl).
1H-NMR (200 MHz, CDCl3, ppm): δ 10.21(2H,s, ArOH (H7)); 4.27 1H, s, ArOH (H7)), 7.48-
7.32 (2H,m, ArazoH (H3′,H5′)), 7,92-7.70 (2H, m, ArazoH (H2′,H6′)), 7.66 (2H,s,
ArcalxH(H9,H11)), 7.16-6.85 (6H, m, ArcalxH(H2,H4)), 6.80-6.61 (3H, m, ArcalxH(H3)), 6.32-
6.25 (1H,m, CH2= (H15)), 6.15-5.90 (1H, m, -CH=,(H13)), 5.89-5.32 (1H, m, CH2= (H14)),
4.11-3.15 (8H,m, ArCH2Ar (H6)). 13C NMR (200 MHz, CDCl3, ppm): δ 163.5 (C=O, C14),
151.1 (C1′), 136.1 (C4′), 124.1 (C2′,C6′), 128.9 (C3′,C5′) (ArazoC); 152.7 (C7), 148.8 (C10),
145.7 (C13), 132.4 (C8,C12), 129.2 (C1, C5), 128.3 (C2,C4), 122.2 (C3), 123.8 (C9, C11)
(ArcalxC); 131.6 (C16), 127.4 (C15) (CH2=CH-); 32.9, 31.6, 25.5 (C6, Ar-CH2-Ar), Anal.
Calcd for C37H29O5N2Cl. 0.5 CH3OH: C, 71.14; H, 4.90; N, 4.42 %. Found: C, 71.46; H, 5.32;
N, 4.47 %.
2.1.7. Synthesis of the triacryloyloxy derivative of monodiazenylcalix[4]arene [5 (4 (-
Chlorophenylazo)-26,27,28-triacryloyloxy-25-hydroxycalix[4]arene]
phenyl)diazenyl)-26,27,28- triacryloyloxy-25-hydroxycalix[4]arene}, 5.
{E-5
((4-chloro-
The procedure used in 4 was used in 5, too. Therefore, 5 was synthesized by using
azocalix[4]arene (2) (0.69 g; 1.23 mmol), fresh metallic sodium (84.6 mg; 3.68 mmol) in dry
THF (40 mL) and acryloyl chloride (0.310 mL; 3.68 mmol) and orange solid product purified
by using THF-water. Yield: 57%, mp: 131-132 ºC, TLC (Acetone/Toluene (1:1)): Rf :0.55, IR
(KBr pellet, cm-1): 3489 (OH), 2927, 2876 (-CH2-), 1753 (C=O), 1651, 1600 (-C=C-), 1247,
1
1165 (C-C(=O)-O), 1087 (C-Cl). H-NMR (200 MHz, CDCl3, ppm): δ 3.71 (1H, s, ArOH
(H7)), 7.45-7.40 (2H,m,ArazoH,(H3′,H5′)), 7.93-7.72 (2H,m,ArazoH,(H2′,H6′)), 7.60 (2H,s,

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ArcalxH(H9,H11)), 7.06-7.03 (6H, m, ArcalxH(H2,H4)), 6.83-6.68 (3H, m, ArcalxH(H3)), 6.57-
6.33 (3H,m, CH2= (H15)), 6.29-5.96 (3H, m, -CH=,(H13)), 5.73-5.21 (3H, m, CH2= (H14)),
13
3.81-3.12 (8H,m, ArCH2Ar (H6)). C NMR (200 MHz, CDCl3, ppm): δ 164.8, 163.5 (C=O,
C14), 151.8 (C1′), 136.3 (C4′), 124.9 (C2′,C6′), 128.1 (C3′,C5′) (ArazoC); 152.0 (C7), 148.5
(C10), 145.4 (C13), 133.7 (C8,C12), 129.2 (C1, C5), 128.9 (C2,C4), 122.5 (C3), 123.7 (C9,
C11) (ArcalxC); 132.4 (C16), 127.5 (C15) (CH2=CH-); 31.7, 31.6 (C6, Ar-CH2-Ar), Anal.
Calcd for C43H33O7N2Cl .1.5 H2O: C, 68.66; H, 4.79; N, 3.72 %. Found: C, 68.74; H, 5.00;
N,3,56 %.
2.1.8. Synthesis of diacryloyloxy derivative of bisdiazenylcalix[4]arene [5,17-Bis(4′-
Chlorophenylazo)-26,28-diacryloyloxy-25,27-dihydroxycalix[4]arene]
{E-5,17-Bis((4-
chlorophenyl)diazenyl)-26,28-diacryloyloxy-25,27-dihydroxycalix[4]arene}, 6.
The procedure used in 4 was used in 6, too. Therefore, 6 was synthesized by using
azocalix[4]arene (3) (0.50 g; 0.72 mmol), freshly metallic sodium (33.0 mg; 1.44 mmol) in dry
THF (40 mL) and acryloyl chloride (0.122 mL; 1.44 mmol) and orange solid product purified
by using THF-water. Yield: 48%, mp: 145-146 ºC, TLC (Acetone/Toluene (1:1)): Rf :0.27, IR
(KBr pellet, cm-1): 3540 (OH), 3387-3193 (OH), 2953, 2876 (-CH2-) 1743 (C=O), 1635, 1594
1
(-C=C-), 1247, 1150 (C-C(=O)-O), 1087 (C-Cl). H-NMR (200 MHz, CDCl3, ppm): δ 10.23
(3H, s, ArOH (H7)), 7.53-7.26 (4H,m, ArazoH (H3′,H5′)), 7,92-7.67 (4H, m, ArazoH (H2′,H6′)),
7.61 (4H,s, ArcalxH(H9,H11)), 7.16-6.92 (4H, m, ArcalxH(H2,H4)), 6.86-6.67 (2H, m,
ArcalxH(H3)), 6.49-6.31 (2H,m, CH2= (H15)), 6.28-6.00 (2H, m, -CH=,(H13)), 5.92-5.40 (2H,
13
m, CH2= (H14)), 4.06-3.62 (8H,m, ArCH2Ar (H6)). C NMR (200 MHz, CDCl3, ppm): δ
164.7, 163.3 (C=O, C14), 151.6, 150.6 (C1′), 136.8 (C4′), 124.0 (C2′,C6′), 128.9 (C3′,C5′)
(ArazoC); 152.6 (C7), 148.6 (C10), 147.2 (C13), 133.5 (C8,C12), 129.3 (C1, C5), 128.3

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(C2,C4), 122.4 (C3), 123.7 (C9, C11) (ArcalxC); 132.7, 132.2 (C16), 128.0, 127.4 (C15)
(CH2=CH-); 33.1, 31.7, 25.6 (C6, Ar-CH2-Ar) Anal. Calcd for C46H34O6N4Cl2.1 Toluene: C,
70.58; H, 4.66; N, 6.21 %. Found: C, 70.50; H, 5,03; N, 5.84 %.
2.1.9. Synthesis of tetracisacryloyloxy derivative of bisdiazenylcalix[4]arene [5,17-Bis(4′-
Chlorophenylazo)-25,26,27,28-tetraacryloyloxycalix[4]arene]
phenyl)diazenyl)-25,26,27,28-tetraacryloyloxycalix[4]arene}, 7.
{E-5,17-Bis((4-chloro-
The procedure used in 4 was used in 7, too. Therefore, 7 was synthesized by using
azocalix[4]arene (3) (70.0 mg; 0.99 mmol), freshly metallic sodium (901.6 mg; 39.2 mmol) in
dry THF (40 mL) and acryloyl chloride (3.33 mL; 39.2 mmol) and dark red solid product
purified by using THF-water. Yield: 43%, mp: 165-166 ºC, TLC (Acetone/Toluene (1:1)): Rf
:0.75, IR (KBr pellet, cm-1): 2927, 2876 (-CH2-), 1753 (C=O), 1594 (-C=C-), 1265, 1151, 1110
1
(C-C(=O)-O), 1089 (-C-Cl). H-NMR (200 MHz, CDCl3, ppm): δ 7.54-7.14 (4H,m, ArazoH
(H3′,H5′)), 7.96-7.75 (4H, m, ArazoH (H2′,H6′)), 7.62-7.58 (4H,m, ArcalxH(H9,H11)), 6.94-6.92
(4H, m, ArcalxH(H2,H4)), 6.83-6.01 (2H, m, ArcalxH(H3)), 6.61-6.35 (4H,m, CH2= (H15)),
6.30-6.01 (4H, m, -CH=,(H13)), 5.65-5.01 (4H, m, CH2= (H14)), 3.82-3.31 (8H,m, ArCH2Ar
(H6)). 13C NMR (200 MHz, CDCl3, ppm): δ 164.9, 164.5 (C=O, C14), 151.6 (C1′), 135.5
(C4′), 125.1 (C2′,C6′), 129.8 (C3′,C5′) (ArazoC); 153.0 (C7), 150.8 (C10), 145.7 (C13), 133.7
(C8,C12), 124.0 (C9, C11) (ArcalxC); 132.6 (C16), 127.0 (C15) (CH2=CH-); 37.3, 30.8, (C6,
Ar-CH2-Ar) Anal. Calcd for C52H40O8N4Cl2.1CH3OH: C, 66.87; H, 4.62; N, 5.88 %. Found: C,
67.53; H, 4.87; N,5,02 %.
3. Results and Discussion

11
ACCEPTED MANUSCRIPT
3.1 Synthesis
In the first step, p-tert-Butylcalix[4]arene and calix[4]arene 1 were synthesized as
described in a previously reported method [29-30]. Diazotisation of the 4-chloroaniline was
synthesized by using n-amyl nitrite [31]. Due to the formation of oily azocalix[4]arene product,
p-chloroaniline was diazotized with n-amlynitrite and later coupled with calix[4]arene in
anhydrous condition. In the second step, the calix[4]arene compounds containing azo groups
were prepared by the reaction of diazotized p-chloroaniline with calix[4]arene in dry condition
in the order of molar ratios 1:1 and 1:2. In the third step, the acryloyl derivatives of p-
chloroazocalix[4]arenes were synthesized by the reactions of these compounds with metallic
sodium and later with acryloyl chloride in N2 atmosphere in the order of molar ratios 1:1, 1:2,
1:3 and 1:4. Figure 1 shows the route of the synthesis of the compounds.
3.2 IR Spectral Analysis of Compounds
In the FT-IR spectra of the azocalix[4]arene compounds, characteristic stretch of the
chloro group of azo phenyl moiety of the synthesized compounds were observed as a strong
absorption band between 1087-1095 cm-1. The stretching frequencies of the OH groups of
azocalix[4]arene compounds were observed at ca. 3528-2981 cm-1 due to very strong
intramolecular hydrogen bonds [11]. After the esterification in molar ratios in the order of 1:1
and 1:2, two kinds of hydroxyl peaks appeared. The first peak was at 3387-3095 cm-1 for the
compounds containing intramolecular hydrogen bond and the second, as narrow peak was at
3540-3489 cm-1 for those with non-intramolecular hydrogen bonds. The intramolecular
hydrogen bonds among the OH group and free forms of O-H bonds showed conformational
changes in the molecules. The hydroxyl group in the tetraacryloyloxy derivative of
azocalix[4]arene 7 was not observed as expected due to the esterification between the hydroxyl

12
ACCEPTED MANUSCRIPT
groups and the acryloyl chloride. The acryloyl derivatives of azocaix[4]arene compounds,
characteristic stretches of the carbonyl groups of the acryloyl moiety were observed as very
strong singlet absorption band at 1753-1743 cm-1. The alifatic C-H stretching bands were
observed as two bands at 2953 cm-1 and 2876 cm-1 and also acryloyl derivatives of
azocalix[4]arene were observed with two bands in this region. The other characterised
stretching bands that appeared at 1651-1594 cm-1 and 1266-1254 cm-1; 1247-1244 cm-1; 1165-
1110 cm-1 in the spectrum of the compounds are attributed to ethenyl (CH2=CH-) and aromatic
–C=C-; -C(O)-O- and Ar-O respectively as given in section 2. In the acryloyl derivatives,
azocalix[4]arene compounds of the Ar-O- stretches are determined with –C(O)-O- strecthes in
the same region. Asymmetrical and symmetrical strecthing vibration of the –N=N- group in the
1635-1584 cm-1 and 1476-1381 cm-1 range was masked by the intense bands due to ring
vibration.
3.3 UV-VIS Spectral Analysis of the Compounds
Typical characteristic UV-vis absorption bands of the compounds 1-7 were analyzed
investigated in different solvents such as absolute ethyl alcohol, chloroform, and DMF
depending on their solubility. Moreover, they were analyzed in DMF of pH=12 and pH=2. The
UV-VIS absorption bands related to the compounds 1-7 were given in Table 1. All
azocalix[4]arene compounds and their acryloyl derivatives resulted in bathochromic shifts
according to calix[4]arene in all solvents because of the electron-withdrawing of chloro and
phenylazo groups. The absorption maxima (λmax.,) for the compounds 1-7 were observed in
ethyl alcohol 339-399 nm and the shoulder at 431-448 nm, in choloroform 341-353 nm and
shoulder with 447-426 nm , in DMF 343-458 nm and the shoulder at 443-431, in pH=2 342-
359 nm and shoulder with 436-499 nm, in pH=12 490-499 nm and the shoulder at 527 nm . In
these results, azocalix[4]arenes and acryloyl derivatives that appear as absorption maxima with

13
ACCEPTED MANUSCRIPT
high extinction coefficient are attributed to the π→π* and n→π*. The azocalix[4]arenes may
exist in two possible tautomeric forms, namely an azo-enol form and keto-hydrazo form are
showed in Figure 2 [24,32]. The UV-Vis spectrum of the compound 6 can be seen in Figure 3.
In the literature, these forms were observed in 420-435 nm and 482-495 nm respectively [33].
1
NH peaks were not dedected in the IR and H-NMR spectrum of compounds. Therefore, all
compounds exist in azo form.
3.4 NMR Spectral Analysis of the Compounds
1
The H-NMR chemical shift values of the azocalix[4]arene and acryloyl derivatives
1
recorded in CDCl3 are given in Table 2. The H-NMR spectrum of the calix[4]arene 4 that
contains one acryloyl group was shown in Figure 4 as a typical example. In the
azocalix[4]arene derivative, the hydroxyl protons are resonated at 10.20 ppm as strong
intramolecular hydrogens bonds. After the esterfication in molar ratios in the order of 1:1, 1:2
and 1:3, the hydroxyl peaks were generally observed at 4.27-3.71 ppm for the compounds with
non-intramolecular hydrogen bonds and at 10.30-10.20 ppm for those containing strong
intramolecular hydrogen bands (see Table 2 and Fig.4). The acryloyl azocalix[4]arene 4
derivative having one acryloyl group, intramolecular hydrogen bond was observed at 10.21
ppm due to the conformational arrengament. However, one hydroxyl groups gave rise to the
peak at 4.27 ppm. Compound 5 that has three acryloyl groups among other azocalix[4]arene
ester derivatives does not represent intramolecular hydrogen bond as it has one hydroxyl group
in its structure. The intramolecular hydrogen bonding in compound 6 that has two acryloyl
group was observed at 10.23 ppm. In the last compound 7, the hydroxyl resonance was not
1
there due to the lack of hydroxyl groups. H-NMR spectra of azocalix[4]arene and acryloyl
derivatives show peaks at 7.96-7.14 ppm which are attributed to the azo phenyl group, and
peaks at 7.68-6.01 ppm which are attributed to the calix[4]arene phenyl group. Because of the

14
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electronic attractive effect of chloro and acryloyl groups, protons of phenyl groups are shifted
to up field increasing the chloro and acryloyl groups. The resonance peaks of ethenyl hydrogen
atoms in acryloyl groups of the compounds 4-7 were identified as three different groups (H13,
H14, H15) at 6.61-5.01 ppm in aggrement with the literature [19-21]. The peaks of the H15 in
Z configuration according to carbonyl group in an acryloyl moiety came at 6.61-6.25 ppm as
multiplets. On the other hand, the peaks of the H14 in E configuration according to carbonyl
group were seen at 5.92-5.01 ppm as multiplets. For the geminal H13, the related peaks
resonate at 6.30-5.90 ppm. All of the acryloyl protons (H15 and H13, except H14) were shifted
to low field with increasing the number of acryloyl group. As a result, increasing the number of
the acryloyl groups in the compounds 4-7, the resonance peaks of ethenyl hydrogen atoms were
observed as mixed multi-peaks.
The 13C-NMR chemical shift values of the compounds 1-7 were summarised in Table 3.
In the 13C-NMR spectra of the compound 4, it is clearly seen that acryloyl group is attached to
the oxygen of the hydroxyl group because of >C=O group signal at 163.5 ppm in agreement
with the literature value [19-21]. The peaks appearing at 131.6 ppm and 127.4 ppm in the
spectra of the compound are attributed to =CH- and =CH2 fragments of the CH2=CH- group, as
expected. These values are in accordance with the literature [21-22]. The peaks at 151.1-128.9
ppm and 152.7-122.2 ppm which are attributed to the azophenyl group and calix[4]arene
phenyl group of carbon atoms respectively. The peak appearing at 32.9, 31.6 and 25.5 ppm in
the spectra of the compound are attributed to Ar-CH2-Ar group. The spectrum of compound 4
are given in Figure 5. 13C-NMR spectra of the synthesized derivatives revealed that their
methylene carbon appears at 31.0 ppm indicating that the synthesized compounds were in their
cone conformation in accordance with the earlier findings on conformational assignment in
calix[4]arene [7,22].

15
ACCEPTED MANUSCRIPT
3.5 Thermal analysis
The thermal behaviors of the compounds were investigated and they could be useful for
effective binding character for a particular set of cations, multiple applications such as the
dyeing of textile fibers, ink-jet printing, photocopying, lasers and electro-optical devices and
industrial process analysis. All thermal analysis measurements in this work were performed
under exactly the same experimental conditions.
The azocalix[4]arene and ester derivatives containing acryloyl groups were subjected to
TG, DTG and DTA analysis from ambient temperature to 1000 ºC. Temperature ranges, phase
transition temperature, and experimental weight loss can be seen in Table 4. It is difficult to
give a detailed decomposition mechanism for the azocalix[4]arene derivatives due to the
complexity of the thermal decomposition process. The compounds basically consist of a
heterolytic splitting of azo bonds known for the most of the azo dyes [25]. The relationship
between thermal stabilities and structures of calix[4]arenes [21] is the only one reported in the
literature.
In the TG curve of azocalix[4]arene 2 decomposes in three stages. The first step is over
the temperature ranges 42-248 ºC with a mass loss of 5.64%. The second step is over 248-354
ºC with a mass loss of 17.76%, and the third step is over 354-686 ºC with a mass loss of
26.41%. The thermal analysis curves for the different samples (parent azocalix[4]arene and
their esters) did not show any marked differences of similar experimental conditions but did
indicate that the samples were not simply calix[4]arene.
In the TG curve, ester derivative of the azocalix[4]arene 6, at the first-stage, there was a
partial thermal decomposition from 107 to 198°C as of endothermic process with a mass loss of
3.79%. The second stage with an exothermic thermal behavior is between 198°C and 302°C
with a sharp mass loss of 9.56% as can be seen in Figure 6. It is also clear that it was not a
melting point in DTA curve with exothermic DTA peaks in maximum DTG points. In the third

16
ACCEPTED MANUSCRIPT
stage, a mass loss of %34.26 can be seen between 302°C and 678°C. Between 678°C and
1000°C, the thermal decomposition continued slowly and in a complex way in terms of
endothermic process. These stages overlap. The total mass loss of this compound is %50.59.
The typical DTA and TG curves of these compounds are similar with each other. Furthermore,
all of them consist of three or four steps of decomposition which can be seen in Table 4.
4. Conclusion
The mixed ratio calix[4]arene compounds containing the acryloyl and azo groups have
been synthesized by reacting of calix[4]arene and 4-chlorophenol diazonium salts in the order
of 1:1, 1:2, 1:3 and 1:4 molar ratio. The structure of these compounds has been characterized
1
by IR, UV-vis, H-NMR and 13C-NMR. In the IR spectra of the azoestercalix[4]arene
compounds, characteristic strectches of the carbonyl groups of the acryloyl moiety were
observed as very strong singlet absorption band at 1743-1753 cm-1. The stretching frequencies
of the OH groups in azo compounds were observed at ca. 3528-2981 cm-1, which shows that
hydroxyl groups made hydrogen bonds with each other. After the esterification, two kinds of
hydroxyl peaks appeared at 3540-3489 cm-1 and 3387-3095 cm-1, which indicates that hydroxyl
groups were free and made hydrogen bonds respectively. In the UV-vis spectra
azocalix[4]arenes and acryloyl derivatives appear as high extinction coefficient with the
increase in the number of azo groups and peaks are attributed to the π→π* and n→π*. In the
1
IR and H-NMR, spectrum of compounds were not dedected –NH peaks. Therefore, all
compounds exist in azo form. Thermal behavior of the synthesized azocalix[4]arene derivatives
have been investigated by means of the TG, DTG and DTA techniques. We can conclude from
the thermic analysis that the azocalix[4]arene and ester derivatives decompose in four or five

17
ACCEPTED MANUSCRIPT
stages and the compounds melt with simultaneous decomposition. The maximal mass loss of all
compounds are similar which is about 400 °C.
The conformational flexibility of calixarene compounds has often been explained by the
presence of intramolecular hydrogen bonds, which is directly correlated with the number of
free phenolic hydroxyls present in the calix[4]arene. Accordingly, azocalix[4]arenes with four
phenolic groups at the lower rim adopt a cone conformation in accordance with the earlier
reports [7].
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CAPTIONS
Table 1.
The UV-VIS data of the compounds 1-7
Table 2.
1H-NMR data of the related compounds 1-7
13C-NMR data of the related compounds 1-7
Thermoanalytical results of the compounds 1-7
Synthesis of azocalix[4]arene and their acryloyl derivatives
The UV-Vis spectrum for the compound 6 in CHCl3, EtOH, DMF, DMF
(pH=1), DMF (pH=12) 1.0x10-5 M
Table 3.
Table 4.
Figure 1.
Figure 2.
Figure 3.
Figure 4.
Figure 5.
Figure 6.
The tautomeric forms of azocalix[4]arene compound
1H-NMR spectrum of the compound 7
13C-NMR spectrum of the compound 7
The TG, DTG and DTA curves for the compound 6

22
ACCEPTED MANUSCRIPT
Table 1 The UV-VIS data of compounds 1-7
Wavelength [λmax (nm)][logε (L/mol.cm)]
Compounds
CHCl3
EtOH
DMF
pH 1-2
pH 12
(DMF)
(DMF)
275 (4.81)
353 (4.23)
352 (4.33)
275 (3.99)
286 (4.12)
308o (3.66)
424 (4.13)
278 (3.83)
287 (4.17)
302o (4.07)
494 (4.42)
1
2
3
4
5
6
7
399 (4.21)
448o (4.05)
378 (4.34)
437o (3.08)
358 (4.52)
437o (4.22)
341 (4,59)
431o (3,92)
342 (4.49)
443o (3.26)
339 (4.88)
433o (3.46)
358 (4.16)
440 o (3.20)
359 (4,43)
446 o (3,59)
355 (4.23)
479 o (3.34)
347 (4.37)
462 o (3.23)
353 (4.39)
499 o (3.54)
342 (4.76)
436 o (3.53)
395(4.35)
443o(4.28)
346 (4.44)
458 (4.08)
343 (4.42)
431o (3.39)
347 (4.21)
435 (4,17)
442 (4.79)
446 (3.72)
491 (4.73)
499 (4.51)
497 (4.61)
490 (4.62)
351 (4.31)
426o (3.15)
344 (4.57)
447o (3.17)
343 (4.51)
427 o (3.23)
341 (5.03)
439o (3.61)
491 (4.60)
527 o (4,47)

ACCEPTED MANUSCRIPT
23
1H-NMR data of the related compounds 1-7
Table 2
R
3
n=0
n=1
n=2
n=1
n=1
n=2
n=2
R′=H
R′=H R′′ =H
R′=H R′′ =H
R′=H R′′ =COCH=CH2
R′=H 3 mol R′′ =COCH=CH2
R′=H 2 mol R′′ =COCH=CH2
R′, R′′=COCH=CH2
1
2
3
4
5
6
7
2
4
9
11
O
15
H
'
'
6
3
6
''
Cl
N
R
R=
=
N
4 -n
13 H
H14
n
'
'
2
5
R
O
'
O
R''
7
-OH
Azo Phenyl Group
Calixarene Phenyl Groups
Acryloyl Group
-CH2-
Compound
H7
H9,H11
-
H2,H4
7,02 (d)
H3
H13
H14
H15
H6
H3′, H5′
H2′ ,H6′
1
2
3
4
5
6
7
10,20 (s)
10,20 (s)
10,30 (s)
-
-
6,72 (t)
-
-
-
-
-
-
4,21 (bs);3,54 (bs)
4,28 (bs)-3,58 (bs)
4,26 (bs)-3,57(bs)
4,11-3,15 (m)
7,44-7,40 (m)
7,44-7,40 (m)
7,78-7,72 (m) 7,68 (s)
7,76-7,70 (m) 7,68 (s)
7,92-7,70 (m) 7,66 (s)
7.93-7.72 (m) 7.60 (s)
7,92-7,67 (m) 7,61 (s)
7,96-7,75 (m) 7,62-7,58 (d)
7,20-7,06 (m)
7,25-7,01 (m)
7,16-6,85 (m)
7.06-7.03 (m)
7,16-6,92 (m)
6.94-6.92 (m)
6,82-6,68 (m)
6,76-6,71 (m)
6,80-6,61 (m)
6.83-6.68 (m)
6,86 -6,67 (m)
6.83-6.01 (m)
-
-
-
10.21 (bs); 4,27 (s) 7,48-7,32 (m)
6,15-5,90 (m)
6.29-5.96 (m)
6,28-6,00 (m)
6,30-6.01 (m)
5,89-5,32 (m)
5.73-5.21 (m)
5,92-5,40 (m)
5,65-5,01 (m)
6,32-6,25 (m)
6.57-6.33 (m)
6,49-6,31 (m)
6,61-6,35 (m)
3.71 (s)
10,23 (s)
-
7.45-7.40 (m)
7,53-7,26 (m)
7,54-7,14(m)
3.81-3.12 (m)
4,06-3,62 (m)
3,82-3,31 (m)

ACCEPTED MANUSCRIPT
24
Table 3 The 13C NMR data of the compounds 1-7
'
'
6
3
R
10
11
4'
1'
Cl
N
n=0
n=1
n=2
n=1
n=1
n=2
n=2
R′=H
R′=H R′′ =H
R′=H R′′ =H
R′=H R′′ =COCH=CH2
R′=H 3 mol R′′ =COCH=CH2
R′=H 2 mol R′′ =COCH=CH2
R′, R′′=COCH=CH2
R=
3
1
2
3
4
5
6
7
N
2
1
4
5
9
8
'
'
2
5
12
13
6
7
O
n
4 -n
''
''
R
O
R
=
H
O
14
15
16
>C=O
Phenol Group
Acryloyl Group
>CH2
Azo Phenyl Group
Compound
C14
C7
C10
C13
C8,C12
C1,C5
C2,C4
C3
C9,C11
C16
C15
C6
C1′
C4′
C2′,C6′
-
C3′, C5′
-
1
2
3
4
-
148,7
151,0
151,1
152,7
-
-
-
128,9
129,2
128,9
129,2
128,2
128,3
128,2
128,3
122,2
122,4
122,3
122,2
-
-
-
31,6
31,7
31,7
32,9
31,6
25,5
31,7
31,6
33,1
31,7
25,6
37,3
30,8
-
-
-
152,0
152,1
148,8
147,2
147,1
145,7
128.9
132,2
132,4
123.8
123,8
123,8
-
-
148,5
148,7
151,1
136,1
136,0
136,1
124,1
124,2
124,1
127,5
127,6
128,9
-
-
-
163,5
131,6
127,4
5
6
164,8
163,5
164,7
163,3
152,0
152,6
148,5
148,6
145,4
147,2
133,7
133,5
129,2
129,3
128,9
128,3
122,5
122,4
123,7
123,7
132,4
127,5
151,8
136,3
136,8
124,9
124,0
128,1
128,9
132,7
132,2
128,0
127,4
150,6
151,6
7
164,9
164,5
153,0
150,8
145,7
133,7
-
-
-
124,0
132,6
127,0
151,6
135,5
125,1
129,8

25
ACCEPTED MANUSCRIPT
Table 4 Thermoanalytical results of the compounds 1-7
Decompose
% Total
Compound
DTGmax (°C)
% Mass Loss
Temperature
range (°C)
93-247
Mass Loss
Stage
C28H24O4 (1)
1
2
3
203 (-)
378 (+)
522 (+)
4,63
247-454
49,82
23,16
454-1393
77,61
C34H27O4N2Cl (2)
1
2
3
42-248
186 (-)
296 (+)
570 (-)
5,64
248-354
354-686
17.76
26.41
54,58
99,60
C40H30O4N4Cl2(3)
C37H29O5N2Cl (4)
1
45-372
350 (-)
99,60
1
2
3
63-198
139 (-)
291 (+)
394 (-)
2.04
198-347
347-775
13.27
45.00
64.20
C43H33O7N2Cl (5)
1
2
3
112-301
301-452
452-853
291 (+)
422 (-)
524 (+)
4,29
28.92
20.84
54,72
50,59
C46H34O6N4Cl2 (6)
1
2
3
107-198
198-302
302-678
142 (-)
287 (+)
411 (-)
3,79
9.56
34.26
C52H40O8N4Cl2 (7)
1
2
3
63-282
275 (-)
372 (+)
424 (-)
6,28
6.97
33.33
282-356
356-778

26
ACCEPTED MANUSCRIPT
4
778-864
799 (-)
2,27
49,36

27
ACCEPTED MANUSCRIPT
Cl
R2
R1
N N
R3
NH2
C5H11NO2, 0oC
H2SO4
+
OH
OH
OH
OH
OH
Cl
HO
OH
OH
1
2 R1, R2, R3 = H
3 R1, R2 = H
N
Cl
R3 =
N
N2, Na
anhydrous
THF
Cl
Cl
R1
R1
R2
R2
N N
N N
R3
R3
CH2=CHCOCl
R'3O
R'3O
OR'4
OR'4
OR'
2OR'1
OR'
2OR'1
4 R'4 = COCH=CH2 ; R'1, R'2, R'3 = H ; R1, R2, R3 = H
5 R'2, R'3, R'4 = COCH=CH2 ; R'1 = H ; R1, R2, R3 = H
6 R'3, R'4 = COCH=CH2 ; R'1, R'2 = H
2a R'1 = Na ; R'2, R'3, R'4 = H ; R1, R2, R3 = H
3b R'1, R'4 = Na ; R'2, R'3 = H
N
Cl
R1, R2 = H R3 =
N
N
Cl
6, 7 R1, R2 = H
R3 =
N
7 R'1, R'2, R'3, R'4 = COCH=CH2
Figure 1. Synthesis of azocalix[4]arene and their acryloyl derivatives

28
ACCEPTED MANUSCRIPT
NO2
N
NO2
NO2
N
NO2
NO2
NO2
O2N
NO2
N
H
N
H
N
H
N
N
O
N
N
N
N
N
N N
H
N
N
O
OH
OH
HO
O
OH
O
keto-hydrazo
azo-enol
Figure 2 The tautomeric forms of the azocalix[4]arene compound.