Synthesis and spectral characterization of azo dyes derived from calix[4]arene and their application in dyeing of fibers

Article abstract of DOI:10.1007/s10847-012-0240-7

In this study, the synthesis and characterization of two new upper rim functionalized azocalix[4]arene dyes have been obtained by coupling calix[4]arene with different diazo compounds of 3,5-dicarboxyaniline and 4-aminobenzene sulphon amide. The character

Full text of DOI:10.1007/s10847-012-0240-7

J Incl Phenom Macrocycl Chem
DOI 10.1007/s10847-012-0240-7
ORIGINAL ARTICLE
Synthesis and spectral characterization of azo dyes derived
from calix[4]arene and their application in dyeing of fibers
•
˙
Serkan El c¸ in Murat Muzaffer Ilhan •
Hasalettin Delig o¨ z
Received: 28 May 2012 / Accepted: 13 August 2012
Ó Springer Science+Business Media B.V. 2012
Abstract In this study, the synthesis and characterization
of two new upper rim functionalized azocalix[4]arene dyes
have been obtained by coupling calix[4]arene with differ-
ent diazo compounds of 3,5-dicarboxyaniline and 4-ami-
nobenzene sulphon amide. The characterization of these
dyes has been carried out by elemental analysis, FT-IR and
because of their essential or deleterious roles [2, 3]. For
2
?
instance, although Cu
is biologically important, its
accumulation in the human body may induce hepatic cir-
rhosis or neurodegenerative diseases [4]. Moreover, they
have effective binding properties for a particular set of
cation and anions.
1
H NMR spectra. The effect of varying dielectric constants
Chromogenic cone calix[4]dibenzothiacrown ethers
containing nitrophenylazo groups have been used for their
cation binding ability for the transition metal ions [5].
Chromogenic azocalix[4]arene was reported that it can be
applied as the liquid crystal [6] and also as ionic and NLO
sensors [7]. However, most of these studies were restricted
to the investigation of absorption spectra of the
azocalixarenes.
of solvents on the absorption spectra of azocalix[4]arenes
(
1, 2, 3, 4) and commercial Isolan Gelb SGL (T) have been
examined by UV–Vis spectrophotometer. These azoca-
lix[4]arene dyes have also been used for dyeing textile
fibers like cotton, wool, acetate, polyester and polyamide
fibers. Their dyeing and fastness properties have also been
discussed.
There were few reports in which macrocyclic calixarenes
have been used as components for the preparation of azo
dyes. Azocalixarenes were frequently reported as the cou-
pling component for various diazotized aromatic amines [8].
A number of azocalix[4]arene derivatives have recently
been prepared [9–13], and used for the recognition of metal
ions and the discrimination of different types of amines,
but scarcely explored for their pH sensing properties.
Calix[4]arene was employed to prepare an azoca-
lix[4]arene derivative with four carboxyl groups, namely
Keywords Calixarene ꢀ Azocalix[4]arene ꢀ Diazo-
coupling reaction ꢀ Solvent effect ꢀ Textile fibers dyeing ꢀ
Fastness properties
Introduction
Calix[4]arenes, obtained from the oligomerization of phe-
nol and formaldehyde, offer useful molecular scaffold for
the construction of multivalent binding sites [1]. Over the
past few decades, much effort has been devoted to the
development of appropriate calix[4]arene chemosensors for
the selective and sensitive detection of heavy metal ions
5,11,17,23-tetrakis(p-carboxy phenyl)azocalix[4]arene. Its
pH sensing properties are virtually unknown. The conver-
sion between azocalix[4]arene and its sodium salt was
reversible accompanying an intriguing reversible color
change [14, 15].
S. El c¸ in (&) ꢀ H. Delig o¨ z
Nowadays, azo dyes and pigments represent the largest
and most varied groups of synthetic organic colorants in
use. More than half of dyes used commercially are azo
dyes [16]. It has been known for many years that azo
compounds are among the most widely used class of dyes
due to their versatile application in various fields such as
Department of Chemistry, Faculty of Science, Pamukkale
University, 20017 Denizli, Turkey
e-mail: serel20@mynet.com
˙
M. M. Ilhan
Deniz Textile Factory, Organized Industrial District, 20017
Denizli, Turkey
123

J Incl Phenom Macrocycl Chem
COOH
COOH
Melting points were measured using an Electrothermal
IA9100 digital melting point apparatus in capillaries sealed
(
(
1) R:
2) R:
N N
N N
R
1
under nitrogen and were uncorrected. H NMR spectra
R
R
were referenced to tetramethylsilane at 0.00 ppm as inter-
nal standard and were recorded on a Bruker 400 MHz
spectrometer at room temperature (25 ± 1 °C). IR spectra
were recorded on a Mattson 1000 FT-IR spectrometer as
KBr pellets. UV–Vis spectra were obtained on a Shimadzu
R
SO
H
3
O
(
3) R:
N N
N N
S
NH
2
1601 UV–Vis recording spectrophotometer. The elemental
O
analysis was performed in the TUBITAK Laboratory
(Center of Science and Technology Research of Turkey).
(
4) R:
COOH
Solvent of crystallization was retained in some of the
analytical samples and affected by the elemental analysis.
In such cases, best fits between the analytical values and
appropriate fractional increments of solvents were used.
Fig. 1 The structures of substituted azocalix[4]arene derivatives 1–4
dyeing of textile fiber, coloring of different materials,
colored plastics, bio-medical studies and advanced appli-
cation in organic synthesis [17–20]. There have been few
reports including macrocycles such as crown ethers [21]
and usage of calixarenes [22–25] as components for the
preparation of azo dyes. However the researches on
azocalix[4]resorcinarene dyes [26] are still on infancy.
The response of chromophoric calix[n]arenes to the pres-
ence of triester groups has been described previously [27].
Azocalix[4]arenes have been rendered chromophoric through
reactions with diazonium salts to generate azo compounds.
Previous reports of chromophoric phenylazocalix[n]arenes
included a description of the autocatalytic nature of azo bond
formation [28], the selectivity for binding to metals [29],
spectral properties of the azophenol–quinine–hydrazone tau-
tomerization [30] and detection of amines with a chromo-
phoric calix[8]arene [31].
Preparation of the ligands
p-tert-Butylcalix[4]arene and calix[4]arene were synthe-
sized as described previously [35, 36]. Commercial Isolan
Gelb SGL was purchased from Dystar, 100 % nylon knit-
ted fabric, 100 % wool woven fabric (SDC Wool Abradant
Fabric-BS EN ISO 12947-1: 1999-Certificate Of Confor-
mity No: 0690-Stock Code: 2016).
Preparation of substituted azocalix[4]arenes (1–4)
Diazotisation of the various carbocyclic amines was affected
with concentrated HCl. A typical procedure was that
described below used for aniline derivatives. 5,11,17,23-
Tetrakis(3,5-dicarboxyphenyl)azocalix[4]arene (1), 5,11,
1
7,23-tetrakis(4-sulphonylphenyl)azocalix[4] arene (2), 5,11,
7,23-tetrakis(4-sulphonylamidophenyl)azocalix[4]arene (3)
In our recent works [32–34], preparation of many
azocalix[n]arenes were described and synthesized by
reacting carbocyclic amines or heterocyclic amines with a
calix[n]arene. The absorption spectra and ability of pre-
pared azocalix[n]arenes was discussed by considering both
the effect of varying pH and solvents.
1
and 5,11,17,23-tetrakis(4-carboxyphenyl)azocalix[4]arene (4)
were obtained using the same method in 64–87 % yield. The
obtained compounds were purified by crystallization using
the same solvent (DMF–H O) and then analyzed.
2
All of the azocalix[4]arenes 1–4 were soluble in water,
0 % HCl, 10 % NaOH, EtOH, acetic acid, acetone, ace-
This study aims the synthesis of water-soluble azocalix
1
[4]arene derivative to develop as a novel calix[4]arene dyes that
tonitrile, DMF and DMSO.
contain an azophenol moiety to provide colour (Fig. 1).
Moreover, fastness properties and other absorption character-
istics of these dyes is determined throughout this study. Syn-
thesized dyes can be used as a dyestuff for cotton, wool, acetate,
polyester and polyamide fibers.
The synthesis of 5,11,17,23-tetrakis(3,5-
dicarboxyphenyl)azocalix[4]arene (1)
A solution of 3,5-dicarboxyphenyldiazonium chloride,
prepared from 3,5-dicarboxy aniline (1.75 g, 9.67 mmol),
sodium nitrite (1.33 g, 19.34 mmol) and concentrated HCl
Experimental
(
(
1.65 mL) in water (5 mL), was added slowly to a cold
General
5 °C) solution of calix[4]arene (1.0 g, 2.36 mmol) and
sodium acetate trihydrate (4.00 g, 29.24 mmol) in H O–
2
All solvents and compounds are commercially graded
reagents that were used without further purification.
DMF (13 mL, 5:8 v/v) to give a dark brown suspension.
After keeping for 2 h at room temperature, the suspension
1
23

J Incl Phenom Macrocycl Chem
was acidified with aqueous HCl (50 mL, 0.25 %) and the
mixture was then warmed to 60 °C for 30 min. After then it
was cooled 50 mL ethyl acetate was added into the mix-
ture. The crude product gave a pale brown solid, which was
filtered and washed with ethyl acetate. After then the
resulting solid was recrystallized from MeOH-EtAc
Dyeing of fibers (nylon and wool)
0.5 % of Azocalix[4]arene dye was dissolved in a neutral or
slightly alkaline solution in dyeing baths and then 5 mL of 30 %
aqueous NaCl or Na SO solution was added. The scoured fiber
2 4
hunk (3.5 g) was then added to the dyeing bath and its temper-
ature was maintained at (*90 °C) for 30 min. The dyed hunks
were then removed by rinsing with cold water and drying.
(
[
50 mL, 5:2 v/v). Yield, 2.17 g (77 %), mp 270 °C (dec.).
Found: C: 60.68 %; H: 3.29 %; N: 9.28 %]; C H N O
6
0 40 8 20
requires C: 60.41 %; H: 3.38 %; N: 9.39 %. FT-IR (KBr) t
-
cm ): 3082 (COOH), 1701 (C=O), 1452 (N=N).
1
1
(
H
Studies for fastness properties [37]
NMR (CDCl , 25 °C) d : 3.18–4.02 (8H, d AB,
3
H
ArCH Ar), 6.64–7.93 (12H, m, ArH–N=N), 8.48 (8H, s,
ArH-calix), 10.02 (4H, s, Ar–OH), 13.20 (8H, s, –COOH).
It is essential to colored fibers under such conditions as
rubbing exposure, washing, perspiration etc. during their
subsequent use and test their standing in such conditions.
Because these conditions usually result in alteration in
depth, or in hue, or in brightness of the fibers. Some of the
parameters that have been studied were as follow:
2
The synthesis of 5,11,17,23-tetrakis(4-
sulphonylphenyl)azocalix[4]arene (2)
Azocalix[4]arene 2 was prepared as Morita et al. method
[
14], using 4-amino benzene sulphonic acid in water/HCl
5/1.65 mL) and obtained as a dark yellow solid, which
Fastness to washing (as per IS: 764-1979)
(
was filtered and washed with water and MeOH, and dried.
Pair of dyed and undyed specimen was immersed in 0.5 %
commercial detergent solution and was agitated for 30 min
at 60 °C. The specimens were removed were rinsed three
times with water and then dried. Change in color was
assessed using the standard gray scale, where a rating of 5
is considered as excellent and 1 is poor.
The final solid was recystallized from DMF/H O (104 mL,
2
8
:5 v/v) mixture that gave a pale brown product. Yield
(
64 %), mp. 250 °C (dec.) (Lit. mp [230 °C (dec.)).
The synthesis of 5,11,17,23-tetrakis(4-
sulphonylamidophenyl)azocalix[4]arene (3)
Fastness to water (as per IS: 767-1988)
Azocalix[4]arene 3 was prepared as described above, using
-aminobenzene sulphonamide in water/HCl (5/1.65 mL)
4
Pair of dyed and undyed specimen was immersed in water
for 30 min, thereafter water was drained and the hunks
were dried separately and the change in color of the dyed
hunks and the staining of the undyed hunks were assessed
by means of the standard grey scale, where a rating of 5 is
considered as excellent and 1 is poor.
and obtained as a pale brown solid, which was filtered and
washed with ethyl acetate, and then dried. The resulting
solid was recystallized from MeOH-EtAc (50 mL, 5:2 v/v)
mixture that gave a dark yellow product. Yield (81 %), mp.
2
90 °C (dec.). [Found: C: 53.79; H: 3.98; N: 14.89;
S:11.02]; C H N O S requires C: 53.97 %; H:
-
5
2 44 12 12 4
1
3
.83 %; N: 14.52 %; S:11.08 %. FT-IR (KBr) t (cm ):
Fastness to perspiration (as per IS: 971-1983)
1
258 (NH ), 1332 (S–NH ), 1466 (N=N), 1165 (S=O). H
3
2
2
NMR (CDCl , 25 °C) d : 3.72 (4H, s, ArCH Ar), 4.44
Both acidic and alkaline solutions were used in this test.
The tests were carried out in dry atmosphere at 38–40 °C in
glass test tube. The change in color of the dyed specimen
and staining of the undyed specimen were assessed.
3
H
2
(
4H, s, ArCH Ar), 7.82 (8H, s, ArH-calix), 7.86–7.92
2
(16H, m, ArH–N=N), 10.03 (4H, s, Ar–OH), 11.80 (8H, s,
Ar-NH2).
The synthesis of 5,11,17,23-tetrakis(4-
carboxyphenyl)azocalix[4]arene (4)
Rubbing test
The rubbing fastness test was carried out using a crock-
meter in accordance with ISO105-X12:2006.
Azocalix[4]arene 4 was prepared as Morita et al. method
described [14], using 4-amino benzoic acid in water/HCl
(
5/1.65 mL) and obtained as a red solid, which was filtered
Chlorinated water test (as per TS 837 EN ISO 105-E03/
April 2006)
and washed with water and MeOH, and then dried. The
resulting solid was recystallized from DMF/H O (104 mL,
2
8
:5 v/v) mixture that gave a dark brown product. Yield
Pair of dyed and undyed specimen was immersed in
20 ppm chlorinated water for 30 min, thereafter water was
(
87 %), mp. 290 °C (dec.) [Lit. mp [250 °C (dec.)].
123

J Incl Phenom Macrocycl Chem
drained and the hunks were dried separately and the change
in color of the dyed hunks and the staining of the undyed
hunks were assessed by means of the standard grey scale,
where a rating of 5 is considered as excellent and 1 is poor.
The absorption spectra of azocalix[4]arene dyes
Synthesized azocalix[4]arene dyes were capable of absorb-
ing light in the chromophore groups and color compounds.
The basic difference of other similar compounds structure
was in water resolutions and their fastness properties in
textile material. These azocalix[4]arene dyes cotton, wool,
acetate, polyester and polyamide fibers’ dyeing ability were
studied dyeing ability. Some dyes dyed nylon and wool fibers
properly. Nylon and wool dyeing of these dyes examined
with the commercial dye (T) and in a comparative analysis of
the comparative values of the dyed and color fastness. In
addition, the resulting water-soluble azocalix[4]arene dyes
were investigated acidic–basic media on the absorption
properties and in varying solvents.
Results and discussion
Synthesis and characterizations
The aim of this study was to synthesize novel water-soluble
azocalix[4]arene dyes using 3,5-dicarboxy aniline, 4-ami-
nobenzene sulphonic acid, 4-aminobenzene sulphonamide
and 4-aminobenzoic acid. Two new (1 and 3) and two
literature (2 and 4) azocalix[4]arene dyes was achieved by
diazo of natrium nitrite using concentrate hydrochloric acid
as the coupling in DMF at room temperature for 30 min
under nitrogen according to previous papers [14, 32, 38,
Solvatochromic effects
3
9]. The purification of these azocalix[4]arenes for char-
Solvatochromism is the ability of a chemical substance to
change color due to a change in solvent polarity. Generally,
the ground state for almost all molecules is less polar than the
excited state so that a polar solvent will tend to stabilize
the excited state more than the ground state. Hence with the
increase in polarity of the solvent a bathochromic shift is
observed. The absorption spectra of azocalix[4]arenes 1–4
were recorded in various solvents at a concentration
acterization required column chromatography on silica gel
using ethyl acetate as an eluent and gave in quantitative
(
64–87 %) yield.
The formulations and molecular structures of azoca-
lix[4]arene dyes (1–4) was given in Fig. 2. These molecular
structures were also supported by the data obtained from
micro analysis, where in the percentage of C, H and N from
the analysis conform the calculated values. The structures of
these novel compounds were fully characterized using
-
4
-6
of *10 to 10 M, the results are summarized in Table 1.
The choice of solvent is based on polarity/dielectric
constant. The electronic absorption spectra of these dyes
(1–4) exhibited one absorption band in the range
300–500 nm corresponding to p–p* and n–p* transitions.
The visible absorption spectra of the dyes were found to
exhibit strong solvent dependency but did not show
expected regular variation with the polarity of the solvent
[8]. In consideration of the results reported in Table 1, we
did not find any regular bathochromic or hypsochromic
shift except that all dyes in all solvents show the negative
solvatochromism with respect to dichloromethane.
1
spectroscopic methods (FT-IR and H NMR) and elemental
analysis. Synthesized dyes (1–4) and the commercial dye
(
Isolan Gelb SGL (T)) had a dyestuff structure for cotton,
wool, acetate, polyester and polyamide fibers.
The FT-IR spectra of azocalix[4]arene dyes 1 and 3
-
showed a weak band within the range 3,350–3,250 cm
1
corresponding to –OH. The low value reveals that the –OH
groups were involved in intramolecular H-bonding, a weak
1
band or shoulder located at 3,082 cm was assigned to
-
dicarboxylic acid for dye 1 and appearance of band in the
-
region 1,332–1,165 cm
1
confirmed the presence of
As an example, absorption spectra of azocalix[4]arenes
1–4 and commercial T dyes, in different solvents, was
shown in Fig. 3. Strong evidence for the existence of these
compounds in an equilibrium was provided by the isos-
bestic points in the visible spectra of, for example, com-
pound 1 in different solvents. This equilibrium may exist
between tautomeric forms. The equilibrium depends on the
basicity of the solvents used; in proton accepting solvents
such as DMSO, DMF, acetonitrile, methanol and acetic
acid, the compounds displayed a red shift of kmax. The
effect of concentration of the compound on absorption
maxima was examined. The kmax of all compounds did not
change with compound concentration which also indicates
that azocalix[4]arenes exist in their tautomeric form in all
solvents used.
S–NH and S=O groups for dye 3, respectively. Asym-
2
metrical stretching vibration of the N=N group leading to
-
the band located in the 1,466–1,452 cm region.
1
These compounds (1 and 3) were examined in solution
1
by high-resolution NMR. The H NMR spectrum showed
broad peak at d = 10.02–10.03 ppm (–OH), singlet peak
for methylene bridge protons (–CH –) at d = 3.18–4.02 to
2
3
.72–4.44 ppm, singlet from d = 7.82–8.48 ppm for aro-
matic protons (ArH-calix), singlet from d = 6.64–7.93 to
.86–7.92 ppm for aromatic protons (ArH–N=N), singlet
7
peak for carboxylate protons (–COOH) at d = 13.20 ppm,
singlet peak for sulphonyl amide protons (–SO NH ) at
2
2
d = 11.80 ppm. The obtained datas were according to the
literature [14, 32, 38, 39].
1
23

J Incl Phenom Macrocycl Chem
R
R
N
N
R
N
N
R
N
N
2
NaNO / HCl
AlCl
3
+
R-NH2
N
N
Toluen
OH
OH OH HO
OH
OH OH HO
OH OH OH HO
COOH
COOH
O
SO
3
H
S
NH2
COOH
R:
O
1
2
3
4
Fig. 2 Diazo-coupled substituted azocalix[4]arene derivatives 1–4
Table 1 Influence of solvent on kmax (nm) of azocalix[4]arene (1–4) and commercial (T) dyes
Dyes
DMSO
379.80
DMF
MeCN
356.32
MeOH
365.10
AcOH
348.78
MeOH ? HCl
MeOH ? KOH
1
382.84
348.34
375.75
(
s)
(s)
4
65.39
346.97
89.99
348.02
83.57
356.15
482.20
2
3
4
T
364.87
374.83
382.75
442.01
363.99
368.67
369.77
438.49
–
359.80
363.03
365.39
430.11
–
386.90
(
s)
s)
4
490.10
383.95
496.91
382.86
518.29
431.96
336.50
358.56
366.49
382.91
345.61
356.10
(
4
(s)
(s)
4
96.34
441.15
337.21
444.16
337.30
(w)
340.17
(w)
(w)
(w)
4
23.34
s Shoulder, w weak
Effect of acid and base
increase in concentration of azocalix[4]arene dyes. It sug-
gested greater availability of dyestuff onto fiber even at low
concentration. The effect of varying the concentration of
salt from 1.0 to 5.0 % was assessed on dyed fibers. The
result showed that 3.0–5.0 % of aqueous salt did not have
much effect on the reflectance of the fibers. When the fibers
were dyed at various pH between 3.0 and 10.5 and its effect
was studied by the reflectance measurements. At a lower
pH the dyeing was incomplete, whereas the dyeing
capacity was maximum between pH 6.5 and 8.0, but
beyond pH 8, the dyeing capacity decreased gradually.
The fastness properties of dyed fibers to washing, water,
perspiration and light were summarized in Table 2. The
results showed that fastness level was in between 3 and 5
indicating very slight alteration in the shade or lose in
depth of the dyes. Light fastness results were found to be
5–6, which indicates slight color loss of dyed fibers.
Washing fastness measurement of the treated dyed
fabrics was carried out according to the standard method
IS: 764-1979. After washing process in these series,
azocalix[4]arene 1 showed the highest improvement in
The effect of acid and base on the absorption of the
azocalix[4]arene dye solutions was investigated and the
results were shown in Fig. 4. With the addition of base
(
0.1 M sodium hydroxide), the kmax of the dyes showed a
hypsochromic shift along with a shoulder at longer wave-
length. The kmax of the compounds in methanol also
showed slightly hypsochromic effects with addition of acid
(
50 % acetic acid). The azocalix[4]arenes (1–4) may exist
in four possible tautomeric forms, namely an azo–enol and
keto–hydrazo form was shown in Fig. 5.
Dyeing and fastness properties
The structural and physical properties of the azoca-
lix[4]arene dyes 1–4, revealed that they may be classified
as direct dyes for the dyeing of cotton, silk, and wool. It
was observed that with the increase in dye concentration
from 0.20 to 0.45 M there was an increase in reflectance,
after which there is negligible effect on reflectance with
123

J Incl Phenom Macrocycl Chem
3
,00
2,5
2,0
3
,00
DM SO
M eOH
3,00
2,5
2
2
1
1
0
,5
,0
,5
,0
,5
DM SO
M eOH
DMF
DMSO
2,0
DM F
MeOH
1,5
1
,5
,0
A
A
A
DM F
1,0
1
AcOH
M eCN
0,5
M eCN
0,5
AcOH
0
,00
0,00
0
,00
3
00,0
400
500
600
300,0
400
500
3
00,0
400
500
600
nm
nm
nm
2
1
3
3,00
2,50
DM F
DM SO
AcOH
2,5
2,0
1,5
1,0
0,5
2,0
1,5
1,0
0,5
M eOH
DM F
M eOH
A
A
DM SO
M eCN
AcOH
400
0
,00
0
,00
3
00,0
500
600
300,0
400
500
600
nm
nm
T
4
Fig. 3 Absorption spectra of azocalix[4]arene (1–4) and commercial (T) dyes
wash fastness properties, which can be attributed to the
presence of both carboxylic acid and hydroxyl groups in
the dye molecule. The presence of these groups in the
azocalix[4]arene 1 caused the easy hydrolysis of the
adsorbed dyes on fibers and then being converted into
water solubilized dye. The dyes on polyamide surface
which are soluble in water can removed easily by the wash-
off treatment. Therefore, the dye remaining on the surface
of the fabric can be eliminated. This property in this group
of dyes improves the wash fastness of the dyeing processes
and also its brightness in this group of dyes [40]. In com-
parison to used commercial dyes, the synthesized dyes had
good washing fastness properties on polyamide fabrics.
The color change of dyed fabrics with commercial Isolan
Gelb SGL (T) against to washing was 4–5, while the
synthesized dyes had good wash fastness.
(T) had relatively better rubbing fastness than the dyed fabrics
with synthesized dyes (1–4).
Measurement of color fastness to perspiration has been
carried out with the dyed fabrics in contact with adjacent
fabrics (i.e., cotton and nylon) in alkaline and acidic
solutions containing histidine. The dyed fabrics were sub-
sequently drained and placed under constant pressure. The
specimens were then placed in an incubator for 4 h at
37 °C. After drying, change in color of the dyed fabrics and
staining of the adjacent fabrics has been evaluated with
Gray Scales. Results showed that the synthesized and
commercial dyes had good perspiration fastness values on
polyamide fabrics in both different solutions containing
alkaline and acidic media (Tables 2, 3).
All dyed samples showed similar high rubbing fastness
values (Tables 2, 3). These results indicated that the used dyes
had moderate to good rubbing fastness values, which could be
related tothe polargroupsindye’s molecular structure likethe
washing fastness. The dyed fabrics with commercial dye
Conclusions
In conclusion, the present paper was reported on the syn-
thesis, characterization, absorption spectra and the industrial
application of a series of water-soluble azocalix[4]arene
1
23

J Incl Phenom Macrocycl Chem
3
,00
3,00
2,5
2,0
2
2
1
1
0
,5
,0
,5
,0
,5
M eOH +HCl
M eOH
M eOH +HCl
M eOH
M eOH +HCl
2,0
1,5
1,0
M eOH
1,5
A
M eOH +KOH
M eOH +KOH
A
A
1,0
0,5
0,5
M eOH +KOH
0,00
0,00
0,00
300,0
400
500
600
300,0
400
500
600
300,0
400
500
600
nm
nm
nm
1
2
3
2,50
2,00
M eOH
2,0
1,5
1,0
1,5
1,0
0,5
M eOH
M eOH +KOH
A
M eOH +KOH
A
M eOH +HCl
M eOH +HCl
0,5
0
,00
0
,00
3
3
00,0
400
500
600
00,0
400
500
600
nm
nm
4
T
Fig. 4 Effect of acid and base absorption spectra of dyes
COOH
HOOC
HOOC
COOH
HOOC
HOOC
COOH
COOH
HOOC
HOOC
COOH
HOOC
COOH
HOOC
COOH
COOH
N
N
N
N
N
H
N
N
N
N
H
N
N
H N
N
H
N
N
N
OH OH
OH
HO
O
O
O
O
azo-enol
keto-hydrazo
acidic solution
basic solution
-
OOC
COO-
COO-
COO-
-OOC
-
-OOC
COO-
-
OOC
OOC
COO-
-OOC
-OOC
COO-
COO-
-OOC
COO-
N-
N-
N-
N-
N
N
N
N
N
N
N
N
N
N
N
N
O
O
OH OH
O
O
OH
HO
Fig. 5 The azo–enol and keto–hydrazo tautomer form of azocalix[4]arene dye 1
123

J Incl Phenom Macrocycl Chem
Table 2 Nylon dyeing fastness values of 1 and T
Applied fastnesses Trash and color change values of multifibre
Acetate
Cotton
Nylon
Pes
Acrylic
Wool
Color change
T
1
T
1
T
1
T
1
T
1
T
1
T
1
4
0 °C Washing fastness
0 °C Washing fastness
4/5
4/5
4/5
4/5
4/5
T
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
1
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
6
Water fastness
Alkaline perspiration F.
Acidic perspiration F.
Wet rubbing fastness
Dry rubbing fastness
4/5
4/5
4/5
4/5
4/5
3/4
2
0 ppm Fastness to chlorinated water
Table 3 Wool dyeing fastness values of 1 and T
Applied fastnesses Trash and color change values of multifibre
Acetate
Cotton
Nylon
Pes
Acrylic
Wool
Color change
T
1
T
1
T
1
T
1
T
1
T
1
T
1
4
0 °C Washing fastness
0 °C Washing fastness
4/5
4/5
4/5
4/5
4/5
T
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
1
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
4/5
6
Water fastness
Alkaline perspiration F.
Acidic perspiration F.
Wet rubbing fastness
Dry rubbing fastness
4/5
4/5
4/5
4/5
4/5
4/5
2
0 ppm Fastness to chlorinated water
compounds. The perspiration fastness and water fastness of
all the synthesized dyes were found to be good and very
good. The azocalix[4]arene dyes were all stable up to 245 °C
as DTA/TG data and hence can be effectively used in almost
all kinds of inks.
azocalix[4]arene dyes. On the other hand, the tautomeric
equilibrium and dissociation of substituted azocalix[4]are-
nes need to be considered in the future. Further studies to
explore their complexing abilities with various metal ions
in solution and solid state are underway.
We synthesized a new class of supramolecular chro-
mogenic azocalix[4]arene dyes (1–4) and a commercial
Isolan Gelb SGL (T) having –N=N– group as well as
Acknowledgments Authors thank to the Research Foundation of
Pamukkale University for the financial support (BAP, 2010FBE011)
and Deniz Textile Factory.
–
COOH and –SO H group to enable it to exhibit both
3
coloring and binding properties. The effects of solvent and
substituent do not exhibit expected regular variation in
bathochromic shift. These azocalix[4]arenes are direct dyes
which can be considered as a good candidate for dyeing
cotton, silk, and wool fibers because of easy dyeing process
just because they don’t require after treatment process and
they posses good fastness properties.
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