The synthesis and characterization of calix[4]arene based azo dyes

Article abstract of DOI:10.1007/s10847-009-9674-y

A series of azocalix[4]arene dyes (1-7) were prepared by linking 2,4-di-chloroaniline, 2,4,5-tri-chloroaniline, 2,4-di-nitroaniline, 2-nitro p-toluidin, 4-nitro o-toluidin, 5-nitro o-toluidin and sulfanilic acid, to calix[4]arene through a diazo-coupling

Full text of DOI:10.1007/s10847-009-9674-y

J Incl Phenom Macrocycl Chem (2010) 67:73–79
DOI 10.1007/s10847-009-9674-y
ORIGINAL ARTICLE
The synthesis and characterization of calix[4]arene based azo dyes
Shobhana K. Menon Æ Ravindra V. Patel Æ
Jayesh G. Panchal
Received: 5 July 2009 / Accepted: 3 September 2009 / Published online: 18 September 2009
Ó Springer Science+Business Media B.V. 2009
Abstract A series of azocalix[4]arene dyes (1–7) were
prepared by linking 2,4-di-chloroaniline, 2,4,5-tri-chloro-
aniline, 2,4-di-nitroaniline, 2-nitro p-toluidin, 4-nitro
o-toluidin, 5-nitro o-toluidin and sulfanilic acid, to
calix[4]arene through a diazo-coupling reaction. These
compounds were characterized by elemental analysis,
FT-IR, 1H NMR, 13C NMR, MALDI-TOF, UV–Vis., DSC,
and DTA. The absorption properties of the synthesized
dyes were studied and the application of the water soluble
dye on cotton and wool was discussed. Solvent based inks
were investigated and the fastness properties of formulated
inks were also discussed.
these studies were restricted to the investigation of
absorption spectra of the azocalixarenes. There are few
reports in which macrocyclic calixarenes have been used as
components for the preparation of azo dyes. Calixarenes
were frequently reported as the coupling component for
various diazotized aromatic amines [9–12]. The attachment
of calixarene unit to the chromophores will increase the
molecular weight of the dyes since the bulky organic
groups acts as ‘‘ballast group’’ and this has been our
strategy in preparing calixarene dyes. This also will
enhance the tinctorial value, solubility and stability. In
earlier report [13] crown ether based disazo dyes were
investigated for application as active coloring agents in
solvent based inks. Since work has been reported so far on
the application of azocalix[n]arenes as active colouring
agents, it was proposed to synthesize and study the appli-
cation of azocalixarene.
Keywords Calix[4]arene dyes ꢀ Spectral properties ꢀ
Application on cotton and wool ꢀ Fastness studies ꢀ
Ink formulation
Thus, the chromogenic compounds reported here were
designed to take advantage of the first series of calixarene
dyes which are to be used as active coloring agents. The
properties of the synthesized dyes and their applications as
active coloring agents in solvent based inks, cotton, wool
and their suitability for the textile industry were investi-
gated extensively.
Introduction
Calixarenes have been widely used as three dimensional
building blocks for the construction of artificial molecular
receptors capable of recognizing neutral molecules, cations
and anions [1–5]. They have effective binding properties
for a particular set of cation and anions. Chromogenic cone
calix[4]dibenzothiacrown ethers containing nitrophenylazo
groups have been used for their cation binding ability for
the transition metal ions [6]. Chromogenic azoca-
lix[4]arene was reported for application as liquid crystal [7]
an also as ionic and NLO sensors [8], however most of
Experimental
General
Compounds 2,4-di-chloroaniline, 2,4,5-tri-chloroaniline,
2,4-di-nitroaniline, 2-nitro p-toluidin, 4-nitro o-toluidin,
5-nitro o-toluidin and sulfanilic acid derivatives were
obtained as gift samples from Anar chemical, Ahmedabad
and were purified before use. All other chemicals and
S. K. Menon (&) ꢀ R. V. Patel ꢀ J. G. Panchal
Department of Chemistry, School of Sciences, Gujarat
University, Ahmedabad 380009, India
e-mail: shobhanamenon07@gmail.com
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solvents used were of analytical grade and were used
without further purification. Melting points were obtained
from DTA thermogram. The FT-IR spectra were recorded
as KBr pellet on Bruker TENSOR-27. Discover Bench-
Mate system-240V (CEM Corporation) microwave syn-
thesizer is used for synthesis. The MALDI-TOF MS was
run on a Micromass TofSpece 2E instrument, using a
which was filtered and washed with water and methanol. A
sample for analysis was obtained as follows: d1 was dis-
solved in 100 mL of hot aqueous NaHCO3 (4.2 g) solution;
to this solution was added activated charcoal (1 g). After
the charcoal was filtered, the filtrate was cooled to room
temperature and acidified with conc. HCl (1 or 2 mL). The
solution was heated to 60 °C for 30 min and then cooled.
The resulting solid was filtered, washed with water and
dried. Recrystallization from DMF/methanol mixture gave
a dark yellow product. The compound is soluble in DMSO,
DMF, chloroform, methanol and slightly soluble in ace-
tone. Yield, 1.95 g (85%), mp dec. [ 230 °C. Anal. calc.
C52H32N8Cl8O4: C: 55.94; H: 4.92; N: 10.04% Found: C:
55.68; H: 4.42; N: 10.47%. FT-IR (KBr) m:3340 cm-1
(–OH), 2950, 1485 cm-1 (N=N). 1H NMR (CDCl3) d 9.82
(s, 4H, Ar OH), 7.5 (s, 12H, Ar H), 2.69 (s, 8H, CH2), 7.80
(s, 8H, Ar H).13C NMR (CDCl3) d 162, 151, 145, 140, 135,
130, 129, 128, 124, 118 and 113 (ArC), 13.0 (–CH2–).
MALDI-TOF MS (m/z) 1,116 (M) 1,117 (M ? 1).
1
nitrogen 337 nm laser (4 ns pulse). H NMR spectra were
scanned on 400 MHz FT-NMR Bruker Avance-400 and
13C NMR spectra were recorded on a Bruker DPX-400
spectrometer with tetramethylsilane (TMS) as internal
standard in deuterated DMSO.
The ink formulations were prepared using a Marshal
MV614 vibroshaker. The resultant formulations were
applied to polyester films, aluminium foils, coated as well
as uncoated paper manually using a barcoater no. 2.
Preparation of the ligands
p-tert-Butylcalix[4]arene was synthesized by microwave
technique developed in our laboratory [11] and the de-
butylation of calix[4]arene was carried out by the reported
method [14].
p-(2,4,5-tri-chlorophenylazo) calix[4]arene (d2)
The dye d2 was prepared as described above, recrystalli-
zation from DMF/methanol mixture gave a dark yellow
product. The compound is soluble in DMSO, DMF, chlo-
roform, methanol and slightly soluble in acetone. Yield,
1.40 g (72%), mp dec. [ 211 °C. Anal. calc. C52H28N8
Cl12O4: C: 49.79; H: 2.25; N: 8.93% Found: C: 50.20; H:
2.05; N: 8.67%. FT-IR (KBr) m:3339 cm-1 (–OH), 2950,
Preparation of phenylazocalix[4]arene dyes (d1–d7)
The diazotisation of the various amines was effected with
sodium nitrite and HCl. A typical procedure is that
described below which is used for the synthesis of 2,4-di-
chloroaniline. p-(2,4,5-tri-chlorophenylazo) calix[4]arene
(d2), p-(2,4-di-nitrophenylazo) calix[4]arene (d3), p-(2-nitro,
4-methylphenylazo) calix[4]arene (d4), p-(4-nitro, 2-meth-
ylphenylazo) calix[4]arene (d5), p-(5-nitro, 2-methylphe-
nylazo) calix[4]arene (d6) and p-(sulfophenylazo) calix[4]
arene (d7) were obtained using the same method in 58–
91% yield. The compounds obtained were purified by
crystallization using the same solvent (DMF–methanol)
and were then analyzed.
1
1490 cm-1 (N=N). H NMR (CDCl3) d 9.82 (s, 4H, Ar
OH), 7.25 (s, 8H, Ar H), 2.69 (s, 8H, CH2), 7.80 (s, 8H, Ar
H). 13C NMR (CDCl3) d 161, 158, 147, 139, 133, 131, 130,
128, 125, 119 and 115 (ArC), 13.0 (–CH2–). MALDI-TOF
MS (m/z) 1,254 (M).
p-(2,4-di-nitrophenylazo) calix[4]arene (d3)
The synthesis of dye d3 is as described above and the,
recrystallization from DMF/methanol mixture gave a dark
brown product. The compound is soluble in most of the
organic solvents. Yield, 1.44 g (80%), mp dec. [ 245 °C.
Anal. calc. C52H32N16O20: C: 49.79; H 2.25; N: 8.93%
Found: C: 50.20; H: 2.05; N: 8.67%. FT-IR (KBr)
Synthesis of p-(2,4-di-chlorophenylazo)
calix[4]arene (d1)
A solution of 2,4-di-chlorophenyldiazonium chloride,
which was prepared from 2,4-chloroaniline (7.84 g,
40 mmol), sodium nitrite (1.69 g, 25 mmol) and conc. HCl
(7 mL) in water (25 mL), was added slowly to a cold (0–
5 °C) solution of calix[4]arene (4.25 g, 10 mmol) and
sodium acetate trihydrate(4.08 g, 30 mmol) in DMF–
methanol (26 mL, 8:5, v/v) to give a dark orange suspen-
sion. After standing for 2 h at room temperature, the
suspension was acidified with aqueous HCl (150 mL,
0.25%) and the mixture was then warmed to 60 °C for
30 min to give (yield, 1.67 g, 72%) a dark yellow solid,
m:3245 cm-1 (–OH), 2950, 1480 cm-1 (N=N). H NMR
1
(CDCl3) d 9.82 (s, 4H, Ar OH), 8.5 (s, 12H, Ar H), 2.69 (s,
8H, CH2), 7.60 (s, 8H, Ar H). 13C NMR (CDCl3) d 160, 155,
148, 144, 139, 135, 131, 128, 122, 119 and 118 (ArC), 13.0
(–CH2–). MALDI-TOF MS (m/z) 1,201(M)1,202(M ? 1).
p-(2-nitro, 4-methylphenylazo) calix[4]arene (d4)
The dye, d4, prepared by following the above method was
above, recrystallized from DMF/methanol mixture gave a
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J Incl Phenom Macrocycl Chem (2010) 67:73–79
75
orange product. The compound is soluble in DMSO, DMF,
chloroform, methanol and slightly soluble in acetone.
Yield, 1.44 g (78%), mp dec. [ 235 °C. Anal. calc.
C56H44N12O12: C: 62.45; H: 4.12; N: 15.61% Found: C:
62.50; H: 4.02; N: 15.66%. FT-IR (KBr) m:3255 cm-1
(–OH), 2950, 1489 cm-1 (N=N). 1H NMR (CDCl3) d 9.80
(s, 4H, Ar OH), 8.32 (s, 8H, Ar H), 2.69 (s, 8H, CH2), 7.68
(s, 12H, Ar H), 2.30 (d, 12H, –CH3). 13C NMR (CDCl3) d
161, 151, 145, 143, 141, 135, 128, 125, 120 118 and 115
(ArC), 13.0 (–CH2–), and 20 (–CH3). MALDI-TOF MS
(m/z) 1,078 (M ? 1).
13C NMR (CDCl3) d 161, 154, 150, 135, 131, 129, 128,
123, 120, 117 and 113 (ArC), and 13.0 (–CH2–). MALDI-
TOF MS (m/z) 1,162 (M ? 1).
Preparation of inks
The synthesized dyes were used for formulating solvent
based inks as reported earlier [15]. To a mixture of 6 g dye,
25 g resin (maleic resin for paper, acrylic resin for poly-
ester film and nitrocellulose resin for aluminium foil) and
60 g of appropriate solvent (ethanol for paper, ethyl acetate
for polyester films, glycol ether and ethyl acetate mixture
for aluminium foils) in a vibroshaker container was added
80 g glass beads and the mixture was shaken for 20 min.
The inks were then transferred to their corresponding
substrates manually using a barcoater rod no. 2, and then
allowedtodryfor3–5 minat35 °C. Thelightandwetfastness
studies were done according to standard method [16, 17].
p-(4-nitro, 2-methylphenylazo) calix[4]arene (d5)
d5 is prepared as described above, recrystallization from
DMF/methanol mixture gave a dark orange product. The
compound is soluble in DMSO, DMF, chloroform, meth-
anol and slightly soluble in acetone. Yield, 1.38 g (70%),
mp dec. [ 220 °C. Anal. calc. C56H44N12O12: C: 63.15; H:
4.02; N: 13.31% Found: C: 63.55; H: 4.32; N: 13.26%. FT-
IR (KBr) m:3255 cm-1 (–OH), 2950, 1487 cm-1 (N=N).
1H NMR (CDCl3) d 9.82 (s, 4H, Ar OH), 8.22 (s, 8H, Ar
H), 2.69 (s, 8H, CH2), 7.60 (s, 12H, Ar H), 2.76 (d, 12H,
–CH3). 13C NMR (CDCl3) d 161, 154, 150, 145, 141, 135,
128, 125, 120, 117 and 113 (ArC), 13.0 (–CH2–), and 16.8
(–CH3). MALDI-TOF MS (m/z) 1,078 (M ? 1).
Dyeing of cotton
The water soluble dye d7 (0.30 g) was added to water
(25 mL) and heated to 60 °C. The scoured cotton hanks
(3.0 g) were added to the dye baths and dyed at 90 °C for
about 1 h. After cooling the baths to room temperature the
dyed hanks were rinsed with cold water and dried.
p-(5-nitro, 2-methylphenylazo) calix[4]arene (d6)
General procedure for spectral studies and ionization
constants (pKa)
d6 is prepared as described above, recrystallization from
DMF/methanol mixture gave a pale orange product. The
compound is soluble in DMSO, DMF, chloroform, meth-
anol and slightly soluble in acetone. Yield, 1.48 g (78%),
mp dec. [ 225 °C. Anal. calc. C56H44N12O12: C: 62.35; H:
3.72; N: 11.51% Found: C: 62.55; H: 3.32; N: 11.86%. FT-
IR (KBr) t:3255 cm-1 (–OH), 2950, 1487 cm-1 (N=N).
1H NMR (CDCl3) d 9.85 (s, 4H, Ar OH), 8.11 (s, 8H, Ar
H), 2.69 (s, 8H, CH2), 7.60 (s, 12H, Ar H), 2.76 (d, 12H,
–CH3). 13C NMR (CDCl3) d 161, 154, 150, 145, 141, 135,
128, 125, 120, 117 and 113 (ArC), 13.0 (–CH2–), and 17.18
(–CH3). MALDI-TOF MS (m/z) 1,078 (M ? 1).
For spectral studies 10-4–10-5 M dye solutions in various
solvents were used and the effect of acid and base was
studied by addition of 50% acetic acid and 0.1 M sodium
hydroxide respectively.
For pKa measurements, 10-4–10-5 M dye solutions in
DMSO in the pH range of 2–13 were made and the spectra
were recorded at 25 °C in the range of 300–650 nm. The
ionization constants were then calculated using the fol-
lowing equation:
A ꢁ Ab
pKa ¼ pH þ log10
Aa ꢁ A
where A is the absorbance at the specific pH, Aa and Ab
are the absorbances for the most acidic and most basic pH,
respectively [18].
Synthesis of p-(sulfo-phenylazo) calix[4]arene (d7)
d7 was prepared as described above, recrystallization from
DMF/methanol mixture gave a dark orange product. The
compound is soluble in water, DMSO, DMF, methanol and
slightly soluble in acetone. yield, 1.44 g (58%), mp
dec. [ 230 °C. Anal. calc. For C52H40N8O16S4: C: 53.79;
H: 3.74; N: 9.65% Found: C: 53.50; H: 3.80; N: 9.88%.
FT-IR (KBr) m:3223 cm-1 (–OH), 2950, 1484 cm-1 (N=N).
1H NMR (CDCl3) d 9.75 (s, 4H, Ar OH), 8.20 (s, 16H, Ar
H), 2.69 (s, 8H, CH2), 7.4 (s, 8H, Ar H), 2.0 (d, 4H, Alip).
Results and discussion
Synthesis and characterizations
Microwave synthesis of calix[4]arene was carried out
(Scheme 1) for the first time by base-catalysed
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Thermal properties
The decomposition temperatures were taken from the DSC
curves of the dyes. The temperature at which the dyes first
exothermic peak starts appearing after the melting point
was taken as the decomposition temperature. The melting
points and decomposition temperatures of all the synthe-
sized dyes are as shown in Table 1. All prepared dyes
showed high melting points (mp 211–251 °C) and conse-
quently high thermal stability.
Microwave 15-20 min
6.2 ml HCHO
0.05g NaOH
7 ml diphenyl Ether
1 ml toluene
4
OH
p-tert butyl phenol
OH
tert-butylcalix[4]arene
Scheme 1 Microwave-assisted synthesis of tert-butyl calix[4]arene
Proton ionization constants
R
The ionization constants are a core property of a molecule
which reflects its structural characteristics, reactivity,
spectral properties and the isolation conditions. All the
measurements were done in DMSO medium. From the
values of the ionization constants summarized in Table 2 it
can be easily concluded that dye d3 is the most acidic in
nature. This implies directly that of all the dyes synthe-
sized, dye d3 has more tendencies to be taken up in an
aqueous solution than into organic solvents. Hence it will
have comparatively less solvent solubility and water fast-
ness than the other dyes.
N
N
NH2
NaNO2, con HCL
+
DMF-MeOH
4
4
OH
OH
R
d1: 2,4 dichloroaniline
d3: 2,4 dinitroanilin
d5: 4 nitro o-toluidin
d7: sulfanilic acid
d2: 2,4,5 trichloroaniline
d4: 2 nitro p-toluidin
d6: 5 nitro o-toluidin
Scheme 2 Synthesis scheme of o-, m- and p-substituted azoca-
lix[4]arene derivatives
Absorption spectra
condensation of p-substituted phenol and formaldehyde
with an improvement of yield to 90–95% [7]. Microwave
synthesis of the parent molecule is adopted to reduce the
cost of the final product. The calix[4]arene macrocycle in
its cone conformation is a very versatile molecule. In this
work, seven azo compounds were synthesized from 2,4-di-
chloroaniline, 2,4,5-trichloroaniline, 2,4-di-nitroaniline,
2-nitro p-toluidin, 4-nitro o-toluidin, 5-nitro o-toluidin and
sulfanilic acid. These compounds (d1–d7) are shown in
Scheme 2. The synthesized azocalix[4]arene compounds
were characterized using elemental analysis, FT-IR, 1H
NMR, 13C NMR and MALDI-TOF MS.
The spectral details of the synthesized calix[4]arene dyes
are summarized in Table 2. The dyes showed colors
ranging from deep red (kmax 521 nm) to pale yellow (kmax
340 nm). The different substituents are in positions slightly
away from the chromophoric systems. Hence they may not
directly influence the absorption maxima. But the general
observation made is that most of the substituted dyes have
higher absorption maxima when compared to their unsub-
stituted analogues.
The molar extinction coefficient (emax) of the dyes
showed that most of them are intensely absorbing. How-
ever, it is the oscillator strength (f) that gives a full measure
of the tinctorial strength rather than molar extinction
coefficient (emax) [19, 20]. Hence, the oscillator strength
was calculated using the following equation:
The FT-IR spectra of all compounds (d1–d7) showed a
band within the range 3,339–3,212 cm-1 corresponding to
m OH. Asymmetrical stretching vibration of the N=N group
leading to the band located in the 1,478–1,490 cm-1
region. The compounds (d1–d7) were examined in solution
Table 1 Thermal properties of dyes d1–d7
1
Dye
Melting point (Decom temp)°C
by high-resolution NMR. The H NMR spectrum showed
broad peak at d = 9.75–9.82 ppm (–OH), singlet peak for
methylene bridge protons (–CH2–) at d = 2.4–2.76 ppm,
singlet from d = 7.20 to 9.12 ppm for aromatic protons
(Aro-H), doublet from d = 2.0 to 2.76 ppm for aliphatic
protons (Alip-H). The 13C NMR spectrum showed aro-
matic (ArC) at d = 112.3–170.1 ppm, methylene bridge
carbon showed peak at d = 13.0 ppm, (–CH3) at d =
17.19–20.4 ppm.
d1
d2
d3
d4
d5
d6
d7
230 ([250)
211 ([250)
245 ([280)
235 ([250)
220 ([250)
225 ([250)
245 ([280)
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77
Table 2 Oscillator strength for
the dyes d1–d7
Dyes
kmax (nm)
Dt1/2 (cm-1
)
emax (mol-1 cm-1
)
f
Ionization constants
d1
d2
d3
d4
d5
d6
d7
501
475
411
479
468
409
521
6,218
5,513
5,488
5,515
5,514
5,467
6,220
55,235
50,516
49,786
52,234
51,965
49,543
57,342
1.48370
1.20309
1.86342
1.24449
1.23783
1.17007
1.54080
11.71
11.39
06.54
08.21
08.93
07.16
08.80
f ¼ 4:23 ꢂ 10ꢁ9 ꢂ Dt1=2 ꢂ emax
Table 4 Effect of acid and base on the dyes d1–d7
Dye
kmax
(nm)
kmax (nm)
Methanol ? 0.5 M
NaOH
kmax (nm)
Methanol ? 0.5 M
acetic acid
where f is Oscillator strength, emax is the molar extinction
coefficient at maximum absorption, Dm is the full width at
half maximum of the absorption curves for the dyes.
Methanol
d1
d2
d3
d4
d5
d6
d7
440
363
367
397
377
342
413
480, 520 s
398, 423 s
397, 456 s
420, 488 s
391, 423 s
375, 433 s
450, 488 s
401
637
346
364
348
331
388
Solvatochromic effects
The absorption spectra of azocalix[4]arenes d1–d7 were
recorded in various solvents at a concentration of
1 9 10-4–1 9 10-5 M; the results are summarized in
Table 3. The electronic absorption spectra of azoca-
lix[4]arene derivatives (d1–d7) exhibited one absorption
band in the range 300–700 nm corresponding to p–p* and
n–p* transitions. The visible spectral properties of the
azocalix[4]arene derivatives were compared with o-, m-,
p-substituents. Electron-withdrawing and electron-donat-
ing substituents in the aryl ring exerted a bathochromic
effect. The visible absorption spectra of the compounds
were found to exhibit strong solvent dependency, which
did not show regular variation with the polarity of the
solvents. Strong evidence for the existence of these
compounds existing in an equilibrium is provided by the
isosbestic points in the visible spectra of, for example,
compound d3 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, chloroform
and methanol, the compounds displayed a red shift of
kmax
.
The effect of concentration of the compound on
absorption maxima was examined (Table 3). The kmax of
all compounds did not change with compound concentra-
tion which also indicates that azocalix[4]arenes exist in
their tautomeric form in all solvents used.
Effect of acid and base
The effect of acid and base on the absorption of the dye
solutions was investigated and the results are shown in
Table 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 wavelength. The kmax
of the compounds in methanol also showed slightly hyp-
sochromic effects with addition of acid (50% acetic acid).
The visible spectral properties of the azocalix[4]arene
derivatives were compared with o-, m-, p-substituents.
Electron-withdrawing and electron-donating substituents in
the aryl ring exerted a bathochromic effect. The azoca-
lix[4]arenes (d1–d7) may exist in two possible tautomeric
forms, namely an azo-enol form A and keto-hydrazo B are
shown in Fig. 1.
Table 3 Influence of solvent on kmax (nm) dyes d1–d7
Dye
DMSO
DMF
Acetonitrile
Methanol
Chloroform
d1
d2
d3
d4
d5
d6
d7
488
456
407
433
418
428
498
501
475
411
479
468
409
521
438
432
387
417
406
409
451
427
363
367
397
377
342
413
425
347
340
355
349
340
378
The effect of concentration of the compound on
absorption maxima was examined. The kmax of all com-
pounds did not change with compound concentration.
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Fig. 1 The tautomeric form of synthesized dye
Table 5 Fastness properties of
Dyes
Uncoated paper
Light fastness
Coated paper
the dyes d1–d6
Wet fastness
Light fastness
Wet fastness
d1
d2
d3
4
4–5
4–5
5
4–5
4
5
6
5–6
5
5–6
4–5
5
5–6
4–5
6
6
d4
d5
d6
5–6
5
1 very poor, 2 poor, 3 moderate,
4 fairly good, 5 good, 6 very
good, 7 excellent and 8
outstanding
4–5
5
4–5
4–5
6
Table 6 Fastness properties of the dye d7
Dye
Washing
Light fastness
Wet fastness
Acid perspiration
Alkaline
perspiration
Cotton
3–4
Wool
4
Cotton
5
Wool
4–5
Cotton
5
Wool
4–5
Cotton
3–4
Wool
4
Cotton
5
Wool
4
d7
1 very poor, 2 poor, 3 moderate, 4 fairly good, 5 good, 6 very good, 7 excellent and 8 outstanding
Fastness properties
of azocalix[4]arene compounds. The light fastness and wet
fastness of all the synthesized dyes were found to be good
and very good. The dyes were all stable up to 245 °C and
hence can be effectively used in almost all kinds of inks.
The light fastness of the dyes on d1–d6 substrates except
uncoated paper was in the range of 4–5 while the wet
fastnesses on d1–d6 substrates were in the range of 5–6
respectively which is considered as good and very good.
The light fastness on uncoated paper and coated paper is
summarized in Table 5. Only water soluble dye d7 was used
for dyeing cotton and wool. The fastness testing involving
dyed cotton on wet fastness, wash fastness, light fastness
and perspiration fastness is summarized in Table 6.
Acknowledgment Financial assistance from UGC, New Delhi is
gratefully acknowledged. The authors wish to thank Lucknow for
spectral data. The facilities provided by Chemical Research and
Development Centre and Anar Chemicals Vatva, Ahmedabad are also
gratefully acknowledged.
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