Quantum chemical studies and dyeing performance of some novel benzoquinoline based heterocyclic monoazo dyes on polyester fiber

Article abstract of DOI:10.1016/j.dyepig.2012.03.014

Some novel benzoquinoline based heterocyclic monoazo dyes have been derived by the diazotization of 1H-benzo[g]pyrazolo[3,4-b]quinoline-3-ylamine with various phenyl pyrazolone as coupling components. All the heterocyclic monoazo dyes have been characterized by elemental analyses and various spectral data (FT-IR, UV-Vis, ¹H NMR and ¹³C NMR), and their 3D model structures were predicted through B3LYP/6-31G(d,p) method. The dyeing performance on polyester fibers inferred that all the dyes gave moderate to excellent fastness properties on fiber. In addition, colorimetric studies of synthesized dyes have also been discussed.

Full text of DOI:10.1016/j.dyepig.2012.03.014

Dyes and Pigments 95 (2012) 142e148
Contents lists available at SciVerse ScienceDirect
Dyes and Pigments
journal homepage: www.elsevier.com/locate/dyepig
Quantum chemical studies and dyeing performance of some novel
benzoquinoline based heterocyclic monoazo dyes on polyester fiber
*
Nikhil M. Parekh, Suban K. Sahoo, Kalpana C. Maheria
Department of Applied Chemistry, S.V. National Institute of Technology, Surat-395 007, Gujarat, India
a r t i c l e i n f o
a b s t r a c t
Article history:
Some novel benzoquinoline based heterocyclic monoazo dyes have been derived by the diazotization of
1H-benzo[g]pyrazolo[3,4-b]quinoline-3-ylamine with various phenyl pyrazolone as coupling compo-
nents. All the heterocyclic monoazo dyes have been characterized by elemental analyses and various
spectral data (FT-IR, UVeVis, 1H NMR and 13C NMR), and their 3D model structures were predicted
through B3LYP/6-31G(d,p) method. The dyeing performance on polyester fibers inferred that all the dyes
gave moderate to excellent fastness properties on fiber. In addition, colorimetric studies of synthesized
dyes have also been discussed.
Received 29 October 2011
Received in revised form
2 February 2012
Accepted 13 March 2012
Available online 3 April 2012
Keywords:
Ó 2012 Elsevier Ltd. All rights reserved.
1H-benzo[g]pyrazolo[3,4-b]quinoline-3-
ylamine
Phenyl pyrazolone
Colorimetric data
Exhaustion-fixation
Fastness properties
Quantum chemical studies
1. Introduction
phenyl pyrazolone based coupling components that give good
dyeing properties.
It has been recognized for several years that azo compounds are
the most widely used compounds in various fields such as the
dyeing of textile fiber, the coloring of different materials, colored
plastic and polymer, biological-medical studies and advanced
applications in organic synthesis. A number of azo dyes have been
prepared from amino heterocycles by using selected quinolines,
benzoquinoline, thiazole and quinazoline derivatives as coupling
components [1e20]. Quinolines and benzoquinolines combined
with five or six member rings in linear approach is known to
possess good pharmacological activities and are also used as
intermediates in dyestuff industry [21e24]. Therefore, keeping the
above facts in view, we have concentrated our research work on
developing quinoline/benzoquinoline containing heterocyclic azo
compounds. Due to the significant dyeing applications of quinoline,
benzoquinoline and quinazoline containing heterocyclic azo
compounds, it appeared expedient to synthesize a series of
heterocyclic monoazo compounds derived from diazotization of
1H-benzo[g]pyrazolo[3,4-b]quinoline-3-ylamine and coupled with
The present paper deals with the facile and convenient
synthesis of novel benzoquinolines based heterocyclic monoazo
dyes and study of their dyeing properties and fastness properties
are reported. The spectral properties and colorimetric data (L*, a*,
b*, C*, H*, K/S) have also been discussed. Further, we have per-
formed DFT calculations at B3LYP/6-31G (d,p) method to get the
theoretical optimized structural parameters, HOMO and LUMO of
the dyes.
2. Experimental
2.1. Materials and methods
All chemicals were of analytical grade and used directly. All
melting points were determined in PMP-DM scientific melting
point apparatus and are uncorrected. The purity of all dyes were
determined by thin-layer chromatography (TLC) [25] using silica
gel-G coated Al-plates (0.5 mm thickness, Merck). Infrared spectra
were recorded on a Shimadzu FT-IR 8400S model using KBr pellets.
1H and 13C NMR spectra were acquired on a Varian 400 MHz model
spectrophotometer using DMSO-d6 as solvent and TMS as internal
* Corresponding author. Tel.: þ91 261 2201793; fax: þ91 261 2228394.
E-mail address: maheria@gmail.com (K.C. Maheria).
reference (chemical shifts in d, ppm). Elemental analysis of C, H and
0143-7208/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.dyepig.2012.03.014

N.M. Parekh et al. / Dyes and Pigments 95 (2012) 142e148
143
N were carried on Carlo Erba 1108 instrument. The light fastness
2.6. Synthesis of1H-benzo[g]pyrazolo[3,4-b]quinoline-3-ylamine(5)
was assessed in accordance with BS: 1006e1978 (Standard test
method, 1978, 1994). The rubbing fastness test was carried out with
a Crock meter (Atlas) in accordance with AATCC-1961 (AATCC test
method, 1961) and the wash fastness test in accordance with IS:
765e1979 (Indian standard ISO, 1979). Colorimetric data (L*, a*, b*,
C*, H*, K/S) were recorded on Reflectance Spectrophotometer
Gretag Macbeth CE: 7000.
2-chloro-benzo[g]quinoline-3-carbonitrile (1.0 mmol) on reac-
tion with hydrazine hydrate (1.2 mmol) in ethanol gave 1H-benzo
[g]pyrazolo[3,4-b]quinoline-3-ylamine. The reaction mixture was
reflux for 24 h. The reaction mixture was poured onto ice cold
water. The yellow color precipitate was filtered and dried. Yield
78%, mp 286e290 ꢀC, IR(KBr disk, cmꢁ1) 3200e3289 (eNH), 1548,
1398 (C]N, CeN), 758 cmꢁ1 (CeCl). 1H NMR (DMSO-d6)
d ppm:
7.48e8.79 (7H, m AreH), 7.85 (2H, s, NH2), 12.56 (1H, s, NH).
2.2. Synthesis of N-naphthalen-2-yl-acetamide (1)
2.7. Diazotization and coupling (6)
A mixture of 1-naphthylamine (1.0 mmol) and catalytic amount
of triethylamine (1.2 mmol) was stirred in acetone at room
temperature for an hour. Thereafter, acetyl chloride (1.2 mmol) was
added dropwise during a period of an hour. During addition of
acetyl chloride white precipitate was formed. The mixture was
further stirred for another 1 h. The completion of reaction was
monitored by TLC. The solution was then poured directly onto
crushed ice. The resulting white precipitate was filtered, washed
with water, and dried in air. The product was recrystallized from
ethanol to give the title compound 1 as white needles. Yield 75%,
mp: 159e160 ꢀC; IR (KBr disk, cmꢁ1): 3270 (NH), 1656 (CO), 1548,
Concentrated HCl was added to a well stirred suspension of 1H-
benzo[g]pyrazolo[3,4-b]quinoline-3-ylamine (0.0048 mol) in water
and the mixture was heated up to 70 ꢀC and maintained at that
temperature till the clear solution is obtained. After cooling the
solution to 0e5 ꢀC in an ice-bath, an aqueous solution of sodium
nitrite 0.66 g in water was added dropwise over a period of 30 min
with continuous stirring. The reaction was stirred at a temperature
below 5 ꢀC for about an hour. The excess of nitrous acid is tested
using starch iodide paper and was removed by adding required
amount of sulfamic acid solution (10%). The clear diazonium salt
solution thus obtained was used immediately in the coupling
reaction.
1398 cmꢁ1 (C]N, CeN); 1H NMR (DMSO- d6,
COCH3), 7.46e8.42 (7H, m AreH).
d ppm): 2.17(3H, s,
Coupling component (6a-e) was dissolved in sodium hydroxide
solution. The solution was cooled to 0-5 ꢀC in an ice-bath. To this
well stirred solution, the above diazonium solution was added
dropwise keeping temperature below 5 ꢀC. The reaction mass was
further stirred for 2 h at 0e5 ꢀC maintaining the pH 8.0 by adding
required amount of 10% sodium carbonate solution. The reaction
mass was then heated up to 60 ꢀC and diluted with water. The dye
was filtered off, washed with hot water until the washings were
neutral, dried, and powdered. The product was purified by dis-
solving it in DMF and pouring in water. The similar coupling
procedure and conditions were followed for all the dyes.
2.3. Synthesis of 2-Chlorobenzo[h]quinoline-3-carbaldehyde (2)
To a solution of N-naphthalen-2-yl-acetamide (5.4 mmol) in dry
DMF (14 mmol) was added POCl3 (102 mmol) and the mixture
stirred at 75 ꢀC for 6 h. The mixture was poured onto crushed ice
and the resulting solid filtered, washed with water and dried in an
oven. The sample was recrystallized from ethyl acetateepetroleum
ether at 60e80 ꢀC to give the title compound as yellow needles.
Yield 72%, mp: 210e212 ꢀC; IR (KBr disk, cmꢁ1): 1685 (CO), 1579,
1365 cmꢁ1 (C]N, CeN); 1H NMR (CDCl3,
AreH), 10.58 (1H, s, CHO).
d ppm): 7.47e8.48 (7H, m,
2.7.1. Dye 6a (p-toluene phenyl methyl pyrazolone)
Yield: 78%; Mp gt; 300 ꢀC; IR (KBr)
n
cmL1: 3250 (NH), 1552
(N]N), 1330 & 1564 (CeN & C]N), 2900e3100 (eCH stretching),
2.4. Synthesis of 2-chloro-benzo[g]quinoline-3-carbaldehyde
oxime (3)
1478 (CH bending); 1H NMR (400 MHz, DMSO-d6)
d
ppm: 2.10 (s,
3H, eCH3 of pyraozlone ring:, 2.42 (s, 3H, CH3 of benzene ring),
7.68e9.07 (m, 11H, AreH), 12.08 (s, 1H, eNH, benzoquinoline ring);
To
a solution of 2-chlorobenzo[g]quinoline-3-carbaldehyde
13C NMR (400 MHz, DMSO-d6)
d ppm: 13.42 (C-32, CH3 group of
(1.0 mmol) in ethanol, hydroxyl amine hydrochloride (1.2 mmol)
and sodium acetate (1.2 mmol) was added at room temperature
and the mixture was stirred for an hour. While stirring, white
precipitate was formed. The completion of the reaction was
monitored by TLC. The reaction mixture was poured onto ice cold
water, filtered, dried and used for further reaction. Yield 80%, mp
172e176 ꢀC, IR(KBr disk, cmꢁ1) 3335 (OeH), 1548, 1398 (C]N,
pyrazolone ring), 21.15 (C-31,CH3 group of benzene ring),
118e152.12 (21C, AreC), 152.61 (C-17, of pyrazole ring carbon
atoms), 158, 160 (C-28, 30 of pyrazolone ring carbon atoms);
C25H19N7O (433.67): Calc. C, 69.27; H, 4.42; N, 22.62, found: C,
69.24; H, 4.38; N, 22.57.
CeN), 758 cmꢁ1 (CeCl). 1H NMR (DMSO-d6)
7.48e8.54 (7H, m AreH).
d ppm: 2.55(1H, s, OH),
2.7.2. Dye 6b (2,5-dichloro phenyl methyl pyrazolone)
Yield: 78%; Mp gt; 300 ꢀC; IR (KBr)
n
cmL1: 3252 (NH), 1548
(N]N), 1333 & 1558 (CeN & C]N), 2982e3100 (CH stretching),
1475 (CH bending), 752e754 (AreCl); 1H NMR (400 MHz, DMSO-
2.5. Synthesis of 2-chloro-benzo[g]quinoline-3-carbonitrile (4)
d6)
AreH), 12.10 (s, 1H, eNH, benzoquinoline ring); 13C NMR (400 MHz,
DMSO-d6) ppm: 13.46 (C-31, CH3 group of pyrazolone ring),
111.24e150.12 (19C, AreC), 152.58 (C-17, of pyrazole ring carbon
atoms), 158.14, 160.12, (C-30, C-28, of pyrazolone ring carbon
atoms; C24H15Cl2N7O (487.07): Calc. C, 59.03; H, 3.10; N, 20.08;
found: C, 59.00; H, 3.12; N, 20.12.
d ppm: 2.04 (s, 3H, CH3 of pyrazolone ring:, 7.44e8.97 (m, 10H,
2-Chloro-benzo[g]quinoline-3-carbaldehyde oxime (1.0 mmol)
was stirred in benzene. Then SOCl2 (3.0 mmol) was added dropwise
at room temperature. After the addition of SOCl2, the reaction
mixture was refluxed for an hour. The completion of reaction was
monitored by TLC. The solvent was removed by vacuum distillation.
A brown yellow needle crystal formed which was used for further
reaction. Yield 82%, mp 184e189 ꢀC, IR(KBr disk, cmꢁ1) 2221 (CeN),
1548, 1398 (C]N, CeN), 754 cmꢁ1 (CeCl). 1H NMR (DMSO-d6)
d
2.7.3. Dye 6c (m-chloro phenyl methyl pyrazolone)
Yield: 82%; Mp gt; 300 ꢀC; IR (KBr)
n
cmL1: 3242 (NH), 1556
d
ppm: 7.48e8.41 (7H, m AreH).
(N]N), 1328 & 1545 (CeN & C]N), 2900-3100 (CH stretching),

144
N.M. Parekh et al. / Dyes and Pigments 95 (2012) 142e148
1478 (CH3 bending), 758 (AreCl); 1H NMR (400 MHz, DMSO-d6)
ppm: 2.00 (s, 3H, CH3 of pyraozlone ring:, 12.10 (s, 1H, NH, ben-
zoquinoline ring), 7.29e8.95 (m, 11H, AreH); 13C NMR (400 MHz,
DMSO-d6) ppm: 13.40 (C-31, eCH3 group of pyrazolone ring),
phase were carried out at DFT level of theory using B3LYP without
any symmetry restrictions. All optimized geometries have been
confirmed by frequency analyses at the same level of theory.
d
d
112.24e150.12 (22C, AreC), 152.58 (C-17, of pyrazole ring carbon
atoms), 157.14, 162.14, (C-30, C-28 of pyrazolone ring carbon
atoms); C24H16ClN7O (453.11): Calc. C, 63.51; H, 3.55; N, 21.60;
found: C, 63.55; H, 3.52; N, 21.64.
3. Results and discussion
3.1. Chemistry
Various routes have been developed for functionalization of
quinolines/benzoquinolines. Among them, the Vilsmeier approach
[27] is found to be the most efficient for achieving useful trans-
formations and heteroannulations. Therefore, we have performed
2.7.4. Dye 6d (o-chloro phenyl methyl pyrazolone)
Yield: 76%; Mp gt; 300 ꢀC; IR (KBr)
n
cmL1: 3252 (NH), 1560
(N]N), 1330 & 1548 (CeN & C]N), 2900e3100 (CH stretching),
1490 (CH bending), 760 (AreCl); 1H NMR (400 MHz, DMSO-d6)
the synthesis of 2-chlorobenzo[h]quinoline-3-carbaldehyde
2
d
ppm: 2.06 (s, 3H, CH3 of pyraozlone ring:, 7.40-8.95 (m, 11H,
AreH), 12.02 (s, 1H, NH, benzoquinoline ring); 13C NMR (400 MHz,
DMSO-d6) ppm:13.38 (C-31, eCH3 group of pyrazolone ring),
from the reaction of N-naphthalen-2-yl-acetamide 1 with Vils-
meier reagent, and then the transformation of the 2-chloro and 3-
carbaldehyde groups into different functionalities (Scheme 1). The
d
111.24e152.12 (22C, AreC), 152.60 (C-17, of pyrazole ring carbon
atoms), 156.11, 160.16 (C-30, C-28 of pyrazolone ring carbon atoms);
C24H16ClN7O (453.11): Calc. C, 63.51; H, 3.55; N, 21.60; found: C,
63.52; H, 3.52; N, 21.65.
required N-naphthalen-2-yl-acetamide
1
intermediate was
obtained in very good yield by the reaction between 1-
naphthylamine and acetyl chloride in presence of catalytically
amount of TEA at room temperature, which was characterized by
the disappearance of eNH2 group and appearance of eNH and
eC¼O groups in IR spectrum which showed bands at 3345 cmꢁ1
and 1710 cmꢁ1 respectively. The Vilsmeier cyclisation of acetani-
lide 1 was carried out by adding POCl3 to the substrate in DMF at
0e5 ꢀC followed by heating to 90 ꢀC to afford 2-chlorobenzo[h]
quinoline-3-carbaldehyde 2 in moderate yield. The IR spectrum of
compound 2 showed a sharp and strong stretching absorption
band in the range of 1680e1700 cmꢁ1 for the aldehyde group, and
absorption at around 2720 and 2830 cmꢁ1 for aldehyde proton.
The bands for eCeN and eC¼N of benzoquinoline ring was
identified at 1342 and 1562 cmꢁ1 respectively. The carbaldehyde
group in quinolines 2 was also transformed into other function-
alities to afford new quinolines which are equally important
synthons for the synthesis of fused quinoline systems. Compound
2 condensed with hydroxyl amine hydrochloride in presence of
sodium acetate at room temperature to give 2-chloro-benzo[g]
quinoline-3-carbaldehyde oxime 3, which was confirmed by the
appearance of a broad eOH stretching band at 3400e3500 cmꢁ1
in IR spectrum. Compound 3 on reflux with SOCl2 gave 2-
chloro-benzo[g]quinoline-3-carbonitrile 4 in good yield, which
was confirmed by the presence of eCN stretching band at
2.7.5. Dye 6e (3,4-dichloro phenyl methyl pyrazolone)
Yield: 84%; Mp gt; 300 ꢀC. IR (KBr)
n
cmL1: 3242 (NH), 1556
(N]N), 1329 & 1552 (CeN & C]N), 2900e3100 (CH stretching),
1474 (CH bending), 760e774 (AreCl); 1H NMR (400 MHz, DMSO-
d6)
AreH), 12.04 (s, 1H, NH, benzoquinoline ring); 13C NMR (400 MHz,
DMSO-d6) ppm: 13.32 (C-31, CH3 group of pyrazolone ring),
d ppm: 2.04 (s, 3H, CH3 of pyraozlone ring:, 7.32-8.97 (m, 10H,
d
110.16e150.10 (20C, AreC), 152.42 (C-17, of pyrazole ring carbon
atoms), 158.11, 164.76, (C-30, C-28 of pyrazolone ring carbon
atoms); C24H15Cl2N7O (487.07): Calc. C, 59.03; H, 3.10; N, 20.08;
found: C, 59.12; H, 3.16; N, 20.12.
2.8. Computational methodology
The Gaussian 09W [26] computer program has been used for all
quantum chemical calculations. The quantum-chemical calcula-
tions of compound have been performed using Becke’s three
parameter exchange function (B3) with Lee-Yang-Parr correlation
function (LYP), with basis-set 6-31G(d,p). Geometry optimizations
of heterocyclic monoazo dyes and their model compounds in gas
CHO
NH2OH.HCl
DMF/POCl3
CH3COCl
TEA
CH3COONA
NHCOCH3
NH2
N
Cl
1
2
N -OH
NH2
C
H
CN
Cl
NH2NH2.H2O
Ethanol
SOCl2
N
Benzene
N
H
N
N
Cl
N
5
4
3
N
N
N
NaNO2/HCl
R
N
H
N
6
R = Various phenyl pyrazolone derivatives as coupling components
Scheme 1. Schematic diagram for the synthesis of heterocyclic monoazo dyes (Table 2).

N.M. Parekh et al. / Dyes and Pigments 95 (2012) 142e148
145
Fig. 1. B3LYP/6-31G(d,p) optimized structure of 6a and 6b along with their HOMO and LUMO diagrams.
2221 cmꢁ1. Compound 4 on further cyclization with hydrazine
hydrate gave 1H-benzo[g]pyrazolo[3,4-b]quinoline-3-ylamine 5
which showed two characteristic band in the region of
3200e3400 cmꢁ1 confirm the presence of eNH2 group.
Compound 5 on diazotization and followed by coupling with
various phenyl pyrazolones yielded benzoquinoline based azo
compounds 6a-e in high yield. The 1H NMR spectra of 6a-e
showed signal at 2.10 and 2.42 ppm due to eCH3 group attached
to pyraozlone ring and benzene ring respectively. Compounds 6a-
e showed singlet at 12.08 ppm due to the presence of eNH in
benzoquinoline ring and the remaining aromatic protons are
resonated at 7.48e9.67 ppm as multiplet. In 13C NMR spectra, the
signals in the range between 13.22 and 13.70 were assigned to
eCH3 group of pyrazolone ring. Whereas the signals in between
18.00 and 21.15 were attributed to the presence of eCH3 group of
benzene ring. The peaks at 160 and 158 ppm were attributed to
the carbon atoms of pyrazolone heteroatom ring while peak at
152.61 was attributed to the carbon atom of the pyrazole
heteroatom ring. Remaining all aromatic carbons was resonated in
the range of 118e152.12. The principle benefit for using benzo-
quinoline based moiety is high percentage yield and simple
workup procedure, which facilitates easy preparation of starting
material.
benzoquinoline ring and azo bond indication for similar energy
absorption in all studied dyes.
3.2. Spectral properties of dyes
The visible absorption spectroscopic properties of dyed fabrics
were recorded by computer color matching instrument and are
presented in Table 2 and Fig. 2. The results summarized in Table 2
inferred that the value of maximum absorbance (lmax) depends
on the nature and position of the coupling component used. The
color change observed for each dye is due to the alternation of
electrons and the presence of additional substituent.
3.3. Dyeing of fibers
Compounds 6a-e was applied on polyester in 2% shade accord-
ing to the literature procedure in the dye-bath containing the
materials listed in Table 3 [28]. The variation in the hues of the dyed
fabric results from the alternation in the coupling components. The
remarkable degree of levelness and brightness after washing
indicates good penetration and excellent affinity of these dyes to
the fabric.
In absence of suitable crystal for X-ray analysis, we performed
quantum chemical calculations by applying B3LYP/6-31G (d,p)
method to predict the possible molecular structure of the
compounds 6a-e in gas phase. The calculated model structure of
the compounds 6a and 6b along with their HOMO and LUMO
diagrams are shown in Fig. 1 and some physical parameters of the
compounds 6a-e are summarized in Table 1. The results obtained
from the DFT calculations inferred that (i) the m-chloro substituted
compounds 6c and 6e are energetically more stable than their
corresponding o-chloro substituted compounds 6d and 6b
(Table 1), (ii) except the structure for the o-chloro substituted
coupling components in compounds 6d and 6b, other coupling
components are planar in compounds 6a, 6c and 6e, (iii) all the
3.4. Exhaustion and fixation study
The percentage dye bath exhaustion and percentage dye bath
fixation of the dyed fabric were determined according to the known
Table 1
Quantum chemical parameters of the compounds obtained at B3LYP/6-31G(d,p)
method.
Compounds Total energy (a.u.)
m
(D)
EHOMO (eV) ELUMO (eV)
DE
6a
6b
6c
6d
6e
ꢁ1422.55973764
ꢁ2302.41645544
ꢁ1842.83373323
ꢁ1842.82419440
ꢁ2302.42286350
3.3889 ꢁ0.20162
3.9209 ꢁ0.20306
5.5780 ꢁ0.20410
2.5770 ꢁ0.20182
7.3513 ꢁ0.20560
ꢁ0.09923
ꢁ0.10255
ꢁ0.10255
ꢁ0.09946
ꢁ0.10475
0.10239
0.10051
0.10155
0.10236
0.10085
compounds have almost similar
DE (D
E ¼ EHOMOeELUMO) values
and (iv) the HOMO and LUMO diagrams (Fig. 1) are lying only on

146
N.M. Parekh et al. / Dyes and Pigments 95 (2012) 142e148
Table 2
Characterization of heterocyclic monoazo dyes 6a-e.
Dye No
Shade of
dyed fiber
lmax
Coupling component
Structure of
coupling
(nm)
components
CH3
6a
Yellow
Yellow
Yellow
432
420
432
p-toluene phenyl
methyl pyrazolone
N
O
N
H3C
Cl
Cl
6b
2,5-dichlorophenyl
methyl pyrazolone
N
O
N
Fig. 2. Visible absorption spectra of reactive dyes 6a-e.
H3C
because of their lower hydrophobicity. The introductions of reac-
tive group like s-triazine ring to the dye molecules have improved
the exhaustion value.
Cl
3.5. Fastness properties
6c
m-chloro phenyl
The light, wash, and rubbing fastness properties were assessed
according to the standard method [30]. As shown in Table 4, the
light fastness of all the dyes is rating 3e5 for polyester which
indicate that the light fastness is moderate to good. Further, wash
fastness and rubbing (dry and wet) fastness of all the dyes rating
3e5 for polyester which showed their fastness is good to
excellent.
N
methyl pyrazolone
O
N
H3C
3.6. Color measurements
Cl
6d
Yellow
430
o-chloro phenyl
methyl pyrazolone
N
The color of a dyeing on polyester fibers are expressed in terms
of CIELAB values (Table 5) and the following CIELAB coordinates
were measured, lightness (L*), chroma (C*), hue angle form
0ꢀe360ꢀ (H), a* value represent the degree of redness (positive)
and greenness (negative) and b* represents the degree of yellow-
ness (positive) and blueness (negative). A reflectance spectropho-
tometer was used for the colorimetric measurements on the dyed
samples. K/S values given by the reflectance spectrophotometer are
calculated at lmax and are directly correlated with the dye
concentration on the substrate according to the Kubelka-Munk
equation [31, 32]: K/S ¼ (1eR) 2/2R, where K, S and R represent
absorbance coefficient, scattering coefficient and reflectance ratio,
respectively.
O
N
H3C
Cl
Cl
6e
Yellow
440
3,4edichloro phenyl
methyl pyrazolone
N
O
N
H3C
Table 3
Dye-bath containing materials.
Heterocyclic monoazo dyes
method [29] and the results are summarized in Table 4. It is
observed that, the percentage dye bath exhaustion of 2% dyeing on
polyester ranges from 62% to 69%. The percentage dye bath fixation
of 2% dyeing for polyester varied from 85% to 87%. The exhaustion
and fixation values of the compounds 6a-e are very good. This is
due to the facts that the diffusion of the dye molecules within the
fabric is rapid, so the rate of diffusion is high. The lower exhaustion
is caused due to the lower substantivity of the dye molecules
Weight of polyester fabric
Amount of dye under study
Dispersing agent -tamol WS
Acetic acid solution (10% w/v)
Total vol. of the solution in dye-bath
pH of dye-bath
2.0 g
40 mg
100 mg
3.5 mL
100 mg
5.0
130 ꢀC
90 min
Dyeing temperature
Time for dyeing

N.M. Parekh et al. / Dyes and Pigments 95 (2012) 142e148
147
Table 4
4. Conclusions
%Exhaustion, %fixation and fastness data of dyes 6a-e.
A series of heterocyclic monoazo dyes containing benzoquino-
line moiety were synthesized by conventional method and applied
to polyester fabrics. The dyes gave shade like yellow or light yellow
color with good fastness properties. The variations in the hues of
the dyed fabrics result from both the nature and position of the
substituents present on the coupler ring. Fairly good exhaustion
and fixation of these dyes indicate that the dyes have good solu-
bility and affinity with the fabric. This type of dye synthesis is
generally convenient and economical for use. Another important
conclusion that the results obtained from the DFT calculations
inferred that the m-chloro substituted compounds 6c and 6e are
energetically more stable than their corresponding o-chloro
substituted compounds 6d and 6b and all the compounds have
Dye No
%Exhaustion
%Fixation
Light
fastness
Wash
fastness
Rubbing
fastness
Dry
P
Wet
P
P
P
P
P
6a
6b
6c
6d
6e
67.00
68.80
63.93
66.12
62.00
85.82
85.75
86.04
85.44
85.48
4
4
3e5
4
3e5
3
4
4e5
5
3e4
4
5
4e5
4
3
5
4
4
3
3e4
Abbreviation: P-Polyester.
Light fastness: (Grading: 1- poor, 2- slight, 3- moderate, 4- fair, 5- good, 6- very
good, 7- excellent).
Wash and Rubbing fastness: (Grading: 1- poor, 2- fair, 3- good, 4- very good, 5-
excellent).
almost similar
DE (D
E ¼ EHOMOeELUMO) values.
The color coordinates (Table 5) indicates that the dyes have
good affinity to polyester fiber. From the data summarized in
Table 5 showed that, for polyester fabric the dyeing obtained
using dye 6a was redder, lighter and brighter than dye 6b; while
dye 6e was redder, darker and duller than dye 6d. The K/S value of
dyes 6a-e for polyester fabric was found to be in the following
order:
Acknowledgements
Authors are thankful to the Director, Sardar Vallabhbhai
National Institute of Technology, Surat for providing research
facility, M/s Mahavir Intermediates and M/s Nutan Dye Chem Surat,
India for providing dyes intermediates, and M/s Atul Ltd, Valsad,
India for providing dyeing facility, fastness properties and colori-
metric data.
6b>6a>6c>6d>6e
Dye 6b having maximum value of color strength (K/S) while
dye 6e having minimum value of color strength (K/S). From the
above data, it is apparent that 6b having highest K/S value on
polyester showed highest affinity for polyester fabric. Further, the
graph of K/S value of all the dyes for polyester fiber is shown in
Fig. 3.
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