Colorimetric studies of heterocyclic monoazo reactive dyes and their dyeing applications on cotton, silk, and wool fibers

Article abstract of DOI:10.1007/s11164-012-1017-8

Heterocyclic quinazolinone-based hot brand monoazo reactive dyes were obtained by diazotization of 3-(4-aminophenyl)-2-phenylquinazolin-4(3H)-one and coupling with a variety of cyanurated coupling components. All the heterocyclic hot brand monoazo reactiv

Full text of DOI:10.1007/s11164-012-1017-8

Res Chem Intermed
DOI 10.1007/s11164-012-1017-8
Colorimetric studies of heterocyclic monoazo reactive
dyes and their dyeing applications on cotton, silk,
and wool fibers
•
Nikhil M. Parekh Kalpana C. Maheria
Received: 7 November 2012 / Accepted: 31 December 2012
Ó Springer Science+Business Media Dordrecht 2013
Abstract Heterocyclic quinazolinone-based hot brand monoazo reactive dyes
were obtained by diazotization of 3-(4-aminophenyl)-2-phenylquinazolin-4(3H)-
one and coupling with a variety of cyanurated coupling components. All the het-
erocyclic hot brand monoazo reactive dyes were characterized by elemental analysis
1
(C, H, N) and by use of spectroscopic techniques (FT-IR, UV–visible, H NMR).
Their performance as reactive dyes was assessed on silk, wool, and cotton fabrics.
The dyes were found to give a variety of color shades with very good depth and
uniformity on the fibers. The fastness of all the dyes on the fibers was moderate to
excellent. Colorimetric data (L*, a*, b*, C*, H*, and K/S) of the synthesized dyes
were also studied in detail.
Keywords 3-(4-Aminophenyl)-2-phenylquinazolin-4(3H)-one Á Exhaustion Á
Fixation Á Dyeing Á Fastness properties Á Colorimetric data
Introduction
Production of reactive dyes with novel structures has recently attracted much
attention, and many novel structures useful in commercial application to silk, wool,
and cotton, and their blends with other fibers, have been obtained. The success of
quinazoline derivatives for production of commercial dyes and pigments, both for
natural and man-made fibers, is well known [1]. Reactive dyes are mainly applied to
cotton fiber to achieve high wash fastness.
In continuation of our previous work on the development of heterocyclic
monoazo compounds, because of their dyeing applications and good fastness
N. M. Parekh Á K. C. Maheria (&)
Department of Applied Chemistry, S. V. National Institute of Technology,
Surat 395007, Gujarat, India
e-mail: maheria@gmail.com
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N. M. Parekh, K. C. Maheria
properties, it seemed appropriate to synthesize a series of hot brand monoazo
reactive dyes [2–4]. Because of their strong interaction with the surfaces of many
synthetic and natural fabrics, several reactive dyes are used for dyeing wool, cotton,
nylon, silk, and modified acrylics [5–16]. It was, therefore, believed to be of interest
to synthesize hot brand monoazo reactive dyes based on 3-(4-aminophenyl)-2-
phenylquinazolin-4(3H)-one by diazotization of 3-(4-aminophenyl)-2-phenylqui-
nazolin-4(3H)-one and coupling with a variety of 4-chloroanilino cyanurated
naphthalene sulfonic acids. Moreover, introduction of a triazine group to the dye
molecule improves the degree of exhaustion and fixation of the dyes studied [17].
These new dyes have been characterized by use of IR and NMR spectroscopy and
on the basis of their dyeing properties on cotton, silk, and wool fabrics. On these
fabrics the dyes had moderate to very good light fastness and good to excellent
washing and rubbing fastness. Colorimetric data (L*, a*, b*, C*, H*, K/S) for the
synthesized dyes were also investigated.
Results and discussion
Chemistry
Synthesis of intermediates and target compounds was accomplished in accordance
with the steps illustrated in Scheme 1. Anthranilic acid is converted into
2-phenylbenzo[d][1,3]oxazine-4-one by reaction with benzoyl chloride in pyridine
as solvent. This was confirmed by the appearance of –C=O group in IR spectrum
which contained a band at 1,662 cm-1. 2-Phenyl-benzo[d][1,3]oxazine-4-one, on
further reaction with p-phenylenediamine, afforded 3-(4-aminophenyl)-2-phenyl-
quinazolin-4(3H)-one in high yield and purity. This was confirmed by the
appearance of an –NH2 group in IR spectrum, which contained two sharp bands
in the region 3,200–3,400 cm-1. This 3-(4-aminophenyl)-2-phenylquinazolin-
4(3H)-one, on diazotization, and followed by coupling with different cyanurated
coupling components yielded quinazolinone-based hot brand monoazo reactive
1
dyes. All the compounds were characterized by IR and H NMR spectroscopy, and
elemental analysis. The 1H NMR spectra of D1–D12 contained signals between 5.20
and 5.86 ppm ascribed to the –NH linkage. The singlet at 4.46 ppm was ascribed to
the –OH group of the naphthalene ring; the other aromatic protons resonated at
6.78–8.90 ppm as a multiplet. The principle benefit of using quinazoline-based
compounds is high yield of the product and fewer steps of the reaction procedure.
Simple work up facilitates preparation of starting material.
Dyeing properties
D1–D12 were applied to silk, wool, and cotton fibers (2 % shade) in accordance with
a literature procedure [18]. Variation in the hues of the dyed fabric results from
alternation of the coupling components. Remarkable uniformity and brightness after
washing indicates good penetration and excellent affinity of these dyes for the
fabric.
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Colorimetric studies of heterocyclic monoazo reactive dyes
NH2
O
N
O
C6H5COCl
pyridine
NH2
p-phenylenediamine
pyridine
N
O
O
C
N
OH
1
2
N
R
O
N
N
Diazotization and coupling reaction
Coupling with DH1-DH12
N
A
Cl
N
N
N
OH NH
Cl
N
OH NH2
pH 7.0
0-5°C
N
N
Cl
+
HO3S
SO3H
Cl
Cl
HO3S
SO3H
c
pH 7.0
b
a
4-chloroaniline
40-50°C
HN
Cl
N
N
OH NH
N
Cl
HO3S
SO3H
B
Scheme 1 Synthesis of quinazolinone-based hot brand monoazo reactive dyes (D1–D12). R = different
cyanurated coupling components as shown in Table 1
Spectral properties of dyes
Absorption maxima (kmax) of D1–D12 were recorded in water; the results are listed
in Table 1. Introduction of electron-donating or electron-attracting groups at a
suitable position in the coupler ring affected the absorption characteristic of the
dyes. D1 had extended conjugation owing to the presence of lone pairs of electrons
on the oxygen atoms of hydroxyl groups. Moreover, the chromophoric group –N=N
is attached ortho to the –OH group, causing resonance effects, which in turn
increases kmax. Comparison of D1 with D2 and D3 shows that D1 has a higher kmax
value because of the presence of additional auxochrome (sulfonic groups). The same
effect is observed when D1 is compared with D3 and D4 [6].
From the results in Table 1, it is clear that the value of kmax depends on the nature
and position of coupling component used. The color change observed for each dye
is because of alternation of electrons and the presence of additional substituents. For
D1 there are more places for alternation of electrons; the presence of –NH and –OH
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N. M. Parekh, K. C. Maheria
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Colorimetric studies of heterocyclic monoazo reactive dyes
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N. M. Parekh, K. C. Maheria
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Colorimetric studies of heterocyclic monoazo reactive dyes
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N. M. Parekh, K. C. Maheria
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Colorimetric studies of heterocyclic monoazo reactive dyes
Fig. 1 Absorption maxima (kmax nm) of D1–D12
groups also contributes to the increase of kmax (546 nm). For D2, D3, D4, D7, and
D9–D12 the effect is slightly lower because of fewer electrons and, thus, kmax values
for all these dyes are lower than for D1. For D5, D6, and D8, the substituents are
same as for D1 but alternation of electrons is rapid because of the vicinity of the
–NH and –SO3Na groups; therefore, neutralization of electrons takes place rapidly
[6]. The dyes’ absorption maxima are plotted in Fig. 1.
The magnitude of bathochromic shift depends on the nature of substituents at the
terminal amino group [2]. Such bathochromic shifts have been observed for J-acid,
N-methyl-J-acid, and N-phenyl-J-acid. D2 has kmax at 480 nm and D3 has kmax at
492 nm. Thus, there is a bathochromic shift of 12 nm in the kmax value of D3
because of the presence of –CH3. Similarly, D4 has kmax 502 nm; thus, there is a
bathochromic shift of 10 nm in the kmax of D3 because of the presence of the –C6H5
ring, which increases kmax by extending the conjugation by resonance. Combina-
tions of chromophores and auxochromes behave as new chromospheres, leading to
extended conjugation involving the lone pair of electrons on the nitrogen atom,
resulting in increased kmax values [6].
Exhaustion and fixation study
Percentage exhaustion and fixation data for D1–D12 were determined by known
methods [19]; again the results are summarized in Table 1. Percentage exhaustion
for 2 % dyeing on silk ranges from 66 to 80 %; maximum exhaustion is 79.40 % for
D7 and minimum exhaustion is 66.45 % for D10. For wool, percentage exhaustion
ranges from 67 to 78 %; maximum exhaustion is 78.00 % for D7 and minimum
exhaustion is 67.65 % for D11. For cotton, percentage exhaustion ranges from 62 to
77 %; maximum exhaustion is 76.25 % for D8 and minimum exhaustion is 62.00 %
for D5.
Percentage fixation for 2 % dyeing on silk ranges from 83 to 92 %; maximum
fixation is 91.05 % for D10 and minimum fixation is 83.16 % for D11. For wool,
percentage fixation ranges from 84 to 92 %; maximum fixation is 91.23 % for D8
and minimum fixation is 84.25 % for D9. For cotton, percentage fixation ranges
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N. M. Parekh, K. C. Maheria
Fig. 2 K/S value of synthesized dyes (D1–D12
)
from 81 to 88 %; maximum fixation is 87.62 % for D7 and minimum fixation is
81.86 % for D12. The data are summarized in Table 1, from which it is apparent
exhaustion and fixation values are very good. This is because diffusion of the dye
molecule within the fabric is rapid.
Fastness properties
The light, wash, and rubbing fastness properties of D1–D12 were determined by a
known method [20]; the results are summarized in Table 2. It is apparent from the
table that light fastness of all the dyes was in the range 3–5 for all three fabrics,
which shows light fastness is moderate to good. The wash fastness for all the dyes
was in the range 3–5 for all three fabrics, which shows wash fastness is good to
excellent. The rubbing (dry and wet) fastness of all the dyes was in the range 3–5 for
all three fabrics which shows rubbing fastness is good to excellent.
Colorimetric data for D1–D12
The color of a dye on silk, wool, and cotton is expressed in terms of CIE lab values
(Table 3). The CIE lab coordinates measured were: Lightness (L*), Chroma (C*),
hue angle from 08 to 3608 (H), a* value representing the degree of redness (positive)
and greenness (negative), and b* representing the degree of yellowness (positive)
and blueness (negative). A reflectance spectrophotometer was used for colorimetric
measurements on dyed samples. K/S values given by the reflectance spectropho-
tometer are calculated at kmax and are directly correlated with the dye concentration
on the substrate according to the Kubelka–Munk equation [21], K/S = (1-R)2/2R,
where K is absorbance coefficient, S is scattering coefficient, and R is reflectance
ratio.
The color coordinates (Table 3) indicate the dyes have high affinity for silk,
wool, and cotton. From the results listed in Table 3 it is apparent that, for silk, the
dyeing achieved by use of dye D1 was redder (lower a* value), brighter (lower C*),
and darker (higher L* value) than that achieved by use of dye D2, and the dyeing
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Colorimetric studies of heterocyclic monoazo reactive dyes
Table 2 Fastness properties of heterocyclic monoazo reactive dyes
Dye
Light fastness
Wash fastness
Rubbing fastness
Dry
Wet
S
S
W
C
S
W
C
S
W
C
W
C
D1
D2
D3
D4
D5
D6
D7
D8
D9
D10
D11
D12
3–4
4
4
5
4–5
3–4
4
3–4
4
5
5
4–5
4
4
5
4–5
4
4
5
4
4
4–5
3
4–5
4
4
4–5
3
4–5
5
4–5
3–4
5–6
5–6
5
5–6
4–5
5
4–5
3
4–5
4
3–4
5
3–4
4
3
4–5
5
3–4
4
5
4–5
3–4
4
3–4
3–4
4
3–4
4
3–4
4
3–4
3–4
4
4–5
5
3–4
4–5
4
4–5
4
5–6
5
4–5
3
5
5
4–5
4
4–5
3
4–5
5
3–4
3–4
4–5
4–5
4–5
4
4–5
4
5
5
4–5
5
4–5
4
3–4
4
4–5
4
4
4–5
4
4–5
4–5
4–5
4
4–5
4–5
4–5
4
3–4
3–4
3–4
4
4
3–4
3–4
3–4
4
4
5
4
4
4
4
4
4
5
4
4
4
4
4
4
5
5
4–5
3–4
3–4
3–4
3–4
Light fastness: 1 poor; 2 slight; 3 moderate; 4 fair; 5 good; 6 very good
Wash and rubbing fastness: 1 poor; 2 fair; 3 good; 4 very good; 5 excellent
S silk, W wool, C cotton
achieved by use of dye D3 was greener, duller, and lighter than that achieved by use
of dye D1. Dyeing achieved by use of dye D6 was redder, brighter, and darker than
that achieved by use of dye D5. Dyeing achieved by use of dye D10 was redder,
brighter, and darker than that achieved by use of dye D9, and dyeing achieved by use
of dye D12 was greener, duller, and lighter than that achieved by use of dye D11. Dye
D6 had the highest value of color strength (K/S) of 0.72. The K/S value for silk was
found to be in the order:
D6 [ D7 [ D4 [ D12 [ D8 [ D10 [ D9 [ D1 [ D5 [ D11 [ D2 [ D3
From the results in Table 3 it is apparent that, for wool, dyeing achieved by use
of dye D1 was redder, duller, and darker than that achieved by use of dye D2
whereas dyeing achieved by use of dye D3 was greener, brighter, and lighter than
that achieved by use of dye D1. Dyeing achieved by use of dye D6 was redder,
brighter, and darker than that achieved by use of dye D5. Dyeing achieved by use of
dye D10 was greener, duller, and lighter than that achieved by use of dye D9. Dyeing
achieved by use of dye D12 was greener, duller, and lighter than that achieved by use
of dye D11. Dye D6 had the highest value of color strength (K/S) of 4.16. The K/S
value for wool was found to be in the order:
D6 [ D1 [ D7 [ D8 [ D5 [ D2 [ D4 [ D8 [ D12 [ D3 [ D9 [ D11
From the results listed in Table 3 it is apparent that, for cotton, dyeing achieved
by use of dye D1 was greener, duller, and lighter than that achieved by use of dye D2
whereas dyeing achieved by use of dye D3 was redder, brighter, and lighter than that
achieved by use of dye D1. Dyeing achieved by use of dye D6 was redder, brighter,
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N. M. Parekh, K. C. Maheria
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Colorimetric studies of heterocyclic monoazo reactive dyes
and darker than that achieved by use of dye D5. Dyeing achieved by use of dye D10
was redder, brighter and darker than that achieved by use of dye D9, and dyeing
achieved by use of dye D12 was greener, duller, and lighter than that achieved by use
of dye D11. Dye D2 had the highest value of color strength (K/S) of 4.88. The K/S
value for cotton was found to be in the order:
D2 [ D1 [ D7 [ D6 [ D8 [ D3 [ D5 [ D4 [ D10 [ D11 [ D12 [ D9
The dyes’ K/S values are plotted in Fig. 2.
Conclusion
In the work discussed in this paper we performed detailed studies on quinazolinone
based heterocyclic monoazo reactive dyes and their applications. Purple, pink,
brown, and yellow shades were obtained on fibers. Characterization of the
synthesized dyes was in agreement with expected values. The excellent exhaustion
and fixation of these dyes indicates they have good solubility and good affinity for
the fabric. Dyes D7 and D8 have good light fastness properties on silk whereas D5
and D6 have very good light fastness properties on wool and D3 and D6 have very
good light fastness properties on cotton. The light fastness of all the dyes was
moderate to very good. Dyes D1, D4, D5, D6, and D12 have excellent wash fastness
properties on silk whereas D3, D7, D9, D10, and D11 have excellent wash fastness
properties on wool. D1, D3, and D8 have excellent wash fastness properties on
cotton. Dyes D1, D2, D6, and D7 (dry) and D1, D5, D9, D10, and D11 (wet) have
excellent rubbing fastness properties on silk whereas D1, D4, D5, D6, D7, and D8
(dry) and D1, D4 and D7 (wet) have excellent rubbing fastness properties on wool.
Dyes, D2, D4, and D6 (dry) and D2, D7, and D8 (wet) have excellent rubbing fastness
properties on cotton. The wash and rubbing fastness studies of all the dyes show that
wash and rubbing fastness are good to excellent. Dyes D6, D6, and D2 have the
highest value of color strength for silk, wool, and cotton, respectively, which
indicates that dyes D6, D6, and D2 have good affinity for silk, wool, and cotton,
respectively. In this case, cotton, for which color strength is highest, has a higher
K/S value than wool and silk because of the high substantivity of the dyes for
cotton. The color coordinates indicate the dyes have good affinity for silk, wool, and
cotton.
Experimental
Materials and methods
All chemicals were of analytical grade and used as received. All melting points were
determined on a PMP-DM scientific melting point apparatus and are uncorrected.
The purity of all dyes were determined by thin-layer chromatography (TLC) [22] on
silica gel-G coated Al foil plates (0.5 mm thickness; Merck). Infrared spectra were
1
recorded on a Shimadzu FT-IR 8400S model using KBr pellets. H NMR spectra
123

N. M. Parekh, K. C. Maheria
were acquired on a Varian 400 MHz model spectrophotometer using DMSO as
solvent and TMS as internal reference (chemical shifts in d, ppm). Elemental
analysis of C, H, and N was performed with a Carlo Erba 1108 instrument. Light
fastness was assessed in accordance with BS 1006-1978 [23]. The rubbing fastness
test was performed with a crockmeter (Atlas) in accordance with AATCC-1961 [24]
and the wash fastness test was in accordance with IS 765-1979 (Indian standard
ISO, 1979) [25]. Colorimetric data (L*, a*, b*, C*, H*, K/S) were recorded with a
Gretag Macbeth CE: 7000 reflectance spectrophotometer.
Synthesis of 2-phenylbenzo[d]1,3]oxazine-4-one
2-Phenylbenzo[d][1,3]oxazine-4-one was prepared in accordance with a reported
procedure [26].
Synthesis of 3-(4-Aminophenyl)-2-phenyl-3H-quinazolin-4-one
3-(4-Aminophenyl)-2-phenyl-3H-quinazolin-4-one was prepared in accordance with
a reported procedure [27, 28].
Diazotization and coupling procedure
Concentrated HCl was added to a well stirred suspension of 3-(4-aminophenyl)-2-
phenylquinazolin-4(3H)-one (0.0048 mol) in water and the mixture was heated to
70 °C and maintained at that temperature until a clear solution was obtained. After
cooling to 0–5 °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 approximately 1 h. Excess of
nitrous acid was tested by use of starch–iodide paper and was removed by adding
required amount of sulfamic acid solution (10 %). The clear diazonium salt solution
(A) thus obtained was used immediately in the coupling reaction.
Cyanuric chloride (0.01 mol) was stirred in acetone at a temperature below 5 °C
for 1 h. A neutral solution of H-acid (0.01 mol) in an aqueous sodium carbonate
solution (10 % w/v) was then added in small amounts in approximately 1 h. The pH
was maintained neutral by simultaneous addition of sodium carbonate solution (1 %
w/v). The reaction mass was stirred at 0–5 °C for a further 4 h when a clear solution
was obtained. The resulting solution was used for condensation reaction with
4-chloroaniline. The temperature of an ice-cooled, well stirred solution of
cyanurated H-acid was gradually increased to 45 °C for 30 min. To this cyanurated
H-acid, 4-chloroaniline (1.73 g, 0.01 mol) was added dropwise at the same
temperature, during a period of 30 min, maintaining the neutral pH by simultaneous
addition of sodium bicarbonate (1 % w/v). After addition was complete, stirring was
continued for a further 3 h. The 4-chloroanilino cyanurated H-acid solution (B) thus
obtained was subsequently used for further coupling reaction.
To an ice-cold and well stirred solution of 4-chloroanilino cyanurated H-acid
(d) (0.01 mol) a freshly prepared diazo solution (0.005 mol) was added dropwise
over a period of 10–15 min. The pH was maintained at 7.5–8.5 by simultaneous
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Colorimetric studies of heterocyclic monoazo reactive dyes
addition of sodium carbonate solution (10 % w/v). During coupling a purple
solution was formed. Stirring was continued for a further 3–4 h, maintaining the
temperature below 5 °C. The reaction mixture was heated to 60 °C and sodium
chloride (12 g) was added until the purple colored dye was precipitated. The
mixture was stirred for approximately 1 h, filtered, and the residue was washed with
a small amount of sodium chloride solution (5 % w/v). The solid was then dried at
80–90 °C and extracted with DMF. The dye was precipitated by diluting the DMF
extract with excess chloroform. A violet dye (D1) was then isolated by filtration,
washed with chloroform, and dried at 60 °C. By following this procedure, the other
reactive dyes D2–D12 were synthesized by use of the 4-chloro anilino cyanurated
coupling components J-acid, NMJ-acid, NPJ-acid, Chicago acid, Koch acid,
Bronner acid, K-acid, Tobias acid, Sulfo Tobias acid, Peri acid, and Metanilic acid
(Table 1).
Dye D1 (4-chloro anilino cyanurated H acid) Yield: 79 %; m.p. [300 °C; IR
(KBr) cm-1: 3,474–3,242 (O–H and NH), 3,076 (C–H), 1,650 (C=O), 1,558, 1,309,
1
848 (C–N), 1,629 (N=N), 1,197, 1,053 (S=O, asym. and sym.), 754 (C–Cl); H
NMR (400 MHz, DMSO-d6): d = 4.46 (1H, s, –OH), 5.80 (1H, s, –NH), 6.30 (1H,
s, –NH), 7.18–8.41 (20H, m, Ar–H); Anal. Calcd. For C39H23Cl2N9Na2O8S2: C,
50.55; H, 2.50; N, 13.60. Found: C, 50.49; H, 2.44; N, 13.56.
Dye D2 (4-chloro anilino cyanurated J acid) Yield 82 %; m.p. [300 °C; IR (KBr)
cm-1: 3,470–3,244 (O–H and NH), 3,078 (C–H), 1,650 (C=O), 1,560, 1,308, 844
1
(C–N), 1,632 (N=N), 1,189, 1,056 (S=O, asym. and sym.), 752 (C–Cl); H NMR
(400 MHz, DMSO-d6): d = 4.48 (1H, s, –OH), 5.80 (2H, s, –NH), 6.78–8.41 (21H,
m, Ar–H); Anal. Calcd. for C39H24Cl2N9NaO5S: C, 56.80; H, 2.93; N, 15.29.
Found: C, 56.77; H, 3.00; N, 15.36.
Dye D3 (4-chloro anilino cyanurated NMJ acid) Yield: 74 %; m.p. [300 °C; IR
(KBr) cm-1: 3,470–3,258 (O–H and NH), 3,076 (C–H), 1,652 (C=O), 1,556, 1,309,
1
842 (C–N), 1,630 (N=N), 1,197, 1,054 (S=O, asym. and sym.), 759 (C–Cl); H
NMR (400 MHz, DMSO-d6): d = 3.48 (1H, s –CH3), 4.46 (1H, s, –OH), 5.80 (1H,
s, –NH), 6.78–8.41 (21H, m, Ar–H); Anal. Calcd. For C40H26Cl2N9NaO5S: C,
57.29; H, 3.12; N, 15.03. Found: C, 57.22; H, 3.19; N, 15.10.
Dye D4 (4-chloro anilino cyanurated NPJ acid) Yield: 81 %; m.p. [300 °C; IR
(KBr) cm-1: 3,480–3,252 (O–H and NH), 3,066 (C–H), 1,658 (C=O), 1,564, 1,307,
1
848 (C–N), 1,634 (N=N), 1,198, 1,054 (S=O, asym. and sym.), 756 (C–Cl); H
NMR (400 MHz, DMSO-d6): d = 4.46 (1H, s, –OH), 5.84 (1H, s, –NH), 6.78–8.41
(26H, m, Ar–H); Anal. Calcd. for C45H28Cl2N9NaO5S: C, 60.01; H, 3.13; N, 14.00.
Found: C, 60.10; H, 3.19; N, 14.07.
Dye D5 (4-chloro anilino cyanurated Chicago acid) Yield: 80 %; m.p. [300 °C;
IR (KBr) cm-1: 3,474–3,242 (O–H and NH), 3,076 (C–H), 1,650 (C=O), 1,558,
1,309, 848 (C–N), 1,629 (N=N), 1,197, 1,053 (S=O, asym. and sym.), 754 (C–Cl);
123

N. M. Parekh, K. C. Maheria
1H NMR (400 MHz, DMSO-d6): d = 4.46 (1H, s, –OH), 5.80 (1H, s, –NH), 6.30
(1H, s, –NH), 7.18–8.41 (20H, m, Ar–H); Anal. Calcd. for C39H23Cl2N9Na2O8S2: C,
50.55; H, 2.50; N, 13.60. Found: C, 50.52; H, 2.44; N, 13.49.
Dye D6 (4-chloro anilino cyanurated koch acid) Yield: 89 %; m.p. [300 °C; IR
(KBr) cm-1: 3,464–3,272 (O–H and NH), 3,074 (C–H), 1,658 (C=O), 1,562, 1,305,
1
842 (C–N), 1,628 (N=N), 1,197, 1,053 (S=O, asym. and sym.), 768 (C–Cl); H
NMR (400 MHz, DMSO-d6): d = 5.80 (1H, s, –NH), 6.30 (1H, s, –NH), 7.18–8.84
(20H, m, Ar–H); Anal. Calcd. for C39H22Cl2N9Na3O10S3: C, 46.25; H, 2.19; N,
12.45. Found: C, 46.18; H, 2.24; N, 12.39.
Dye D7 (4-chloro anilino cyanurated bronner acid) Yield: 89 %; m.p. [300 °C;
IR (KBr) cm-1: 3,480–3,254 (O–H and NH), 3,076 (C–H), 1,660 (C=O), 1,558,
1,310, 848 (C–N), 1,629 (N=N), 1,197, 1,056 (S=O, asym. and sym.), 752 (C–Cl);
1H NMR (400 MHz, DMSO-d6): d = 5.80 (2H, s, –NH), 6.78–8.41 (22H, m,
Ar–H); Anal. Calcd. for C39H24Cl2N9NaO4S: C, 57.93; H, 2.99; N, 15.59. Found: C,
57.84; H, 2.88; N, 15.62.
Dye D8 (4-chloro anilino cyanurated K acid) Yield: 78 %; m.p. [300 °C; IR
(KBr) cm-1: 3,474–3,242 (O–H and NH), 3,076 (C–H), 1,650 (C=O), 1,558, 1,309,
1
848 (C–N), 1,629 (N=N), 1,197, 1,053 (S=O, asym. and sym.), 754 (C–Cl); H
NMR (400 MHz, DMSO-d6): d = 5.80 (2H, s, –NH), 6.78–8.41 (22H, m, Ar–H);
Anal. Calcd. for C39H24Cl2N9NaO4S: C, 57.93; H, 2.99; N, 15.59. Found: C, 57.88;
H, 2.87; N, 15.64.
Dye D9 (4-chloro anilino cyanurated Tobias acid) Yield: 79 %; m.p. [300 °C; IR
(KBr) cm-1: 3,468–3,242 (O–H and NH), 3,079 (C–H), 1,666 (C=O), 1,560, 1,310,
1
848 (C–N), 1,629 (N=N), 1,197, 1,056 (S=O, asym. and sym.), 754 (C–Cl); H
NMR (400 MHz, DMSO-d6): d = 5.22 (1H, s, –NH), 5.72 (1H, s, –NH), 7.18–8.41
(23H, m, Ar–H); Anal. Calcd. for C39H25Cl2N9O: C, 66.29; H, 3.57; N, 17.84.
Found: C, 66.22; H, 3.54; N, 17.90.
Dye D10 (4-chloro anilino cyanurated sulfo Tobias acid) Yield: 80 %;
m.p. [300 °C; IR (KBr) cm-1: 3,476–3,242 (O–H and NH), 3,085 (C–H), 1,650
(C=O), 1,558, 1,309, 846 (C–N), 1,634 (N=N), 1,197, 1,053 (S=O, asym. and sym.),
1
752 (C–Cl); H NMR (400 MHz, DMSO-d6): d = 5.80 (2H, s, –NH), 7.18–8.50
(22H, m, Ar–H); Anal. Calcd. for C39H24Cl2N9NaO4S: C, 57.93; H, 2.99; N, 15.59.
Found: C, 57.88; H, 2.85; N, 15.64.
Dye D11 (4-chloro anilino cyanurated peri acid) Yield: 85 %; m.p. [300 °C; IR
(KBr) cm-1: 3,476–3,254 (O–H and NH), 3,070 (C–H), 1,662 (C=O), 1,560, 1,309,
1
850 (C–N), 1,629 (N=N), 1,197, 1,053 (S=O, asym. and sym.), 760 (C–Cl); H
NMR (400 MHz, DMSO-d6): d = 4.46 (1H, s, –OH), 5.80 (2H, s, –NH), 7.15–8.41
(21H, m, Ar–H); Anal. Calcd. for C39H24Cl2N9NaO4S: C, 57.93; H,2.99; N, 15.59.
Found: C, 57.82; H, 3.10; N, 15.46.
123

Colorimetric studies of heterocyclic monoazo reactive dyes
Dye D12 (4-chloro anilino cyanurated metanilic acid) Yield: 89 %; m.p. [300 °C;
IR (KBr) cm-1: 3,472–3,268 (O–H and NH), 3,082 (C–H), 1,658 (C=O), 1,566,
1,314, 848 (C–N), 1,638 (N=N), 1,197, 1,056 (S=O, asym. and sym.), 752 (C–Cl);
1H NMR (400 MHz, DMSO-d6): d = 5.80 (2H, s, –NH), 7.18–8.50 (20H, m, Ar–
H); Anal. Calcd. for C35H22Cl2N9NaO4S: C, 55.42; H, 2.92; N, 16.62. Found: C,
55.12; H, 2.84; N, 16.50.
Acknowledgments The authors are grateful to M/s Mahavir Intermediates, Surat, India, for providing
dye intermediates, and to M/s Atul Ltd, Valsad, India, for providing dyeing facility, fastness data, and
colorimetric data.
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