Novel 2-phenyl-3-{4'-[N-(4"-aminophenyl)carbamoyl]-phenyl}- quinazoline-4(3H)one-6-sulphonic acid based mono azo reactive dyes

Article abstract of DOI:10.2298/JSC090225021P

A series of new heterocyclic mono azo reactive dyes 7a-m were prepared by diazotization of 2-phenyl-3-{4'-[N-(4"-aminophenyl)carbamoyl]-phenyl}- quinazoline-4(3H)-one-6-sulphonic acid (3) and coupling with various cyanurated coupling components 6a-m and their dyeing performance on silk, wool and cotton fibres was assessed. These dyes were found to give a variety of colour shades with very good depth and levelness on the fibres. All the compounds were identified by conventional method (IR and 1H-NMR) and elemental analyses. The percentage dye bath exhaustion on different fibres was reasonably good and acceptable. The dyed fibre showed moderate to very good fastness to light, washing and rubbing.

Full text of DOI:10.2298/JSC090225021P

J. Serb. Chem. Soc. 76 (2) 177–188 (2011)
UDC 547.856+542.913:667.281.1
JSCS–4110
Original scientific paper
Novel 2-phenyl-3-{4’-[N-(4”-aminophenyl)carbamoyl]-phenyl}-
-quinazoline-4(3H)one-6-sulphonic acid
based mono azo reactive dyes
*
DIVYESH R. PATEL and KESHAV C. PATEL
Department of Chemistry, Veer Narmad South Gujarat University,
Surat 395 007, Gujarat, India
(Received 25 February 2009, revised 23 September 2010)
Abstract: A series of new heterocyclic mono azo reactive dyes 7a–m were pre-
pared by diazotization of 2-phenyl-3-{4’-[N-(4”-aminophenyl)carbamoyl]-phe-
nyl}-quinazoline-4(3H)-one-6-sulphonic acid (3) and coupling with various cy-
anurated coupling components 6a–m and their dyeing performance on silk,
wool and cotton fibres was assessed. These dyes were found to give a variety
of colour shades with very good depth and levelness on the fibres. All the com-
pounds were identified by conventional method (IR and 1H-NMR) and elemen-
tal analyses. The percentage dye bath exhaustion on different fibres was rea-
sonably good and acceptable. The dyed fibre showed moderate to very good
fastness to light, washing and rubbing.
Keyword: quinazoline-4(3H)-one; mono azo reactive dyes; dyeing; fastness
properties.
INTRODUCTION
In recent years, the development of new structures of reactive dyes has been
a subject of interest and many novel structures useful in commercial application
to silk, wool and cotton, as well as their blends with other fibres, have been dis-
covered. The utility of quinazoline derivatives for the production of some com-
1,2
mercial dyes and pigment, both for natural and man-made fibre, is known.
Intensive efforts have been made in the investigation of mono azo dyes con-
3
taining a heterocyclic moiety, such as amino quinazoline, as the diazo compo-
nent owing to the marked bathochromic effect of such groups compared to the
4
corresponding benzoid compound.
In view of encouraging reports about the technical applications of the dyes
5,6
based on the 4-oxoquinazoline system, it was considered of interest to under-
*Corresponding author. E-mail: divyeshpatel_905@yahoo.com
doi: 10.2298/JSC090225021P
177
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178
PATEL and PATEL
take the synthesis and study of the dyeing properties of azo dyes based on
2-styryl-3-(2’-chlorophenyl)-6-amino-4-oxoquinazoline.
In the present investigation, the synthetic pathway to 2-phenyl-3-{4’-[N-(4”-
-aminophenyl)carbamoyl]-phenyl}-quinazoline-4(3H)-one-6-sulphonic acid (3)
from a readily available starting material, i.e., 5-sulpho anthranilic acid, was exa-
mined. The effect of the presence of the –SO Na and –CONH–groups in the
3
quinazoline-based structure of the reactive dyes was studied in relation to the
colour and dyeing properties of the heterocyclic reactive dyes 7a–m.
The general structure of the reactive dyes 7a–m is:
O
O
NaO3S
N
C
NH
N
N
R
N
where R = various 4-nitroanilino cyanurated coupling components (6a–m).
RESULTS AND DISCUSSION
Chemistry
The new series of reactive dyes 7a–m containing the quinazolinone and
benzanilide moieties were synthesized by condensation of benzoxazine derivative
1 and the diaminobenzanilide moiety 3. This condensed product on diazotization
and coupling with various 4-nitroanililno cyanurated coupling components 6a–m
produced a novel series of heterocyclic reactive dyes. These series of dyes have
found wide application in the dyeing of wool, silk and cotton fibres. The pre-
sence of quinazolinone structure in the dye molecule results in excellent dyeing
properties, including low sublimation and high thermal stability.
Characterization of the isolated intermediates and dyes
2-Phenyl-4-oxo-3,1-benzoxazine-6-suphonic acid (1). Yield 85 %; m.p. 107
°C; Anal. Calcd. for C H O NS: C, 55.44; H, 2.99; N, 4.62 %. Found: C, 55.40;
14
9 5
–1
H, 2.95; N, 4.60 %. IR (KBr, cm ) 1750 (C=O stretching of benzoxazine), 1380
(C–N stretching of benzoxazine), 1042 (S=O stretching of sulphonic acid group).
1
H NMR (300 MHz, DMSO-d , δ / ppm): 11.2 (1H, s, SO H), 6.72–8.05 (8H, m,
6
3
Ar–H).
4,4’-Diaminobenzanilide (2). Yield 75 %; m.p. 205 °C; Anal. Calcd. for
C H ON : C, 68.70; H, 5.77; N, 18.49 %. Found: C, 68.65; H, 5.72; N, 18.44 %.
13 13
3
–1
IR (KBr, cm ) 1695 (C=O stretching of amide group), 3325, 2985 (N–H stretch-
ing (asym. and sym.) of amide group). H-NMR (300 MHz, DMSO-d , δ / ppm):
1
6
8.62 (1H, s, –CONH), 5.74 (4H, s, 2 –NH ), 6.72–8.25 (8H, m, Ar–H).
2
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SYNTHESIS OF REACTIVE DYES BASED ON QUINAZOLINONE
179
2-Phenyl-3{4’-[N-(4”-aminophenyl)carbamoyl]-phenyl}-quinazoline-4-(3H)-
-one-6-sulphonic acid (3). Yield 75 %, m. p. 193 °C. Anal. Calcd. for
C H O N S : C, 63.27; H, 3.93; N, 10.93 %. Found: C, 63.92; H, 3.88; N,
27 20
5 4 1
–1
10.90 %. IR (KBr, cm ): 3515 (N–H stretching of primary –NH group), 1675
2
(C=O stretching of quinazolinone), 1395 (C–N stretching of quinazoline struc-
ture), 1040 (S=O stretching of –SO H group), 3415, 2995 (asym. and sym. N–H
3
1
stretching of amide). H-NMR (300 MHz, DMSO-d , δ / ppm) 5.78 (2H, s,
6
–NH ), 8.64 (1H, s, –CONH), 11.6 (1H, s, –SO H), 6.78–8.15 (16H, m, Ar–H).
2
3
Sodium 5-(4-chloro-6-(4-nitrophenylamino)-1,3,5-triazin-2-ylamino)-4-hyd-
roxy-3-((4-(imino(4-(4-oxo-2-phenyl-6-sulfonatoquinazolin-3(4H)-yl)phenyl)me-
thoxy)phenyl)diazenyl)naphthalene-2,7-disulfonate (7a). Yield: 85 %; Anal. Calcd.
for C H O N ClS Na : C, 47.69; H, 2.35; N, 13.30. Found: C, 47.63; H, 2.31;
46 27 14 11
3
3
–1
N, 13.28 %. IR (KBr, cm ): 3360–3680 (O–H and N–H stretching of –OH and
–NH groups), 1660 (C=O stretching of quinazoline ring), 1430 (N=N stretching
2
of azo group), 1382 (C–N), 1360, 1112, 1049 (S=O stretching of sulphonates),
1501, 1308 (N=O asym. and sym. stretching of nitro group), 762 (C–Cl stretch-
1
ing of chloro group). H-NMR (300 MHz, DMSO-d , δ / ppm): 4.32 (1H, s,
6
–OH), 4.16 (2H, s, 2 –NH), 8.65 (1H, s, –CONH), 6.82–7.95 (23H, m, Ar–H).
Sodium 3-(4-((4-((7-(4-chloro-6-(4-nitrophenylamino)-1,3,5-triazin-2-ylami-
no)-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl)phenoxy)(imino)methyl)phe-
nyl)-4-oxo-2-phenyl-3,4-dihydroquinazoline-6-sulfonate (7b). Yield: 83 %; Anal.
Calcd. for C H O N ClS Na : C, 52.30; H, 2.67; N, 14.58 %. Found: C, 52.26;
46 28 11 11
2
2
–1
H, 2.63; N, 14.55 %, IR (KBr, cm ): 3360–3680 (O–H and N–H stretching of
–OH and –NH groups), 1662 (C=O stretching of quinazoline ring), 1425 (N=N
2
stretching of azo group), 1380 (C–N), 1360, 1115, 1055 (S=O stretching of sul-
phonates), 1510, 1310 (N=O asym. and sym. stretching of nitro group), 765 (C–Cl
1
stretching of chloro group). H-NMR (300 MHz, DMSO-d , δ / ppm): 4.35 (1H,
6
s, –OH), 4.12 (2H, s, 2 –NH), 8.62 (1H, s, –CONH), 6.81–7.90 (24H, m, Ar–H).
Sodium 3-(4-((4-((6-(4-chloro-6-(4-nitrophenylamino)-1,3,5-triazin-2-ylami-
no)-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl)phenoxy)(imino)methyl)phe-
nyl)-4-oxo-2-phenyl-3,4-dihydroquinazoline-6-sulfonate (7c). Yield: 78 %; Anal.
Calcd. For C H O N ClS Na : C, 52.30; H, 2.67; N, 14.58 %. Found: C,
46 28 11 11
2
2
–1
52.25; H, 2.62; N, 14.56 5. IR (KBr, cm ): 3350–3700 (O–H and N–H stretching
of –OH and –NH groups), 1656 (C=O stretching of quinazoline ring), 1420
2
(N=N stretching of azo group), 1385 (C–N), 1340, 1110, 1045 (S=O stretching of
sulphonates), 1505, 1315 (N=O asym. and sym. stretching of nitro group), 760
1
(C–Cl stretching of chloro group). H-NMR (300 MHz, DMSO-d , δ / ppm):
6
4.38 (1H, s, –OH), 4.18 (2H, s, 2 –NH), 8.66 (1H, s, –CONH), 6.85–7.92 (24H,
m, Ar–H).
Sodium 3-(4-((4-((6-((4-chloro-6-(4-nitrophenylamino)-1,3,5-triazin-2-yl)-
(methyl)amino)-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl)phenoxy)(imi-
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PATEL and PATEL
no)methyl)phenyl)-4-oxo-2-phenyl-3,4-dihydroquinazoline-6-sulfonate (7d). Yield:
82 %; Anal. Calcd. for C H O N ClS Na : C, 52.74; H, 2.83; N, 14.39 %.
47 30 11 11
2
2
–1
Found: C, 52.70; H, 2.80; N, 14.36 %. IR (KBr, cm ): 3355–3690 (O–H and N–H
stretching of –OH and –NH groups), 1670 (C=O stretching of quinazoline ring),
2
1435 (N=N stretching of azo group), 1380 (C–N), 1365, 1115, 1045 (S=O stre-
tching of sulphonates), 1510, 1310 (N=O asym. and sym. stretching of nitro
1
group), 766 (C–Cl stretching of chloro group). H-NMR (300 MHz, DMSO-d ,
6
δ / ppm): 4.31 (1H, s, –OH), 4.20 (1H, s, –NH), 8.57 (1H, s, –CONH), 8.62 (1H,
s, –CONH), 6.86–7.92 (24H, m, Ar–H).
Sodium 3-(4-((4-((6-((4-chloro-6-(4-nitrophenylamino)-1,3,5-triazin-2-yl)-
(phenyl)amino)-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl)phenoxy)(imi-
no)methyl)phenyl)-4-oxo-2-phenyl-3,4-dihydroquinazoline-6-sulfonate (7e). Yield:
84 %; Anal. Calcd. for C H O N ClS Na : C, 55.15; H, 2.85; N, 13.60 %.
52 32 11 11
2
2
–1
Found: C, 55.10; H, 2.81; N, 13.57 %. IR (KBr, cm ): 3360–3700 (O–H and N–H
stretching of –OH and –NH groups), 1665 (C=O stretching of quinazoline ring),
2
1430 (N=N stretching of azo group), 1385 (C–N), 1370, 1110, 1040 (S=O stretch-
ing of sulphonates), 1505, 1310 (N=O asym. and sym. stretching of nitro group), 765
1
(C–Cl stretching of chloro group). H-NMR (300 MHz, DMSO-d , δ / ppm): 4.32
6
(1H, s, –OH), 4.15 (H, s, –NH), 8.68 (1H, s, –CONH), 6.78–8.05 (29H, m, Ar–H).
Sodium 4-(4-chloro-6-(4-nitrophenylamino)-1,3,5-triazin-2-ylamino)-5-hyd-
roxy-6-((4-(imino(4-(4-oxo-2-phenyl-6-sulfonatoquinazolin-3(4H)-yl)phenyl)me-
thoxy)phenyl)diazenyl)naphthalene-1,3-disulfonate (7f). Yield: 77 %; Anal. Calcd.
for C H O N ClS Na : C, 47.69; H, 2.37; N, 13.30 %. Found: C, 47.63; H,
46 27 14 11
3
3
–1
2.33; N, 13.28 %. IR (KBr, cm ): 3345–3690 (O–H and N–H stretching of –OH
and –NH groups), 1670 (C=O stretching of quinazoline ring), 1425 (N=N stre-
2
tching of azo group), 1365 (C–N), 1375, 1105, 1042 (S=O stretching of sulpho-
nates), 1510, 1315 (N=O asym. and sym. stretching of nitro group), 765 (C–Cl
1
stretching of chloro group). H-NMR (300 MHz, DMSO-d , δ / ppm): 4.30 (1H,
6
s, –OH), 4.12 (2H, s, 2 –NH), 8.65 (1H, s, –CONH), 6.83–7.98 (23H, m, Ar–H).
Sodium 3-(4-((4-((1-(4-chloro-6-(4-nitrophenylamino)-1,3,5-triazin-2-ylami-
no)-5-sulfonatonaphthalen-2-yl)diazenyl)phenoxy(imino)methyl)phenyl)-4-oxo-2-
-phenyl-3,4-dihydroquinazoline-6-sulfonate (7g). Yield: 76 %; Anal. Calcd. for
C H O N ClS Na : C, 53.11; H, 2.71; N, 14.81 %. Found: C, 53.09; H, 2.68;
46 28 10 11
2
2
–1
N, 14.78 %. IR (KBr, cm ): 3355–3705 (O–H and N–H stretching of –OH and
–NH groups), 1662 (C=O stretching of quinazoline ring), 1430 (N=N stretching
2
of azo group), 1372 (C–N), 1372, 1115, 1052 (S=O stretching of sulphonates),
1505, 1315 (N=O asym. and sym. stretching of nitro group), 766 (C–Cl stretch-
1
ing of chloro group). H-NMR (300 MHz, DMSO-d , δ / ppm): 4.18 (2H, s, 2
6
–NH), 8.70 (1H, s, –CONH), 6.75–7.93 (25H, m, Ar–H).
Sodium 3-(4-((4-((2-(4-chloro-6-(4-nitrophenylamino)-1,3,5-triazin-2-ylami-
no)-6-sulfonatonaphthalen-1-yl)diazenyl)phenoxy)(imino)methyl)phenyl)-4-oxo-
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SYNTHESIS OF REACTIVE DYES BASED ON QUINAZOLINONE
181
2-phenyl-3,4-dihydroquinazoline-6-sulfonate (7h). Yield: 80 %; Anal. Calcd. for
C H O N ClS Na : C, 53.11; H, 2.71; N, 14.81 %. Found: C, 53.08; H, 2.67;
46 28 10 11
2
2
–1
N, 14.77 %. IR (KBr, cm ): 3350–3715 (O–H and N–H stretching of –OH and
–NH groups), 1665 (C=O stretching of quinazoline ring), 1435 (N=N stretching
2
of azo group), 1380 (C–N), 1360, 1118, 1050 (S=O stretching of sulphonates),
1505, 1310 (N=O asym. and sym. stretching of nitro group), 762 (C–Cl
1
stretching of chloro group). H-NMR (300 MHz, DMSO-d , δ / ppm): 4.17 (2H,
6
s, 2 –NH), 8.68 (1H, s, –CONH), 6.82–7.98 (25H, m, Ar–H).
Sodium 3-(4-((4-((2-(4-chloro-6-(4-nitrophenylamino)-1,3,5-triazin-2-
ylamino)naphthalene-1-yl)diazenyl)phenoxy)(imino)methyl)phenyl)-4-oxo-2-phe-
nyl-3,4-dihydroquinazoline-6-sulfonate (7i). Yield: 82 %; Anal. Calcd. for
C H O N ClSNa : C, 58.88; H, 3.12; N, 16.04 %. Found: C, 58.84; H, 3.09;
46 28
7
11
2
–1
N, 16.01 %. IR (KBr, cm ): 3350–3700 (O–H and N–H stretching of –OH and
–NH groups), 1670 (C=O stretching of quinazoline ring), 1422 (N=N stretching
2
of azo group), 1388 (C–N), 1365, 1120, 1060 (S=O stretching of sulphonates),
1510, 1315 (N=O asym. and sym. stretching of nitro group), 760 (C–Cl stre-
1
tching of chloro group). H-NMR (300 MHz, DMSO-d / δ, ppm): 4.15 (2H, s, 2
6
–NH), 8.65 (1H, s, –CONH), 6.86–7.95 (26H, m, Ar–H).
Sodium 3-(4-((4-((2-(4-chloro-6-(4-nitrophenylamino)-1,3,5-triazin-2-ylami-
no)-5-sulfonatonaphthalen-1-yl)diazenyl)phenoxy)(imino)methyl)phenyl)-4-oxo-
-2-phenyl-3,4-dihydroquinazoline-6-sulfonate (7j). Yield: 85 %; Anal. Calcd. for
C H O N ClS Na : C, 48.36; H, 2.38; N, 13.49 %. Found: C, 48.32; H, 2.34;
46 27 13 11
3
3
–1
N, 13.46 %. IR (KBr, cm ): 3360–3700 (O–H and N–H stretching of –OH and
–NH groups), 1660 (C=O stretching of quinazoline ring), 1445 (N=N stretching
2
of azo group), 1380 (C–N), 1360, 1113, 1047 (S=O stretching of sulphonates),
1505, 1308 (N=O asym. and sym. stretching of nitro group), 765 (C–Cl stretch-
1
ing of chloro group). H-NMR (300 MHz, DMSO-d , δ / ppm): 4.14 (2H, s, 2
6
–NH), 8.61 (1H, s, –CONH), 6.85–7.93 (25H, m, Ar–H).
Sodium 3-(4-((4-((1-(4-chloro-6-(4-nitrophenylamino)-1,3,5-triazin-2-ylami-
no)-8-sulfonatonaphthalen-2-yl)diazenyl)phenoxy)(imino)methyl)phenyl)-4-oxo-
-2-phenyl-3,4-dihydroquinazoline-6-sulfonate (7k). Yield: 80 %; Anal. Calcd.
For C H O N ClS Na : C, 53.11; H, 2.71; N, 14.81 %. Found: C, 53.06; H,
46 28 10 11
2
2
–1
2.68; N, 14.76 %. IR (KBr, cm ): 3355–3700 (O–H and N–H stretching of –OH
and –NH groups), 1675 (C=O stretching of quinazoline ring), 1440 (N=N stre-
2
tching of azo group), 1385 (C–N), 1360, 1112, 1055 (S=O stretching of sulpho-
nates), 1511, 1307 (N=O asym. and sym. stretching of nitro group), 763 (C–Cl
1
stretching of chloro group). H-NMR (300 MHz, DMSO-d , δ / ppm): 4.16 (2H,
6
s, 2 –NH), 8.66 (1H, s, –CONH), 6.78–7.96 (25H, m, Ar–H).
Sodium 8-(4-chloro-6-(4-nitrophenylamino)-1,3,5-triazin-2-ylamino)-7-((4-
-(imino(4-(4-oxo-2-phenyl-6-sulfonatoquinazolin-3(4H)-yl)phenyl)methoxy)phe-
nyl)diazenyl)naphthalene-1,3,6-trisulfonate (7l). Yield: 85 %; Anal. Calcd. for
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PATEL and PATEL
C H O N ClS Na : C, 44.40; H, 2.11; N, 12.38 %. Found: C, 44.36; H, 2.08;
46 26 16 11
4
4
–1
N, 12.34 %. IR (KBr, cm ): 3360–3705 (O–H and N–H stretching of –OH and
–NH groups), 1662 (C=O stretching of quinazoline ring), 1445 (N=N stretching
2
of azo group), 1382 (C–N), 1365, 1120, 1048 (S=O stretching of sulphonates),
1510, 1315 (N=O asym. and sym. stretching of nitro group), 766 (C–Cl stretch-
1
ing of chloro group). H-NMR (300 MHz, DMSO-d , δ / ppm): 4.18 (2H, s, 2
6
–NH), 8.62 (1H, s, –CONH), 6.76–7.96 (23H, m, Ar–H).
Sodium 4-(4-chloro-6-(4-nitrophenylamino)-1,3,5-triazin-2-ylamino)-5-hyd-
roxy-6-((4-(imino(4-(4-oxo-2-phenyl-6-sulfonatoquinazolin-3(4H)-yl)phenyl)me-
thoxy)phenyl)diazenyl)naphthalene-1,7-disulfonate (7m). Yield: 78 %; Anal.
Calcd. for C H O N ClS Na : C, 47.69; H, 2.35; N, 13.30 %. Found: C,
46 27 14 11
3
3
–1
47.64; H, 2.31; N, 13.26 %. IR (KBr, cm ): 3370–3705 (O–H and N–H stre-
tching of –OH and –NH groups), 1665 (C=O stretching of quinazoline ring),
2
1445 (N=N stretching of azo group), 1380 (C–N), 1355, 1120, 1045 (S=O stre-
tching of sulphonates), 1505, 1310 (N=O asym. and sym. stretching of nitro
1
group), 760 (C–Cl stretching of chloro group). H-NMR (300 MHz, DMSO-d ,
6
δ / ppm): 4.35 (1H, s, –OH), 4.15 (2H, s, 2 –NH), 8.62 (1H, s, –CONH), 6.75–
7.98 (23H, m, Ar–H).
Spectral properties
The absorption maxima (λ ) and logarithm of the molar extinction
max
coefficient (log ε) of all the prepared dyes 7a–m are given in Table I. The
absorption maxima of 7a–m were recorded in DMF solution. The absorption
maxima were in the range of 475–543 nm. The value of logarithm of molar
extinction co-efficient (log ε) of the dyes 7a–m were in the range 4.15–4.42,
indicating their good absorption intensity.
TABLE I. Exhaustion and fixation data of the synthesised dyes 7a–m (S – silk, W – wool, C –
cotton)
Exhaustion, %
W
Fixation, %
W C
Dye
Colour
λmax / nm log ε
S
C
S
7a
7b
7c
7d
7e
7f
7g
7h
7i
Pink
Reddish brown
Brown
543
503
495
485
475
520
485
480
475
490
485
475
525
4.42
4.30
4.22
4.15
4.27
4.32
4.30
4.15
4.40
4.25
4.27
4.30
4.23
75.50 70.80 70.55 91.53 91.08 91.44
73.30 66.82 67.66 88.78 89.25 84.85
70.80 70.47 69.72 85.54 92.42 85.57
69.55 65.55 73.78 89.14 87.81 88.89
67.87 66.18 69.45 91.84 85.54 87.55
72.60 71.15 69.57 84.02 88.75 86.87
70.35 68.80 71.88 85.70 84.65 91.49
75.45 66.27 71.52 90.12 91.81 88.78
68.80 68.40 65.17 86.73 86.84 84.38
71.23 67.23 72.60 90.45 87.45 87.58
75.95 65.17 68.28 91.82 84.47 85.88
69.95 69.96 70.70 90.16 89.29 86.57
72.55 68.82 68.04 91.52 88.91 88.92
Orange
Reddish brown
Light brown
Light orange
Orange
Orange
Light yellow
Brown
7j
7k
7l
Orange
7m Greenish yellow
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SYNTHESIS OF REACTIVE DYES BASED ON QUINAZOLINONE
183
Dyeing of fibres
All the dyes (7a–m) were applied on silk, wool and cotton fabrics in 2 %
7
shade according to the usual procedure. The variation in the hues of the dyed
fabric result from both the nature and position of the substituent present on the
naphthalene ring. The remarkable degree of levelness after washing indicates
good penetration and affinity of these dyes for the fabric.
Exhaustion and fixation study
Dye uptake by the fibre was measured by sampling the dye bath before and
dyeing. The absorbance of diluted dye solution was measured at the λ
of the
max
dye. Percentage dye bath exhaustion was calculated using following relationship:
Initial O.D.− Final O.D.
Exhaustion (%) =100
Initial O.D.
8
The percentage exhaustion of 2 % dyeing on cotton ranged from 65 to 74 %, for
silk fabric from 67 to 75 % and wool from 65 to 71 %. The percentage fixation
9
of 2 % dyeing on cotton fabric ranged from 84 to 91 %, for silk from 84 to 92%
and for wool from 84 to 90 % (the obtained results are summarized in Table I).
Fastness properties
The light fastness of all the reactive dyes (7a–m) on silk, wool and cotton
fibres is moderate to very good. The obtained result of washing fastness of the
dyes for silk, wool and cotton fibres showed they are good to excellent. Fastness
to rubbing (dry and wet) of the dyed pattern was moderate to very good for silk,
wool and cotton fibres (Table II). These are attributed to the good penetration and
affinity of the dyes for the fibres.
TABLE II. Fastness properties of the synthesised dyes 7a–m (S – silk, W – wool, C – cotton;
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)
Light fastness
Wash fastness
Rubbing fastness
Dry
W
4–5 3–4
Dye
Wet
W
4
4
6
4–5 3–4
4–5
4
4
4–5
3
S
W
C
S
W
C
S
C
3
4
5
4
3
S
3–4
4
3–4
4
C
5
3
4
7a
7b
7c
7d
7e
7f
7g
7h
7i
5
4
5
3
4
4–5
6
4
4
3–4
4
6
4
5
4
5
4
4–5
4
3–4
4
4
4–5 4–5
5
4
3–4
4
4
5
5
5
4–5
3–4 3–4
3
4–5
3
3
5
3
4
3
4–5
4–5
3
3
4
5
4
3–4
3
3–4 3–4
4–5
3
4
4
5
3
4
3–4
4
5
5
4
4
5
4
3
4–5 4–5 3–4 3–4 3–4
3–4 4–5
4
3–4
4–5
4
3–4
3
4
4
4
3
3–4
3
3
4
5
3
5
4
3
5
4
7j
7k
3–4
5
4
4–5
3
4
4
4–5 3–4
3–4
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184
PATEL and PATEL
TABLE II. Continued
Light fastness
Dye
Wash fastness
Rubbing fastness
Dry
Wet
W
3
S
W
C
S
W
C
S
4
W
4–5
4
C
3
S
4–5
4
C
3–4
4–5
7l
4
5
4
3–4 3–4
4
5
7m
5–6
5
4–5 3–4 4–5 3–4
3–4
3
EXPERIMENTAL
General
All the melting points (m.p.) were determined in open capillaries and are uncorrected.
Elemental analysis for carbon, hydrogen and nitrogen were realised on a Carlo Erba 1108 ele-
mental analyzer. The purity of all the dyes has been checked by TLC10 using aluminium plates
coated with silica gel 60 F254 (Merck), eluent iso-butanol:n-propanol:ethyl acetate:water
(2:4:1:3). The IR spectra were recorded in KBr on a Perkin-Elmer model-881 spectrophoto-
meter and the 1H-NMR spectra on a Brucker DRX-300 (300 MHz FT-NMR) instrument using
TMS as the internal standard and DMSO-d6 as the solvent. Chemical shifts are given in δ
(ppm). Absorption spectra were recorded on a Beckman DB-GT Grating spectrophotometer.
The light fastness was assessed in accordance with BS: 1006-1978.11 The rubbing fastness test
was performed with a Crockmeter (Atlas) in accordance with AATCC-196112 and the wash
fastness test in accordance with IS: 765-1979.13
Preparation of 2-phenyl-4-oxo-3,1-benzoxazine-6-suphonic acid (1)14
Benzoyl chloride (140.5 g, 1.0 mol) was added dropwise over the period of 1 h to
5-sulpho anthranilic acid (217 g, 1.0 mol) dissolved in pyridine (60 ml), under constant stir-
ring at 8 °C. After the completion of the addition, the reaction mixture was stirred for 30 min
at room temperature. At the end of the reaction, a solid mass was obtained, which was filtered,
washed successively with sodium bicarbonate solution (to remove unreacted acid) and then
with water, dried and recrystallized from rectified spirit. (The general route for the preparation
of 2-phenyl-4-oxo-3,1-benzoxazine-6-suphonic acid (1) is outlined in Scheme 1).
O
HO3S
COOH
HO3S
O
Pyridine
8 °C
+
COCl
NH2
N
C6H5
(1)
Scheme 1. Synthetic route to 2-phenyl-4-oxo-3,1-benzoxazine-6-sulphonic acid (1).
Preparation of 4,4’-diaminobenzanilide (2)
The title compound was prepared by the process described in the literature.15 (The gene-
ral route for the preparation of 4,4’-diaminobenzanilide (2) is outlined in Scheme 2).
Preparation of 2-phenyl-3{4’-[N-(4”-aminophenyl)carbamoyl]-phenyl}-quinazoline-4-(3H)-
16
-one-6-sulphonic acid (3)
A mixture of compound 1 (0.05 mol) and 2 (0.05 mol) in dry pyridine (50 ml) was
heated under reflux for 6 h under anhydrous reaction conditions and then allowed to cool to
room temperature. The reaction mixture was treated with dilute HCl and stirred. A solid sepa-
rate out which was filtered off and washed with water to remove any adhered pyridine. The
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SYNTHESIS OF REACTIVE DYES BASED ON QUINAZOLINONE
185
thus obtained crude quinazoline was dried under vacuum and recrystallized from 50 vol.% etha-
nol in water). (The general route for the preparation of compound 3 is outlined in Scheme 3).
SOCl2, DMF
H2N
NO2
O2N
COCl
O2N
COOH
+
65 - 70 °C, 4 - 5 h
90 - 95 °C
4.5 h
C6H5Cl, TEA
Fe, H2O, HCl
95 - 98 °C, 2 h
O2N
CONH
NO2
H2N
CONH
NH2
(2)
Scheme 2. Synthetic route to the diaminobenzanilide (2).
Diazotation of 2-phenyl-3{4’-[N-(4”-aminophenyl)carbamoyl]-phenyl}-quinazoline-4-(3H)-
-one-6-sulphonic acid (4)
Compound 3 (2.56 g, 0.005 mol) was suspended in water (60 ml). Hydrochloric acid
(0.36 g) was added dropwise to this well-stirred suspension. The mixture was gradually heated
up to 70 °C until a clear solution was obtained. The solution was cooled to 0–5 °C in an ice
bath. A solution of NaNO2 (0.6 g) in water (4 ml) previously cooled to 0 °C was then added
over a period of five minutes with stirring. The stirring was continued for 1 h, maintaining the
same temperature. The excess of nitrous acid (gave a positive test on starch-iodide paper) was
decomposed with the required amount of sulphamic acid. The thus obtained clear diazo solu-
tion 4 at 0–5 °C was used for the subsequent coupling reaction. (The general route for the
preparation of compound 4 is outlined in Scheme 3).
O
HO3S
Pyridine
Reflux
N
NH2
CONH
(1) + (2)
N
(3)
O
N
HO3S
N
N
Cl
NaNO2/HCl
0 - 5 °C
N
CONH
(4)
Scheme 3. Synthetic route to 2-phenyl-3-{4’-[N-(4”-aminophenyl)carbamoyl]-phenyl}-
quinazoline-4-(3H)-one-6-sulphonic acid (3) and its diazonium salt 4.
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186
PATEL and PATEL
Preparation of 4-nitro anilino cyanurated H-acid
Cyanuration of H-acid (5a). Cyanuric chloride (1.85 g, 0.01 mol) was stirred in acetone
(25 ml) at a temperature below 5 °C for a period of an hour. A neutral solution of H acid (3.19
g, 0.01mol) in aqueous sodium carbonate solution (10 % w/v) was then added in small
amounts over about an hour. The pH was maintained neutral by the simultaneous addition of
sodium carbonate solution (1 % w/v). The reaction mixture was stirred at 0–5 °C for further
4 h when a clear solution was obtained. (The general route for the preparation of compound
5a is outlined in Scheme 4). The resultant solution was used for the condensation reaction
with 4-nitro aniline.
Cl
N
OH
NH2
OH HN
N
N
Cl
Cl
N
pH 7.0
0-5 °C
Cl
+
N
N
HO3S
SO3H
HO3S
SO3H
Cl
(5a)
O2N
NH2
40-50 °C
pH 7.0
Cl
N
N
N
OH HN
NH
NO2
HO3S
SO3H
(6a)
Scheme 4. Synthetic route to the cyanurated H-acid 5 and 4-nitro anilinocyanurated H-acid 6a.
Condensation with 4-nitro aniline (preparation of 4-nitro anilino cyanurated H-acid 6a)
The temperature of the ice-cooled well-stirred solution of cyanurated H-acid 5 (4.67 g,
0.01 mol) was gradually raised to 45 °C in about 30 min. To this cyanurated H-acid, 4-nitro
aniline (1.38 g, 0.01 mol) was added dropwise at the same temperature, during a period of 30
min, maintaining the pH neutral by the simultaneous addition of sodium bicarbonate (1 % w/v).
After completion of the addition, stirring was continued for a further 3 h. The thus obtained
4-nitro anilino cyanurated H-acid solution was subsequently used for the further coupling re-
action. (The general route for the preparation of compound 6a is outlined in Scheme 4).
Formation of the dye 7a
To an ice cold and stirred solution of 4-nitro anilino cyanurated H-acid 6a (5.68 g, 0.01
mol), a freshly prepared diazo solution 4 (2.8 g, 0.005 mol) was added dropwise over a period
of 10–15 min. The pH was maintained at 7.5 to 8.5 by the simultaneous addition of sodium
carbonate solution (10 % w/v). During the coupling, a purple solution was formed. The stir-
ring was continued for 3–4 h, maintaining the temperature below 5 °C. The reaction mixture
o
was heated to 60 C and sodium chloride was added until a coloured material precipitated.
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SYNTHESIS OF REACTIVE DYES BASED ON QUINAZOLINONE
187
The mixture was stirred for 1 h, filtered and washed with a small amount of sodium chloride
solution (5 % w/v). The solid was dried at 80–90 °C and extracted with DMF. The dye was
precipitated by diluting the DMF-extract with excess chloroform. The violet dye was then
filtered, washed with chloroform and dried at 60 °C. Yield: 85 %. (The general route for the
preparation of compound (7a) is outlined in Scheme 5).
Coupling Reaction
pH 7.5-8.5
(4) + (6a)
0 - 5 °C
Cl
R
N
N
N
O
N
OH HN
NaO3S
N
CONH
N
N
NO2
NH
SO3Na
C6H5
NaO3S
(7a)
Scheme 5. Synthetic route to dye 7a (R: different 4-nitro aniline cyanurated
coupling components (6a–m)).
Following the above-described procedure, other reactive dyes 7b–m were synthesized
using the required 4-nitro anilino cyanurated coupling components, i.e., Gamma acid (6b),
J-acid (6c), N-methyl-J-acid (6d), N-phenyl-J-acid (6e), Chicago acid (6f), Laurant acid (6g),
Bronner acid (6h), Tobias acid (6i), sulpho Tobias acid (6j), Peri acid (6k), Koch acid (6l) and
K-acid (6m).
CONCLUSIONS
Reactive dyes based on 2-phenyl- 3-{4’-[N-(4”-aminophenyl)carbamoyl]-
-phenyl}-quinazoline-4-(3H)-one-6-sulphonic acid were synthesized. These dyes
give mostly pink, yellow and brown shades on silk, wool and cotton fabric hav-
ing good to excellent washing fastness properties. The remarkable degree of le-
velness after washing indicates good penetration and affinity of these dyes for the
fabrics. Exhaustion and fixation of these dyes are very good, which indicates that
the dyes have good affinity and solubility with the fabrics. The presence of the
quinazolinone structure in the dye molecules results in low sublimation and high
thermal stability.
Acknowledgements. The authors express their gratitude to the Head, Department of Che-
mistry, V. N. S. G. University, Surat, India, for providing the necessary research facility. In
addition, thanks go to SAIF, Chandigarh for the spectral data and Atul Ltd., Atul for providing
the dyeing and analytical facilities.
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188
PATEL and PATEL
И З В О Д
НОВЕ АЗО БОЈЕ ДОБИЈЕНЕ ИЗ 2-ФЕНИЛ-3-{4’-[N-(4”-АМИНОФЕНИЛ)КАРБАМОИЛ]-
-ФЕНИЛ}-КИНАЗОЛИН-4-(3H)-OН-6-СУЛФОНСКЕ КИСЕЛИНЕ
DIVYESH R. PATEL и KESHAV C. PATEL
Department of Chemistry, Veer Narmad South Gujarat University, Surat 395 007, Gujarat, India
Серија нових хетероцикличних моно азо реактивних боја 7a–m добијена је купловањем
производа диазотовања 2-фенил-3-{4’-[N-(4”-аминофенил)карбамоил]-фенил}-киназолин-4-
-(3H)-oн-6-сулфонске киселине (3) са различитим цијануринским компонентама за куплова-
ње (6a–m) и испитиване су њихове способности бојења свиле, вуне и памука. Утврђено је да
ове боје дају различиту покривеност са добром дубином и нијансом бојења влакана. Сва је-
дињења окарактерисана су уобичајеним спектроскопским методама (IC и NMR) и елемен-
талном анализом. Обојена влакна имају добру постојаност према светлу, прању и трљању.
(Примљено 25. фебруара 2009, ревидирано 23. септембра 2010)
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