Synthesis and antibacterial studies of azodispersed dyes derived from 2-(thiazol-2-yl)phthalazine-1,4-diones

Article abstract of DOI:10.1007/s00706-010-0392-3

A dibenzobarrelene derivative was used as key intermediate for the synthesis of 2-(4-(methyl/phenylthiaz-ol-2-yl)-2,3,4a,5,10,10a-hexahydro-5,10- benzenobenzo[g]phthalazine-1,4-diones. These compounds were coupled with the appropriate diazonium chlorides

Full text of DOI:10.1007/s00706-010-0392-3

Monatsh Chem (2010) 141:1353–1360
DOI 10.1007/s00706-010-0392-3
ORIGINAL PAPER
Synthesis and antibacterial studies of azodispersed dyes derived
from 2-(thiazol-2-yl)phthalazine-1,4-diones
•
•
•
A. M. Khalil M. A. Berghot M. A. Gouda
S. A. El Bialy
Received: 18 January 2010 / Accepted: 17 August 2010 / Published online: 30 September 2010
Ó Springer-Verlag 2010
Abstract A dibenzobarrelene derivative was used as key
intermediate for the synthesis of 2-(4-(methyl/phenyl)thiaz-
ol-2-yl)-2,3,4a,5,10,10a-hexahydro-5,10-benzenobenz-
o[g]phthalazine-1,4-diones. These compounds were coupled
with the appropriate diazonium chlorides to give the corre-
sponding 5-(arylazo)thiazole derivatives. The synthesized
dyes were applied to polyester as disperse dyes, and their
antibacterial, color measurement, and fastness properties
were evaluated.
On the other hand, the class of phthalazines possesses a
broad spectrum of biological effectiveness such as anti-
bacterial [13–15], anticonvulsant [16], cardiotonic [17], and
vasorelaxant [18] activities. In view of the above biological
importance, in continuation of our studies on the chemistry
of 2-(4-(methyl/phenyl)thiazol-2-yl)-2,3,4a,5,10,10a-hexa-
hydro-5,10-benzenobenzo[g]phthalazine-1,4-diones 3 [13],
and as part of our program directed towards developing new
approaches to a variety of heterocycles incorporating
the thiazole moiety [13, 14, 19] of expected potential
activity, we now report on the successful synthesis of some
new 2-[5-(arylazo)-4-substituted-thiazol-2-yl]-2,3,4a,5,10,-
10a-hexahydro-5,10-benzenobenzo[g]phthalazine-1,4-diones
4a–4n starting from dibenzobarrelene 1 [20] and their appli-
cation as disperse dyes for dyeing polyester fabrics.
Keywords Thiazole ꢀ Azodispersed dyes ꢀ
Polyester fabrics ꢀ Antibacterial ꢀ Color measurements ꢀ
Fastness properties
Introduction
Thiazoles and their derivatives have attracted continued
interest over the years because of their various biological
activities [1, 2]. Recently they have found application in
drug development for treatment of allergies [3], hyperten-
sion [4], inflammation [5], as central nervous system (CNS)
depressant [6, 7], bacterial [8] and human immune-defi-
ciency virus (HIV) infections [9], pain [10], as fibrinogen
receptor antagonists with antithrombotic activity [11], and
as new inhibitors of bacterial DNA gyrase B [12].
Results and discussion
Coupling of 3a and 3b with various aryldiazonium chlo-
rides in pyridine afforded the corresponding 4-substituted
5-(arylazo)thiazole derivatives 4a–4n. The spectral data of
4a–4n were consistent with their structure. Their infrared
(IR) spectra showed bands at v = 3,360–3,196 (NH),
1,736–1,702 (CO), and 1,530–1,506 cm-1 (N=N). 1H
nuclear magnetic resonance (NMR) of 4b showed signals
at d = 2.35 (s, 3H, CH3), 2.45 (s, 3H, CH3-tolyl), and
7.1–7.6 (m, 12H, Ar–H) ppm. Also, the 1H NMR spectrum
of 4c revealed two singlet signals at d = 2.4 and 3.85 ppm
corresponding to CH3 and OCH3 groups, in addition to two
doublet signals at d = 6.9 and 7.7 ppm due to four protons
of the p-substituted arylazo moiety and multiplet signals at
7.1–7.4 ppm due to eight aromatic protons. Moreover, the
1H NMR spectrum of 4i revealed among the characteristic
signals a singlet at d = 2.4 ppm due to CH3 protons, in
A. M. Khalil ꢀ M. A. Berghot ꢀ M. A. Gouda (&)
Chemistry Department, Faculty of Science,
Mansoura University, Mansoura 35516, Egypt
e-mail: dr_mostafa_chem@yahoo.com
S. A. El Bialy
Pharmaceutical Organic Chemistry Department, Faculty of
Pharmacy, Mansoura University, Mansoura 35516, Egypt
123

1354
A. M. Khalil et al.
addition to two doublet signals at d = 7.1 and 8.1 ppm due
to four protons of the p-substituted arylazo moiety and
multiplet signals at d = 7.2–7.6 ppm due to 13 aromatic
protons.
S is a measure of the light scattering. On textiles, K is
determined primarily by the dyestuffs and S only by the
substrate. From the wavelength, Kubelka and Munk cal-
culate Eq. (1) for the reflectance R of thick, opaque samples
with the constants of K and S:
Furthermore, the 1H NMR spectrum of 4l showed
multiplet signals at d = 7.1-8.0 ppm due to 17 aromatic
protons. In addition, the H NMR spectrum of 4n revealed
2
K=S ¼ ð1 ꢁ RÞ =2R:
ð1Þ
1
signals at d = 1.4 (t, 3H, CH3), 3.9 (q, 2H, CH2O), and
7.1–7.6 (m, 17H, Ar–H) ppm. As an example, the ESI(?)
mass spectrum of 4c showed three quasimolecular ion
peaks at 522 ([M ? H]?), 544 ([M ? Na]?), and 1064
([2M - H ? Na]?), and the ESI(-) mass spectrum
showed one quasimolecular ion peak at 520 ([M - H]-)
pointing at 521 as the molecular mass of the compound
(Scheme 1).
In this equation R is used as a ratio, e.g., 32% reflectance
as 0.32. The K/S value at kmax was taken as a measure of
color depth.
On the other hand, the psychometric coordinates (L*, a*,
b*) for each dyed sample were obtained to illustrate the
color hues, where L* is the lightness, ranging from 0 to 100
(0 for black and 100 for white); a* is the red-green axis,
(?) for red, zero for grey, and (-) for green; and b* is the
yellow-blue axis, (?) for yellow, zero for grey, and (-) for
blue.
Dyeing of polyester fabrics and dyeing properties
The parent dyestuff in each group is taken as the stan-
dard in color difference calculation (DL*, DC*, DH*, and
DE) [21–23]. The results are measured using CIE-LAB
techniques and given in Table 1, where DL* is the lightness
difference, DC* the chroma difference, DH* the hue dif-
ference, and DE the total color difference. A negative sign
of DL* indicates that the dyed fiber becomes darker than
the standard, but a positive sign indicates that the dyed
fiber becomes lighter than the standard. A negative sign of
Color measurement
The effect of the nature of different substituents on dyeing
behavior, color hue, and depth was investigated. This
investigation depends on some spectral data of the dyed
materials. The most commonly used function f(R) is that
developed theoretically by Kubelka and Munk. In their
theory, the optical properties of a sample are described by
two values: K is the measure of the light absorption, and
Scheme 1
O
R
O
S
H
N
C
Cl
Phth
NH2
H2N N C NH2
R
O
Phth
3a, R= CH3
S
S
EtONa
DMF
2
O
3b
, R= Ph
1
+
N2 Cl-
Pyridine
O
X
N
Phth=
HN
R
N
O
N
N
Phth
S
X
4a 4n
-
R
X
R
X
4a CH3
H
4h Ph
H
4b
4i
4j
CH3
CH3
CH3
OCH3
Cl
Br
NO2
Ph
CH3
OCH3
Cl
Br
NO2
4c
Ph
4d CH3
4e CH3
4k Ph
4l
4m
Ph
Ph
4f
CH3
4g CH3 COOEt
4n Ph COOEt
123

Synthesis and antibacterial studies of azodispersed dyes
1355
Table 1 Optical measurements of compounds 4a–4n
Dye
R%
a*
b*
L*
C*
H*
DL*
DC*
DH*
DE*
K/S
4a
4b
4c
4d
4e
4f
5.63
7.33
8.0
8.28
28.63
24.6
51.09
53.48
62.14
53.2
29.71
25.74
36.35
32.52
43.67
24.7
1.29
1.27
1.42
1.3
–
–
–
–
7.91
5.86
7.58
5.66
2.39
11.05
2.11
-3.97
-0.02
0.13
4.63
35.9
6.64
2.81
12.89
3.51
14.18
8.38
3.89
–
5.29
5.28
2.85
3.88
5.3
8.6
31.3
0.01
8.5
9.82
42.55
21.79
23.78
57.61
63.15
59.2
48.58
44.37
47.4
1.34
1.08
0.99
1.23
1.19
1.24
1.14
1.19
1.02
1.1
-2.51
-6.72
-3.69
–
13.96
-5.01
-1.21
–
0.05
16.56
11.91
8.46
11.63
15.71
20.26
25.12
20.19
29.13
27.21
21.84
25.01
-0.21
-0.3
–
4g
4h
4i
28.5
6.1
66.11
57.14
63.01
53.46
62.17
48.76
61.96
61.08
68.3
7.20
2.6
-8.97
-3.1
7.22
-0.04
-0.01
-0.09
-0.04
-0.21
-0.13
11.51
3.43
15.41
13.2
26.07
6.96
18.24
9.51
4j
4.77
2.08
2.95
4.88
7.12
62.56
69.85
73.68
41.62
55.49
1.48
4k
4l
63.5
-12.6
-3.94
-17.3
-4.15
8.77
23.05
15.96
9.27
68.46
35.43
49.53
12.6
4m
4n
-19.46
-5.59
6.06
R reflectance; a* red-green axis; b* yellow-blue axis; L* lightness; C* chroma; H* hue; DL* lightness difference; DC* chroma difference; DH* hue
difference; DE total color difference
DC* indicates that the dyed fiber becomes duller than the
standard, but a positive sign indicates that the dyed fiber
becomes brighter than the standard. A negative sign of DH*
Antibacterial activity
Fourteen compounds were screened in vitro for their anti-
bacterial activity against two strains of bacteria, Bacillus
thuringiensis and Escherichia coli, by the agar diffusion
technique [25]. A 2 mg/cm3 solution in dimethyl sulfoxide
(DMSO) was used. The bacteria were maintained on
nutrient agar. DMSO showed no inhibition zones. The agar
media were incubated with different microorganism cul-
tures tested. After 24 h of incubation at 30 °C, the diameter
of inhibition zone (mm) was measured (Table 3). Ampi-
cillin and chloramphenicol were used at concentration of
2 mg/cm3 as references.
indicates that the color directed to red color, while a
positive sign indicates that the color directed to yellowish.
The values of K/S of 4a–4n vary from 5.29 to 23.05. The
introduction of methyl, methoxy, chloro, bromo, and nitro
groups in dyes 4d, 4e, 4f, 4g, 4i, 4j, 4k, 4l, and 4m
increases the strength of K/S values and deepens the color
compared with the parent dyes 4a and 4h (Table 1).
The replacement of the methyl by a phenyl group in the
thiazole moiety decreases the value of K/S, indicating that
the dyes 4h–4n show higher affinity towards dyeing of
polyester fabrics than 4a–4g. Dyes 4c–4e and 4i–4l with
positive DC values are brighter than the parent dyes 4a and
4h, while the other dyes are duller than the parent dyes.
Dyes 4b–4d with positive DL* values are lighter than the
parent dye 4a, while the other dyes with negative DL* are
darker than the parent. The positive value of a* and b*
indicates that all groups shift the color hues of the dye to
reddish direction on the red-green axis and to the yellowish
direction in the yellow-blue axis, respectively.
The results presented in Table 3 reveal that compounds
4a, 4c, 4k, 4l, and 4m exhibited interestingly high activities
compared with the reference chemotherapeutics against
both B. thuringiensis and E. coli. Compounds 4a, 4d, 4e,
4f, 4g, 4i, 4j, and 4n exhibited high activity against
B. thuringiensis and moderate activity against E. coli. In
general, the compounds under investigation show more
significant activities against B. thuringiensis than against
E. coli. In conclusion, we report herein a simple and con-
venient route for the synthesis of some new azo dyes based
on phthalazine with antibacterial activities.
Assessment of color fastness
Most influences that can affect fastness are light, washing,
heat, perspiration, and atmospheric pollution. Conditions of
such tests are chosen to correspond closely to treatments
employed in manufacture and ordinary use conditions [24].
Results are given after usual matching of tested samples
against standard reference (the grey scale) [24]. The results
revealed that these dyes have good fastness properties
(Table 2).
Conclusions
Fourteen useful disperse dyes 4a–4n were synthesized by
azo coupling and were investigated for their dyeing char-
acteristic on polyester, and showed good light, washing,
heat, and acid perspiration fastness with antibacterial
activities. The remarkable degree of brightness after
123

1356
A. M. Khalil et al.
Table 2 Fastness properties of
compounds 4a–4n
Dye
Washing, 75 °C
Rubbing
Dry
Sublimation
Acid perspiration
Light, 4 h
Wet
180 °C
210 °C
4a
4b
4c
4d
4e
4f
4
2–3
2–3
2–3
2–3
2–3
2–3
2–3
2–3
4–5
2–3
2–3
2–3
4
3–4
3–4
2–3
2–3
3–4
3–4
4–5
3–4
4–5
3–4
3–4
4
3
2–3
2–3
2–3
3
4
4
4
3–4
3–4
4
3–4
4
5
4
2–3
4
4
4
4–5
4
3–4
3–4
4
2–3
2–3
3
3–4
3–4
4
6
4
4g
4h
4i
4
2–3
2–3
4
4–5
4–5
4–5
4–5
4
2–3
2–3
3–4
2–3
4
1–2
1–2
2–3
1–2
2–3
2–3
3–4
4
4
4j
4
2–3
4
4k
4l
3–4
3–4
3–4
4–5
4
4m
4n
4
4
3–4
4–5
6
4
2–3
4
2–3
analysis was carried out on silica gel 60 F254 precoated alu-
minum sheets. Infrared spectra were recorded on FTIR 5300
Spectrometer and Perking Elmer Spectrum RXIFT-IR Sys-
tem at the Faculty of Science, El-Azhar University, using the
potassium bromide wafer technique. 1H and 13C NMR
spectra were recorded on a Bruker 400 MHz spectrometer
using the indicated solvents and tetramethylsilane (TMS) as
an internal reference at the Georgia State University, Atlanta,
GA and on a Varian XL 200 MHz, at the Microanalytical
Center of Cairo University. Mass spectra were recorded on
ESI MS with Quattro Triple Quadruple Mass Finingan
MAT-Incos 50 ESILCQ (Finingan) at the Georg-August
University Goettingen, Germany. Elemental analyses (C, H,
N) were carried out at the micro-analytical Center of Cairo
University, Giza, Egypt. The elemental analyses were found
to agree favorably with the calculated values. The dyeing
assessment, fastness tests, and color measurements were
carried out at El-Nasr Company for Spinning and Weaving,
El-Mahalla, El-Kubra, Egypt.
Table 3 Inhibition zone (mean diameter of inhibition/mm) as a cri-
terion of antibacterial activity of the newly synthesized compounds
(2 mg/cm3 solution in DMSO)
Compound
Inhibition zone (mm)
B. thuringiensis
(Gram positive)
E. coli
(Gram negative)
4a
30
25
30
30
35
25
30
15
40
30
33
35
30
43
18
23
14
20
20
10
15
15
15
20
–
4b
4c
4d
4e
4f
4g
4h
4i
4j
15
20
20
20
10
19
19
4k
4l
The syntheses of dibenzobarrelene 1 [20], thioamide 2
[26], and the thiazole derivatives 3a and 3b [13] were
conducted according to known procedures.
4m
4n
Ampicillin
Chloramphenicol
Synthesis of 2-[5-(arylazo)-4-substituted-thiazol-2-yl]-
2,3,4a,5,10,10a-hexahydro-5,10-benzenobenzo-
[g]phthalazine-1,4-diones 4a–4n
washings is an indication of good penetration and the
excellent affinity of these dyes for the fabric due to the
accumulation of polar groups.
A well-stirred solution of aromatic amine (5 mmol) in
1.2 cm3 conc. HCl and 2 cm3 H2O was cooled in an ice
bath and diazotized with the solution of 0.345 g NaNO2
(5 mmol) in 2 cm3 H2O. The cold diazonium solution was
added slowly to a well-stirred solution of 1.937 g 3a or
2.248 g 3b (5 mmol) in 15 cm3 pyridine. The reaction
mixture was stirred for another 2 h. The crude product was
Experimental
All melting points were determined on a Gallenkamp electric
melting point apparatus. Thin-layer chromatography (TLC)
123

Synthesis and antibacterial studies of azodispersed dyes
1357
128.9, 127.1, 126.9, 126.7, 126.4, 125.1, 124.1, 103.6,
45.5, 42.3, 19.8 ppm.
filtered off, thoroughly dried, and recrystallized from a
suitable solvent to give 4a–4n.
2-[4-Methyl-5-(phenylazo)thiazol-2-yl]-2,3,4a,5,10,10a-
hexahydro-5,10-benzenobenzo[g]phthalazine-1,4-dione
(4a, C28H21N5O2S)
2-[5-(4-Bromophenylazo)-4-methylthiazol-2-yl]-
2,3,4a,5,10,10a-hexahydro-5,10-benzenobenzo[g]-
phthalazine-1,4-dione (4e, C28H20BrN5O2S)
Crystallization from EtOH-benzene afforded 1.97 g (80%)
4a, reddish brown. M.p.: 248 °C; IR (KBr): v = 3,220
Crystallization from DMF-MeOH afforded 2.054 g (72%)
4e, reddish brown. M.p.: 295 °C; IR (KBr): v = 3,208
1
(NH), 1,770, 1,696 (CO), 1,506 (N=N) cm-1; H NMR
1
(NH), 1,760, 1,698 (CO), 1,520 (N=N) cm-1; H NMR
(200 MHz, DMSO-d6): d = 2.4 (s, 3H, CH3), 3.4 (s, 2H,
C11-H, C12-H), 4.9 (s, 2H, C9-H, C10-H), 7.0–7.7 (m,
13H, Ar–H), 12.0 (s, 1H, NH) ppm; 13C NMR (100 MHz,
DMSO-d6): d = 172.1, 169.4, 142.6, 139.6, 129.3, 128.8,
127.6, 126.8, 125.5, 124.7, 108.3, 45.0, 40.8, 20.5 ppm.
(400 MHz, DMSO-d6): d = 2.5 (s, 3H, CH3), 3.2 (s, 2H,
C11-H, C12-H), 4.8 (s, 2H, C9-H, C10-H), 7.2–7.6 (m,
12H, Ar H), 10.9 (br, 1H, NH) ppm; 13C NMR (100 MHz,
DMSO-d6): d = 171.9, 171.1, 168.9, 142.5, 139.6, 132.8,
128.5, 126.8, 125.5, 124.7, 106.4, 45.0, 40.8, 20.1 ppm.
2-[4-Methyl-5-(4-methylphenylazo)thiazol-2-yl]-
2,3,4a,5,10,10a-hexahydro-5,10-benzenobenzo[g]-
phthalazine-1,4-dione (4b, C29H23N5O2S)
2-[4-Methyl-5-(4-nitrophenylazo)thiazol-2-yl]-
2,3,4a,5,10,10a-hexahydro-5,10-benzenobenzo[g]-
phthalazine-1,4-dione (4f, C28H20N6O4S)
Crystallization from EtOH-benzene afforded 2.33 g (92%)
4b, orange. M.p.: 304 °C; IR (KBr): v = 3,128 (NH),
Crystallization from DMF-MeOH afforded 2.039 g (76%)
4f, brown. M.p.: 263 °C; IR (KBr): v = 3,216 (NH), 1,702
1,714 (CO), 1,512 (N=N) cm-1 1H NMR (200 MHz,
;
(CO), 1,514 (N=N), 1332 (NO2) cm-1
;
1H NMR
DMSO-d6): d = 2.35 (s, 3H, CH3–C6H4), 2.45 (s, 3H,
CH3), 3.3 (s, 2H, C11-H, C12-H), 4.8 (s, 2H, C9-H, C10-
H), 7.1–7.6 (m, 12H, Ar–H), 11.9 (s, 1H, NH) ppm; 13C
NMR (100 MHz, DMSO-d6): d = 173.6, 171.4, 169.0,
145.3, 140.0, 138.5, 138.4, 129.5, 127.0, 126.8, 126.0,
125.1, 124.2, 104.4, 45.2, 43.5, 21.4, 20.1 ppm.
(200 MHz, DMSO-d6): d = 2.25 (s, 3H, CH3), 3.35 (s,
2H, C11-H, C12-H), 4.85 (s, 2H, C9-H, C10-H), 7.1–7.9
(m, 12H, Ar–H), 12.3 (s, 1H, NH) ppm; 13C NMR
(100 MHz, DMSO-d6): d = 176.4, 174.8, 169.0, 149.6,
147.2, 141.0, 139.4, 135.2, 129.8, 126.9, 126.8, 125.7,
124.3, 103.6, 46.6, 45.4, 18.9 ppm.
2-[5-(4-Methoxyphenylazo)-4-methylthiazol-2-yl]-
2,3,4a,5,10,10a-hexahydro-5,10-benzenobenzo[g]-
phthalazine-1,4-dione (4c, C29H23N5O3S)
Ethyl 4-[2-(3,4,4a,5,10,10a-hexahydro-1,4-dioxo-5,10-
benzenobenzo[g]phthalazin-2(1H)-yl)-4-methylthiazol-5-
ylazo]benzoate (4g, C31H25N5O4S)
Crystallization from DMF-H2O afforded 2.217 g (85%) 4c,
reddish brown. M.p.: 245 °C; IR (KBr): v = 3,225 (NH),
Crystallization from EtOH afforded 1.945 g (69%) 4g, red.
M.p.: 241 °C; IR (KBr): v = 3,240 (NH), 1,706 (br, CO),
1,706 (CO), 1,509 (N=N) cm-1 1H NMR (200 MHz,
;
1,514 (N=N) cm-1 1H NMR (400 MHz, DMSO-d6):
;
CDCl3): d = 2.4 (s, 3H, CH3), 3.3 (s, 2H, C11-H, C12-H),
3.85 (s, 3H, OCH3), 4.85 (s, 2H, C9-H, C10-H), 6.9 (d, 2H,
Ar–H), 7.1–7.4 (m, 8H, Ar–H), 7.7 (d, 2H, Ar–H), 10.3 (s,
1H, NH) ppm; 13C NMR (100 MHz, DMSO-d6):
d = 172.3, 171.9, 168.8, 142.6, 139.6, 128.8, 127.6,
126.7, 125.5, 124.6, 115.1, 56.0, 45.1, 40.8, 20.6 ppm;
ESI (?) MS: m/z = 522 ([M ? H]?), 544 ([M ? Na]?),
1064 ([2 M - H ? Na]?); ESI (-) MS: m/z = 520
([M - H]-).
d = 1.3 (t, 3H, CH3, J = 7.2), 2.6 (s, 3H, CH3), 3.4 (s, 2H,
C11-H, C12-H), 4.3 (q, 2H, CH2, J = 7.2), 4.9 (s, 2H, C9-H,
C10-H), 7.1–7.9 (m, 12H, Ar H), 11.1 (br, 1H, NH) ppm;
13C NMR (100 MHz, DMSO-d6): d = 171.1, 169.6, 165.8,
150.1, 142.3, 139.9, 128.6, 127.4, 126.8, 125.5, 124.7,
102.1, 60.9, 45.1, 40.8, 21.3, 14.7 ppm.
2-[4-Phenyl-5-(phenylazo)thiazol-2-yl]-2,3,4a,5,10,10a-
hexahydro-5,10-benzenobenzo[g]phthalazine-1,4-dione
(4h, C33H23N5O2S)
2-[5-(4-Chlorophenylazo)-4-methylthiazol-2-yl]-
2,3,4a,5,10,10a-hexahydro-5,10-benzenobenzo[g]-
phthalazine-1,4-dione (4d, C28H20ClN5O2S)
Crystallization from EtOH-benzene afforded 1.938 g
(70%) 4h, orange. M.p.: 287 °C; IR (KBr): v = 3,360
Crystallization from DMF-MeOH afforded 2.183 g (83%)
4d, orange. M.p.: 286 °C; IR (KBr): v = 3,250 (NH),
(NH), 1,734 (CO), 1,528 (N=N) cm-1 1H NMR
;
(200 MHz, DMSO-d6): d = 3.3 (s, 2H, C11-H, C12-H),
4.8 (s, 2H, C9-H, C10-H), 7.2–7.6 (m, 18H, Ar–H), 11.3 (s,
1H, NH) ppm; 13C NMR (100 MHz, DMSO-d6):
d = 173.2, 171.4, 170.1, 169.4, 150.3, 142.5, 139.6,
130.0, 129.0, 129.8, 127.4, 127.2, 126.8, 125.6, 125.0,
124.7, 124.6, 105.1, 45.2, 40.8 ppm.
1,712 (CO), 1,508 (N=N) cm-1 1H NMR (200 MHz,
;
DMSO-d6): d = 2.3 (s, 3H, CH3), 3.3 (s, 2H, C11-H, C12-
H), 4.9 (s, 2H, C9-H, C10-H), 7.0–7.9 (m, 12H, Ar–H),
12.2 (s, 1H, NH) ppm; 13C NMR (100 MHz, DMSO-d6):
d = 173.1, 171.3, 168.7, 148.5, 141.1, 139.0, 134.5, 130.0,
123

1358
A. M. Khalil et al.
2-[5-(4-Methylphenylazo)-4-phenylthiazol-2-yl]-
2,3,4a,5,10,10a-hexahydro-5,10-benzenobenzo[g]-
phthalazine-1,4-dione (4i, C34H25N5O2S)
2-[5-(4-Nitrophenylazo)-4-phenylthiazol-2-yl]-
2,3,4a,5,10,10a-hexahydro-5,10-benzenobenzo[g]-
phthalazine-1,4-dione (4m, C33H22N6O4S)
Crystallization from EtOH-benzene afforded 2.413 g
Crystallization from EtOH-benzene afforded 2.395 g
(80%) 4m, red. M.p.: 303 °C; IR (KBr): v = 3,196 (NH),
(85%) 4i, orange. M.p.: 290 °C; IR (KBr): v = 3,220
(NH), 1,736 (CO), 1,530 (N=N) cm-1
;
1H NMR
1,707 (CO), 1,560, 1,494, 1,332 (N=N, NO2) cm-1; H
1
(200 MHz, DMSO-d6): d = 2.4 (s, 3H, CH3), 3.4 (s, 2H,
C11-H, C12-H), 4.9 (s, 2H, C9-H, C10-H), 7.1 (d, 2H, Ar–
H), 7.2–7.6 (m, 13H, Ar–H), 8.1 (d, 2H, Ar–H), 10.8 (s,
1H, NH) ppm; 13C NMR (100 MHz, DMSO-d6):
d = 172.4, 171.5, 169.4, 142.4, 139.5, 138.8, 130.6,
129.0, 127.7, 126.8, 125.6, 125.1, 124.7, 124.6, 122.5,
105.2, 44.9, 40.8, 21.4 ppm; ESI (?) MS: m/z = 568
([M ? H]?), 590 ([M ? Na]?), 1,156.9 ([2 M ? Na]?);
ESI (-) MS: m/z = 566 ([M-H]-).
NMR (400 MHz, DMSO-d6): d = 3.4 (s, 2H, C11-H, C12-
H), 4.9 (s, 2H, C9-H, C10-H), 7.1–8.3 (m, 17H, Ar–H),
11.4 (br, 1H, NH) ppm. 13C NMR (100 MHz, DMSO-d6):
d = 173.2, 170.6, 169.5, 151.3, 147.9, 142.4, 134.8, 129.1,
127.5, 126.8, 125.5, 124.7, 123.9, 104.0, 45.0, 40.8 ppm.
Ethyl 4-[2-(3,4,4a,5,10,10a-hexahydro-1,4-dioxo-5,10-
benzenobenzo[g]phthalazin-2(1H)-yl)-4-phenylthiazol-5-
ylazo]benzoate (4n, C36H27N5O4S)
Crystallization from EtOH afforded 2.253 g (72%) 4n, red.
M.p.: 286 °C; IR (KBr): v = 3,250 (NH), 1,714, 1,650
2-[5-(4-Methoxyphenylazo)-4-phenylthiazol-2-yl]-
2,3,4a,5,10,10a-hexahydro-5,10-benzenobenzo[g]-
phthalazine-1,4-dione (4j, C34H25N5O3S)
1
(CO), 1,508 (N=N) cm-1; H NMR (200 MHz, CDCl3):
d = 1.4 (t, 3H, CH3), 3.4 (s, 2H, C11-H, C12-H), 3.9 (q,
2H, CH2), 4.9 (s, 2H, C9-H, C10-H), 7.1–7.6 (m, 17H, Ar–
H), 10.6 (br, 1H, NH) ppm; 13C NMR (100 MHz, DMSO-
d6): d = 174.1, 171.6, 165.8, 150.3, 142.0, 139.9, 133.5,
129.8, 129.3, 128.8, 127.8, 127.0, 126.7, 125.5, 124.8,
104.1, 61.5, 45.1, 44.8, 15.3 ppm.
Crystallization from EtOH-benzene afforded 2.539 g
(87%) 4j, orange. M.p.: 260 °C; IR (KBr): v = 3,226
(NH), 1,726 (CO), 1,534 (N=N) cm-1
;
1H NMR
(200 MHz, DMSO-d6): d = 3.3 (s, 2H, C11-H, C12-H),
4.1 (q, 2H, OCH3), 4.9 (s, 2H, C9-H, C10-H), 7.9–8.0 (m,
17H, Ar–H), 11.0 (s, 1H, NH) ppm; 13C NMR (100 MHz,
DMSO-d6): d = 173.0, 171.9, 168.5, 149.5, 142.9, 139.5,
133.2, 129.4, 129.1, 129.0, 127.7, 127.6, 126.8, 125.8,
124.6, 108.1, 56.0, 45.1, 42.8 ppm.
Dyeing procedures
Preparation of dye dispersion
The required amount of dye (2% shade) was dissolved in
DMF and added dropwise with stirring to a solution of
Dekol-N (2 g/dm3), an anionic dispersing agent of BASF,
then the dye was precipitated in a fine dispersion ready for
use in dyeing.
2-[5-(4-Chlorophenylazo)-4-phenylthiazol-2-yl]-
2,3,4a,5,10,10a-hexahydro-5,10-benzenobenzo[g]-
phthalazine-1,4-dione (4k, C33H22ClN5O2S)
Crystallization from EtOH-benzene afforded 2.646 g
(90%) 4k, red. M.p.: 258 °C; IR (KBr): v = 3,310 (NH),
1,730 (CO), 1,508 (N=N) cm-1 1H NMR (400 MHz,
;
Dyeing of polyester at 130 °C under pressure using
Levegal PT (carrier of Bayer)
DMSO-d6): d = 3.3 (s, 2H, C11-H, C12-H), 4.8 (s, 2H,
C9-H, C10-H), 7.2–7.7 (m, 17H, Ar H), 11.0 (br, 1H, NH)
ppm; 13C NMR (100 MHz, DMSO-d6): d = 173.2, 171.3,
169.2, 142.5, 139.5, 129.8, 127.6, 126.8, 125.5, 124.7,
104.1, 45.0, 40.8 ppm.
The dye bath (1:20 liquor ratio), containing 5 g/dm3 Lev-
egal PT (Bayer) as carrier, 4% ammonium sulfate, and
acetic acid at pH 5.5, was brought to 60 °C, the polyester
fabric was entered and run for 15 min. The fine dispersion
of the dye (2%) was added, and the temperature was raised
to boiling within 45 min, dyeing was continued at boiling
temperature for about 1 h, then the dyed material was
rinsed and soaped with 2% nonionic detergent to improve
rubbing and wet fastness.
2-[5-(4-Bromophenylazo)-4-phenylthiazol-2-yl]-
2,3,4a,5,10,10a-hexahydro-5,10-benzenobenzo[g]-
phthalazine-1,4-dione (4l, C33H22BrN5O2S)
Crystallization from EtOH-benzene afforded 2.625 g (83%)
4l, orange. M.p.: 230 °C; IR (KBr): v = 3,300 (NH), 1,734
(CO), 1,510 (N=N) cm-1; 1H NMR (200 MHz, DMSO-d6):
d = 3.47 (s, 2H, C11-H, C12-H), 4.87 (s, 2H, (C9-H, C10-
H), 7.1–8.0 (m, 17H, Ar–H), 11.0 (br, 1H, NH) ppm; 13C
NMR (100 MHz, DMSO-d6): d = 172.5, 171.4, 169.1,
150.5, 142.0, 139.3, 133.4, 132.6, 129.6, 128.9, 128.8,
127.6, 126.8, 125.5, 124.3, 106.4, 46.0, 44.8 ppm.
Assessment of color fastness (Table 2)
Fastness to washing, perspiration, light, and sublimation
was tested according to the reported methods.
123

Synthesis and antibacterial studies of azodispersed dyes
1359
Fastness to washing
according to the following blue scale: 1-poor, 3-moderate,
5-good, and 8-very good.
A specimen of dyed polyester fabric was stitched between
two pieces of undyed cotton fabric, all of equal diameter,
and then washed at 50 °C for 30 min. The staining on the
undyed adjacent fabric was assessed according to the fol-
lowing grey scale: 1-poor, 2-fair, 3-moderate, 4-good, and
5-excellent.
Color assessment
Table 1 reports the color parameters of the dyed fabrics
assessed by tristimulus colorimetry. The color parameters
of the dyed fabrics were determined using a SPECTRO
multichannel photodetector (model MCPD1110A), equip-
ped with a D65 source and barium sulfate as a standard
blank. The values of the chromaticity coordinates, lumi-
nance factor, and the position of the color in the CIE-LAB
color solid are reported.
Fastness to perspiration
The samples were prepared by stitching pieces of dyed
polyester fabric between two pieces of undyed cotton
fabric, all of equal diameter, and then immersing in the
acid medium for 30 min. The staining on the undyed
adjacent fabric was assessed according to the following
grey scale: 1-poor, 2-fair, 3-moderate, 4-good, and 5-
excellent. The acid solution (pH 3.5) contained sodium
chloride 10 g/dm3, lactic acid 1 g/dm3, disodium ortho-
phosphate 1 g/dm3, and histidine monohydrochloride
0.25 g/dm3.
In vitro antimicrobial activity
The tested compounds were evaluated by the agar diffusion
technique [25] using a 2 mg/cm3 solution in DMSO. The
test organisms were B. thuringiensis as Gram-positive
bacteria and E. coli as Gram-negative bacteria. DMSO was
used as a control for each organism. Ampicillin and
chloramphenicol in DMSO were used as reference drugs.
Fastness to rubbing
Acknowledgments We are grateful to Dr. M. Ismail, Dr. A. Ellab-
ady, and Dr. K. Attai Shaaban for spectral measurements, also Dr.
A. EL-Moursey and Dr. A. Shawky for microbiological screening.
The dyed polyester fabric was placed on the base of crock-
meter (Atlas electronic type), so that it rested flat on the
abrasive cloth with its long dimension in the direction of
rubbing. A square of white testing cloth was allowed to slide
on the tested fabric back and forth 20 times by making ten
complete turns of the crank. For wet rubbing test, the testing
square was thoroughly wet in distilled water. The rest of the
procedure was the same as the dry test. The staining on the
white testing cloth was assessed according to grey scale:
1-poor, 2-fair, 3-moderate, 4-good, and 5-excellent.
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