Synthesis and biological activity of novel arylazothiazole disperse dyes containing selenium for dyeing polyester fibers

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Phosphorus, Sulfur, and Silicon and the Related

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Synthesis and biological activity of novel

arylazothiazole disperse dyes containing selenium for

dyeing polyester fibers

Mohamed E. Khalifa^ab, Shams H. Abdel-Hafez^ac, Adel A. Gobouri^a& Mohamed I. Kobeasy^ad

^aDepartment of Chemistry, Faculty of Science, Taif University, Taif 21974, Saudi Arabia

^bDepartment of Chemical Engineering, Higher Institute of Engineering and Technology, New

Damietta, Egypt

^cDepartment of Chemistry, Faculty of Science, Assiut University, Assiut, Egypt

^dDepartment of Biochemistry, Faculty of Agriculture, Cairo University, Giza, Egypt

Accepted author version posted online: 18 Aug 2014.

To cite this article: Mohamed E. Khalifa, Shams H. Abdel-Hafez, Adel A. Gobouri & Mohamed I. Kobeasy (2014): Synthesis and

biological activity of novel arylazothiazole disperse dyes containing selenium for dyeing polyester fibers, Phosphorus, Sulfur,

and Silicon and the Related Elements, DOI: 10.1080/10426507.2014.948622

To link to this article: http://dx.doi.org/10.1080/10426507.2014.948622

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ACCEPTED MANUSCRIPT

SYNTHESIS AND BIOLOGICAL ACTIVITY OF NOVEL

ARYLAZOTHIAZOLE DISPERSE DYES CONTAINING SELENIUM FOR

DYEING POLYESTER FIBERS

Mohamed E. Khalifa, ^a,b,* Shams H. Abdel-Hafez,^a,cAdel A. Gobouri^aand Mohamed I.

Kobeasy^a,d

^aDepartment of Chemistry, Faculty of Science, Taif University, Taif 21974, Saudi Arabia

^bDepartment of Chemical Engineering, Higher Institute of Engineering and Technology, New

Damietta, Egypt

Email: mohamedezzat200@hotmail.com

^cDepartment of Chemistry, Faculty of Science, Assiut University, Assiut, Egypt

^dDepartment of Biochemistry, Faculty of Agriculture, Cairo University, Giza, Egypt

Abstract The synthesis of novel heterocyclic aryl mono azo organic compounds, including

3-amino-4,6-dimethyl-N-(5-arylazothiazol-2-yl)selenopheno[2,3-b]pyridine-2-

carboxamide,

3-amino-4,6-diphenyl-N-(5-arylazothiazol-2-yl)selenopheno[2,3-

b]pyridazine-2-carboxamide and 3-amino-5,6,7,8-tetrahydro-4-(4-methoxyphenyl)-N-(5-

arylazothiazol-2-yl)selenopheno[2,3-b]quinoline-2-carboxamide using a condensation

reaction involving different 2-(N-chloroacetyl)-5-arylazo-thiazole derivatives with seleno

derivatives of pyridine, pyridazine and/or quinolone, respectively, was undertaken.

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Analytical and spectroscopic data confirm the proposed structures. The novel synthesized

thiazole-selenium disperse dyes were applied for dyeing polyester fabrics. Color

characteristics and fastness properties were investigated. The novel synthesized

compounds exhibited high efficiency based on in vitro screening of their antioxidant

activity, antitumor activity against Ehrlich ascites carcinoma cell EACC cell line and

antimicrobial activity against various pathogenic bacteria and fungi. The colored polyester

fibers could be applied as sterile and/or biological active fabrics used in various life

applications.

Me

H₂N

N

Me

N

N N

N

H

Se

N

Me

S

CN

Ar

O

OCH₃

Me

SeH

OCH₃

10a-c

O

CN

Ar

N

Ph

S

H₂N

N

N SeH

Ph

CN

Cl

NH

N

Ph

N

H₂N

Ph

N N

SeH

N

Se N

S

N

H

Ar

3a-c

O

N

N N

N

Se

S

12a-c

Ar

H

O

11a-c

Keywords 2- Aminothiazole, Heterocycles, Antimicrobial activity, Antitumor agents, Dyes,

Selenium

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INTRODUCTION

The past three decades have witnessed considerable innovation in the field of azo dye

chemistry based on heterocyclic systems.¹Heterocyclic-based azo dyes are not only important

due to their excellent properties as dyes for polyester textiles but they also have been utilised in

non-textile applications, such as photodynamic therapy, lasers, reprographic technology,

functional dye applications and non-linear optical systems.²The level of interest, as indicated by

the patent literature in the field of thiazolyl azo disperse dyes has grown, and the monoazo

disperse dyes with thiazole diazo components have been extensively investigated to produce

bright and strong color shades ranging from red to greenish blue on synthetic fibers.³These

results led to commercial products that replaced the conventional azobenzene disperse dyes.⁴The

Color Index described various basic, direct, vat and disperse dyes that contain the thiazole

nucleus.⁵However, these compounds are still of interest in organic chemistry due to medicinal

applications (i.e., antitumor activity, cytotoxic, antimicrobial, anti-inflammatory, mitodepressive,

hypotensive, anti-HIV, hypoallergenic, tuberculosis, and agriculture pesticide action).⁶Organo-

selenium compounds have continued to attract the attention of a wide range of investigators due

to their unique properties, which include antimicrobial, antitumor and anticancer activities.^7-9

Therefore, many medicinal preparations have been produced based on organic derivatives of

selenium.¹⁰

In addition, organo-selenium compounds are capable of sensitising processes in living

organisms, and the selenium atom is also a primary constituent of four proteins. Therefore, its

deficiency in human and animal organisms might be related to various chronic diseases,

especially necrosis of the liver.¹¹In a continuation of our previous study on the synthesis of S

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and/or N heterocyclic compounds and their applications as disperse dyes and biological active

compounds,^12-20which was stimulated by our recent work on the synthesis of selenium

21-23

containing sulfa drugs, amino acids and nucleosides,

we expanded our focus by introducing

organoselenium compounds to the thiazolyl moiety, which is expected to exhibit high affinity for

dyeing polyester fabrics with acceptable fastness properties and biological activity, in order to

get colored sterile and/or biological active fabrics which could be used in various fields of life

applications.

RESULTS AND DISCUSSION

Chemistry

To successfully introduce the organoselenium compounds into the thiazolyl moiety, we

first studied the reaction of 5-arylazo-2-chloro-N-(thiazol-2-yl)acetamide derivatives 3a-c with

selenol derivatives of pyridine 4, pyridazine 5 and quinoline 6 in dimethyl formamide (DMF)

containing 10 % aqueous potassium hydroxide, which afforded the corresponding seleno

derivatives "7a-c- 9a-c", respectively. Then, treatment of compounds "7a-c- 9a-c" with an excess

of 10% aqueous potassium hydroxide in (DMF) caused a Thorpe-Ziegler cyclisation, to yield the

corresponding

carboxamide derivatives 10a-c, 3-amino-4,6-diphenyl-N-(5-arylazothiazol-2-yl)selenopheno[2,3-

b]pyridazine-2-carboxamide derivatives 11a-c and 3-amino-5,6,7,8-tetrahydro-4-(4-

3-amino-4,6-dimethyl-N-(5-arylazothiazol-2-yl)selenopheno[2,3-b]pyridine-2-

methoxyphenyl)-N-(5-arylazothiazol-2-yl)selenopheno[2,3-b]quinoline-2-carboxamide

derivatives 12a-c (Schemes 1 and 2).

The chemical structures of selenol derivatives "7a-c-9a-c" were established based on

their elemental analysis and spectral data. In general, the IR spectra of compounds "7a-c-9a-c"

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were characterized by the presence of strong absorption bands at 3333 cm^-1corresponding to NH

stretching, 2221 cm^-1corresponding to the nitrile group (CN) and 1699 cm^-1corresponding to the

1

carbonyl group (CO). For example, the H NMR spectrum of 7b was characterized by the

presence of three singlet peaks at δ 2.43, 2.56 and 2.69 corresponding to three methyl protons as

well as a singlet peak at δ 4.27 for the methylene group. In addition, the spectra exhibited a

singlet peak at δ 7.08 corresponding to the pyridine C5-H proton, multiplet peaks at δ 7.25-7.73

corresponding to the aromatic protons and a singlet peak at δ 7.91 corresponding to the thiazole

proton. The IR spectra of 3-amino-N-(5-arylazothiazol-2-yl)selenopheno[2,3-b]pyridine,

pyridazine and/or quinoline-2-carboxamide derivatives "10a-c-12a-c" clearly indicated the

absence of the cyano group band and the appearance of characteristics absorption bands at 3177

and 3280 cm^-1corresponding to the NH₂group as well as at 1652 cm^-1corresponding to the

carbonyl group. The strong decrease in the carbonyl absorption frequencies was due to the highly

1

chelated intramolecular H-bonded structure. For example, the H NMR spectrum of 10b

confirmed the absence of the characteristic signal of the methylene group (Scheme 2). In

addition, the results exhibited three singlet peaks corresponding to the three methyl protons at δ

2.44, 2.83, 3.09, a singlet peak at δ 7.33 corresponding to the pyridine C5-H proton and multiplet

peaks at δ 7.47-7.95 corresponding to the aromatic protons. In addition, the peaks corresponding

13

to the NH groups were absent due to the use of CF₃COOD as a solvent. The C NMR spectra

were also recorded for synthesized compounds "10a-c-12a-c" (see experimental part).

Dyeing and Fastness Properties

For dyeing polyester fabrics, only disperse dyes are suitable for practical applications.

Due to their hydrophobic properties, these dyes are capable of penetrating into similarly

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hydrophobic polyester fibers. The synthesized disperse dyes under investigation were applied to

polyester fabrics at 2 % color depth (weight of dye to fabric w.o.f.) using a high-temperature

dyeing technique HT (pH 5.5, liquor ratio (LR) 20 : 1, temperature 130 °C for 60 min), where

the range of visual color hues obtained ranged from yellow to brown. In general, the variation in

the color of these dyes resulted from the change in the diazonium salts and coupling components.

The dyes on the polyester fabrics were evaluated based on their fastness properties using

standard methods.²⁴The results are provided in Table 1, where fastness to perspiration,

sublimation and light were performed according to AATCC-15 (1985), the rubbing fastness test

was performed according to AATCC-88 (1988) and the wash fastness test was performed

according to ISO: 765-1979. The prepared dyes exhibited excellent leveling, uniformity of

coloration and exhaustion of dye liquor. In addition, excellent behavior for fastness to washing

and perspiration were observed. Most of the dyes exhibited good rubbing fastness, good

sublimation fastness and moderate to good light fastness. Several reports suggested that fading of

azo dyes is primarily due to the decomposition of the –N=N– moiety by oxidation, reduction

and/or photolysis, and the rates of these processes should be sensitive to the chemical structure of

the dye, the type of substrate and treatment conditions.²⁵Because the dyed substrate employed in

this study is a polyester fabric (i.e., non-proteinic), the fading process likely occurs by oxidation.

The ease of oxidation of azo linkages should be a function of electron density. Therefore,

electron-donating substituents on this moiety should increase the fading rate. This hypothesis is

in agreement with the observed results (Table 1), which indicated that the presence of a methyl

group in the synthesized dyes results in a decrease in the light fastness to 3-4.

Color assessment

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The color on polyester fibers is expressed in terms of CIELAB values²⁶(Table 2), and

the CIELAB coordinates measured included lightness (L*), chroma (C*), hue angle (h) from 0º

to 360º, the (a*) value, which represents the degree of redness (positive) and greenness

(negative), and the (b*) value, which represents the degree of yellowness (positive) and blueness

(negative). K/S values given by the reflectance spectrometer are calculated at λmax and are

directly correlated with the dye concentration on the dye substrate according to the Kubelka–

Munk equation: K/S = (1-R)²/2R, where K is the absorbance coefficient, S is the scattering

coefficient and R is the reflectance ratio. The difference in color strength depends on the

substituent present (auxochromes) and/or their position in the synthesized dyes, where a

bathochrome (i.e. electron-donating substituent, such as OH, NH₂and CH₃) may shift the

absorption towards higher wavelengths and therefore the color of the dye will deepen

(bathochromic effect). In contrast, a hypsochrome (i.e., electron-attracting substituent, such as

CHO, COR and NO₂) exhibits a hypsochromic effect, where color of the dye will lighten.

As shown in Table 2, the application of dyes "10a-c - 12a-c" to polyester fabrics

indicated that such dyes exhibit a good affinity for polyester fibers due to the satisfactory color

yields and accepted values of K/S. The color hue represented degrees of redness to yellowness as

indicated by the positive values of a* and b* on the red-green axis. Dyes 10 and 11 were lighter

than dyes 12 according to the color lightness values (L*). Figure 1 shows the build-up properties

of dyes "10a-c - 12a-c" under high temperature (HT) dyeing conditions, and no direct correlation

was observed between the relative molecular mass of these dyes and the build-up. This result

most likely reflects the importance of other parameters, such as dye solubility, which are dictated

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by the type of structural features within the dye. These results are consistent with those

previously reported by Műller, who studied the effect of substituents in the dye structure.²⁷

In vitro antioxidant potential of synthesized compounds

Antioxidant efficiency was performed using the DPPH free radical scavenging method

(H-donor method) and hydroxyl radical scavenging assay. These methods are based on different

mechanisms to provide complementary insight into the antioxidant activity of the synthesized

compounds.^28,29The antioxidant and hydroxyl radical scavenging activities (Tables S 1 and S 2,

Supplemental Materials) increased when the concentration of the tested compounds was doubled,

and most of the synthesized compounds exhibited very good antioxidant activity (i.e., pyridazine

 pyridine  quinoline analogues) relative to ascorbic acid, which was used as a standard due to

its higher antioxidant activity. The high antioxidant and scavenging activities of the tested

compounds may be due to the resonance phenomena of double bonds and lone pair electrons on

nitrogen. This structure may lead to radical formation in more than one site, especially on the

benzene ring attached to the nitro group, which is a highly electron withdrawing group that

enables the benzene ring to convert to a radical form and forms a new covalent bond with

another radical (e.g.,10c and 11a-c). In addition, protection against peroxides, peroxynitrite,

glutathione, peroxidase-like activity and metal–binding capacity due to organoselenium

analogues leads to antioxidant activity. This conclusion is also supported by previously reported

results.³⁰

Acute toxicity and antitumor activity

The median lethal dose (LD50) of the selected compounds (10a and 11a-c) based on their

in vitro antioxidant potential results, was measured in mice. The results indicated that the

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selected compounds were non–toxic at doses up to 500 mg kg-1B.wt (bodyweight of tested

mice).

Finally, the novel synthesized compounds were evaluated in vitro for their cytotoxic

activity against the Ehrlich Ascites Carcinoma Cell (EACC) line, and the viability percentage

was determined and listed in Table S 3. The synthesized compounds exhibited broad-spectrum

antitumor activity in the following order: pyridazine  pyridine  quinoline analogues.

Compounds 10b,c and 11b,c exhibited higher antitumor activity compared to the other tested

compounds, and compound 11c was the most active member in this study. The viability

percentage of the treated EACC decreased from 100 % in the control sample to 0 %, 4 %, 5 %

and 8 % at a concentration of 300 µM for compounds 11c, 11b, 10c and 10b respectively.

However, compounds 10a, 11a, 12b and 12c, exhibited moderate cytotoxicity and a decrease in

the viability percentage from 18 % to 12 % at a concentration of 300 µM of each compound. The

presence of the 4-phenyl function with a nitro group (e.g.,11c and 10c) and a methyl group

(e.g.,11b and 10b) increased the antitumor activity due to their high antioxidant and free radical

scavenging activities, as previously discussed and supported by previously reported results.³¹

Antimicrobial performance

An antimicrobial screening of synthesized compounds "10a-c–12a-c" against selected

Gram-positive, Gram-negative bacteria and fungi compared to tetracycline, which is a standard

antibacterial agent, and Amphotericin B, which is a standard antifungal agent, was performed,

and the results are listed in Table S 4. All of the tested compounds exhibited high broad-

spectrum antimicrobial activities against both gram-positive and gram-negative bacteria with

inhibition percentages in the range of 50 % to 78 %. These compounds exhibited moderate

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activities against the studied fungi with inhibition percentages in the range of 24 % to 40 %. The

presence of a strong electron-withdrawing group (e.g., compound 11c) resulted in higher activity

against the microorganisms under study.

CONCLUSIONS

A series of novel monoazo disperse dyes based on 3-amino-N-(5-arylazothiazol-2-

yl)selenopheno- (pyridine, pyridazine and quinoline)-2-acetamide was synthesized by

condensation reaction of different 2-(N-chloroacetyl)-5-arylazo-thiazole derivatives with seleno-

(pyridine, pyridazine and quinoline)carbonitrile derivatives. Analytical and spectral data

confirmed the proposed structures. The synthesized disperse dyestuffs were subsequently applied

to polyester fibers using a high temperature dyeing method at 130 °C, resulting strong shades

that varied from orange to brown. The color measurements and fastness properties of the dyed

fabrics indicated a high affinity of the synthesized dyes for the polyester fibers and very good to

excellent fastness properties. Finally, the entire novel synthesized compounds exhibit antioxidant

activity due to the protection against peroxide and peroxynitrite radicals, as well as antitumor

activity. In addition, these compounds are emerging as promising downstream candidates for

cancer therapy due to their ability to modulate multiple physiological functions implicated in

cancer development due to their antioxidant and anticancer chemo preventive or apoptotic

activities while being nontoxic. These compounds also have the potential for use as antibacterial

agents against different pathogenic bacteria and fungi.

EXPERIMENTAL

Materials and instrumentation

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The reagents were analytical grade or chemically pure. Elemental analyses (C, H, N, S)

were conducted using the Perkin-Elmer 2400 Analyzer, series II (Perkin Elmer Co., Shelton,

UK), their results were found to be in good agreement (±0.3%) with the calculated values. All of

the corrected melting points were determined using a Stuart SMP 20 melting point apparatus

(Bibby Scientific Limited, Staffordshire, UK). The infrared spectra were recorded on a Perkin

1

Elmer Alpha platinum-ATR spectrometer, and the H NMR spectra were measured on a Bruker

WP 300 (Bruker, MA, USA) in CF₃COOD using TMS as an internal standard. All of the

microanalyses and spectral analyses were performed at the Micro Analytical Centres of Taif (IR,

CHN) and King Abdel-Aziz University (¹H NMR and ¹³C NMR analysis), Kingdom of Saudi

Arabia. The dyeing processes, color assessments and color fastness properties were performed by

a chemical laboratory (i.e., Dakahlia for Spinning and Weaving Company, Mansoura, Egypt).

The dyeing process was carried out using a Galvanin-Marino VI dyeing machine (Galvanin Co.,

Saint Marino, Italy), and the colourimetric measurements for the dyed polyester fabrics were

performed using a reflectance GretagMacbeth CE 7000a spectrophotometer (GretagMacbeth

Co., Windsor, USA). Fastness to washing was performed using the automatic launder Rotadyer

(Texcare Co., Delhi, India), which was sponsored by the British Standard Institute, Society of

Dyers and Colourists. Fastness to perspiration was assessed according to the standard method of

testing sponsored by the British Standard Institute- Society of Dyers and Colourist (BSS).

Fastness to rubbing was carried out according to the standard method of testing sponsored by

(BSS) using a Crockmeter FD-17 apparatus (Electric Hungarian Co., Budapest, Hungary).

Fastness to sublimation was performed using the scorch tester M247 A (Atlas Electric Devices

Co., Chicago, IL, USA), and fastness to light was performed using the “Weather-o-meter” (Atlas

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Electric Devices Co., Chicago, IL, USA) according to the American Association of Textiles

Chemist and Colourist (AATCC) standard test method. The biological tests were performed by

the "Biotechnology Unit", Faculty of Agriculture, Cairo University, Egypt. The Ehrlich Ascites

Carcinoma Cell (EACC) line was supplied by "The National Cancer Institute", Egypt.

Synthesis and spectroscopic characterisation

General method for the synthesis of 5-aryl azo-2-aminothiazol derivatives (2a-c)

Coupling of molar ratio of 2-aminothiazole 1 with different diazotised aromatic amines

(aniline, p-toluidine, p-nitroaniline) in ethanol/sodium acetate at -5 °C was performed to obtain

the corresponding derivatives of 5-arylazo-2-aminothiazol 2a-c. The precipitate which formed

1

was collected by filtration, dried and recrystallized from ethanol. The IR and H NMR spectra

for the obtained compounds were recorded to characterise the structure of these compounds, and

were found to be in agreement with the literature.

2-Amino-5-phenylazo-thiazole (2a). Reddish brown solid; yield 84%; m.p.: 270-271 ºC;

Lit. m.p.: 270-271 ºC.³²

2-Amino-5-(p-tolyl)azo-thiazole (2b). Brown solid; yield 73%; m.p.: 207-209 ºC; Lit.

m.p.: 205 ºC. ³²

2-Amino-5-(p-nitrophenyl)azo-thiazole (2c). Brown solid; yield 80%; m.p.: 167-169

ºC; Lit. m.p.: 167-169 ºC.²⁰

General method for the synthesis of 2-[N-(chloroacetyl)amino]-5-arylazo-thiazoles

(3a-c).

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To a solution of 2-amino-5-arylazothiazoles 2a-c (10 mmol) in DMF (25 mL) containing

0.5 mL triethyl amine, chloroacetyl chloride (1.2 mL, 15 mmol) was added dropwise with

stirring at room temperature. Stirring was continued for 2 h and the reaction mixture was poured

to ice cooled water. The precipitate which formed was collected by filtration, dried and

recrystallized from the appropriate solvent. The structure of the synthesized compounds were

1

characterised using IR and H NMR spectra, and were found to be in agreement with those

previously reported.²⁰

2-[N-(chloroacetyl)amino]-5-phenylazo-thiazole (3a). Greenish yellow solid (EtOH);

yield 78%; m.p.: 220-222 ºC; Lit. m.p.: 220-222 ºC

2-[N-(chloroacetyl)amino]-5-(p-tolyl)azo-thiazole (3b). Yellowish brown solid

(EtOH); yield 82%; m.p.: 235-237 ºC; Lit. m.p.: 235-237 ºC

2-[N-(chloroacetyl)amino]-5-(p-nitrophenyl)azo-thiazole (3c). Dark brown solid

(EtOH-DMF); yield 85%; m.p.: 186-187 ºC; Lit. m.p.: 186-187 ºC

Synthesis of hydroseleno-(pyridine, pyridazine and quinoline)carbonitrile

derivatives (4-6)

2-hydroseleno-4,6-dimethylpyridine-3-carbonitrile

4,

3-hydroseleno-5,6-

diphenylpyridazine-4-carbonitrile and 5,6,7,8-tetrahydro-2-hydroseleno-4-(4'-

5

methoxyphenyl)quinoline-3-carbonitrile 6 were synthesized according to previously reported

1

methods and their characterized data (m.p., IR and H NMR) were in agreement with the

literature.

2-Hydroseleno-4,6-dimethylpyridine-3-carbonitrile (4). Brown solid (EtOH); yield

79%; m.p.: 214-215 °C, Lit. 214-216 °C.²¹

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3-Hydroseleno-5,6-diphenylpyridazine-4-carbonitrile (5). Brown solid (EtOH); yield

90%; m.p.: 219 °C, Lit. 218-220 °C.²³

5,6,7,8-Tetrahydro-2-hydroseleno-4-(4'-methoxyphenyl)quinoline-3-carbonitrile (6).

Dark brown solid (EtOH); yield 67%; m.p.: 171 °C; Lit.170-172 °C.³³

General procedure for the synthesis of seleno-(pyridine, pyridazine and/or

quinoline)carbonitrile derivatives (7a-c- 9a-c)

The mixtures of 2-(N-chloroacetyl)-5-arylazothiazole derivatives 3a-c (10 mmol) with 2-

hydroseleno-4,6-dimethylpyridine-3-carbonitrile 4 (2.12 g, 10 mmol), 3-hydroseleno-5,6-

diphenylpyridazine-4-carbonitrile 5 (3.36 g, 10 mmol) and/or 5,6,7,8-tetrahydro-2-hydroseleno-

4-(4'-methoxyphenyl)quinoline-3-carbonitrile 6 (3.43 g, 10 mmol) dissolved in DMF (30 mL)

containing aqueous KOH (10 %, 5 mL), were stirred for 2 h. The precipitates that formed were,

filtered, washed with water and recrystallised from ethanol affording seleno-(pyridine,

pyridazine and/or quinoline)carbonitrile derivatives "7a-c- 9a-c".

2-(3-Cyano-4,6-dimethylpyridin-2-yl-selanyl)-N-(5-phenylazothiazol-2-yl)acetamide

(7a). Yellow solid; yield 43 %; m.p.: 265- 268 °C; IR: υ= 3333 (NH), 2221 (CN) and 1697 (CO)

1

cm^-1. H NMR (CF₃COOD): /ppm=2.44 (s, 3H, CH₃), 2.51 (s, 3H, CH₃), 4.26 (s, 2H, CH₂),

6.91 (s, 1H, pyridine H-5), 7.41-7.51 (m, 5H, Ar-H), 7.92 (s, 1H, CH-thiazole). Anal. calcd. for

C₁₉H₁₆N₆OSSe (455.39): C, 50.11; H, 3.54; N, 18.45. Found; C, 49.87; H, 3.31; N, 18.23.

2-(3-Cyano-4,6-dimethylpyridin-2-yl-selanyl)-N-[5-(4-tolylazo)thiazol-2-

yl]acetamide (7b). Red solid; Yield 60 %; m.p.: 146- 148 °C; IR: υ= 3322 (NH), 2222 (CN) and

1

1693 (CO) cm^-1. H NMR (CF₃COOD): /ppm=2.43 (s, 3H, CH₃), 2.56 (s, 3H, CH₃), 2.69 (s,

3H, CH₃), 4.27 (s, 2H, CH₂), 7.08 (s, 1H, pyridine H-5), 7.25-7.73 (m, 4H, Ar-H), 7.91 (s, 1H,

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CH-thiazole). Anal. calcd. forC₂₀H₁₈N₆OSSe (469.42): C, 51.17; H, 3.86; N, 17.90. Found: C,

50.89; H, 4.1; N, 17.61.

2-(3-Cyano-4,6-dimethylpyridin-2-yl-selanyl)-N-[5-(4-nitrophenylazo)thiazol-2-

yl]acetamide (7c). Brown solid; yield 72 %; m.p.: 160-161 °C; IR: υ= 3304 (NH), 2228 (CN)

and 1698 (CO) cm^-1. ¹H NMR (CF₃COOD): /ppm=2.44 (s, 3H, CH₃), 2.55 (s, 3H, CH₃), 2.68 (s,

3H, CH₃), 4.29 (s, 2H, CH₂), 7.07 (s, 1H, pyridine H-5), 7.29-7.91 (m, 4H, Ar-H), 8.01 (s, 1H,

CH-thiazole). Anal. calcd. for C₁₉H₁₅N₇O₃SSe (500.39): C, 45.60; H, 3.02; N, 19.59. Found: C,

45.45; H, 3.37; N, 19.27.

2-(3-Cyano-4,6-diphenylpyridazin-2-yl-selanyl)-N-(5-phenylazothiazol-2-

yl)acetamide (8a). Brown solid; yield 53 %; m.p.: 158- 160 °C; IR: υ= 3331 (NH), 2221 (CN)

1

and 1695 (CO) cm^-1. H NMR (CF₃COOD): /ppm= 4.26 (s, 2H, CH₂), 7.48-7.89 (m, 15H, Ar-

H), 8.12 (s, 1H, CH-thiazole). Anal. calcd. for C₂₈H₁₉N₇OSSe (580.52): C, 57.93; H, 3.30; N,

16.89. Found; C, 57.61; H, 3.12; N, 16.60.

2-(3-Cyano-4,6-diphenylpyridazin-2-ylselanyl)-N-[5-(4-tolylazo)thiazol-2-

yl)acetamide (8b). Brown solid; yield 58 %; m.p.: 183 °C; IR: υ= 3220 (NH), 2224 (CN) and

1696 (CO) cm^-1. ¹H NMR (CF₃COOD): /ppm= 2.41 (s, 3H, CH₃), 4.28 (s, 2H, CH₂), 7.25-7.92

(m, 14H, Ar-H), 8.28 (s, 1H, CH-thiazole). Anal. calcd. for C₂₉H₂₁N₇OSSe (594.55): C, 58.58;

H, 3.56; N, 16.49. Found: C, 58.21; H, 3.75; N, 16.16.

2-(3-Cyano-4,6-diphenylpyridazin-2-yl-selanyl)-N-[5-(4-nitrophenylazo)thiazol-2-

yl)acetamide (8c). Brown solid; yield 63 %; m.p.: 169-170 °C; IR: υ= 3313 (NH), 2227 (CN)

and 1698 (CO) cm^-1. ¹H NMR (CF₃COOD): /ppm= 4.18 (s, 2H, CH₂), 7.34-8.55 (m, 15H, Ar-H

15

ACCEPTED MANUSCRIPT

and CH-thiazole). Anal. calcd. for C₂₈H₁₈N₈O₃SSe (625.52): C, 53.76; H, 2.90; N, 17.91. Found:

C, 53.57; H, 2.82; N, 17.60.

2-{[3-Cyano-4-(4'-methoxyphenyl)quinolin-2-yl-selanyl]-N-[5-(phenylazo)thiazol-2-

yl]}acetamide (9a). Brown solid; yield 63 %; m.p.: 133- 134 °C; IR: υ= 3331 (NH), 2221 (CN)

and 1697 (CO) cm^-1. ¹H NMR (CF₃COOD): /ppm= 1.89-3.22 (m, 8H, CH₂-cyclic), 3.85 (s, 2H,

CH₂), 4.04 (s, 3H, OCH₃), 7.41-7.51 (m, 9H, Ar-H), 7.95 (s, 1H, CH-thiazole). Anal. calcd. for

C₂₈H₁₈N₈O₃SSe (625.52): C, 53.76; H, 2.90; N, 17.91. Found: C, 53.57; H, 2.82; N, 17.60.

2-{[3-Cyano-4-(4'-methoxyphenyl)quinolin-2-yl-selanyl]-N-[5-(4-tolylazo)thiazol-2-

yl]}acetamide (9b). Brown solid; yield 49 %; m.p.: 141- 142 °C; IR: υ= 3328 (NH), 2221 (CN)

and 1695 (CO) cm^-1. ¹H NMR (CF₃COOD): /ppm= 1.81-3.24 (m, 8H, CH₂-cyclic), 2.52 (s, 3H,

CH₃), 3.85 (s, 2H, CH₂), 4.04 (s, 3H, OCH₃), 7.52-7.83 (m, 8H, Ar-H), 7.91 (s, 1H, CH-

thiazole). Anal. calcd. for C₂₉H₂₆N₆O₂SSe (601.58): C, 57.90; H, 4.36; N, 13.97. Found: C,

57.61; H, 4.43; N, 13.69.

2-{[3-cyano-4-(4'-methoxyphenyl)quinolin-2-yl-selanyl]-N-[5-(4-

nitrophenylazo)thiazol-2-yl]}acetamide (9c). Brown solid; yield 56 %; m.p.: 148 °C; IR: υ=

3314 (NH), 2225 (CN) and 1698 (CO) cm^-1. ¹H NMR (CF₃COOD): /ppm= 1.82-3.21 (m, 8H,

CH₂-cyclic), 3.85 (s, 2H, CH₂), 4.04 (s, 3H, OCH₃), 7.52-7.84 (m, 8H, Ar-H), 7.91 (s, 1H, CH-

thiazole). Anal. calcd. for C₂₈H₂₃N₇O₄SSe (632.55): C, 53.17; H, 3.66; N, 15.50. Found: C,

52.90; H, 3.87; N, 15.48.

General procedure for the synthesis of 3-amino substituted N-(5-arylazothiazol-2-

yl)selenopheno-pyridine, pyridazine and/or quinoline-2-carboxamide Derivatives (10a-c-

12a-c)

16

ACCEPTED MANUSCRIPT

Treatment of resultant compounds "7a-c- 9a-c" (10 mmol) with an excess amount of

aqueous 10 % KOH (5 mL) in DMF, and stirring for an additional 2 h., affording the

corresponding derivatives "10a-c-12a-c". The precipitates formed were filtered and recrystallised

from ethanol.

3-Amino-4,6-dimethyl-N-(5-phenylazothiazol-2-yl)selenopheno[2,3-b]pyridine-2-

acetamide (10a). Orange solid; yield 39 %; m.p.: 300°C; IR: υ= 3177, 3280 (NH, NH₂) and

1

1632 (CO) cm^-1. H NMR (CF₃COOD): /ppm = 2.43 (s, 3H, CH₃), 2.54 (s, 3H, CH₃), 7.15 (s,

1H, pyridine H-5), 7.32-7.81 (m, 5H, Ar-H), 7.93 (s, 1H, CH-thiazole). ¹³C NMR (300 MHz,

DMSO, TMS): δ 163.9 (CONH), 162.8 (CH-S), 148.6 (C-NH₂), 149.1 (C-Se), 158.1, 122.5,

149.1, 142.3, 129.1 (pyridine C), 162.6, 147, 108.2 (thiazole C) and 142.4, 158.2 (2 C-CH₃of

pyridine ring), 128.8, 129.1, 125.4. Anal. calcd. for C₁₉H₁₆N₆OSSe (455.39): C, 50.11; H, 3.54;

N, 18.45. Found: C, 50.08; H, 3.30; N, 18.17.

3-Amino-4,6-dimethyl-N-[5-(4-tolylazo)thiazol-2-yl]selenopheno[2,3-b]pyridine-2-

actamid (10b). Yellowish brown solid; yield 42 %; m.p.: 156-157°C; IR: υ= 3494, 3329, 3189

1

(NH, NH₂) and 1636 (CO) cm^-1. H NMR (CF₃COOD): /ppm =2.44 (s, 3H, CH₃), 2.83 (s, 3H,

CH₃), 3.09 (s, 3H, CH₃), 7.33 (s, 1H, pyridine H-5), 7.47-7.95 (m, 4H, Ar-H), 8.65 (s, 1H, CH-

13

thiazole). C NMR (300 MHz, DMSO, TMS): δ 163.6 (CONH), 162.7 (CH-S), 148.5 (C-NH₂),

149.3 (C-Se), 158.4, 122.4, 149.3, 142.3, 129 (pyridine C), 162.7, 147, 108.2 (thiazole C), 138

(C-CH₃of aromatic ring), 142.3, 158.4 (2 C-CH₃of pyridine ring) and 128.7, 129, 125.5. Anal.

calcd. for C₂₀H₁₈N₆OSSe (469.42): C, 51.17; H, 3.86; N, 17.90. Found: C, 50.86; H, 3.68; N,

17.63.

17

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3-Amino-4,6-dimethyl-N-[5-(4-nitrophenylazo)thiazol-2-yl]selenopheno[2,3-

b]pyridine-2-actamide (10c). Dark brown solid; yield 62 %; m.p.: 176 °C; IR: υ= 3418, 3293

1

(NH, NH₂) and 1644 (CO) cm^-1. H NMR (CF₃COOD): /ppm =2.43 (s, 3H, CH₃), 2.81 (s, 3H,

13

CH₃), 7.19 (s, 1H, pyridine H-5), 7.48-7.92 (m, 4H, Ar-H), 8.31 (s, 1H, CH-thiazole). C NMR

(300 MHz, DMSO, TMS): δ 163.7 (CONH), 162.4 (CH-S), 148.3 (C-NH₂), 149.3 (C-Se), 158.1,

122.3, 149.3, 142.3, 129 (pyridine C), 162.8, 147.1, 108.3 (thiazole C), 148 (C-NO₂of aromatic

ring), 142.5, 158.3 (2 C-CH₃of pyridine ring), 128.1, 129, 122.1. Anal. calcd. for

C₁₉H₁₅N₇O₃SSe (500.39): C, 45.60; H, 3.02; N, 19.59. Found: C, 45.37; H, 2.86; N, 19.32.

3-Amino-4,6-diphenyl-N-(5-phenylazothiazol-2-yl)selenopheno[2,3-b]pyridazine-2-

acetamide (11a). Brown solid; yield 41 %; m.p.: 168-169 °C; IR: υ= 3178, 3291 (NH, NH₂) and

1

1635 (CO) cm^-1. H NMR (CF₃COOD): /ppm= 7.41-7.82 (m, 15H, Ar-H), 8.30 (s, 1H, CH-

13

thiazole). C NMR (300 MHz, DMSO, TMS): δ 163.1 (CONH), 162.7 (CH-S), 164.1 (C-NH₂),

164 (C-Se), 164.5, 164, 31.1, 31.9 (pyridazine C) and 162.7, 147, 108.1 (thiazole C), 140.6,

140.5, 133.8, 131.2, 129.2, 129.1, 128.8, 128.7, 128,5, 127.9, 127.8, 120.44. Anal. calcd. for

C₂₈H₁₉N₇OSSe (580.52): C, 57.93; H, 3.30; N, 16.89. Found; C, 57.76; H, 3.34; N, 16.68.

3-Amino-4,6-diphenyl-N-[5-(4-tolylazo)thiazol-2-yl]selenopheno[2,3-b]pyridazine-2-

acetamide (11b). Reddish brown solid; yield 57 %; mp: 230-233 °C; IR: υ= 3490, 3328, 3189

(NH, NH₂) and 1639 (CO) cm^-1. ¹H NMR (CF₃COOD): /ppm= 2.40 (s, 3H, CH₃), 7.21-7.87 (m,

13

14H, Ar-H), 8.20 (s, 1H, CH-thiazole). C NMR (300 MHz, DMSO, TMS): δ 163.2 (CONH),

162.7 (CH-S), 164.2 (C-NH₂), 164 (C-Se), 164.5, 164, 31.1, 31.9 (pyridazine C), 162.7, 147,

108.1 (thiazole C) and 138.3 (C-CH₃of aromatic ring), 140.6, 140.5, 133.8, 131.2, 129.2, 129.1,

18

ACCEPTED MANUSCRIPT

128.8, 128.7, 128,5, 127.9, 127.8, 120.42. Anal. calcd. for C₂₉H₂₁N₇OSSe (594.55): C, 58.58; H,

3.56; N, 16.49. Found: C, 58.73; H, 3.70; N, 16.38.

3-Amino-4,6-diphenyl-N-[5-(4-nitrophenylazo)thiazol-2-yl]selenopheno[2,3-

b]pyridazine-2-acetamide (11c). Dark brown solid; yield 62 %; m.p.: 180 °C; IR: υ= 3423,

1

3291 (NH, NH₂) and 1650 (CO) cm^-1. H NMR (CF₃COOD): /ppm = 7.34-8.42 (m, 14H, Ar-

H), 8.25 (s, 1H, CH-thiazole). ¹³C NMR (300 MHz, DMSO, TMS): δ 163.2 (CONH), 162.7

(CH-S), 164.2 (C-NH₂), 164 (C-Se), 164.5, 164, 31.1, 31.9 (pyridazine C), 162.7, 147, 108.1

(thiazole C) and 148.2 (C-NO₂of aromatic ring), 140.6, 140.5, 133.8, 131.2, 129.2, 129.1, 128.8,

128.7, 128,5, 127.9, 127.8, 120. Anal. calcd. for C₂₈H₁₈N₈O₃SSe (625.52): C, 53.76; H, 2.90; N,

17.91. Found: C, 53.61; H, 2.84; N, 17.76

3-Amino-5,6,7,8-tetrahydro-4-(4-methoxyphenyl)-N-(5-phenylazothiazol-2-

yl)selenopheno[2,3-b]quinoline-2-acetamide (12a). Brown solid; yield 43 %; m.p.: 142-144

1

°C; IR: υ= 3176, 3283 (NH, NH₂) and 1637 (CO) cm^-1. H NMR (CF₃COOD): /ppm = 1.80-

3.20 (m, 8H, CH₂-cyclic), 4.04 (s, 3H, OCH3), 7.40-7.50 (m, 9H, Ar-H), 7.85 (s, 1H, CH-

thiazole). ¹³C NMR (300 MHz, DMSO, TMS): δ 163.1 (CONH), 162.6 (CH-S), 161.3 (C-

OCH₃), 148.2 (C-NH₂), 115.3 (C-Se), 135, 156.8, 128, 147.1 (pyridine C), 147, 108.2 (thiazole

C) and 128.3, 114.6, 130.1, 128, 65, 23. Anal. calcd. for C₂₈H₂₄N₆O₂SSe (587.55): C, 57.24; H,

4.12; N, 14.30. Found: C, 57.09; H, 4.29; N, 14.11.

3-Amino-5,6,7,8-tetrahydro-4-(4-methoxyphenyl)-N-[5-(4-tolylazo)thiazol-2-

yl]selenopheno[2,3-b]quinoline-2-acetamide (12b). Reddish brown solid; yield 50 %; m.p.:

1

154-155 °C; IR: υ= 3491, 3329, 3190 (NH, NH₂) and 1640 (CO) cm^-1. H NMR (CF₃COOD):

/ppm = 1.80-3.20 (m, 8H, CH₂-cyclic), 2.50 (s, 3H, CH₃), 4.04 (s, 3H, OCH₃), 7.50-7.80 (m,

19

ACCEPTED MANUSCRIPT

8H, Ar-H), 7.90 (s, 1H, CH-thiazole). ¹³C NMR (300 MHz, DMSO, TMS): δ 163.6 (CONH),

162.5 (CH-S), 161.4 (C-OCH₃), 148.4 (C-NH₂), 115.3 (C-Se), 135, 156.7, 128, 147.2 (pyridine

C), 147.1, 108.2 (thiazole C), 24.2 (C-CH₃) and 128.5, 114.6, 129.7, 128, 65, 23. Anal. calcd. for

C₂₉H₂₆N₆O₂SSe (601.58): C, 57.90; H, 4.36; N, 13.97. Found: C, 57.65; H, 4.27; N, 13.63.

3-Amino-5,6,7,8-tetrahydro-4-(4-methoxyphenyl)-N-[5-(4-nitrophenylazo)thiazol-2-

yl]selenopheno[2,3-b]quinoline-2-acetamide (12c). Dark reddish brown solid; yield 58 %;

m.p.: 168-170 °C; IR: υ= 3423, 3295 (NH, NH₂) and 1649 (CO) cm^-1.¹H NMR (CF₃COOD):

/ppm = 1.80-3.20 (m, 8H, CH₂-cyclic), 4.04 (s, 3H, OCH₃), 7.50-7.80 (m, 8H, Ar-H), 7.95 (s,

13

1H, CH-thiazole). C NMR (300 MHz, DMSO, TMS): δ 163.5 (CONH), 162.6 (CH-S), 161.1

(C-OCH₃), 148.6 (C-NH₂), 115.4 (C-Se), 135.1, 156.9, 128, 147.1 (pyridine C), 146.8, 108

(thiazole C), 148.2 (C-NO₂) and 129.5, 134.6, 121, 1114.7, 31, 23, 22.8. Anal. calcd. for

C₂₈H₂₃N₇O₄SSe (632.55): C, 53.17; H, 3.66; N, 15.50. Found: C, 53.02; H, 3.72; N, 15.31.

Dyeing and dyeing performance

Dye bath preparation and dyeing procedure

The dispersion of each dye was achieved by dissolving the appropriate amount of dye

(0.1g dye/ 5g fiber, 2 % shade) in acetone (1 mL) followed by dropwise addition with stirring to

a solution of Setamol WS (0.5 – 1.5), which is an anionic dispersing agent made from BASF

(sodium salt of a condensation product of naphthalene sulfonic acid and formaldehyde). Then,

the dyestuff dispersion was added to the dyebath at 60 ºC through a fine mesh sieve or filter

cloth. Dyeing was performed at a mass liquor ratio of 20:1 in sealed, stainless steel dye pots with

a 200 cm³capacity using a “Galvanin-Marino VI” dyeing machine. An appropriate volume of

the dye stock solution was placed in each pot to provide the desired quantity of dye (2.0 %

20

ACCEPTED MANUSCRIPT

o.m.f.). An additional dispersing agent (1.0 g/L Setamol WS of BASF) was added, and the pH of

the bath was adjusted to 5.5 using glacial acetic acid. A pre-weighed, wetted-out polyester fibre

was immersed in each pot, and the high temperature (HT) dyeing process was performed by

raising the dye bath temperature from 20 to 130 ºC at a rate of 3 ºC /min, which was maintained

for 60 min and followed by rapid cooling (9.9ºC/min) to 50 ºC, as shown in Fig. 2. Then, the

dyed fibers were rinsed with cold water and reduction cleared [2 mL/L caustic soda solution 32.5

% (71ºTw), 2 g/L sodium hydrosulphite and 0.5 g/L Hostapal CV conc., non-ionic wetting agent

made from Clariant] at 60 ºC for 10 minutes. After clearing, the samples were soaped with a 2 %

non-ionic detergent and ammonia (pH 8.5) at 50 ºC for 30 minutes to improve washing fastness

and then rinsed successively with hot and cold water. Finally, the dyed samples were dried in a

pre-drier without contact up to residual moisture of approximately 30 % followed by final drying

on a hot flue.

Dyeing Characteristics of the polyester fibers

Color fastness tests

The color fastness properties of the dyed fibers to washing, perspiration, rubbing,

sublimation and light were evaluated using standard methods.²⁴The results are listed in Table 1,

and the staining of adjacent cotton fabrics was assessed using the grey scale (i.e., 1-poor, 2-fair,

3-moderate, 4-good and 5-excellent), except for light fastness, which was scaled from 1-8 on the

grey scale.

Color properties of the dyes on polyester

21

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The colorimetric properties of the dyeing (D₆₅illumination, 10° observer) were

determined using a Color Eye reflectance spectrophotometer (GretagMacbeth CE 7000a).

Screening of biological activities of the synthesized dyes

In vitro antioxidant potential of synthesized compounds

DPPH radical scavenging activity

The scavenging effect of the 2,2 diphenyl-1-picrylhydrazyl (DPPH) free radical was

measured by the method reported by Chou et al. and is expressed in terms of the inhibition

percentage (I %).²⁸Different concentrations of the synthesized compounds (100, 200 and

300µM) with 0.1 mL of a 1 mM DPPH-methanol solution were incubated at room temperature

for 30 min. The absorbance (A) of each solution was measured at 517 nm against a blank

containing ascorbic acid using equation 1.

Acontrol  Asample

I % 

100

Eq.1.

Acontrol

ydroxyl radical scavenging assay

The hydroxyl radical scavenging activity was measured according to Nagai et al.,²⁹where

mixtures of various concentrations of the synthesized compounds (100, 200, 300 µM) with 0.45

mL of a sodium phosphate buffer solution (0.2M), 0.15 mL of a 2-deoxyribose solution (10

mM), 0.15 mL of an FeSO₄-EDTA solution (10 mM) and 0.15 mL of H₂O₂(10 mM) were

prepared and filled to the final volume (1.5 mL) with distilled water. The solutions were

incubated at 37 °C for 4 h, and the reaction was terminated by adding 0.75 mL of a

trichloroacetic acid solution (70 % w/v) and 0.75 mL of a thiobarbituric acid solution (50 mM).

22

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The absorbance (A) was measured at 520 nm, and the inhibition of deoxyribose degradation as a

percentage (I %) was calculated according to equation 1.

In vitro acute toxicity and antitumor activity

Acute toxicity (LD50)

The median lethal dosage (LD₅₀) values of selected compounds (10c, 11a, 11b and 11c)

based on in vitro antioxidant potential results were determined in mice. LD₅₀represents the

individual dose required to kill 50 % of a population of tested animals (e.g., rats, fish, mice,

cockroaches). A group of five female adult albino mice (25-30g) was injected intraperitoneally

(I.P) with graded doses of 100-1000 mg Kg^-1of body weight for each selected compound

suspended in DMSO. The percentage of mortality was determined 72 h after injection. The LD₅₀

calculation was processed using a graphical method.³⁴

In vitro antitumor activity

Female Swiss albino mice (25-30g) were housed at a constant temperature (24±2 ^oC) with

alternating 12 h of light and dark cycles and were fed standard laboratory food (Milad Co) along

with ad libitum water. The care and handling of the animals were performed according to the

guidelines of "The World Health Organization, Geneva, Switzerland". A strain of Ehrlich Ascites

Carcinoma Cells (EACC) was supplied by "The National Cancer Institute", Egypt. The tumour

cell line was maintained in female Swiss albino mice through serial intraperitoneal inoculation at

7 or 8 day intervals in the form of ascites.

In vitro cytotoxicity

The EACC cells were obtained by needle aspiration of the ascitic from preinoculated

mice under aseptic conditions according to the method reported by Uma Dev et al.³⁵The tumour

23

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cell suspension (2×10⁶cells per mL) was prepared in RPMI-1640 media, 10 % Foetal bovine

serum and L-glutamine. The tested compounds with different concentrations (i.e., 100, 200, 300

µM) in DMSO were incubated overnight with 2 mL of suspended tumour cells under 5 % CO₂at

o

37 C. The trypan blue exclusion method reported by Bennett et al. was used to calculate the

viability percentage of tumour cells using equation 2.³⁶

No.ofviablecells

Cellviability% 

100

Eq.2

.

Totalno.ofcells

tibacterial and antifungal activities

The antibacterial activity of novel synthesized compounds "10a-c – 12a-c" (100 µg/mL

in DMSO) was determined in vitro using the disc diffusion method,³⁷against a variety of

pathogenic microorganisms, such as Gram-positive bacteria (i.e., Bacillus subtilis and

Staphylococcus aureus) and Gram-negative bacteria (i.e., Escherichia coli and Salmonella

typhimurium), in nutrient agar media by measuring the zone of inhibition in mm. The antifungal

screening of the synthesized compounds was also carried out in vitro using the same method

against two fungi strains of Aspergillus flavus and Candida albicans. In addition, Tetracycline

and Amphotericin B served as standard antibacterial and antifungal agents, respectively, and both

served as positive controls for antimicrobial activity.

ACKNOWLEDGEMENTS

The authors wish to thank the research sector of the Faculty of Science, Taif University,

Kingdom of Saudi Arabia, for their financial and technical support of this project (research no.1-

434-2327).

24

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ACCEPTED MANUSCRIPT

O

Ar

N

Ar

N

S

N

ArN₂

ClCH₂COCl

NH₂

Cl

NH

N

2a-c

N

3a-c

1

Compound

2,3a

Ar

Ph

4-CH₃-Ph

4-O₂N-Ph

2,3b

2,3c

Scheme 1 Synthesis of 5-arylazo-2-chloro-N-(thiazol-2-yl)acetamide derivatives 3a-c.

28

ACCEPTED MANUSCRIPT

Me

CN

Me

N

Me

N

H₂N

NC

N

Me

N

SeH

O

N

DMF/KOH

4

N N

N C CH₂

S

N N

N

Se

Me

Se

Me

S

H

DMF/KOH

Ar

H

Ar

O

10a-c

7a-c

Ph

CN

Ph

H₂N

Ph

N

NC

Ph

N

DMF/KOH

Ar

N

SeH

O

N

3

N N

N

N C CH₂

5

N

S

N N

N

Se N

Se

N

H

S

DMF/KOH

OCH₃

Ar

H

O

8a-c

11a-c

OCH₃

CN

H₂N

NC

N

DMF/KOH

Ar

N

6

SeH

O

N

N N

N C CH₂

S

N N

N

Se N

DMF/KOH

Se

N

S

H

Ar

H

O

9a-c

12a-c

Compound

7-12a

Ar

Ph

4-CH₃-Ph

4-O₂N-Ph

7-12b

7-12c

Scheme

2

Synthesis of 3-amino-N-(5-arylazothiazol-2-yl)selenopheno[2,3-b]pyridine,

pyridazine and/or quinoline-2-carboxamide derivatives "10a-c-12a-c"

29

ACCEPTED MANUSCRIPT

Article Doi

Synthesis and biological activity of novel arylazothiazole disperse dyes containing selenium for dyeing polyester fibers

DOI: 10.1080/10426507.2014.948622

Source and publish data:

Authors:

Article abstract of DOI:10.1080/10426507.2014.948622

Full text of DOI:10.1080/10426507.2014.948622

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