Journal

of Chemical
Technology
Metallurgy,
1, 2015
Journal
of Chemical
Technology
andand
Metallurgy,
50,50,
1, 2015,
20-25

SYNTHESIS AND INVESTIGATION

OF SOME ACID AZO DYES FOR WOOL
Polya M. Miladinova1, Reny K. Vaseva1, Varbina R. Lukanova2

Department of Organic Synthesis,

University of Chemical Technology and Metallurgy
8 Kl. Ohridski, 1756 Sofia, Bulgaria
E-mail: ppolya@uctm.edu
2
Department of Textile and Leather,
University of Chemical Technology and Metallurgy
8 Kl. Ohridski, 1756 Sofia, Bulgaria
1

Received 15 July 2014

Accepted 21 November 2014

ABSTRACT
The present paper describes the synthesis of one mono and two bisazo dyes with yellow, orange and red colour, which
can be used as dyes for wool. They were obtained by the diazotization of a monoazo component of the mono-azobenzene
type, followed by coupling with I-acid and H-acid. The monoazo components were obtained by the diazotization of sulphanilic acid and coupling with p-toluidine. All synthesized dyes were later analyzed by chromatography, IR and UV-Vis
spectrometry. The dyeing performance of all dyes was evaluated on wool fabrics and their fastness properties were studied.
Keywords: acid mono and disazo dyes, UV-Vis spectroscopy, fastness properties on wool.

INTRODUCTION
Synthetic azodyes are extensively used in textile
dyeing, paper printing, color photography, pharmaceutical, food, cosmetics and other industries [1, 2]. Among
them the textile industry is a major consumer. These
dyes have characteristically good tinctorial strength as
well as stability. Their preparation procedures by the
classic diazotization and coupling reactions, are very
simple and of low cost. They have found wide application in dyeing of protein fibers such as wool, angora,
cashmere, and silk, as well the milk protein fiber called
Silk Latte, the soy protein fiber called Soy Silk, and
the synthetic polyamide fiber nylon [3 - 16], prints, inks,
and toners, dyes for food [17] and cosmetics. Azo compounds have also found their way into high-technology

20

areas, such as colorants for liquid-crystalline materials

and photoconductors for photoreceptors in copiers and
laser printers [18].
H-acid (1-amino-8-naphtol-3,6-disulfonic acid)
and I-acid (6-amino-1-naphtol-3-sulfonic acid) are of
the most important dye intermediates. They are widely
used in the chemical and the pharmaceutical industries
for the synthesis of direct, acid, reactive and azoic dyes.
The present study is focused on mono and disazo
acid dyes, which are H-acid and I-acid derivatives, and
investigates their application in the textile industry.
EXPERIMENTAL
Materials, equipment and analysis
I-acid, p-toluidine and sulfanilic acid (4-aminobenzenesulfonic acid) were bought from Fluka. H-acid

Polya M. Miladinova, Reny K. Vaseva, Varbina R. Lukanova

was Sigma-Aldrich product. Infrared (IR) spectra were

recorded on a Specord 71 IR Spectrophotometer (Carl
Zeiss, Germany), using potassium bromide (KBr) pellets. Ultravioletvisible (UV-Vis) absorption spectra
were recorded on a Hewlett Packard 8452A UV Vis
spectrophotometer (Germany) in a water solution (2.5 x
10-4 g ml for monoazo dyes and 3 x 10-5 gml for bisazo
dyes). The thin-layer chromatography (TLC) measurements were performed on ready-to-use plates (20 x 20
mm), pre-coated with 0.2 mm silica gel 60F254. 100 %
wool fabrics, mass per unit area 19510 g.m-2, linear
density: warp tex 20 x 2, weft tex 20 x 2 were also used.
Synthesis of the compounds
Synthesis of dye 1
For the synthesis of 1, 0.1 mol (17.3 g) sulphanilic
acid is dissolved into a solution of 0.056 mol (5.9 g)
sodium carbonate into 200 ml water, to which 0.1 mol
(6.9 g) sodium nitrite as 30 % water solution are added.
This solution is further poured slowly, upon continuous
stirring, over a mixture of 22.6 ml 30 % hydrochloric
acid and 100 g ice. The temperature is kept 0 - 5.
After an hour the reaction of diazotization was finished.
0.1 mol (10.7 g) p-toluidine was dissolved at room
temperature into 35 ml water to which 15 ml 30 % hydrochloric acid were added. The solution of the coupling
component is slowly poured with continuous stirring

into the diazo derivative solution. The reaction was

performed at 10 - 15 and pH 4 - 4.5 (7 g of sodium
acetate). The process was monitored by TLC on silica
gel plates using as an eluent system chloroform : acetone
(2:1, vv). After 3 h when the process was completed, to
the mixture 15.9 g sodium carbonate were added until
reaching pH 8 - 8.5. Dye 1 was isolated using 15 % NaCl,
filtered off and dried at 40 under vacuum.
The monoazo dye 1 was characterized and identified,
the obtained data are given in Table 1.
Synthesis of dye 2
For the synthesis of 2, 0.007 mol (2.037 g) of the
monoazo dye 1 is dissolved into a solution of 0.005 mol
(0.500 g) sodium carbonate into 8 ml water, to which
0.007 mol (0.483 g) sodium nitrite as 30 % aqueous solution are added. This solution is further poured slowly,
upon continuous stirring, over a mixture of 2.2 ml 30
% hydrochloric acid and 50 g ice. The temperature is
kept 0 - 5. After an hour the reaction of diazotization
is finished. The diazotized dye 1 without isolation was
used for coupling with I acid or H acid.
0.007 mol (1.673 g) of l acid were dissolved at room
temperature into 35 ml water by adding of 4 ml 20 %
sodium carbonate. To this solution the diazotized dye 1
was slowly poured with continuous stirring. The reaction
was performed at 10 - 15 and pH 8 - 8.5 using 1 g of

Table 1. Characteristic data for the mono and bisazo dyes.

Dye

Yield,

[%]

93

Rf*
0.46

max,

log ,

nm

-1

l.mol .cm

cm-1

436

5.05

3442, 3379 and 1600 (NH2); 3022, 2917 and

IR (KBr),
-1

1450 (C-H); 2860 and 1302 (CH3); 1513 and

1032 (N=N); 1211 (S-O); 885 and 819 (=CH)
2

88

0.50

492

6.25

3581 and 2431 (OH); 3435 and 1592 (NH);

3042, 2905 and 1484 (C-H); 1572 and 1032
(N=N); 1204 (S-O); 876, 843 and 755 (=CH)

83

0.39

538

6.32

3428, 3380 and 1577 (NH2); 3025, 2917, 1610

and 1508 (C-H); 2860 and 1341 (CH3);1577
and 1042 (N=N); 1424 (S-O); 1042 (C-N); 974,
and 812 (=CH)

LC on silica gel in a solvent system - chloroform: acetone 2:1

21

Journal of Chemical Technology and Metallurgy, 50, 1, 2015

sodium carbonate. The process was monitored by TLC

on silica gel plates with chloroform : acetone (4:1, vv)
as eluent system. After 5 h the process was completed.
The dye 2 was isolated using 15 % of NaCl, filtered off
and dried at 40 under vacuum.
Synthesis of dye 3
0.007 mol (2.233 g) of H acid were dissolved at room
temperature into 35 ml water by adding of 6 ml 20 %
sodium carbonate. To these solutions the diazotized dye
1, prepared previously was slowly poured with continuous stirring. The reaction was performed at 10 - 15
and pH 8 - 8.5 using with 0.9 g of sodium carbonate.
The process was monitored by TLC on silica gel plates
with chloroform : acetone (4:1, vv), as eluent system
After 6 h the process was completed. The dye 3 was
isolated using 15 % of NaCl, filtered off and dried at
40 under vacuum.
Dyeing procedure
Dyeing was carried out using all of the synthesized
dyes of 2 % on weight of fibre, usually expressed as
percentage (o.w.f.), unless otherwise specified in water
with a liquor ratio 50:1. The dyes solutions were obtained
by dissolving the dyes in water. To these solutions at
temperature 35 - 40, 10 % sodium sulphate and 4 %
acetic acid with concentration of 30 % were added. Then
the previously wetted wool material (1 g) was dipped
into the dye bath and dyed for 30 min at this temperature. Then the temperature was raised to boiling and the
material was boiled for 30 min. After dyeing, the wool
samples were withdrawn and washed at 40.
Measurements and analyses
Dye exhaustion
The uptake of the acid azodyes by wool in the
blend fabric was measured by sampling the dye bath

before and after the dyeing. The concentration (g/l) of

the dye bath was measured on a HP8452A UV/visible
spectrophotometer at max of the corresponding dye.
The percentage of the individual dye exhaustion on
wool (% E) was calculated using Eq. (1) [19]. Data are
given in Table 2.
%E =

C1 - C2
C1

. 100

(1)

where: E - degree of dye exhaustion from the dyeing

bath, %, C1, C2 - concentration of the dye before and
after dyeing, respectively.
Dye fixation
The dye fixation ratio (% F), the percentage of the
exhausted dye chemically bound on the blend fabric,
was measured by refluxing the dyed samples in water for
15 min to extract the unfixed dye. This procedure was
repeated until the extract was clear. The concentration
of the extract was then measured spectrophotometrically
at max and the percentage dye fixation ratio (% F) on
wool was calculated with eq. (2) [20]. The obtained data
are given in Table 2.
%F =

C1 - C2 - C3
C1 - C2

. 100

From the dye bath exhaustion (E) and dye fixation

ratio (F), the total dye fixation (T), which is the percentage of dye chemically bound relative to the total amount
of dye used, was calculated for dyeing wool (% T) using
eq. (3) [20]. The obtained data are given in Table 2.

%T =

%E . %F

(3)

100

Table 2. Exhaustion (E), fixation (F) and total fixation (T) of acid azo dyes on wool.

22

(2)

Dyes

E, %

F, %

T, %

78

79

62

79

86

68

82

88

72

Polya M. Miladinova, Reny K. Vaseva, Varbina R. Lukanova

Fastness testing
The dyed samples were tested, after washing-off
using 2 g/l non-ionic detergent at 40 for 15 min, according to the ISO standard methods. The specific tests
were: BDS EN ISO 105-X12 (2004), colour fastness
to rubbing; BDS EN ISO 105-C06/A1S (2010), colour
fastness to washing; and BDS EN ISO 105-E04 (2013),
colour fastness to perspiration.
RESULTS AND DISCUSSION
Synthesis of the dyes
The paper presents the synthesis and the description
of three synthesized azo dyes (monoazo dye 1 and bisazo
dyes 2 and 3) with the structures presented in Fig. 1.
The bisazo dyes were obtained from the diazotization of the monoazo dye 1 and the coupling of the
resulting diazonium salt with I acid (for dye 2) or H
acid (for dye 3).
The monoazo dyes 1 was obtained from the diazotization of the sulphanilic acid and the coupling of the
resulting diazonium salt with p-toluidine.
Spectral investigations
In order to characterize the synthesized compounds
and to determine the influence of the functional groups

on their spectral properties, spectrophotometric investigations were carried out. The absorption UVVis spectra
of the compounds in water were recorded. The data are
presented in Table 1.
One can see from the data shown that all compounds
absorb in the visible region between 436 and 538 nm.
The coupling of the yellow monoazo dye 1 with I acid
and H acid show bathochromic shift in max of absorption (the dye with I acid is orange and the dye with H
acid is red in colour). The values of the logarithm of
the molar extinction coefficient (log ) of all dyes were
in the range of 5.05 - 6.32, consistent with their high
absorption intensity.
Dyeing and fastness properties of the dyes
The dyes were applied at 2 % depth on wool fabric
and intensively colored samples were obtained. The
percentage exhaustion, fixation and total fixation were
calculated for all dyed samples by measuring visible
absorbance at the given max of the dye solutions before
and after dyeing. The results are shown in Table 2. The
total fixation percentages of the dyes lie in the range of
62 to 72.
The results from the fastness tests of washing, rubbing and perspiration of samples that had been dyed with

Fig. 1. Structures of the synthesized azo dyes.

23

Journal of Chemical Technology and Metallurgy, 50, 1, 2015

Table 3. Fastness properties of dyed wool fabrics.

Dye

Washing

Perspiration fastness

Rubbing
fastness

fastness
Acid

Alkaline

Dry

Wet

5/5/4

5/4/4

5/4/4

5/3/4

5/3/3

5/ 3 / 3

5/3/5

5/3/3

5/3/3

Fastness: 1 - poor, 2 - fair, 3 - good, 4 - very good, 5 - excellent

the synthesized dyes are given in Table 3. The dyeing

showed a good to very good fastness to washing, perspiration and rubbing.
CONCLUSIONS
As a result of the present study, three new acid dyes,
one mono and two bisazo dyes were obtained. All newly
synthesized dyes exhibited good to very good fastness
to washing, perspiration and rubbing. They can be used
as dyes for wool.
REFERENCES
1. H. Zollinger, Color chemistry, Weinheim: WileyVCH, 2003.
2. P. F. Gordon, P. Gregory, Organic chemistry in color,
New York: Springer-Verlag, 1983.
3. S. Waheed, C.M. Ashrat, Synthesis and Studies of
Some Acid Dyes, Jour. Chem. Soc. Pak., 22, 2000,
49-53.
4. B.C. Dixit, H.M. Patel, R.B. Dixit, D.J. Desai,
Studies on Dyeing Performance of Novel Acid
Azo Dyes and Mordent Acid Azo Dyes Based
on 2,4-Dihydroxybenzophenone, Coden Ecjhao
E-Journal of Chemistry, 6, 2009, 315-322.
5. M. Dolaz, H. Yilmaz, Synthesis, Characterization and
Applications of New Azo Compounds Containing
Phosphonic Acid, Asian Jour. Chem., 21, 2009,

24

5085-5094.
6. B. C. Dixit, H. M. Patel, R. B. Dixit, D. J. Desai,
Synthesis, characterization and dyeing assessment of
novel acid azo dyes and mordent acid azo dyes based
on 2-hydroxy-4-methoxybenzophenone on wool and
silk fabrics, J. Serb. Chem. Soc., 75, 2010, 605-614.
7. Y. Wang, B. Tang, W. Ma, S. Zhang, Synthesis and
UV-protective properties of monoazo acid dyes based
on 2-hydroxy-4-methoxybenzophenone, Procedia
Engineering, 18, 2011, 162-167.
8. D.G. Patel, N.K. Prajapati, Formation Of Some
Novel Acid Azo Dyes: Synthesis, Characterisation
& Application Properties, Asian J. Biochem. Pharm.
Res., 2, 2012, 255-261.
9. E. Yildiz, H. Boztepe, Synthesis of Novel Acidic
Mono Azo Dyes and an Investigation of Their Use
in the Textile Industry, Turk. J. Chem., 26, 2002,
897-903.
10. A.A. Ehsan, I. Sebe, Acid Azo Dyes and Pigments
Derived from 2-dmino-4-nitrodiphenylamine,
U.P.B. Sci. Bull., 74, 2012, 77-84.
11. C.V. urcas, I. Sebe, Azo Dyes Complexes,
Synthesis and Tinctorial Properties, U.P.B. Sci.
Bull., 74, 2012, 109-118.
12. J.O. Otutu, D. Okoro, E.K. Ossai, Preparation of
Dis-Azo dyes Derived from p-Aminophenol and
Their Fastness Properties for Synthetic PolymerFibres, J. Appl. Scien, 8, 2008, 334-339.
13. K.R. Raghavendra, K. Ajay Kumar, Synthesis Of

Polya M. Miladinova, Reny K. Vaseva, Varbina R. Lukanova

Some Novel Azo Dyes And Their Dyeing, Redox

And Antifungal Properties, Int. J. Chem. Tech. Res.,
5, 2013, 1756-1760.
14. A.A. Ali, Synthesis and Spectroanalytical Studies
of a New Azodye Derived From 2-Amino6-ethoxybenzothiazole and 4-Chloro-3,5dimethylphenol and its Complexes With Fe (III)
Ion, Pak.. J. Chem., 3, 2013, 91-99.
15. M.A. Zayed, G.G. Mohamed, S. A. M. Abdullah,
Synthesis, structure investigation, spectral characteristics and biological activities of some novel
azodyes, Spectrochim. Acta Part A, 78, 2011,
1027-1036.
16. M.H. Patel, Synthesis, Characterization and
Dyeing Assessment of Novel Bisazo-Acid Dyes
Derived from 2-hydroxy-4-Methoxybenzophenone-

5-sulphonic acid, Int. J. Sci. Eng. Res., 5, 2014,

2213-2217.
17. T. Baltac, G. Vlad, I. Sebe, The Synthesis of Some
Food Azo Dyes, Rev. Chim. (Bucharest), 63, 2012,
18-21.
18. K. Hunger (Ed.), Industrial Dyes. Chemistry,
Properties, Applications, Wiley-VCH Verlag GmbH
& Co. KGaA, Weinheim, 2003.
19. Z.W. Wu, Z. Wang, A study of novel bisazo reactive
red dyes with good wet fastness, Color Technol.,
125, 2009, 216-221.
20. R. M. El-Shishtawy, Y.A. Youssef, N. Ahmed,
A.A. Mousa, The use of sodium edate in dyeing:
II. Union dyeing of cotton/wool blend with hetero
bi-functional reactive dyes, Dyes Pigments, 72,
2007, 57-65.

25