Original Article
Int. J. Chem. Sci, Volume: 15( 2)

Synthesis, Characterization and Applications of Some New Reactive Dyes Based on 5,5'-Methylenebis (2-Aminobenzenesulfonic Acid)

*Correspondence:
Keshav C Patel , Department of Chemistry, Veer Narmad South Gujarat University, Surat, Gujarat, India, Tel: +91-9033572550; E-mail: [email protected]

Received: May 08, 2017; Accepted: June 08, 2017; Published: June 14, 2017

Citation: Gamit EA, Patel SM, Savant SS, et al. Synthesis, Characterization and Applications of Some New Reactive Dyes based on 5,5'-methylenebis (2-aminobenzenesulfonic acid). Int J Chem Sci 2017;15(2):142.

Abstract

Coupling of 2-chloro anilino cyanurated acids with 5,5'-methylenebis(2-sulfobenzenediazonium) chloride to give the corresponding methylene based reactive dyes in good yields. They were characterized by nitrogen elemental analysis, IR and 1H NMR spectra. The dyeing performance of synthesized dyes has been examined on silk, wool and cotton. The synthesized dyes gave moderate to good light fastness, good to excellent wash fastness and rubbing fastness.

Keywords

5,5'-methylenebis (2-aminobenzenesulfonic acid); Dyeing; Silk; Cotton; Wool; Fastness properties

Introduction

The structural development of new reactive dyes has been a subject of interest and many novel structures are useful in commercial application to wool, silk and cotton as well as their blends with other fibers has been discovered [1]. Reactive dyes have an efficient utilization and also a facile ease of washing out of the non-fixed portions which is the requirement of dyeing. They should have a high reactivity and good yield and should have produced high degrees of fixing in particular dyeing [2].

In the dye stuff research, reactive dyes are the newest addition and is the center of attention [3,4]. Hot brand reactive dyes are commercially important in reactive dyeing [5]. Due to their higher fixation yields on various fibres, they have been extensively recognized [6]. The popularity of reactive dyes is increased due to the ease of dyeing cellulosic fibres as they have wide range of shades, easy application and very good wet fastness properties. The structural improvement of reactive chromogens, number and selection of reactive groups led to an increment in their use [7].

The chemicals containing s-Triazine nucleus have been widely applied in different fields viz, dyes, , explosives, polymers, pesticides and trade good chemicals [8] as a result, experimental and theoretical research on these types of compounds have been widely carried out [9,10]. The s-triazine ring is an important conjugated heterocycle whose electronics properties are suitably different from those of benzene due to the alternate substitution of -CH- group by N atoms [11].

Materials and Methods

All the raw materials used were of commercial grade and were further purified by recrystallization and re-distillation before used. All the acid couplers were received from Atul Ltd., Valsad (Table 1). Melting points of all synthesized dyes were taken by open capillary method which expressed in °C and are uncorrected. Thin layer chromatography was carried out on silica gel G F254-coated aluminium sheets. IR spectra were recorded on a Perkin-Elmer Model 377 system using the KBr pellet. 1H-NMR (400 MHz) in D2O solvent, TMS is an internal standard, for UV-vis absorption spectra, thermo scientific evolution 300. Spectrophotometer is used at the wavelength of maximum absorption (λmax) using water as solvent. The rota dyer instrument was used for dyeing in laboratory.

No. -R Molecular formula Mol. weight Yield
(%)
% of Nitrogen Rfvalue
Found Required
10a Bronner acid C51H30O12N14C14S4Na4 1393 89 14.02 14.08 0.48
10b Koch acid C51H26O24N14C14S8Na8 1801 88 17.97 18.01 0.37
10c Sulphotobias acid C51H30O12N14C14S4Na4 1392 90 14.03 14.08 0.36
10d K-acid C51H28O20N14C14S6Na6 1629 84 12.00 12.04 0.44
10e N-methyl acid C53H34O14N14C14S4Na4 1453 90 13.47 13.50 0.39
10f Chicago acid C51H28O20N14C14S6Na6 1629 88 11.98 12.04 0.44
10g Tobias acid C51H32O6N14C14S2Na2 1188 91 14.02 14.08 0.40
10h Laurent acid C51H30O12N14C14S4Na4 1393 88 16.42 16.49 0.43
10i J-acid C51H30O14N14C14S4Na4 1425 90 13.68 13.76 0.34
10j M-acid C51H30O14N14C14S4Na4 1425 88 13.70 13.76 0.35
10k H-acid C51H28O20N14C14S6Na6 1629 90 12.00 12.04 0.38
10l Peri acid C51H30O12N14C14S4Na4 1393 88 14.01 14.08 0.40

Table 1: Qualities associated with minion coils.

Synthesis

Synthesis of 5,5'-methylenebis-(2-aminobenzenesulfonic acid) [3]

At 50°C concentrated hydrochloric acid (50 mL) is added to the aqueous solution of 0.1 mol Orthonilic acid [1] (17.3 g), followed by the addition of 35 mL 3% aqueous formaldehyde [2] solution at 60°C with constant stirring. The reaction mass was stirred for an hour with maintaining the temperature at 60°C, which is then neutralized with 10% sodium hydroxide solution to obtain 5, 5'-methylenebis-(2-aminobenzenesulfonic acid) [3]. It was then filtered, washed with hot water, dried and recrystallized from alcohol. Yield: 88%, m.p. 130°C.

Tetrazotization of 5,5'-methylenebis-(2-aminobenzenesulfonic acid) [4]

To the suspension of 5, 5'-methylenebis-(2-aminobenzenesulfonic acid) [3] (3.58 g, 0.01 mol) in water (60 mL), conc. hydrochloric acid (1.5 mL) was added drop wise with stirring. To obtain clear solution, the temperature of mixture was gradually raised up to 70°C. Then the reaction mass was cooled at 0°C -5°C in an ice bath and NaNO2 (1.38 g, 0.02 mol) in water (16 mL) was mixed to the above solution over a period of five minutes with stirring. The mixture is stirred further for an hour by maintaining the temperature, with positive test for nitrous acid on starch iodide paper. The excess of nitrous acid was destroyed by sulphamic acid solution in water. The clear solution of titled product was obtained and used for coupling reaction.

Cyanuration of Bronner acid [7a]

In 25 mL acetone, Cyanuric chloride [6] (1.85 g, 0.01 mol) is added and stirred at below 5°C for an hour. To this solution, a solution of Bronner acid [5a] (2.23 g, 0.01 mol) in aqueous sodium carbonate (10% w/v), was then added in small portions. The pH was maintained 7.0 by subsequent addition of 1% w/v Na2CO3 solution. The reaction mass was further stirred at 0-5°C for 4 h to obtain a clear solution. The cyanurated bronner acid solution thus obtained was used for condensation reaction.

Synthesis of 2-chloro anilino cyanurated Bronner acid (9a)

The temperature of ice-cooled well stirred solution of compound [7a], (2.23 g, 0.01 mol) was gradually raised to 45°C for 30 min. To this mixture, the 2-chloro aniline [8] (1.275 g, 0.01 mol) was added gradually by maintaining the temperature at 45°C, during a period of 30 min. The pH was maintained at 7.0 by sodium bicarbonate solution (1% w/v). After the addition was done, stirring was continued for further 3 h. The 2-chloro anilino cyanurated Bronner acid solution was formed and proceeds further for coupling reaction.

Coupling of tetrazotized solution with 2-chloro anilino cyanurated acid coupling component (10a-1)

A freshly prepared tetrazo solution [4] (4.53 g, 0.01 mol) was added to an ice cooled solution of compound [9a] (9.24 g, 0.02 mol) over a period of 10-15 min. The pH was maintained at 7.5 to 8.5 by simultaneous addition of 10% w/v Na2CO3. Yellow solution was formed during coupling. By maintaining the same temperature, the stirring was continued for 3-4 h. The solution of NaCl was added for the precipitation of coloring material. The reaction mass then stirred for 1 h, filtered and washed with 5% w/v NaCl solution. The compounds [10a-l] was dried at 80-90°C and extracted by DMF. By adding excess of chloroform to the extract, the synthesized dye was precipitated. A yellow dye was then filtered, washed with chloroform and dried yield 88%.

Reaction scheme

image

Where, R=

a: Bronner acid;

b: Koch acid;

c: Sulpho tobias acid;

d: K-acid;

e: N-methyl-J-acid;

f: Chicago acid;

g: Tobias acid;

h: Laurent acid;

i: J-acid;

j: M-acid;

k: H-acid;

l: Peri acid

Result and Discussion

Characterization

All the synthesized dyes have been characterized by visible absorption spectra, some representative IR spectra and PMR spectra.

Visible absorption spectra: The visible absorption spectra of all synthesized dyes have been recorded in water and observed in the range of 550-383 nm. The color observed for each dye is due to the presence of substituents and oscillation of electrons.

IR Spectra: IR spectra of dye 10c showed N-H stretching vibration of secondary amine at 3365 cm-1, C-H stretching vibration of -CH2- group at 2865 cm-1, C=C stretching vibration of aromatic ring at 1570 cm-1, N=N stretching vibration of azo group at 1462 cm-1, C-N stretching vibration of tertiary amine group at 1542 cm-1, S=O stretching vibration of -SO3Na group at 1180 and 1090 cm-1, C-Cl stretching vibration of chloro group at 716 cm-1.

IR spectra of dye 10i showed O-H stretching vibration of -OH group at 3490 cm-1, N-H stretching vibration of secondary amine at 3365 cm-1, C-H stretching vibration of -CH2- group at 2860 cm-1, C=C stretching vibration of aromatic ring at 1580 cm-1, N=N stretching vibration of azo group at 1452 cm-1, C-N stretching vibration of tertiary amine group at 1531 cm-1, S=O stretching vibration of -SO3Na group at 1190 and 1080 cm-1, C-Cl stretching vibration of chloro group at 723 cm-1.

IR spectra of dye 10l showed N-H stretching vibration of secondary amine at 3355 cm-1, C-H stretching vibration of -CH2- group at 2860 cm-1, C=C stretching vibration of aromatic ring at 1575 cm-1, N=N stretching vibration of azo group at 1450 cm-1, C-N stretching vibration of tertiary amine group at 1533 cm-1, S=O stretching vibration of -SO3Na group at 1190 and 1090 cm-1, C-Cl stretching vibration of chloro group at 720 cm-1.

1H NMR Spectra: 1H NMR Spectra of dye 10a showed signals at 3.89 (s, 2H, -CH2), 4.17 (s, 4H, -NH), 6.2-8.6 (m, 24 H, Ar-H). 1H NMR Spectra of dye 10k showed signals at 3.952 (s, 2H, -CH2), 3.958 (s, 2H, -OH) 4.12 (s, 4H, -NH), 6.7-8.3 (m, 20H, Ar-H). 1H NMR Spectra of dye 10l showed signals at 3.92 (s, 2H, -CH2), 4.15 (s, 4H, -NH), 6.4-8.5 (m, 24H, Ar-H).

Applications

Dyeing of fibres

All the dyes were applied on wool, cotton and silk fibres by using the standard procedure [12].

Exhaustion and fixation study: The percentage exhaustion of 2% dyeing on silk fabric ranges from 68-74%, for wool ranges from 67-74% and for cotton ranges from 64-75%. The percentage fixation of 2% dyeing on silk fabric ranges from 80-92%, for wool ranges from 80-93% and for cotton ranges from 81-96% (Table 2), (Figure. 1 and 2).

international-journal-of-chemical-sciences-Exhaustion-dye

Figure 1: % Exhaustion of dye 10a-1.

international-journal-of-chemical-sciences-Fixation-dye

Figure 2: % Fixation of dye 10a-1.

Dye No. Shade on
silk
fabric
Shade on
wool
fabric
Shade on
cotton fabric
λmax % Exhaustion % Fixation
S W C S W C
10a Orange
brown
Dark yellow Yellow 458 68.80 68.28 73.63 87.94 82.75 82.17
10b Light
brown
Light
brown
Light
maroon
496 73.93 72.20 69.90 82.52 83.10 85.12
10c brown yellow Maroon 441 69.95 71.70 69.70 86.49 82.98 82.50
10d Yellow Light
yellow
Light
yellow
476 71.80 74.30 63.88 84.96 81.43 90.20
10e Maroon Red Maroon 503 72.33 67.23 70.05 87.11 87.02 84.23
10f Red Orange Yellow 448 73.63 73.33 74.43 80.14 85.92 83.98
10g Brown yellow Dark maroon 426 69.90 71.55 71.83 90.13 82.46 85.62
10h Light
orange
Light
yellow
Light
yellow
478 72.20 71.33 73.80 84.49 82.72 85.37
10i Red Red Yellow 434 69.75 73.63 68.53 89.61 80.81 86.10
10j orange Orange Orange 496 71.70 72.20 73.90 82.98 83.80 81.87
10k Violet Light
violet
violet 426 69.05 68.83 70.60 85.45 90.10 83.57
10l Light
brown
Yellow Light
brown
451 72.40 72.40 73.93 90.30 84.25 89.28

Table 2: Determination of XIP in Epitens tablets.

Fastness properties [13]

Fastness to light was assessed in accordance with BS: 1006-1978 (Standard Test Method, 1994) [14]. The rubbing fastness test was carried out by using Crock meter (Atlas) in accordance with the AATCC-1961(AATCC Test, 1961) and the wash fastness was carried out in accordance with IS:765-1979 (Indian Standard,1979) [15]. All the dyes show generally fair to good light fastness properties. The washing and rubbing fastness properties ranges from very good to excellent fastness on silk, wool and cotton (Table 3).

Dye Light Fastness Wash Fastness   Rubbing Fastness  
  Dry Wet  
S W C S W C S W C S W C
10a 4 3 4 4 4 4 4 3 5 3 5 3
10b 4 4 5 4 4 5 4 3 3 4 4 4
10c 5 5 5 5 5 5 5 3 4 3 4 3
10d 4 5 4 4 4 4 4 4 3 3 3 5
10e 4 4 5 4 4 4 3 5 3 5 5 5
10f 3 5 3 5 5 4 4 4 3 4 5 4
10g 4 4 4 4 4 4 5 4 4 3 4 5
10h 5 5 3 5 5 5 4 5 3 5 3 5
10i 4 3 4 4 4 4 5 5 4 4 3 4
10j 3 4 3 4 4 4 4 5 5 5 3 5
10k 5 4 4 5 5 5 5 3 3 5 4 5
10l 5 5 5 3 3 4 4 3 5 5 3 5

Table 3: Fastness properties.

Conclusion

Tetrazotization of 5, 5'-methylenebis-(2-aminobenzenesulfonic acid) followed by coupling with various 2-chloro anilino cyanurated acid coupling components gave corresponding bisazo reactive dyes (10a-l). These dyes gave violet to yellow shade on silk, wool and cotton fibres. The dyeing performance of all these dyes on various fibres gave moderate to good light fastness, good to excellent wash fastness and rubbing fastness. The presence of triazine group of dye molecule improves the exhaustion, fixation and fastness properties. Thus, exhaustion and fixation of these dyes are very good in order.

Acknowledgement

Authors are thankful to Department of Chemistry, Veer Narmad South Gujarat University, Surat, Gujarat, India for providing research facility, Atul Products Ltd., Atul, Valsad, India for providing dyeing facility, fastness, colorimetric data and SAIF, Chandigarh for spectral data.

References