Imperial Journal of Interdisciplinary Research (IJIR) Vol-3, Issue-2, 2017 ISSN: 2454-1362, http://www.onlinejournal.in
Synthesis And Effect Of Dye 1-(4Aminobenzamido)-4-(4-Methoxy-3Mehylphenyl)-5-(4-Nitrophenylhydrazono)2,6-(1h)-Pyridinedione On Polyester Fiber Anita Gour
Professor – Department Of Chemical Science Christian Eminent College Indore Abstract: Dyes are chemical compounds that can attach themselves to fabrics or surfaces to give them colour. Most dyes are complex organic molecules and need to be resistant to weather and the action of detergents. Dyes add color to textiles. They are incorporated into the fibre by chemical reaction, absorption or dispersion. Dyes differ in their resistance to sunlight, perspiration, washing, gas, alkalies, and other agents; their affinity for different fibres; their reaction to cleaning agents and methods and their solubility and method of application. In short, dyes are coloured, ionising, aromatic organic compounds1. In ancient past, Indigo, obtained from plants was being used by the Egyptians 5000 years ago, and natural dyes obtained from plants and animal sources are still used today. In 1856, Perkin developed the first synthetic dye based upon aniline. Colour in dyes is invariably explained as a consequence of the presence of a Chromophore. Since, by definition, dyes are aromatic compounds their structure includes aryl rings, which have delocalised electron systems. These are responsible for the absorption of electromagnetic radiation of varying wavelengths, depending on the energy of the electron clouds. For this reason, Chromophores do not make dyes coloured in the sense that they confer on them the ability to absorb radiation. Rather, Chromophores function by altering the energy in the delocalised electron cloud of the dye, and this alteration results in the compound absorbing radiation from within the visible range instead of outside it2., 3,4,5 Our eyes detect that absorption and respond to the lack of a complete 0 to 5 °C NaNO 2
ArNH 2
+
+ HCl
HNO 2
+
range of wavelengths by seeing colour. Dye should be fast to light, water, soap, acid and alkali. So it must be permanently attached to the fibre by stable chemical bond. This stable chemical bond formed due to presence of auxochrome group in dye may be either acidic or basic in nature. Introduction Synthesis of dye 1-(4-Aminobenzamido)-4-(4methoxy-3-mehylphenyl)-5-(4nitrophenylhydrazono)-2,6-(1H)-pyridinedione was prepared in order to demonstrate the student of chemical science studying on organic chemistry on various subjects of dyes and their effect over latest textile polyester fabric, Actually dyes are chemical compounds that can attach themselves to fabrics or surfaces to give them colour. Most dyes are complex organic molecules and need to be resistant to weather and the action of detergents. Dyes add color to textiles. They are incorporated into the fiber by chemical reaction, absorption or dispersion. Dyes differ in their resistance to sunlight, perspiration, washing, gas, alkalis, and other agents; their affinity for different fibers; their reaction to cleaning agents and methods and their solubility and method of application. In short, dyes are coloured, ionising, aromatic organic compounds.These are synthesized by two-stage process : Diazotisation & Coupling. Diazotisation: - The process in which primary aromatic amino compound convert into the diazonium salt is known as Diazotisation, this reaction is carried out in presence of HNO2 at low temperature 0-5oC6,7,8. HNO 2
+
NaCl
ArN2Cl
HCl
+
2H2O
Aryl Diazoni um Chloride
Coupling: - When diazonium ring gets attached to another aromatic ring, then it is called
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Imperial Journal of Interdisciplinary Research (IJIR) Vol-3, Issue-2, 2017 ISSN: 2454-1362, http://www.onlinejournal.in coupling. It can be represented by general formula (1) given below, where D is Aromatic or Heterocyclic group of the diazo component.
Materials and Methods 1) Preparation of 3-(4-Methoxy-3methylphenyl)-2-pentene-1,5-dioic acid (1) : To the acetone dicarboxylic acid prepared from citric acid (400 gm, 2.25 mole) and concentrated sulphuric acid (98 %) (640 ml, d=1.83) 2-methyl anisole (140 ml, 2.10 mole) was added slowly with stirring at –2 to 00C over a period of 1 hour. Stirring was continued further, for a period of 3 hours and the temperature of the reaction was maintained at 0-50C. The contents were then poured in about 150ml cold water under stirring. The precipitated solid was filtered & washed with water. The solid thus obtained was crystallized from boiling water to get the colorless needles of the product9,10,11. Melting point : 161-1620C Yield : 180 gm ( 32 % ) Elemental Analysis : Found : C, 62.46; H, 5.62 Calc. For C13H14O5 : C, 62.40; H, 5.60 2) Preparation of [ 4-(4-Methoxy-3methylphenyl)-5H-pyran-2,6-dione] (2): Compound 1(12.5 gm, 0.05 mole) was mixed with acetic anhydride (12 ml, 0.124 mole) and the mixture was gently refluxed for about 15 minutes. Then the reaction mixture was allowed to stand at room temperature for about 2 hours, whereupon the anhydride, separated out in crystalline form. It was filtered and washed with solvent ether. The solid thus obtained was crystallized from dry benzene to get pale yellow needles of the product. Melting point : 155-1560C12,13 Yield : 8.23gm (71%) Elemental Analysis : Found :C, 67.22 ; H, 5.20 Calc. For C13H12O4 : C, 67.24 ; H, 5.17 3) Preparation of 4-Aminobezoyl hydrazine (3): 80 ml of absolute ethyl alcohol was placed in a 250ml conical flask equipped with a two-holed cork and a wash-bottle tube. Dry hydrogen chloride gas was passed through alcohol until saturated. The
Imperial Journal of Interdisciplinary Research (IJIR)
solution was transferred to a 250ml round bottomed flask. 4-Aminobenzoic acid (12 gm) was introduced in round bottomed flask and the reaction mixture was refluxed for 3 hours. After 3 hours, the hot solution was poured into excess of water and sodium carbonate was added to the clear solution until it was neutral to litmus. The precipitated ester was filtered and dried in air. It was crystallized from rectified spirit14,15 Melting point : 910C Yield : 10gm (70%) Ethyl 4-aminobenzoate thus obtained was refluxed in excess of hydrazine hydrate (15ml). After 4 hours the excess of hydrazine hydrate was removed by distillation. About 10ml of ice cold water was added into it. The solid obtained was filtered, washed with cold water and crystallized from ethanol. Melting point : 225-2270C Yield : 7.2 gm (80%) 4) Preparation of 1-(4-Aminobenzamido) 4- (4-methoxy-3-methylphenyl)-2, 6(1H, 5H)-pyridinedione (4) : To a solution of compound 2(23.2gm, o.1mole) in pyridine (25ml),4-aminobenzoylhydrazine 3(15.1gm, 0.1 mole) was added and then the reaction mixture was refluxed for 4 hours. Excess of pyridine was removed by distillation. The reaction mixture was cooled and the residual mass was poured on to crushed ice containing conc. hydrochloric acid (5ml) to neutralize the excess of pyridine. The product was filtered, washed several times with water, dried and crystallized from DMFwater to give compound 4 Melting point : 280 –2810C Yield : 31 gm (85%) Elemental Analysis : Found : C, 65.63 ;H, 5.22 ;N, 11.54 Calc for C20H19N3O4 : C, 65.75 ;H, 5.20 ;N, 11.50 5) Preparation of 1-{4-[4-N,N-di(2hydroxyethyl)amino-2methyl]phenylazo} benzamido- 4 -(4methoxy-3-methylphenyl)-2,6(1H,5H)pyridinedione: A solution of 4(0.365 gm, 0.001mole) in propionic acid (1ml) and glacial acetic acid (5ml) was added drop wise with stirring over a period of 45 minutes to a cold (50C) mixture of nitrosyl sulphuric acid [ prepared by dissolving solid sodium nitrite (0.069gm, 0.001mole) in conc. sulphuric acid (8ml) at 700C ]. The reaction mixture was stirred for an additional period of 2 hours at 5-100C. The reaction mixture was then added to propionic acid-acetic acid mixture (2ml-10ml) under stirring. The excess of nitrous acid was destroyed using urea (about 0.2
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Imperial Journal of Interdisciplinary Research (IJIR) Vol-3, Issue-2, 2017 ISSN: 2454-1362, http://www.onlinejournal.in gm). The mixture was filtered to get a clear diazonium salt solution.16,17 3-Methyl-N,N-di(2-hydroxyethyl)aniline (0.195gm, 0.001 mole) was dissolved in propionic acid-acetic acid mixture (4ml-20ml). The solution was externally cooled to 50C. The previously cooled diazonium salt solution was slowly added to the above solution maintained at 5-100C over a time period of 1 hour. The pH of the reaction mixture was maintained acidic (4-5) throughout the coupling period by addition of solid sodium acetate. After the addition of diazonium salt solution was over the reaction mixture was stirred further, for a period of 3 hours. The mixture was neutralized with sodium acetate solution. The
separated monoazo dye was filtered, washed thoroughly with cold water and dried. The monoazo dye was crystallized from DMF-toluene mixture. 18 Melting point :242-2470C Yield : 0.331 gm (58%) Elemental Analysis : Found : Nitrogen 12.30% Calc. For C31H33N5O6 : Nitrogen 12.25% All the other dyes (30a,b d-f) were synthesized by using the same method. The characterization data of the dyes thus prepared is depicted in the table :
Elemental Analysis Compound No.
Coupler
Yield %
M.P.
(
Molecular Formula
0C )
Nitrogen % Calculated
Found
CH2CH2OH N
A
57
215-219
C30H30ClN5O6
11.83
11.86
62
227-232
C30H31N5O6
12.56
12.52
58
242-247
C31H33N5O6
12.25
12.30
61
218-221
C32H34N6O7
13.68
13.63
59
235-238
C32H34N6O5
14.43
14.47
CH2CH2OH Cl CH2CH2OH N
B
CH2CH2OH CH2CH2OH N
C
CH2CH2OH H3 C CH 2CH 2OH N
D
CH 2CH 2OH CH 3COHN
CH 2CH 3 N
E
CH 2CH 3 CH 3COHN
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Imperial Journal of Interdisciplinary Research (IJIR) Vol-3, Issue-2, 2017 ISSN: 2454-1362, http://www.onlinejournal.in OCH 3 CH 2CH 3
F
55
N
250-254
C33H36N6O6
13.72
13.76
CH 2CH 3 CH 3COHN
Result and Discussion Effect of dye 1-(4-Aminobenzamido)-4-(4-methoxy-3-mehylphenyl)-5-(4-nitrophenylhydrazono)-2,6(1H)-pyridinedione on Polyester Fabric, Its VISIBLE SPECTRAL DATA AND DYEING PROPERTIES : Dye No.
Colour of Dye on polyester fabric
A B C D E F
Pale Yellow Pale Yellow Pale Yellow Pale Yellow Yellowish Orange Yellowish Orange
α β -
-
λ
max (nm ) 408 412 417 422 428 435
Log €
Pick - up
4.016 4.032 4.062 4.086 4.102 4.108
2 2 2 2 2 3
Xeno
α
4 4 4 4-5 4 4-5
Thermo β 4-5 4-5 5 5 5 5
Recorded in DMF – Methanol ( 1 : 99 ) For light fastness Sublimation fastness at 2000C for one minute
The pyridone skeleton as diazo component and different N,N-dialkylsubstitutedaniline derivatives as couplers of monoazo dyes A-F, showed an absorption range 408 nm to 435 nm and 440 nm to 455 nm respectively. It was observed that the value of the absorption maxima increased with increasing number of electron donating substituents on dyes. In these chromophore systems coupler serves as donor end, while the pyridone skeleton is the acceptor end. Monoazo dyes A-F showed absorption intensity in the range of 4.01 to 4.10 and 4.03 to 4.11 respectively. Most of the dyes of these series demonstrated moderately high absorption intensities. Monoazo dyes A-F gave pale yellow to yellowish orange shades on the polyester. The pick-up of the dyes A-F were in the range of 2 – 3, which was moderate to good pick – up. The light fastness of the dyes was fairly good to good. The sublimation fastness was good-excellent that is in the range of 4 – 5.
Conclusion: Recent Textile production technology got more advanced and polyester fibre utilization has increased by no. of times as compare to 19th century, In order to produce versatile hues azo dyes plays a significant role since there affinity to polyester fibre strengthen the product, azo dyes are widely used in industries, not only for textile production as well as utility commodities
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production too, like manufacturing of plastic utensils, furniture, and modular structures. Numerous possibilities to modify the azo dyes synthesis is being utilized to produce desired range of hue of industrial use. In current scenario of Make in India, above synthesis research could be developed to produce economic dyes in our country and we could save significant foreign investment through import. Acknowledment : I Express my deep sense of gratitude to respected prof. Dr. S.L. Garg ,under whose able supervision ,this research work was carried out
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Imperial Journal of Interdisciplinary Research (IJIR) Vol-3, Issue-2, 2017 ISSN: 2454-1362, http://www.onlinejournal.in 5. Straley, J. M. Chemistry of Synthetic Dyes, vol.3,385, (1997). 6. Venkatraman, K., Analytical Chemistry of Synthetic Dyes Pg., 18 (1977). 7. Shuttleworth, L., Weaver, M.A., In : Waring, D. R., Hallas, G.,editors. The Chemistry and Application of Dyes. New york : Plenum, chapter 4 (1990). 8. Gordon, P. F., In : Waring, D. R., Hallas, G., editors. The Chemistry and Application of Dyes., New york : Plenum, chapter 8 (1990) . 9. Egli, R., In : Peters, A. T., Freeman, H. S., Colour Chemistry: the designand synthesis of organic dyes and pigments., London: Elsevier, chapter1 (1991). 10. Rangnekar, D. W. Jhaveri, P. V., Indian J. Fibre Text Res., 15,(1) 26 (1990). 11. Rangnekar, D. W., Rajadhyaksha, D. D., Indian J. Technol., 56, 401 (1993).
12. Desai, N. B., Ramanathan, V., Indian P., 1, 443, 54 (1978); CA: 92, 24253 (1980). 13. Chandankar, N. K., Joshi, S. D., Sequoria, S., Seshadri, S., Ind. Journal of Chem., 26(B), 427 (1987). 14. Rangnekar, D. W., Lokhande, S. B., Ind. Journal of Chem., 25 (B),485 (1986). 15. Straley, J. M., “ The Chemistry of Synthetic Dyes “, Vol. III, Academic press, New York, P - 385 (1962). 16. Rangnekar, D. W. and Kanitkar, V. R., Indian J. Fibre Text. Res., 15 (3), 132 –134 (1990). 17. Samant, S. D., Pednekar, S. R., Deval, S. D. and Deodhar, K. D., Indian J. Chem., 20 (B),1047 (1981). 18. Pednekar, S. R., Samant, S. D., Deval, S. D. and Deodhar, K. D., Indian J. Chem., 20 (B),709 (1981).
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