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ORIGINAL ARTICLE Application of newly synthesized bisazodichloro- s -triazinyl reactive dyes bearing1,3,4-oxadiazole molecule Divyesh R. Patel a, * , Bhavesh M. Patel b , Naitik B. Patel a , Keshav C. Patel a a Department of Chemistry, Veer Narmad South Gujarat University, Surat 395007, Gujarat, India b Sir P.T. Sarvajanic College of Science, Athwalines, Surat 395001, Gujarat, India Received 12 March 2011; accepted 25 June 2011Available online 6 July 2011 KEYWORDS Dichloro- s -triazinyl reactivedyes;1,3,4-Oxadiazole;Exhaustion;Fixation;Fastness properties;Colorimetric data Abstract Novel bisazo dichloro- s -triazinyl (DCT) reactive dyes (5a–h) containing 1,3,4-oxadiazolemolecule as a tetrazo component were synthesized and applied on silk, wool and cotton fibers byexhaust dyeing method. The structures of these dyes were confirmed by UV–vis, FT-IR, 1 H and 13 C NMR and elemental analyses. The exhaustion, fixation and fastness properties of the dyed fab-ric were assessed and the results demonstrated that these dyes showed moderate to very good lightand good to excellent washing and rubbing fastness properties. The colorimetric data (L * , a * , b * , C * ,H * , K / S ) of these dyes have also been studied in detail. ª 2011 King Saud University. Production and hosting by Elsevier B.V. All rights reserved. 1. Introduction Reactive dyes are textile colorants applied by exhaust and con-tinuous dyeing method to achieve relatively high wash fastnesson different fibers due to the formation of a covalent bondduring the fixation step (Waring, 1990; Aspland, 1997). Thebisazo reactive dyes are more valuable than monoazo reactivedyes, as they are tinctorially more stable and potentially moreeconomic than monoazo reactive dyes (Ayyangar et al., 1987,1991) furthermore the bisazo dyes possess two reactive groupswhich give higher fixation efficiency than monoazo dyes be-cause if one dye fiber bond is hydrolyzed, another bond isavailable for fixation (Bredereck and Schumacher, 1993;Masaki et al., 1988).The use of heterocyclic intermediates in the dyes synthesis iswell established and the resultant molecule exhibits remarkabletinctorial strength and brighter dyeing properties than thosederived from aniline based diazo components (Penchev et al.,1991; Peters and Gbadamosi, 1992; Kraska and Sokolwska-Gajda, 1987, 1991, 1992). The 1,3,4-oxadiazole molecule is widely used in the synthesis of drugs, polymers, dyes and alsoin photography as light screening agents. Also, it has an out-standing capability of transporting electrons, especially itsgood thermostability and antioxygenation given by its specialstructure (Chen et al., 2002). Bisazo dyes containing *Corresponding author. Tel.: +91 0261 2258384; fax: +91 02612256012.E-mail address:
[email protected] (D.R. Patel).1319-6103 ª 2011 King Saud University. Production and hosting byElsevier B.V. All rights reserved.Peer review under responsibility of King Saud University.doi:10.1016/j.jscs.2011.06.018 Production and hosting by Elsevier Journal of Saudi Chemical Society (2014) 18 , 245 – 254 King Saud University Journal of Saudi Chemical Society www.ksu.edu.sawww.sciencedirect.com 1,3,4-oxadiazole molecule give brilliant yellowish red hue withfairly to moderate light fastness and very good to excellentwash fastness and sublimation fastness on polyester and nylonfabric (Palekar et al., 2010).We now report the synthesis and evaluation of some novelhetero bisazo reactive dyes, containing a dichloro- s -triazinyl(DCT) reactive group. These dyes were synthesized by cou-pling the tetrazonium salt derived from the bisazo intermediate2,5-bis(3 0 -amino-4 0 -chlorophenyl)-1,3,4-oxadiazole (2) withdifferent cyanurated coupling components (4a–h) . Visibleabsorption spectra, fastness properties and colorimetric dataare also examined. 2. Experimental 2.1. Materials and methods All the chemicals used in the dyes synthesis were of commercialgrade and were further purified by crystallization and distilla-tion. Melting points were determined by the open capillarymethod. Thin layer chromatography (TLC) (Fried and Sher-ma, 1982) used for monitoring reactions includes aluminumplates coated with silica gel G F 254 (Merck) as stationary phaseand a mobile phase consisting of toluene:ethyl acetate (7.5:2.5v/v) solvent system. The developed plates were visualized un-der both short and long wavelength ultraviolet light (254 nm,365 nm).IR spectra were recorded on a Perkin-Elmer model 377 sys-tem using the KBr pellet. Both 1 H NMR (400 MHz) and 13 CNMR (100 MHz) spectra were determined on Bruker AvanceII spectrophotometer in DMSO- d 6 solvent using TMS as inter-nal standard, the chemical shifts were expressed in d valuescompared to Me 4 Si. UV–vis absorption spectra were recordedon a Thermo Scientific Evolution 300 spectrophotometer atthe wavelength of maximum absorption ( k max ). Elementalanalysis were carried out using C, H and N elemental analyzer,Carlo Erba 1108 elemental anayser, Italy. The dyeing was doneby using Laboratory Rota Dyer instrument containing stain-less steel dye pots. Colorimetric data (L * , a * , b * , C * , H * and K / S ) were recorded on Reflectance Spectrophotometer GretagMacbeth Color-Eye: 7000A. 2.2. Synthesis of 1,2-Bis(3 0 -amino-4 0 -chlorobenzoyl)-hydrazine(Qian et al., 2007 ) ( 1 ) A mixture of 3-amino-4-chlorobenzoic acid (17.2 g, 0.1 mol),polyphosphoric acid (50 mL) and hydrazine hydrate (5 g,0.05 mol) was stirred for 10 h at 130 C temperature undernitrogen atmosphere. The mixture was poured into ice water.This was then neutralized, filtered and washed with dilute so-dium carbonate (10% w/v) solution to give compound 1 (13.69 g, 80.52%) as yellowish white crystal, M.p. 230 C(recrystallized from absolute ethanol). Anal. Calcd. forC 14 H 12 O 2 N 4 Cl 2 (339.18 g/mol): C, 49.58; H, 3.57; N, 16.52.Found: C, 49.45; H, 3.43; N, 16.40; IR (KBr, cm 1 ): 3482,3455 (N–H), 1665 (C ‚ O), 760 (C–Cl); 1 H NMR (400 MHz,DMSO- d 6 ) d H ppm: 3.75 (s, 4H, NH 2 ), 7.22–7.78 (m, 6H,Ar–H), 10.32 (s, 2H, NH); 13 C NMR (100 MHz, DMSO- d 6 ) d C ppm: 169.44 (C ‚ O), 110.17, 115.36, 120.66, 125.85,134.71, 145.12 (C–Ar) (Scheme 1). 2.3. Synthesis of 2,5-bis(3’-amino-4’-chlorophenyl)-1,3,4-oxadiazole (Qian et al., 2007 ) ( 2 ) Compound 1 (17.0 g, 0.05 mol) and POCl 3 (150 mL) wereadded to a flask and refluxed for 8 h under nitrogen atmo-sphere; this was then cooled to room temperature. The reac-tion mixture was slowly poured into ice water andneutralized with dilute sodium carbonate solution (10% w/v). Then the precipitate was filtered and dried after washingwith water to give compound 2 (10.57 g, 65.83%) as reddishbrown needles, M.p. 322 C (recrystallized from chloro-form:methanol). Anal. Calcd. for C 14 H 10 ON 4 Cl 2 (321.16 g/mol): C, 52.36; H, 3.14; N, 17.45. Found: C, 52.25; H, 3.04;N, 17.32; IR (KBr, cm 1 ): 3485, 3450 (N–H), 1645 (C ‚ N),1278 (C–O–C), 775 (C–Cl); 1 H NMR (400 MHz, DMSO- d 6 ) d H ppm: 3.83 (s, 4H, NH 2 ), 7.10-7.94 (m, 6H, Ar–H); 13 CNMR (100 MHz, DMSO- d 6 ) d C ppm: 110.09, 115.84, 120.66,124.90, 133.26, 142.74, 162.55 (Scheme 1). Cl CN H 2 OOH NH 2 NH 2 . H 2 O ClNH NHClO ON H 2 NH 2 (1) PPAPOCl 3 Reflux ClON NClN H 2 NH 2 (2) NaNO 2 +HCl 0-5 o C ClON NClN NN lCNCl + ClNH 2 COO H + Coupling with 2-moles of 4a 0-5°CpH 7.5-8.5 (3) ClON NClN NN RNR (5a-h) Where R = Different cyanurated coupling components (4a-h) (Table 1) Scheme 1 Synthesis of monochloro- s -triazine bisazo reactivedyes 5a . 246 D.R. Patel et al. 2.4. Tetrazotization 2,5-bis(4-aminophenyl)-1,3,4-oxadiazole( 3 ) Compound 2 (3.21 g, 0.01 mol) was suspended in H 2 O(60 mL). Hydrochloric acid (0.38 mL, 0.03 mol) was addeddrop wise to this well stirred suspension. The mixture wasgradually heated up to 70 C, till clear solution was obtained.The solution was cooled to 0–5 C in an ice-bath. A solution of NaNO 2 (0.7 g, 0.01 mol) in water (4 mL) previously cooled to0 C, was then added over a period of 5 minutes with stirring.The solution was stirred for 30 min and excess HNO 2 wasdecomposed by adding sulfamic acid. Activated carbon wasadded with stirring and the mixture was filtered at 0–5 C togive the clear yellow solution (4) (Scheme 1). 2.5. Cyanuration of H-acid ( 4a ) Cyanuric chloride (1.85 g, 0.01 mol) was stirred in acetone(25 mL) at a temperature 0–5 C for a period of an hour. Aneutral solution of H-acid (3.19 g, 0.01 mol) in aqueous so-dium carbonate solution (10% w/v) was then added in smalllots in about an hour. The pH was maintained neutral bysimultaneous addition of sodium carbonate solution (1% w/v). The reaction mass was then stirred at 0–5 C for furtherfour hours. The clear solution of cyanurated H-acid (4a) thusformed was used for subsequent coupling reaction (Scheme 2). 2.6. Synthesis of reactive dye ( 5a ) Freshly prepared tetrazonium salt solution (0.005 mol) (3) wasadded dropwise to well-stirred solution of cyanurated H-acid (4a) (0.005 mol). The solution was maintained at pH 9 by add-ing 20% (w/v) Na 2 CO 3 and the coupling step was continuedfor 4 h at 0–5 C. Then, 10% (w/v) urea was added (Raviku-mar et al., 1998) and the dye was isolated by salting out of solution using NaCl (12 g). The pH was adjusted to 7 usingHCl (6% w/v) and stirring was continued for 2 h. The dyewas collected by filtration and washed with 5% (w/v) NaCl.Salt was removed by stirring the crude dyes with dimethyl-formamide (DMF), followed by the dye precipitation by add-ing EtOAc to the filtrate. The dye 5a was collected, washedwith EtOAc and dried at 45 C for 12 h keeping loss of drying(LOD) between 4% and 5%. The eluent system for TLC was2-BuOH:EtOH:NH 4 OH:pyridine (4:1:3:2 v/v). Dye 5a had R f = 0.40, with minor impurities at R f = 0.24 (Scheme 1).Following the above procedure other reactive dyes 5b to 5j were synthesized by using various cyanurated coupling compo-nents such as Gamma acid (4b) , N-phenyl-gamma acid (4c) , J-acid (4d) , N-methyl-J-acid (4e) , N-phenyl-J-acid (4f) , Chicagoacid (4g) and K-acid (4h) . All cyanurated coupling compo-nents are shown in Table 1.The characterization data of the synthesized dyes are asfollows: 2.6.1. Dye 5a Dye 5a was synthesized by using H acid as coupling compo-nent (5.46 g, 80.04%) as purple powder; M.p. >300 C(DMF: EtOAc); R f = 0.40; UV/vis (Water) k max ( e max ) = 530 nm (28540.12 l mol 1 cm 1 ); IR (KBr, cm 1 ):3475–3580 (O–H and N–H), 3016 (C–H), 1525 (N–H bnd.),1612 (N ‚ N), 1540, 1416, 822 (C–N), 1586, 1479 (C ‚ C),1338, 1194 (S ‚ O), 1270 (C–O–C), 783 (C–Cl); 1 H NMR(400 MHz, DMSO- d 6 ) d H ppm: 3.36 (2H, s, OH), 4.70 (2H,s, NH), 7.00–8.18 (12H, m, Ar–H); 13 C NMR (100 MHz,DMSO- d 6 ) d C ppm: 109.12, 112.70, 115.25, 120.62, 122.85,125.75, 129.72, 130.09, 132.68, 135.80, 136.77, 140.66, 142.15,145.65, 155.12, 164.77, 166.34, 169.10; Anal. Calcd. forC 40 H 16 O 15 N 14 S 4 Cl 6 Na 4 (1365.58 g/mol): C, 35.18; H, 1.18;N, 14.36. Found: C, 35.03; H, 1.04; N, 14.22. 2.6.2. Dye 5b Dye 5b was synthesized by using Gamma acid as couplingcomponent (4.57 g, 78.60%) as yellow powder; M.p.>300 C (DMF: EtOAc); R f = 0.36; UV/vis (Water) k max ( e max ) = 470 nm (23747.35 l mol 1 cm 1 ); IR (KBr, cm 1 )3462–3570 (O–H and N–H), 3010 (C–H), 1528 (N–H bend.),1620 (N ‚ N), 1565,1422, 825 (C–N), 1592, 1484 (C ‚ C),1341, 1185 (S ‚ O), 1268 (C–O–C), 780 (C–Cl); 1 H NMR(400 MHz, DMSO- d 6 ) d ppm: 3.42 (2H, s, OH), 4.64 (2H, s,NH), 7.06–8.02 (14H, m, Ar–H); 13 C NMR (100 MHz,DMSO- d 6 ) d C ppm: 108.77, 111.15, 117.20, 121.38, 123.80,125.54, 128.27, 130.11, 132.94, 134.90, 136.81, 140.49, 142.28,145.03, 154.10, 163.21, 165.30, 169.15; Anal. Calcd. forC 40 H 18 O 9 N 14 S 2 Cl 6 Na 2 (1161.49 g/mol): C, 41.36; H, 1.56; N,16.88. Found: C, 41.23; H, 1.44; N, 16.75. 2.6.3. Dye 5c Dye 5c was synthesized by using N -phenyl-gamma acid as cou-pling component (4.95 g, 75.32%) as orange powder; M.p.>300 C (DMF: EtOAc); R f = 0.37; UV/vis (Water) k max ( e max ) = 495 nm (26866.42 l mol 1 cm 1 ); IR (KBr, cm 1 )3465–3584 (O–H), 3005 (C–H), 1535 (N–H bend.), 1622(N ‚ N), 1562,1430, 828 (C–N), 1595, 1480 (C ‚ C), 1355,1176 (S ‚ O), 1260 (C–O–C), 775 (C–Cl); 1 H NMR(400 MHz, DMSO- d 6 ) d ppm: 3.46 (2H, s, OH), 6.95–8.12(24H, m, Ar–H); 13 C NMR (100 MHz, DMSO- d 6 ) d C ppm: NNNClCl Cl + OH NH 2 SO 3 HHO 3 S 0-5 °CAcetone OH NHSO 3 HHO 3 SNNNCl Cl (4a) Scheme 2 Preparation of cyanurated H-acid (4a) . Application of newly synthesized bisazo dichloro- s -triazinyl reactive dyes bearing 1,3,4-oxadiazole molecule 247 108.52, 110.08, 111.54, 115.25, 117.88, 120.57, 123.76, 125.90,126.45, 128.20, 130.63, 132.15, 134.70, 136.35, 138.43, 141.29,144.88, 148.63, 154.03, 162.16, 165.56, 169.10; Anal. Calcd.for C 52 H 26 O 9 N 14 S 2 Cl 6 Na 2 (1313.68 g/mol): C, 47.54; H, 1.99;N, 14.93. Found: C, 47.40; H, 1.86; N, 14.80. 2.6.4. Dye 5d Dye 5d was synthesized by using J-acid as coupling component(4.77 g, 82.15%) as yellow powder; M.p. >300 C (DMF:EtOAc); R f = 0.42; UV/vis (Water) k max ( e max ) = 475 nm(22832.65 l mol 1 cm 1 ); IR (KBr, cm 1 ) 3462–3580 (O–Hand N–H), 3012 (C–H), 1536 (N–H bend.), 1610 (N ‚ N),1558, 1426, 821 (C–N), 1590, 1477 (C ‚ C), 1359, 1168(S ‚ O), 1272 (C–O–C), 770 (C–Cl); 1 H NMR (400 MHz,DMSO- d 6 ) d ppm: 3.51 (2H, s, OH), 4.48 (2H, s, NH), 6.98– 7.92 (14H, m, Ar–H). 13 C NMR (100 MHz, DMSO- d 6 ) d C ppm: 109.17, 112.44, 116.27, 120.30, 122.94, 125.82, 128.34,130.57, 132.44, 133.48, 137.38, 141.12, 143.25, 145.23, 155.29,162.64, 165.33, 169.72; Anal. Calcd. for C 40 H 18 O 9 N 14 S 2 Cl 6 Na 2 (1161.49 g/mol): C, 41.36; H, 1.56; N, 16.88. Found: C, 41.26;H, 1.42; N, 16.72. 2.6.5. Dye 5e Dye 5e was synthesized by using N -methyl-J-acid as couplingcomponent (5.01 g, 84.24%) as orange powder; M.p.>300 C (DMF: EtOAc); R f = 0.40; UV/vis (Water) k max Table 1 Different cyanurated coupling components (4a – j) (Arrow indicate the coupling position). 4a OH NHHO 3 S SO 3 HNNNCl Cl 4b OHHO 3 SNHNNNCl Cl 4c OHHO 3 SNNNNCl Cl 4d OHHO 3 S NNNNHClCl 4e OHHO 3 S NCH 3 NNNClCl 4f OHHO 3 S NNNNClCl 4g OH NHSO 3 HSO 3 HNNNCl Cl 4h OH NHHO 3 SSO 3 HNNNCl Cl 248 D.R. Patel et al. ( e max ) = 488 nm (25507.92 l mol 1 cm 1 ); IR (KBr, cm 1 )3472–3578 (O–H), 2865, 3002 (C–H), 1540 (N–H bend.),1616 (N ‚ N), 1562, 1433, 826 (C–N), 1592, 1484 (C ‚ C),1365, 1175 (S ‚ O), 1265 (C–O–C), 772 (C–Cl); 1 H NMR(400 MHz, DMSO- d 6 ) d ppm: 2.52 (3H, s, N–CH 3 ), 3.55(2H, s, OH), 6.97–7.85 (14H, m, Ar–H); 13 C NMR(100 MHz, DMSO- d 6 ) d C ppm: 22.40, 22.52 (CH 3 ), 109.10,112.49, 114.19, 118.35, 123.90, 125.44, 128.30, 130.71, 132.75,133.38, 136.10, 140.15, 143.35, 145.80, 155.27, 162.96, 165.30,169.09; Anal. Calcd. for C 42 H 22 O 9 N 14 S 2 Cl 6 Na 2 (1189.54 g/mol): C, 42.41; H, 1.86; N, 16.48. Found: C, 42.35; H, 1.75;N, 16.33. 2.6.6. Dye 5f Dye 5f was synthesized by using N -phenyl-J-acid as couplingcomponent (5.26 g, 80.06 g) as red powder; M.p. >300 C(DMF: EtOAc); R f = 0.38; UV/vis (Water) k max ( e max ) = 497 nm (27422.30 l mol 1 cm 1 ); IR (KBr, cm 1 )3482–3575 (O–H), 3022 (C–H), 1542 (N–H bend.), 1620(N ‚ N), 1556,1430, 823 (C–N), 1586, 1474 (C ‚ C), 1368,1180 (S ‚ O), 1262 (C–O–C), 776 (C–Cl); 1 H NMR(400 MHz, DMSO- d 6 ) d ppm: 3.58 (2H, s, OH), 7.07–8.10(24H, m, Ar–H); 13 C NMR (100 MHz, DMSO- d 6 ) d C ppm:109.11, 110.55, 112.72, 115.35, 118.53, 120.74, 122.10, 123.25,126.02, 128.93, 130.73, 132.94, 135.10, 136.55, 138.56, 141.33,145.80, 147.58, 154.58, 162.90, 165.38, 169.22; Anal. Calcd.for C 52 H 26 O 9 N 14 S 2 Cl 6 Na 2 (1313.68 g/mol): C, 47.54; H, 1.99;N, 14.93. Found: C, 47.43; H, 1.88; N, 14.84. 2.6.7. Dye 5g Dye 5g was synthesized by using Chicago acid as couplingcomponent (5.33 g, 78.10%) as yellow powder; M.p.>300 C (DMF: EtOAc); R f = 0.37; UV/vis (Water) k max ( e max ) = 465 nm (20249.11 l mol 1 cm 1 ); IR (KBr, cm 1 )3465–3578 (O–H and N–H), 3025 (C–H), 1522 (N–H bend.),1626 (N ‚ N), 1537, 1411, 826 (C–N), 1580, 1482 (C ‚ C), Figure 1 IR spectra of dye 5a . Figure 2 1 H NMR spectra of dye 5a . Application of newly synthesized bisazo dichloro- s -triazinyl reactive dyes bearing 1,3,4-oxadiazole molecule 249
