Indian Journal of Fibre & Textil e Research Vol. 24, December 1999, pp. 297-302 Disperse Red 60 analogs David a Ukponmwan, Chris A Odilora" & Mercy NaIlor Department of Chemistry, Faculty of Science, University of Benin, Benin Cit y. Nige ri a and Harold S Freeman Department of Textile Engineering, Chemistry and Science, Co ll ege of Textiles , North Carolina State University, Ralei gh, North Carolina 27695-830 I, USA Received 29 May 1998; revised received alld accepled 18 March 1999 The sy nth esis and properties of a series of Disperse Red 60 analogs containing substituents in th e phello xy moi ety arc described. While th e introduction of substilU ents into the phenoxy ring does not result in a signifi cant shift in the ;Ihso rption maximum of the parent compound, mo st of the dyes synthesized afford better li ght fastness, was h fa stn ess. crock fa sl nes.s and sublimation fas tness. The stru cture of each dye has been confirmed by IR , 'H NMR , 2- D NMR and mass spectromelric analyses. The mutagenic properties of th ese dyes have also been determined in th e stand ard Ames test. usi ng S({/IIIII//I' /1({ ryphimuriul11 strains TA98 and TA I 00. The results indicate th at all of the dyes arc non-mutage ni c. SO llle of lh e dyes arc toxic towards strain TA I 00, with toxicit y co rrel atin g well with partition coeflicien t values. Keywords: Disperse Red 60, Mutagenic properties, Partition coefficient, Polyester IIber 1 Introduction substitution of auxochromes suc h as -HO, -OMe and Derivatives of l-aminoanthraquinone such as -OROH (where R= 1-4 C atoms) into the phe noxy ring ] -amino-2-alkoxy-4-hydroxyanthraqui nones a nd have been reported to g ive derivatives of Dispe rse ] -amino-2-aryloxy-4-hydroxyanthraquinones were the Red 60 having bright red shades and excell e nt original bright red dyes for cellulose acetate fibers fastness on cellulose acetate". and are now widely used for dyeing polyester fibers I . The present work was a imed at synthesizin g a Despite the apparent declining importance of group of anthraquinone red dispe rse dyes havin g the anthraquinone disperse dyes, dyes such as Disperse general structure shown in Table I. This was Red 60 (I) and Disperse Red 91 (II) are quite popular achieved by the reacti on of l-amino-2-bromo- for the coloration of PET for automobile upholster/ ' 4-hydroxyanthraquinone with the appropriate Since the polyester fiber has gained commercial phenolic compounds in an alkaline medium at importance in recent times, the search for improved moderately high te mperatures'. The e ffect of ring disperse dyes has continued to be a commercially substituents on fastness prope rti es and reac ti on yie lds important undertaking. was investigated . While much has been publis hed about th e mutageni c properties of azo dyes, the o pe n lite rature $OR contains very little information on the mutagenicity o f anthraquinone dyes. Among the few pape rs that have been published in this area is one from S igman el (// ~ o OH dealing with selected anthraquinone va t dyes. 1n A=CsHs; II R=(CH2)60H addition, Brown and De ithric lY' summarized the It is known that the sublimation ' fastness of mutagenicity of a large group o f mono-and di­ Disperse Red 60 is only moderate and that, the substituted anthraquinones, most of whic h are not introduction of substituents into the phenoxy ring dyes. In view of the pauc ity o f information in thi s leads to hi gher sublimation fastness. Thus, area as well as our inte rest in developing new dyes based on toxicological conside rations. mutageni c ity testing of the synthesized anthraquinone di sperse a Present address: Department of Chemistry, Edo St ate University, Ekpoma, Nigeria dyes was also carried out. 298 INDIAN J. FIBRE TEXT. RES .. DECEMBER 1999 2 Materials and Methods was then evaluated uSlIl g th e Grey scale for co lor All the chemicals and reagents used were obtained transfer. from Aldrich Chemical Company (Milwaukee, WI, Mutagenicity testin g was condu cted usin g th e USA) and Fisher Chemical Company (Pittsburgh, PA, method of Ames and Maron') and th e meth od of USA). Melting points were determined on a MEL­ Claxton et ai. 10 was used to characteri ze th e dyes as TEMP capillary melting point apparatus and are mutagenic, non-mutageni c or equi voca l. Partiti on uncorrected. coefficients were measured at 300nl11 usin !2; th e Infrared spectra were recorded in a KBr disc on a method of Conway and Ito ll. ~ Nicolet 5lOP FT-IR spectrophotometer. Visible spectra were recorded on a Varian CARY 3E UV­ 2.1 Preparation of l-amino-4-hydroxy-2-phcnoxyanthra­ visible spectrophotometer in 2-methoxyethanol at a quinone (Dye I) concentration of 4 x 10.5 M, using a 1.0 cm cell. Thin A mixture of phenol (5.33g. 0.057 mol). KOH layer chromatography (TLC) was performed using (0.52g, 0.009 mol) and I -amino-2-broIll0-4- What man 250 Ilm silica gel 60 AMK6F plates. Dry hydroxyanthraquinone (2.0g, 0.006 mol) was st irred 1 column chromatograph/ was conducted using silica at 155-160 °C for 6h. the mi xture was cooled to 100 gel (Merck grade 60, 230-400 mm mesh type 60A). DC, diluted with 8 ml of 2- meth oxyethanol ove r 15 I H NMR spectra were recorded on a Geo-Omega min and stirred for I h at 100 °C. The mi xture was 500 MHz NMR instrument and CI and EI mass then cooled to room temperature, stirred for 30 min spectrometric analyses were recorded on a Hewlett­ and filtered . The collected solid was washed with Packard 5985B qu adrupole mass spectrometer with methanol and then with warm water C'iO-60DC) to give the aid of an RTE-VI data system. a dark red powder. The crude product was purified by Dyeings were obtained on 100% polyester fabric dry column chromatograph y usin g sili ca gc l (230-400 (Dacron 54) at I % depth using an Ahiba Polymat mm mesh) and toluene : hex an e (4: I ) to yield (type PN) pressure dyein g machine at 130 DC for I.5 h 1.64 g (82.6%) pure Dye L m.p.= 180-1 82DC. from a dyebath containing 0.1% (owf) dispersing R,(4: I :: toluene: hexane)=0 .3 1. agent (lrgasol DA( The light fastness of the 1% (owf) dyeings was 2.2 Preparation of 1-amillo-4-hydroxy-2 -( .f -1-hul.vlphl'l1ox~ · ) determined using an Atlas ES 25 Weather-Ometer anthraquinone (Dye III) (Xenon arc) according to AA TCC Test Method 16E- 4-t-Butylphenol (5.33g, 0.035 111 01). KOH (O.52 g. 8 1993 . The test conditions were: 0.009 11101 ) and l-amino-2- bromo-4-hydroxyalllhra­ quinone (2.00g, 0.006 mol ) we re combin ed, stirred Bl ack panel temp . 60 DC for 15 min at room temperature and th en at 155- Relative humidity 30±5% 160°C for 6h. The reacti on mi xture was cooled to Chamber temp. 50 DC 100DC, 8 ml of 2-methoxyethanol was added and th c Irradiance 0.75W/m2 mixture was stirred at this temperature for 30 min . Counter setting 54 kJ/m 2 Thereafter, the reaction mi xture was allowed to cool to room temperatu \'e over a peri od of :2 h and stirred The samples were rated with the aid of ACS for 20 min . The crude produ ct was co llected by Spectro-Sensor n in strument. Sublimation fastness filtration, washed first with methanol and th en with testing was conducted with the aid of an Atlas Scorch warm water, and dri ed in vacu o at 40-45DC. D Tester at 177±2 C for 30s and 60s according to Purification of crude was achieved hy dry column 8 AATCC Test Method i 77- I 984 . The change in color chromatograph y usin g sili ca gel (70-nOlllm mesh) of the dyed fabric and color staining and transfer on and toluene: hexane (4 : I) to give 0.48g (22 .5 %) shin y the multifiber warp were evaluated using the Grey dark red crystals of Dye Ill, m.p. =2()() -20 I DC. RI scale. (4: I :: toluene: hexane)=0.36. Fastness to washing was assessed by washing the sampl es of dyed fabrics with 0.2% soap solution in an 2.3 Preparation of l-alllino-4-hydroxy-2-(2' -naphthoxy) Atlas Launder-O-meter at 49DC for 45 min according anthraquinone (Dye IV ) 8 to AATCC Test Method 61- I 993 . Evaluation was 2-Naphthol (5.33g, 0.037 mol), KOH (O.5 2g. O()09 also conducted with the aid of th e Grey scale. mol) were mix ed with vi go rous st irring. 1-<Ill1in o-~­ Crock fastness was determined using a: n AATCC bromo-4-hydroxy-anthraquinonc (2 .00g. 0.006 111 <.1 crockmeter (AATCC Test Method- I 989 8 ). The fabric was added and th e resu ltant mi xture ,,',IS st irred kr UKPONMWAN e/ al.: DISPERSE RED 60 ANALOGS 299 IS min. This mixture was then stirred under reflux at 0.43g ( 19.0%) pure Dye VIII, m.p.=209.8°C, Rr(4: I ISS-160 °e for 6h. The reaction mi xture was cooled :: toluene: hexane)=0.40. to 100oe , whereupon 8ml of 2-methoxyethanol was added all at once, and stirred at thi s temperature for 2.8 Preparation of I-amino-4-hydroxy-2-(2' -methylphen­ oxy)anthraquinone (Dye IX ) 30 min .