Disperse Red 60 Analogs
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- 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 . Following cooling to 2S-28 °e over a 2h A mi xture of a-cresol (S.33g, 0.049 mol), KOH period, the mixture was stirred for 20 min. The crude (0. S2g, 0.009 mol ) and l-am in o-2-broIll0-4- product was collected by filtration, washed with hydroxyanthraquinone (2.0g, 0.006 mol) was heated methanol and warm water to give a dark purple so lid . at ISS-160 °e with stirring for 6h. The crud e product Purificat ion of the impure product by dry column was iso lated and purified usin g th e proced ure chromatography using sili ca gel (230-400mm mesh) described for Dye III to give a redd ish pink powder and toluene: hexane (4 : I) afforded pure Dye IV as pure Dye IX (0.44g, 23 .0%), m.p.=174°C, NrH: I (0.394g, 18.7%) , m.p.=2 12°e, Rr (4:1 :: toluene: toluene: hexane) =0.32. f hexane)=0.28. 2.4 Preparation of l-amino-4-hydroxy-2-(4'-methylphen 3 Results and Discussion oxy) anthraquinone (Dye V) Replacement of th e 2-bromo substitu ent in 1- By the procedure described for the preparati on of amino-2-bromo-4-h ydrox yanthraq uin one (Fig. I) with dye I, p-cresol (S.33g, 0.049 mol), KOH (0.S2g, 0.009 different phenoli c compou nds in th e prese nce or mol ) and l-amin o-2-bromo-4-h ydroxyanthraquinone potassium hydroxide gave l-a min o-2 -aryloxy --+ (2.0g, 0.006 mol ) afforded 1.35g (70.9%) of pure Dye hydroxyanthraqu in ones in low yield s. with th e V, m.p.=1 82- 183°e , Rr(4: 1 :: tolu ene: hexane)=0.32. excepti on of dyes I, V and Vil. Alth ough th e reaso n for the low yield s of dyes HI, IV , VI, VIII and IX is 2.5 Preparation of l-amino-4-hydroxy-2-(2'-chlorophenoxy) not entirel y understood, the steri c hindrance caused anthraquinone (Dye VI) by the bulky naphtho group in the "2. 3-pos iti on" is A mixture of 2-chlorophenol (S.33g, 0.042 mol) beli eved to account for th e low yield obtained for dye and KOH (0.S2g, 0.009 mol) was stirred vigorously IV. The chemi cal reacti vity of 2- meth yl and 4- for IS min and l-amin o-2-bromo-4-hydroxyanthra meth ylphenol s is ex pected to be quite similar cl ue to quinone (2.0g, 0.006 mol ) was added. The mixture the comparable electronic effec ts of a meth yl gro up in was kept at ambi ent temperature for 10 min and then ortho and para positions, but a low yield wa s obtained stirred at ISS-160oe for 6h. Iso lation of the product for dye IX in contrast to th e relati ve ly good yield ror was accomplished as described for dye III. The dye V. It would appear th at a meth yl group in th e product was recrystalli zed from 2- meth oxyethanoll ortho position is large enough to exert a steri c effect methanol to give a dark purple-red powder ( 1.97g). in th e reaction between 2-metth ylph enol and I-ami no- Purification as described for dye I yielded pure Dye 2-bromo-4-hydrox yanthraqu i none. VI (0.676g, 33.4%), m.p.= 190oe , Rr (4: I :: toluene: In the sy nthesis of dye VII, th e rin g deacti vatin g hexane)=0.3S. effects of a chlorine atom in th e para pos iti on mu st have been offset by the + I effects or a methyl group 2.6 Preparation of l-amino-4-hydroxy-2-(4' -chloro- in the meta position, thereby makin g 4-c hl oro-3 - 3-methyl-phenoxy)anthraquinone (Dye VII) methyl phenol of simil ar chemi ca l reacti vity to J2 Usi ng the procedure described fo r the synthes is of phenol . Thus, th e yield ohtained I' OJ dye VII , is dye III, a mixture of 4-chl oro-m-cresol (S. 33g, 0.037 good. Moving the chl oro group to th e orth o pos iti on mol), KOH (0.S2g, 0.009 mol) and l-amin o-2-bromo- causes a signifi cant redu cti on in yield (dye VI. ). Also. 4-hydroxyanthraquinone (2.0g, 0.006 mol) afforded a large group in the para pos iti on ha s a negati ve Dye VII ( 1.49g, 71.2%), m.p.=210-211 °e , Rr(4: 1 .. impact on yield (dyes III and VIII). toluene: hexane)=O .4 I. OH 2.7 Preparation of I-amino-4-hydroxy-2-(4'-bromophenoxy) QrZ anthraquinone (Dye VIII) ~Br ~ ~ ~I0;~1 /O'R\ x By the procedure described for th e preparati on of ~ KOH " '- - o OH 15 5 - 16 0·C . dye Ill, 4-bromophenol (S.33g, 0.03 1 mol), KOH o OH Z V (0.S2g, 0.009 mol ) and l-amino-2-bromo-4- Fig. I-Reaction sc heme ror th e preparatioll or dyes I :tlld /If-IX hydroxyanthraquinone (2.0g, 0.006 mol) afforded (X . Y, Zas perTlhk I ) 300 INDIA J. FIBRE TEXT. RES ., DECEMBER 1999 The electroni c spectral data fo r dyes I and III-IX are shown in Tab le I. All of th e dyes showed a multiplet of absorption bands corresponding to bands in the region of 250-260,480 (v. weak), 518-519 and 553-554nm. The introduction of substituent s into the phenoxy rin g does not result in a signi ficant shift in the position of these bands. Th is is in agreement with the previou findings" As expected, the molar absorpti viti es of these dyes are relatively low l4 compared to those of azo dyes . The I-butyl III 4-t-Bu 387 60.6 388 16.6 387 33 .7 388 100 IV 3 ,4-(benzo) 38 1 100 382 21i.4 38 1 30.6 3112 100 V 4-Me 345 100 346 22.6 345 30.5 346 100 c ;:>:: VI 2-CI 365 59.6 366 13.7 365 29.8 366 100 -0 0 VII 4-C1,3-Me 379 100 380 23.3 379 34.5 380 100 z 3::: :E VIll 4-Br 409 99 4 10 24.4 409 33 .7 410 94.0 » z 411 100 412 21.8 411 53.7 412 100 ~ ~ IX 2-Me 345 100 346 22.7 345 31.4 346 100 S2 C/l -0 tTl Table 3--Wash fastness and sublimation fastness data for dyes I and III-IX ;>:l C/l tTl Wash fastness a (Color staining/Color transfer) ;>:l Dye No. Sublimation fastne~ a (Exl2ressed as results for 30s/60s~ tTl 0 Color Acetate Cotton Nylon PET PAN Wool Acetate Cotton Nylon PET PAN Wool Color 0- 0 change change » z 5 4/4 515 4/4 4-5/5 515 515 3/2-3 4/4 211-2 111 4-5/4-5 4/3-4 4-5/3-4 » r 0 III 5 4-5/4-5 515 4-5/4 515 515 515 4-5/4 4/3-4 3-4/3 3/2-3 4-5/4 4/3-4 5/4-5 Cl C/l IV 5 515 5/5 4-5/4-5 515 515 515 4-5/4 4-5/4 4/3 3/2-3 4-5/4 5/4-5 5/5 V 5 4-5/5 5/5 4-5/4 5/5 5/5 5/5 3/2-3 4/3-4 2/1-2 III 4-5/4 4-5/4 5/4 VI 5 4-5/4 5/5 4/4 4-5/4-5 5/5 515 3-4/3 4/3-4 2-3/2 1/ 1 4/3-4 4/3 5/4-5 VII 5 4-5/4-5 5/5 4-5/4 5/5 515 515 4/3-4 4/3-4 2-3/2 III 4-5/4 4-5/4 5/4-5 VIII 5 4-5/4-5 5/5 4-5/4 5/5 5/5 5/5 4-5/4 4/3-4 3-4/3 2-3/2 4/3-4 4/4 5/5 IX 5 4-5/4-5 5/5 4- 5/4 4-5/5 5/5 SIS 3-4/3 4/3-4 2-3/1 1-211 4/3 -4 4/3-4 5/4-5 ' All samples were rated on a scale of 1-5. c' J ~ 302 INDIAN J. FIBRE TEXT. RES ., DECEMBER 1999 Dose/plate was also found that these three dyes had th e hi ghest 50- O.OOmg butanol water partition coeffic ie nts (Table 4). ~ LJ 00 r- 0.05mg ~~r- ~ ~~ O.tOmg 4 Conclusion ISO ~~ i>' 0.30mg Despite the reported declining importance or t-~ 0.50mg r- r- ~ anthraquinone dyes, Dispe rse Red 60 and re lated 100· ~ t;- l.00mg structures remain one of the most w id e ly used group 1300mg l 6 50· of dyes in the world . The se ven analogs o f Disperse 5.00mg f>- Red 60 prepared in this study are bri ght red dyes 0 Dye I DyeVII Dye IX which exhibit excell ent dyein g prope rti es on polyester. From fastness evaluations, these analogs Fig.2-TA 100 co loni es vs dose leve l generally possess better properti es than th e parent compound. Specifically, the most of the analogs ha ve Table 4--Panition coefficients and toxicity des ignalions for been rated hi gher than the parent dye in th e li ght dyes I and III-IX fastness, wash fastness and sublimation tests. From a Dye Partition coefficienl T A IOO tox icity commercial perspecti ve, the best of th ese dyes will 0.660 Y es not be useful unless a process can be developed to III 0.056 No significantly enhance their reacti on yie ll. whi ch is a IV 0.122 No perennial problem in anthraquinone dye chemi stry. V 0.393 No Similarly, it is unlikely that th e observed ability of VI 0. 11 7 No some of these dyes to kill Salmone lla (TA 100) is VII 0.460 Yes potent enough to make th e m use ful an tihacteri al VIII 0.2 15 No agents. IX 0.496 Yes References molecul ar weight of the compounds synthesized I Annen 0, Egli R. Henzi 8 . ./ ;IK(lh II 8:.. I'v L \t l. in~ cr P. /{"I' is: VIII> III> IV> VII> VI> IX, V> I, and the order Prog Color , 17 ( 1987) 72. of sublimation fastness for these dyes is IV> VIII> 2 Pizzarell o R A & GU lol'! B. US IJ{/I 1.77.,.07 1 (1 0 Interchemical Corporation ), 1956. III> VII> IX, VI> V> I. However, the data indicated 3 Aiga H, Kawakami M, Tsukahara R. Uchi d" R 8:.. Kallliji N. that significant staining of some fibers (especially lflll Kokai Tokkvo Kollf) 79.39.-+.17 (\() Mil,ui Toaisli spun polyester and spun polyamide) had occurred in Chemicals Inc), 1979. the multi-biber strip. This may be attributed to the 4 Sigman C C, Papa P A , Doelt !. M K . Perry L R. Twhi ~~ f\ M lack of strong ly polar substituents in the phenoxy & Helmes C T , 1 EIII'iroll Sci H('({llh A20(-I ) ( 1'))0;5 ) -1 27. 5 Brown J P & Dietrich P S. MIII(II N('s. (J6 ( I 'n ')) '). moiety. Dyes devoid of strongly polar groups sublime 6 Free man H S, Williard C S 8:.. !-I Sli W N . Ihl'.l· PIglII. 7 more readily and are absorbed by adjacent fibers ( 1986) 39 7. having hi gh affinity for the dyes I'. 7 Freeman H S & Posey J C (Jr. ). iJrl's IJIglII. 2() ( l lJ')2 ) 1-1 7. When dyes I and III-IX were evaluated for 8 Techllical /I1 allll([1 (Ameri ca n Assllciati'Jll or Textile mutagenicity in the standard Salmonella/mammalian Chemists and Co lori sts, Resea rch Tr ian ~ 1c ParK. N()nh microsomal assay, common Iy known as the Ames Carolina), 1994,23-25 , 33 -43,94-97 . 22)0; -22') & 2:\ 2-2)0;:1 9 M aron 0 & Ames B, Mlilal Res , 11 3 ( 19)0; ., ) 17.\ . test, all of the dyes proved to be non-mutagenic in 10 Clax ton L 0 , Dearlield K L. Spanggord R ./ . Ri cc i() E S 8:.. both strains e mployed (T A98 and TA I 00). Mortelmans K , Mlllal Res, 176 ( 19 )0;7 ) 1)0;') . Interestingly, some of the dyes exhibited toxicity II Conway W D & Ito y , .I Lilillill Chmlllllll!gl.7(2) ( 1'))0;-1 ) towards bacteria strain TAl 00 at dose levels of 1- 275. 3mg/plate. The data in Fig.2 show the changes in 12 Final' L , Orgallic chelllislrr.6lh edn ( L 'lIl~ l lI ~ \n Group Lt d. bacteria colonies as a function of dye dose for th e Essex) , 1973,702. three dyes observed to be toxic towards TA 100 in the 13 Ukponl11 wan 0 0 , Green h , li ~ h Malc()lm 8:.. 1\;l cr, t\ T. { <'II absence of S9 metaboli c activati on. It is clear from Chelll Color . 18( 5) ( 19R6 ) 24. Fig.2 that little change in the number of bacteri a 14 Esa ncy J F, All ([11/1I'(){} c iJ In IIII' d l'si g ll O/lliill -IIIIII([gcllic ([~(! dyes, Ph 0 lhesis. Nonh Ca rolina S I ~llC lilll\' cr, il y. I <' ~ \ lci ~ h. colonies occurs over a dose range of O-Img/plate. 1988. Dye IX started to kill the bacteria at a dose le vel 15 Schroeder H E & Boyd S N. 1"1'.1'1 NI'.I .I. n(-I ) ( I lJ5 7) . 275. above 1.0mg/plate and the dyes I and VII began to 16 Maguire R J & Tkacz R J. W([ll'r PilI/III i