Abstract:
Described are mixtures of dyes of the general formulae (1) and (2) ##STR1## where M is hydrogen, ammonium, an alkali metal or the equivalent of an alkaline earth metal, R 1  is hydrogen or sulfo, R 2  is hydrogen or sulfo, X 1  and X 2  are each fluorine, chlorine, amino, which may be mono- or disubstituted by lower alkyl or optionally substituted aryl and one of the radicals possesses a group of the formula --SO 2  --Y 1  or --SO 2  --Y 2 , where Y 1  and Y 2  are each vinyl or ethyl substituted in the β-position by an alkali-eliminable grouping, or X 1  and X 2  are each optionally substituted morpholino or pyrimidino, cyanoamino, hydroxyl, lower alkoxy or optionally substituted aryloxy and where the groups --SO 2  --Y 1  and --SO 2  --Y 2  are attached to the benzene nucleus meta or para to the azo or amino group. The novel dye mixtures are used for dyeing hydroxyl- and/or carboxamido-containing material, preferably fiber material, such as cellulose fiber materials, wool and synthetic polyamide fibers.

Description:
DESCRIPTION 
     This invention relates to the technical field of fiber-reactive azo dyes. 
     U.S. Pat. No. 4,485,041, European Patent Application Publication No. 0,094,055 and German Offenlegungsschrift No. 4,417,719 disclose dyes which conform to the hereinbelow indicated and defined general formulae (1) and (2). They have certain application defects, for example insufficient washfastness, an excessive dependence of the color yield on changing dyeing parameters in the dyeing process, an insufficient solubility in the aqueous dyebath at higher dye concentrations in the presence of electrolyte salts or an insufficient color build-up on cotton and especially viscose (good color build-up follows from the ability of a dye to produce a correspondingly stronger dyeing from an increased dye concentration in the dyebath). Possible consequences of these deficiencies are poor reproducibilities for the dyeings which are obtainable. However, it is particularly important to obtain dyeings having a good color yield, i.e., dyeings whose depth of shade is very high in relation to the amount of dye used, for example in comparison with other dyes, because of the coloring property of the dye itself (high absorbance) and because of the dyeing characteristics of this dye, such as good affinity and a high yield of fixation. If mixtures of dyes having a certain color yield are used, the color yield of this mixture of dyes will generally be the sum total of the color yields of the individual dyes; by this, the color yield of a mixture of, for example, two dyes will be less than the color yield resulting from the dye having the larger color yield property being used as a single dye in the same amount of the mixture of the two individual dyes. 
     The present invention, then, provides dye mixtures of the azo dyes comprising one or more, such as two or three, azo dyes conforming to the general formula (1) and one or more, such as two or three, azo dyes conforming to the general formula (2), whose color strength is surprisingly higher than the sum total of the color strengths provided by the individual dyes of the dye mixture. This synergistic effect also shows itself in improved build-up characteristics and better washfastness on the part of the mixture of the invention compared with individual dyes present in the mixture. ##STR2## In these formulae: M is hydrogen, ammonium, an alkali metal or the equivalent of an alkaline earth metal; 
     R 1  is hydrogen or sulfo; 
     R 2  has one of the meanings of R 1  ; 
     X 1  is fluorine or chlorine or a group of the general formula --NR 3  R 4  or --OR 3 , where R 3  is H or C 1  -C 4  -alkyl or aryl (such as phenyl), which is optionally substituted, and R 4  has one of the meanings of R 3  or is a Y 1  --SO 2  -- or Y 2  --SO 2  -- bearing aryl (such as phenyl) or C 1  -C 4  -alkyl group, or --NR 3  R 4  is optionally substituted morpholino or pyrimidino or --NHCN; 
     x 2  has one of the meanings of X 1  ; 
     Y 1  is vinyl or is a group of the general formula --CH 2  --CH 2  --Z, where Z is a substituent which can be eliminated by the action of alkali, especially sulfato, thiosulfato or acetyloxy; 
     Y 2  has one of the meanings of Y 1  ; 
     the groups --SO 2  --Y 1  and --SO 2  --Y 2  are disposed meta or para to the azo group or amino group. 
     In general, the azo dye of the general formula (1) and the azo dye of the general formula (2) are present in the mixture in a mixing ratio of 90:10% by weight to 10:90% by weight, preferably in a ratio of 70:30% by weight to 30:70% by weight. They are particularly preferably present in the mixture in a ratio of 55:45 to 45:55% by weight. 
     Preferably, in the general formulae (1) and (2), R 1  ═R 2  =hydrogen, M=H, Li or Na and preferably X 1  ═X 2  are each chlorine or fluorine. Also, preferably, Y 1  and Y 2  are --CH 2  --CH 2  --Z where Z=sulfato. 
     In the foregoing general formulae and also in the subsequent general formulae, the individual elements of the formulae, whether they bear identical or different designations within any one general formula, can have meanings under their definition which are mutually identical or different. 
     The terms &#34;sulfo&#34;, &#34;thiosulfato&#34;, &#34;phosphato&#34; and &#34;sulfato&#34; cover not only the acid form but also the salt form of the respective groups. Accordingly, sulfo groups are groups conforming to the general formula --SO 3  M, thiosulfato groups are groups conforming to the general formula --S--SO 3  M, phosphato groups are groups conforming to the general formula --OPO 3  M 2 , and sulfato groups are groups conforming to the general formula --OSO 3  M, where each M is as defined above. 
     The dye mixtures of the invention can be present as a preparation in solid or in liquid (dissolved) form. In solid form, they generally include the electrolyte salts customary for water-soluble and especially for fiber-reactive dyes, such as sodium chloride, potassium chloride and sodium sulfate, and may further comprise the auxiliaries customary in commercial dyes, such as buffer substances capable of setting a pH in aqueous solution between 3 and 7, such as sodium acetate, sodium borate, sodium bicarbonate, sodium dihydrogenphosphate, sodium tricitrate and disodium hydrogenphosphate, small amounts of siccatives or, if they are present in liquid, aqueous solution (including the presence of thickeners of the type customary in print pastes), substances which ensure a long life for these preparations, for example mold preventatives. 
     In general, the dye mixtures of the invention are present as dye powders comprising from 10 to 80% by weight, based on the dye powder or the preparation, of an electrolyte salt, which is also known as a standardizing agent. These dye powders may further comprise the abovementioned buffer substances in a total amount of up to 5% by weight, based on the dye powder. If the dye mixtures of the invention are present in aqueous solution, the total dye content of these aqueous solutions is up to about 50% by weight, for example between 5 and 50% by weight, and the electrolyte salt content of these aqueous solutions is preferably below 10% by weight, based on the aqueous solution; the aqueous solutions (liquid preparations) may include the aforementioned buffer substances in an amount which is generally up to 10% by weight, preferably up to 2% by weight. 
     The dye mixtures of the present invention are preparable in a conventional manner, as by mechanically mixing the individual dyes known from the abovementioned publications and present in solid or in liquid form, in the requisite proportions or by synthesis by means of the customary diazotization and coupling reactions and conversion reactions with the halotriazine components using appropriate mixtures of such components in a manner familiar to the person skilled in the art and with the requisite mixing ratios. For instance, in one possible procedure, which is preferably carried out as a one-pot reaction, a 2,4,6-trihalo-s-triazine, especially 2,4,6-trichloro- or 2,4,6-trifluoro-s-triazine, is initially reacted in a conventional manner with 1-amino-8-naphthol-3,6-disulfonic acid, for example at a temperature of 0 to 40° C., preferably of 0 to 10° C., and a pH of 0 to 5, preferably of 1 to 2, and then with one or more amino compounds of the general formula (3A) or (3B) ##STR3## where R 1 , R 2 , Y 1  and Y 2  are each as defined above, or a mixture of one or more amino compounds of the general formulae (3A) and (3B) in a conventional manner, for example at a temperature between 0 and 60° C., preferably between 20 and 40° C., and at a pH between 2 and 8, preferably between 3 and 5. The resulting diaminohalotriazine compounds can then be coupled with a diazonium salt prepared from an identical or different amine of the general formula (3A) or (3B) or two such amines in a well-known manner to form the mixture of the dyes (1) and (2) in a conventional manner, for example at a temperature between 10 and 50° C., preferably between 20 and 40° C., and at a pH between 3 and 7, preferably between 4 and 5. Dyes of the general formulae (1) and (2) where X 1  and X 2  are not halogen are prepared by reacting the mixture with the compounds HOR 3  or HNR  3  R 4  in a conventional manner, for example at a temperature between 10 and 100° C., preferably between 40 and 80° C., and at a pH between 3 and 7, preferably between 4 and 5. 
     Starting compounds of the general formula (3B) are for example 4-(β-sulfatoethylsulfonyl)aniline, 3-(β-sulfatoethylsulfonyl)aniline, 2-sulfo-4-(β-sulfatoethylsulfonyl)aniline and 2-sulfo-5-((β-sulfatoethylsulfonyl)aniline, especially 4-(β-sulfatoethylsulfonyl)aniline, and also derivatives of these compounds in which the β-sulfatoethylsulfonyl is replaced by a vinylsulfonyl or β-thiosulfatoethylsulfonyl or β-chloroethylsulfonyl group. 
     The separation from their synthesis solution of the chemically produced dye mixtures of the invention can be effected by commonly known methods, for example either by precipitating from the reaction medium by means of electrolytes, for example sodium chloride or potassium chloride, or by evaporating or spray-drying the reaction solution, in which case this reaction solution may have a buffer substance added to it. 
     The dye mixtures of the invention have useful application properties. They are used for dyeing or printing hydroxyl- and/or carboxamido-containing materials, for example in the form of sheetlike structures, such as paper and leather or of films, for example composed of polyamide, or in bulk, as for example of polyamide and polyurethane, but especially for dyeing or printing these materials in fiber form. Similarly, the solutions obtained in the synthesis of the azo compounds after their mixing to form the dye mixtures of the invention, if desired after or with addition of a buffer substance, and also if desired after concentrating or diluting, can be used directly as liquid preparation for dyeing. 
     The present invention thus also provides for the use of the dye mixtures of the invention for dyeing or printing these materials, or rather to processes for dyeing or printing these materials in a conventional manner, by using a dye mixture of the invention as colorant. The materials are preferably employed in the form of fiber materials, especially in the form of textile fibers, such as woven fabrics or yarns, as in the form of hanks or wound packages. 
     Hydroxyl-containing materials are those of natural or synthetic origin, for example cellulose fiber materials or their regenerated products and polyvinyl alcohols. Cellulose fiber materials are preferably cotton, but also other vegetable fibers, such as linen, hemp, jute and ramie fibers; regenerated cellulose fibers are for example staple viscose and filament viscose. 
     Carboxamido-containing materials are for example synthetic and natural polyamides and polyurethanes, especially in the form of fibers, for example wool and other animal hairs, silk, leather, nylon-6,6, nylon-6, nylon-11 and nylon4. 
     The dye mixtures of the invention can be applied to and fixed on the substrates mentioned, especially the fiber materials mentioned, by the application techniques known for water-soluble dyes, especially fiber-reactive dyes. 
     For instance, on cellulose fibers they produce from a long liquor by the exhaust method and by means of various acid-binding agents with or without neutral salts, such as sodium chloride or sodium sulfate, dyeings having very good color yields which are improved compared with the individual dyes. They are preferably dyed from an aqueous bath at temperatures between 40 and 105° C., if desired at temperatures up to 130° C. under superatmospheric pressure, and if desired in the presence of customary dyeing auxiliaries. One possible procedure is to introduce the material into the warm bath and to gradually heat the bath to the desired dyeing temperature and to complete the dyeing process at that temperature. The neutral salts which speed up the exhaustion of the dyes can if desired not be added to the bath until after the actual dyeing temperature has been reached. 
     The padding process likewise produces excellent color yields and a very good color build-up on cellulose fibers, on which fixing can be effected by batching at room temperature or elevated temperature, for example at up to about 60° C., by steaming or with dry heat in a conventional manner. 
     Similarly, the customary printing processes for cellulose fibers, which can be carried out either single-phase, for example by printing with a print paste comprising sodium bicarbonate or some other acid-binding agent and by subsequent steaming at 100 to 103° C., or two-phase, for example by printing with a neutral or weakly acidic print paste and subsequent fixation either by passing the printed material through a hot electrolyte-comprising alkaline bath or by overpadding with an alkaline electrolyte-comprising padding liquor with subsequent batching of this treated material or subsequent steaming or subsequent treatment with dry heat, produce strong prints with well-defined contours and a clear white ground. The appearance of the prints is not greatly affected by variations in the fixing conditions. 
     When fixing by means of dry heat in accordance with the customary thermofix processes, hot air from 120 to 200° C. is used. In addition to the customary steam at 101 to 103° C. it is also possible to use superheated steam and high-pressure steam at temperatures of up to 160° C. 
     The acid-binding agents which effect the fixation of the dyes of the dye mixtures of the invention on the cellulose fibers include for example water-soluble basic salts of the alkali metals and likewise alkaline earth metals of inorganic or organic acids or compounds which liberate alkali in the heat. Especially suitable are the alkali metal hydroxides and alkali metal salts of weak to medium inorganic or organic acids, the preferred alkali metal compounds being the sodium and potassium compounds. Such acid-binding agents include for example sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium dihydrogenphosphate, disodium hydrogenphosphate, sodium trichloroacetate, waterglass or trisodium phosphate. 
     The dye mixtures of the invention are notable for a high yield of fixation when applied to the cellulose fiber materials by dyeing or printing. The cellulose dyeings obtained following the customary aftertreatment by rinsing to remove unfixed dye portions exhibit excellent wetfastnesses, in particular since such unfixed dye portions are easily washed off on account of their good solubility in cold water. 
     The dyeings and prints obtainable with the dye mixtures of the invention have bright hues; especially the dyeings and prints on cellulose fiber materials have good lightfastness and very good wetfastnesses, such as wash, milling, water, seawater, crossdyeing and acidic and also alkaline perspiration fastness properties, also good fastness to pleating, hotpressing and rubbing. 
     Furthermore, the dye mixtures of the invention can also be used for the fiber-reactive dyeing of wool. Moreover, wool which has been given a nonfelting or low-felting finish (cf. H. Rath, Lehrbuch derTextilchemie, Springer-Verlag, 3rd Edition (1972), p. 295-299, especially the finish by the so-called Hercosett process (p. 298); J. Soc. Dyers and Colourists 1972, 93-99, and 1975, 33-44) can be dyed with very good fastness properties. 
     The process of dyeing on wool is here carried out in a conventional manner from an acidic medium. For instance, acetic acid and/or ammonium sulfate or acetic acid and ammonium acetate or sodium acetate may be added to the dyebath to obtain the desired pH. To obtain a dyeing of acceptable levelness, it is advisable to add a customary leveling agent, for example on the basis of a reaction product of cyanuric chloride with 3 times the molar amount of an aminobenzenesulfonic acid and/or of an aminonaphthalenesulfonic acid or on the basis of a reaction product of for example stearylamine with ethylene oxide. For instance, the dye mixture of the invention is preferably subjected to the exhaustion process initially from an acidic dyebath having a pH of about 3.5 to 5.5 under pH control and the pH is then, toward the end of the dyeing time, shifted into the neutral and perhaps weakly alkaline range up to a pH of 8.5 to bring about, especially for very deep dyeings, the full reactive bond between the dyes of the dye mixtures of the invention and the fiber. At the same time, the dye portion not reactively bound is removed. 
     The procedure described herein also applies to the production of dyeings on fiber materials composed of other natural polyamides or of synthetic polyamides and polyurethanes. In general, the material to be dyed is introduced into the bath at a temperature of about 40° C., agitated therein for some time, the dyebath is then adjusted to the desired weakly acidic, preferably weakly acetic acid, pH and the actual dyeing is carried out at a temperature between 60 and 98° C. However, the dyeings can also be carried out at the boil or in sealed dyeing apparatus at temperatures of up to 106° C. Since the water solubility of the dye mixtures of the invention is very good, they can also be used with advantage in customary continuous dyeing processes. The color strength of the dye mixtures of the invention is very high. 
     The dye mixtures of the invention produce bright, yellowish to bluish red dyeings on the materials mentioned, preferably fiber materials. 
     The Examples hereinbelow serve to illustrate the invention. Parts and percentages are by weight, unless otherwise stated. Parts by weight relate to parts by volume as the kilogram relates to the liter. The compounds described in the Examples in terms of a formula are indicated in the form of the free acids; in general, they are prepared and isolated in the form of their salts, preferably sodium or potassium salts, and used for dyeing in the form of their salts. The starting compounds mentioned in the form of the free acid in the following Examples, especially Table Examples, can similarly be used in the synthesis as such or in the form of their salts, preferably alkali metal salts, such as sodium or potassium salts. 
    
    
     EXAMPLE 1 
     a) A suspension of 319.2 parts of 1-amino-8-naphthol-3,6-disulfonic acid in 1000 parts of water and 300 parts of ice is admixed with 190.1 parts of cyanuric chloride with thorough stirring; the reaction batch is additionally stirred for four hours between 0 and 15° C. and at a pH between 1.7 and 2.2 adjusted by means of sodium bicarbonate. 
     b) The solution of the dichlorotriazine compound of a) is combined with a pH 5.5 to 6.0 solution of 133.0 parts of 4-(β-sulfatoethylsulfonyl)aniline and 156 parts of 1-amino-8-naphthol-3,6-disulfonic acid in 640 parts of water. The pH is maintained at about 5 and the reaction mixture is warmed to a temperature of 30 to 45° C. in the course of one to two hours. 
     c) Separately, the diazonium salt of the diazo component is prepared: A pH 6.7 to 6.8 solution of 410.4 parts of 4-(β-sulfatoethylsulfonyl)aniline in 500 parts of water is admixed with 192 parts of a 40% strength aqueous sodium nitrite solution. This mixture is added with thorough stirring to a mixture of 800 parts of comminuted ice and 160 parts of a 31% strength aqueous hydrochloric acid. The mixture is subsequently stirred at between 0° C. and 5° C. for an hour and then, as usual, excess nitrous acid is decomposed with a little amidosulfonic acid. 
     c) The secondary condensation product prepared under b) is combined with the diazonium salt solution described under c). To carry out the coupling reaction, the strongly acidic reaction mixture is adjusted with sodium carbonate to a pH of 4.5 to 5.0 at a temperature of about 15° C. and the temperature is raised to 20 to 25° C. Stirring is continued at that pH and temperature for a few hours until the coupling has ended. 
     d) A pH between 6.0 and 6.5 is then set by means of sodium carbonate, the batch is clarified by filtration and the filtrate is spray-dried, affording about 1650 parts of a powder which comprises an electrolyte salt, predominantly sodium chloride and sodium sulfate, and about 42% of the sodium salt of the compound of the formula (A) ##STR4## and about 28% of the sodium salt of the compound of the formula (B) ##STR5## 
     This mixture has very good dye properties and applied by the application and fixing methods customary in the art for fiber-reactive dyes to the materials mentioned in the description part, such as cellulose fiber materials, especially cotton and viscose, produces strong red dyeings and prints having very good fastness properties, especially very good wash, light, alkali, acid, water, seawater, perspiration and rub fastness properties. The dyeings are also notable for their high degree of fixation and good build-up on the cellulose materials. 
     EXAMPLE 2 
     47.5 parts of cyanuric chloride and 79.8 parts of 1-amino-8-naphthol-3,6-disulfonic acid are rapidly added with thorough stirring to a mixture of 330 parts of water and 140 parts of ice, the batch is subsequently stirred for about 3.5 hours at a pH between 1.5 and 2.0 and a temperature between 10 and 15° C., and the solution of this primary condensation product is clarified by means of kieselguhr and filtration. The pH is then adjusted to 5 by means of calcium carbonate, and 33.2 parts of 3-(β-sulfatoethylsulfonyl)aniline and 39.1 parts of 1-amino-8-naphthol-3,6-disulfonic acid are added, the batch is stirred for two to three hours at a temperature of 18 to 22° C., then heated to 50 to 55° C. and is maintained at that temperature for 30 minutes while the pH of 4.0 to 4.5 is kept constant by means of calcium carbonate. The batch is stirred for a few hours more at 18 to 20° C. 
     The solution is combined with a suspension (conventionally produced by diazotization with sodium nitrite and sulfuric acid in aqueous medium) of the diazonium salt of 102.1 parts of 3-(β-sulfatoethylsulfonyl)aniline, the strongly acidic coupling mixture is then adjusted to a pH of 4.0 to 4.5 by means of calcium carbonate at a temperature of about 10° C., and stirred for a few hours more at 10 to 14° C. and within this pH range, the calcium sulfate is filtered off with suction, washed with water, and the calcium ions in the combined filtrate and wash liquor are precipitated by means of sodium oxalate at a pH of 4.5 to 5.0 and at a temperature of 30° C. Stirring for one hour is followed by filtration, and the dye mixture of the invention is isolated from the filtrate by spray drying. 
     This yields about 390 parts of a dark red powder which, as well as electrolyte salts, is about 44% strength with regard to the sodium salt of the compound of the formula (C) ##STR6## and about 28% strength with regard to the sodium salt of the compound of the formula (D) ##STR7## 
     This dye mixture of the invention has very good application properties and applied by the printing and dyeing methods customary in the art for fiber-reactive dyes to cellulose fiber materials, for example, produces strong red dyeings and prints having very good manufacturing and use fastness properties, especially lightfastness, wash, perspiration, water and sea water fastness properties and also resistance to chlorinated tap water (chlorinated bath water). The fixation yield of this dye mixture of the invention on cellulose fiber materials is very high. 
     EXAMPLES 3 to 77 
     The Table Examples which follow describe further dye mixtures according to the invention of monoazo compounds of the general formulae (1) and (2) in terms of their components. They can be prepared in a manner according to the invention either by mechanically mixing the individual dyes or chemically, for example similarly to one of the above Operative Examples, with the aid of their starting components (cyanuric chloride, cyanuric bromide or cyanuric fluoride, 1-amino-8-naphthol-3,6-disulfonic acid and an amino compound (3A) and/or (3B) as second condensation component and a further amino compound (3A) and/or (3B) as diazo component and optionally with a further amine of the general formula HNR 3  R 4  or a compound of the general formula HOR 3 . 
     The dye mixtures of the invention have very good application properties and applied by the dyeing and printing methods customary in the art, preferably by the application and fixing methods customary in the art for fiber-reactive dyes, to the materials mentioned in the description part, especially cellulose fiber materials, produce strong dyeings and prints having good fastness properties and good color build-up in the hue reported in the respective Table Example. 
     The numerical ratios reported in the MR column specify the molar ratio in percent of the dye or dyes (1) to the dye or dyes (2) in which the dyes are present in the respective dye mixture. 
     
            - Dye(1) Dye (2)   Ex. R.sup.1 R.sup.2 X.sup.1 --SO.sub.2 --Y.sup.1 --SO.sub.2 --Y.sup.2 R.sup.1 R.sup.2 X.sup.2 --SO.sub.2 --Y.sup.1  --SO.sub.2 --Y.sup.2  MR Hue   3 H H Cl 4-(β-sulfatoethylsulfonyl) 4-(β-sulfatoethylsulfonyl  ) H H Cl 4-(β-sulfatoethylsulfonyl) 4-(β-sulfatoethylsulfonyl)   90:10 yellowish red   4 H H Cl &#34; &#34; H H Cl &#34; &#34; 80:20 yellowish red   5 H H Cl &#34; &#34; H H Cl &#34; &#34; 70:30 yellowish red   6 H H Cl &#34; &#34; H H Cl &#34; &#34; 60:40 yellowish red   7 H H Cl &#34; &#34; H H Cl &#34; &#34; 55:45 red   8 H H Cl &#34; &#34; H H Cl &#34; &#34; 50:50 red   9 H H Cl &#34; &#34; H H Cl &#34; &#34; 45:55 red   10 H H Cl &#34; &#34; H H Cl &#34; &#34; 40:60 bluish red   11 H H Cl &#34; &#34; H H Cl &#34; &#34; 30:70 bluish red   12 H H Cl &#34; &#34; H H Cl &#34; &#34; 20:80 bluish red   13 H H Cl &#34; &#34; H H Cl &#34; &#34; 10:90 bluish red   14 H H F &#34; &#34; H H Cl &#34; &#34; 45:55 red   15 H H F &#34; &#34; H H Cl &#34; &#34; 50:50 red   16 H H F &#34; &#34; H H Cl &#34; &#34; 55:45 red   17 H H F &#34; &#34; H H Cl &#34; &#34; 60:40 red   18 H H F &#34; &#34; H H Cl &#34; &#34; 40:60 bluish red   19 H H Cl vinyl vinyl H H Cl vinyl vinyl 60:40 yellowish red   20 H H Cl vinyl vinyl H H Cl vinyl vinyl 55:45 red   21 H H Cl vinyl vinyl H H Cl vinyl vinyl 50:50 red   22 H H Cl vinyl vinyl H H Cl vinyl vinyl 45:55 red   23 H H Cl vinyl vinyl H H Cl vinyl vinyl 40:60 bluish red   24 H H F vinyl vinyl H H F vinyl vinyl 60:40 yellowish red   25 H H F vinyl vinyl H H F vinyl vinyl 55:45 red   26 H H F vinyl vinyl H H F vinyl vinyl 50:50 red   27 H H F vinyl vinyl H H F vinyl vinyl 45:55 red   28 H H F vinyl vinyl H H F vinyl vinyl 40:60 yellowish red   29 H H F 3-(β-sulfatoethylsulfonyl) 3-(β-sulfatoethylsulfonyl  ) H H Cl 3-(β-sulfatoethylsulfonyl) 3-(β-sulfatoethylsulfonyl)   45:55 red   30 H H F &#34; &#34; H H Cl &#34; &#34; 50:50 red   31 H H F &#34; &#34; H H Cl &#34; &#34; 55:45 red   32 H H F &#34; &#34; H H Cl &#34; &#34; 60:40 red   33 6-sulfo H Cl &#34; &#34; 6-sulfo H Cl &#34; &#34; 70:30 yellowish red   34 6-sulfo H Cl &#34; &#34; 6-sulfo H Cl &#34; &#34; 60:40 yellowish red   35 6-sulfo H Cl &#34; &#34; 6-sulfo H Cl &#34; &#34; 45:55 red   36 6-sulfo H Cl &#34; &#34; 6-sulfo H Cl &#34; &#34; 50:50 red   37 6-sulfo H Cl &#34; &#34; 6-sulfo H Cl &#34; &#34; 55:45 red   38 6-sulfo H Cl &#34; &#34; 6-sulfo H Cl &#34; &#34; 40:60 bluish red   39 6-sulfo H Cl &#34; &#34; 6-sulfo H Cl &#34; &#34; 70:30 yellowish red   40 6-sulfo H Cl &#34; &#34; 6-sulfo H Cl &#34; &#34; 40:60 bluish red   41 H H methoxy &#34; &#34; H H methoxy &#34; &#34; 70:30 bluish red   42 H H methoxy &#34; &#34; H H methoxy &#34; &#34; 80:20 bluish red   43 H H NHCN &#34; &#34; H H NHCN &#34; &#34; 90:10 bluish red   44 6-sulfo H NHCN &#34; &#34; 6-sulfo H NHCN &#34; &#34; 45:55 red   45 H H morpholino &#34; &#34; H H morpholino &#34; &#34; 50:50 red   46 6-sulfo H morpholino &#34; &#34; 6-sulfo H morpholino &#34; &#34; 45:55 red     47 6-sulfo H chlorine &#34; &#34; 6-sulfo H chlorine &#34; &#34; 50:50 red  48 H H Cl 4-(β-phosphato- 4-(β-phosphato-) H H Cl 4-(β-phosphato- 4-(β-phosphato- 45:55 yellowish red  ethylsulfonyl) ethylsulfonyl)    ethylsulfonyl) ethylsulfonyl) 49 H H Cl 4-(β-phosphato- 4-(β-phosphato-) H H Cl 4-(β-phosphato- 4-(β-phosphato-) 50:50 red  ethylsulfonyl) ethylsulfonyl)    ethylsulfonyl) ethylsulfonyl) 50 H H Cl 4-(β-phosphato- 4-(β-phosphato-)  H H Cl 4-(β-phosphato- 4-(β-phosphato-)  55:45 red  ethylsulfonyl) ethylsulfonyl)    ethylsulfonyl) ethylsulfonyl) 51 H H Cl 4-(β-phosphato- 4-(β-phosphato-) H H Cl 4-(β-phosphato- 4-(β-phosphato-)  40:60 red  ethylsulfonyl) ethylsulfonyl)    ethylsulfonyl) ethylsulfonyl) 52 H 2-sulfo Cl 4-(β-thiosulfato- 4-(β-thiosulfato- H 2-sulfo Cl 4-(β-thiosulfato- 4-(β-thiosulfato- 45:55 red       ethylsulfonyl) ethylsulfonyl)    ethylsulfonyl) ethylsulfonyl)   53 H 2-sulfo Cl  4-(β-thiosulfato- 4-(β-thiosulfato- H 2-sulfo Cl 4-(β-thiosulfato- 4-(β-thiosulfato-  50:50 red      ethylsulfonyl) ethylsulfonyl)    ethylsulfonyl) ethylsulfonyl)   54 H 2-sulfo Cl 4-(β-thiosulfato- 4-(β-thiosulfato-  H 2-sulfo Cl 4-(β-thiosulfato- 4-(β-thiosulfato-  55:45 red      ethylsulfonyl) ethylsulfonyl)    ethylsulfonyl) ethylsulfonyl)   55 H 2-sulfo Cl 4-(β-thiosulfato- 4-(β-thiosulfato-  H 2-sulfo Cl 4-(β-thiosulfato- 4-(β-thiosulfato-  40:60 bluish red  ethylsulfonyl) ethylsulfonyl)    ethylsulfonyl) ethylsulfonyl) 56 H H Cl 4-(β-sulfatoethylsulfonyl) 4-(β-sulfatoethylsulf  onyl) H H Cl 3-(β-sulfatoethylsulfonyl) 3-(β-sulfatoethylsulfo  nyl) 70:30 yellowish red   57 H H Cl &#34; &#34; H H Cl &#34; &#34; 80:20 yellowish red   58 H H Cl &#34; &#34; H H Cl &#34; &#34; 90:10 yellowish red   59 H H F &#34; &#34; H H Cl &#34; &#34; 45:55 red   60 H H F &#34; &#34; H H Cl &#34; &#34; 50:50 red   61 H H F &#34; &#34; H H Cl &#34; &#34; 55:45 red   62 H H F &#34; &#34; H H Cl &#34; &#34; 60:40 red   63 H H 3-sulfo- &#34; &#34; H H 3-sulfo- 4-(β-sulfato- 4-(β-sulfato-   40:60 red phenylamino      phenylamino ethylsulfonyl) ethylsulfonyl)   64 H H Cl  &#34; &#34; H H 3-sulfo- 4-(β-sulfato- 4-(β-sulfato- 40:60 red      phenylamino ethylsulfonyl) ethylsulfonyl)   65 H H N-ethyl- &#34; &#34; H H N-ethyl- 4-(β-sulfato- 4-(β-sulfato-    40:60 red phenylamino     phenylamino ethylsulfonyl) ethylsulfonyl)   66 H H Cl &#34; &#34; H H N-ethyl- 4-(β-sulfato- 4-(β-sulfato- 60:40   red      phenylamino ethylsulfonyl) ethylsulfonyl)   67 H H 3-sulfo- &#34; &#34; H H N-ethyl- 4-(β-sulfato- 4-(β-sulfato-   55:45 red phenylamino     phenylamino ethylsulfonyl) ethylsulfonyl)   68 2-sulfo 2-sulfo N-ethyl- &#34; &#34; H H  N-ethyl- 4-(β-sulfato- 4-(β-sulfato- 50:50 red phenylamino     phenylamino ethylsulfonyl) ethylsulfonyl)   69 H H Cl &#34; &#34; H H Cl  4-(β-sulfato- 4-(β-sulfato- 45:55 red       ethylsulfonyl) ethylsulfonyl)   70 H H 3-carbamoyl- &#34; &#34; H H 3-carbamoyl- 4-(β-sulfato- 4-(β-s  ulfato- 40:60 red pyridinium      pyridinium ethylsulfonyl) ethylsulfonyl)   71 H H 3-carbamoyl- &#34; &#34; H H 3-carbamoyl-  4-(β-sulfato- 4-(β-  sulfato- 50:50 red pyridinium     pyridinium ethylsulfonyl) ethylsulfonyl)   72 H H 4-chloro- &#34; &#34; H H Cl 4-(β-sulfato- 4-(β-sulfato- 50:50 red phenylamino      ethylsulfonyl) ethylsulfonyl)   73 H H 4-chloro- &#34; &#34; H H 4-chloro- 4-(β-sulfato- 4-(β-sulfato  - 50:50 red phenylamino     phenylamino ethylsulfonyl) ethylsulfonyl)   74 H H F &#34; &#34; H H N-ethyl- 4-(β-sulfato- 4-(β-sulfato-  45:55   red      phenylamino ethylsulfonyl) ethylsulfonyl)   75 H H F &#34; &#34; H H 3-sulfo- 4-(β-sulfato- 4-(β-sulfato-  50:50   red      phenylamino ethylsulfonyl) ethylsulfonyl)   76 H H 3-sulfo- &#34; &#34; H H Cl  4-(β-sulfato- 4-(β-sulfato- 45:55 red phenylamino      ethylsulfonyl) ethylsulfonyl)   77 H H 3-carbamoyl- &#34; &#34; H H Cl  4-(β-sulfato- 4-(β-sulfato- 60:40 red pyridinium      ethylsulfonyl) ethylsulfonyl)