Abstract:
A monoazo reactive red dyestuff of the formula (I),  
                         
 
     wherein the R 1 , R 2 , R 3 , X, D, Z and n are as defined in the description. These kinds of dyestuffs are suitable for dyeing and printing of materials containing either cellulose fibers, such as cotton, artificial cotton, linen, and artificial linen, or synthetic polyamide, such as wool, silk, and nylon etc., as well as on mixed or cross-linked cellulose fibers and other fibers. Dyed materials with excellent properties can be obtained, showing especially outstanding performance in of wash-off, level-dyeing, light fastness and perspiration-light fastness.

Description:
BACKGROUND OF THE INVENTION  
         [0001]    1. Field of the Invention  
           [0002]    The invention relates to the technical field of the fiber-reactive dyes, in particular relates to a novel monoazo reactive red dyestuff.  
           [0003]    2. Description of Related Art  
           [0004]    The practice of dyeing with fiber-reactive dyes has led to heightened expectations of the quality of the dyeings. Consequently there continues to be a demand for novel fiber-reactive dyes that have improved properties. Especially in demand are red reactive dyes having high fastness properties. It is true that British Patent No. 836,248, U.S. Pat. No. 2,979,498 and European Patent Application Publication No. 0 070 806 disclose numerous red fiber-reactive dyes, but the fastness properties of the dyeings obtainable with these dyes, especially the lightfastness and the perspiration lightfastness, are in need of improvement.  
           [0005]    U.S. Pat. No. 5,227,475 discloses fiber-reactive dyestuffs having the following formula:  
                         
 
           [0006]    The practice of dyeing using reactive dyestuffs has improved the quality of the dyeings and the efficiency of the dyeing process. Reactive dyestuffs generally display good dyeing and fastness properties but the light fastness, alone and in presence of perspiration, of red fiber-reactive dyestuffs is generally only modest and in need of improvement.  
         SUMMARY OF THE INVENTION  
         [0007]    The present invention provides novel azo compounds having improved properties in this respect and are azo derivatives which compounds conform to the formula (I),  
                         
 
           [0008]    wherein:  
           [0009]    X is —NHCN, —OH, —SCH2COOH, —NHSO2CH3, 3-carboxypyridinium,  
                         
 
           [0010]     halogen; preferably X is —NHCN, 3-carboxypyridinium or halogen, wherein the halogen is preferably fluorine or chlorine;  
           [0011]     D is a phenyl or naphthyl group having 0 to 3 substituent groups, said substituent groups are selected from the groups consisting of halogen, C 1-4  alkyl, C 1-4  alkoxyl, nitro, amino, hydroxyl, carboxyl, phosphonic acid and sulfo group; preferably D is phenyl having 0 to 3 substituent groups;  
           [0012]     Z is —SO 2 —CH═CH 2  or SO 2 —CH 2 —CH 2 —U; U is —OSO 3 H, Cl, Br, —OPO 3 H 2 , —SSO 3 H or  
                         
 
           [0013]     preferably Z is ‘ 3 SO 2 CH═CH 2  or —SO 2 —CH 2 —CH 2 —OSO 3 H;  
           [0014]     R 2  is sulfo, carboxy, halogen or C 1-4  alkoxy; preferably R 2  is sulfo or carboxy;  
           [0015]     n is 0 or 1, and preferably n is 1;  
           [0016]     when X is a halogen atom, R 1  is limited to a hydrogen atom and R 3  is limited to C 1-4  alkyl or C 1-4  alkyl having at least one substituent; preferably when X is fluorine atom or chlorine atom, R 1  is hydrogen atom and R 3  is C 1-4  alkyl;  
           [0017]     when X is —NHCN, —OH, —SCH 2 COOH, —NHSO 2 CH 3 , 3-carboxypyridinium or  
                         
 
           [0018]     R 1  and R 3  independently can be any group selected from hydrogen atom, C 1-4  alkyl, phenyl,  
                         
 
           [0019]     or C 1-4 alkyl having one or more substituent group selected from hydroxyl, carboxyl, sulfo, carbamoyl or methoxy carbonyl; preferably R 1  and R 3  is hydrogen atom or C 1-4  alkyl.  
           [0020]    The dyestuffs of the present invention is preferably represented by the following formula (Ia),  
                         
 
           [0021]    wherein:  
           [0022]    X is —NHCN, —OH, —SCH 2 COOH, —NHSO 2 CH 3 , 3-carboxypyridinium,  
                         
 
           [0023]     halogen; preferably X is —NHCN, 3-carboxypyridinium fluorine or chlorine;  
           [0024]     D is a phenyl or naphthyl having 0 to 3 substituent groups, said substituent groups are selected from the group consisting of halogen, C 1-4  alkyl, C 1-4  alkoxyl, nitro, amino, hydroxyl, carboxyl, phosphonic acid and sulfo group;  
           [0025]     preferably D is phenyl having 0 to 3 substituent groups;  
           [0026]     Z is —SO 2 —CH═CH 2  or SO 2 —CH 2 —CH 2 —U; U is —OSO 3 H, Cl, Br, —OPO 3 H 2 , —SSO 3 H or  
                         
 
           [0027]     preferably Z is —SO 2 CH═CH 2  or —SO 2 —CH 2 —CH 2 —OSO 3 H;  
           [0028]     n is 0 or 1, and preferably n is 1;  
           [0029]     when X is a halogen atom, R1 is limited to a hydrogen atom and R 3  is limited to C 1-4  alkyl or C 1-4  alkyl having at least one substituent; preferably when X is fluorine atom or chlorine atom, R1 I is hydrogen atom and R 3  is C 1-4  alkyl;  
           [0030]     when X is —NHCN, —OH, —SCH 2 COOH, —NHSO 2 CH 3 , 3-carboxypyridinium or  
                         
 
           [0031]     R 1  and R 3  independently can be any group selected from hydrogen atom, C 1-4  alkyl, phenyl,  
                         
 
           [0032]     or C 1-4  alkyl having one or more substituent group selected from hydroxyl, carboxyl, sulfo, carbamoyl or methoxy carbonyl; preferably R 1  and R 3  is hydrogen atom or C 1-4  alkyl.  
           [0033]    The formula (I) dyestuff of the present invention is also preferably represented by the following formula (Ib),  
                         
 
           [0034]    wherein:  
           [0035]    X is —NHCN, —OH, —SCH 2 COOH, —NHSO 2 CH 3 , 3-carboxypyridinium,  
                         
 
           [0036]     halogen; preferably X is —NHCN, 3-carboxypyridinium, chlorine or fluorine;  
           [0037]     Z is —SO 2 —CH═CH 2  or SO 2 —CH 2 —CH 2 —U ; U is —OSO 3 H, Cl or Br; preferably  
           [0038]     Z is —SO 2 —CH 2 —CH 2 —OSO 3 H;  
           [0039]     n is 0 or 1, and preferably n is 1;  
           [0040]     when X is a chlorine atom or fluorine atom, R 1  is limited to a hydrogen atom and R 3  is limited to C 1-4  alkyl; preferably R 1  is hydrogen atom and R 3  is methyl or ethyl;  
           [0041]     when X is —NHCN, —OH, —SCH 2 COOH, —NHSO 2 CH 3 , 3-carboxypyridinium or  
                         
 
           [0042]     R 1  and R 3  independently can be any group selected from hydrogen atom, C 1-4  alkyl, or C 1-4  alkyl having one or more substituent group selected from hydroxyl, carboxyl, sulfo, carbamoyl or methoxy carbonyl;  
           [0043]     preferably when X is fluorine atom or chlorine atom, R 1  and R 3  is hydrogen atom, methyl, or ethyl.  
           [0044]    The formula (Ib) dyestuff is preferably the following formula (I-1) dyestuff:  
                         
 
           [0045]    The formula (Ib) dyestuff is preferably the following formula (I-2) dyestuff:  
                         
 
           [0046]    The formula (Ib) dyestuff is preferably the following formula (I-3) dyestuff:  
                         
 
           [0047]    The formula (Ib) dyestuff is preferably the following formula (I-4) dyestuff:  
                         
 
           [0048]    The formula (Ib) dyestuff is preferably the following formula (I-1) dyestuff:  
                         
 
           [0049]    The formula (Ib) dyestuff is preferably the following formula (I-6) dyestuff  
                         
 
           [0050]    These kinds of dyestuffs are suitable for dyeing of materials containing either cellulose fibers, such as cotton, synthetic cotton, hemp, and synthetic hemp, or synthetic polyamide and polyurethane fibers, such as wool, silk, and nylon. Dyed materials with excellent properties can be obtained, showing especially outstanding performance in light fastness.  
           [0051]    Other objects, advantages, and novel features of the invention will become more apparent from the following detailed description when taken in conjunction with the accompanying drawings.  
         DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT  
         [0052]    Dyestuffs (I) of the present invention can be synthesized by the following reaction sequence step (a) to step (c).  
           [0053]    Step (a):  
           [0054]    The compound of the formula (III) is reacted with 1,3,5-trihalogen triazine of formula (IV) to obtain the following compound of formula (V),  
                         
 
           [0055]    wherein Hal is —F, —Cl, —Br; R 1 , R 2 , and n are defined as above formula (I). The reaction is carried out in aqueous solution at a temperature between 0 to 30° C., and below 20° C. is preferred. The acid generated in the reaction is neutralized by adding an acid-binding agent, and the pH is controlled between 3 to 7. Upon completion of the reaction, the product of formula (V) is obtained.  
           [0056]    Step (b):  
           [0057]    If while the X is not halogen, the compound of formula (V) is reacted with the compound of formula (VI) to obtain compound of formula (VII),  
                         
 
           [0058]    wherein Hal is —F, —Cl, —Br; X is —NHCN, —OH, —SCH 2 COOH, —NHSO 2 CH 3 , 3-carboxypyridinium,  
                         
 
           [0059]    R 1 , R 2 , and n are defined as for formula (I) above. The reaction temperature is controlled between 20 and 80° C., 40 to 60° C. is preferred. The acid generated in the reaction is neutralized by adding an acid binding agent. The pH is controlled between 4 and 12, and 6 to 10 is preferred. Upon completion the product of formula (VII) is obtained.  
           [0060]    Step (c):  
           [0061]    After the above reaction is completed, the compound of formula (VIII),  
                         
 
           [0062]    wherein R 3 , D, and Z are defined as above, is then added to the solution of the compound of formula (VII). IF X is halogen, the compound of formula (VIII) wherein R 3 , D, and Z are defined as the above, is then added to the solution of the compound of formula (V). The reaction temperature is controlled between 30 to 100° C., and 55 to 85° C. is preferred. The acid generated in the reaction is neutralized by adding an acid binding agent. The pH is controlled between 3 to 11, 3 to 7 is preferred. Upon completion of the reaction, dyestuffs represented by formula (I) are obtained.  
           [0063]    In the above reaction steps (a) to (c), the compounds of formula (III) and (IV) and (VI) and (VIII) can be reacted with one another in any sequence to yield the derivatives represented by formula (I).  
           [0064]    The preparation of the compound of formula (III) is described in U.S. Pat. No. 4,837,310.  
           [0065]    Compound (III) can be produced from a nitro compound of formula (X), which is diazotized at −10 to 20° C. in conventional manner, followed by coupling with a naphthol of formula (XI) at a temperature of −10 to 50° C., preferably 0 to 30° C., while controlling the pH within a range of 1 to 7, preferably 1 to 5. The resulting compound (XII) obtained is then reduced at a temperature of 40 to 100° C. in the presence of sodium sulfide. According to any one of the above sequences, the monoazo naphthol compound of the formula (III) can be obtained.  
                         
 
           [0066]    Examples of compounds of formula (X) include:  
           [0067]    2-methoxy-4-nitroaniline, 2-ethoxy-4-nitroaniline, 2-propoxy-4-nitroaniline,  
           [0068]    2-butoxy-4-nitroaniline, 4-nitroaniline-2-sulfonic acid,  
           [0069]    2-carboxy-4-nitroaniline, 2-fluoro-4-nitroaniline, 2-chloro-4-nitroaniline,  
           [0070]    2-bromo-4-nitroaniline.  
           [0071]    Examples of the compounds of formula (XI) are:  
                         

                         

                         
 
           [0072]    The above compounds of formula (VIII) can be synthesised by reacting the compound of formula (XIII) with an alkylating agent.  
           H 2 N—D-Z   (XIII)  
           [0073]    Examples of the alkylation reagents are: alkylhalide, dialkylsulfate, monosubstituted ethylene, or alkene oxide.  
           [0074]    Examples of the alkylhalide are:  
           [0075]    methylchloride, ethylchloride, n-propylchloride, isopropylchloride, n-butylchloride, isobutylchloride, sec-butylchloride, methylbromide, ethylbromide, n-propylbromide, isopropylbromide, n-butylbromide, isobutylbromide, sec-butylbromide.  
           [0076]    Examples of the dialkylsulfate are: dimethylsulfate, diethylsulfate, dipropylsulfate. Examples of the monosubstituted ethylene are: acrylonitrile, acrylic acid, methylacrylate, ethylacrylate, acrylamide, vinylsulfonic acid. Examples of the alkene oxide are: ethyleneoxide, propyleneoxide, glycol, trimethyleneoxide, β-buthyloxide, 2-methyl-α-buthyleneoxide, 2-ethyl-3 -methyleneoxide, methoxyethyleneoxide, or n-buthoxyleneoxide.  
           [0077]    Examples of compound of formula (XIII) are:  
           [0078]    1-aminobenzene-3-β-sulfatoethylsulfone,  
           [0079]    1-aminobenzene-4-β-sulfatoethylsulfone,  
           [0080]    1-aminobenzene-3 -phosphatoethylbenzene,  
           [0081]    1-amino-4-methylbenzene-3-β-sulfatoethylsulfone,  
           [0082]    1-aminobenzene-3-β-chloroethylsulfone,  
           [0083]    1-amino-4-methoxybenzene-3-β-sulfatoethylsulfone,  
           [0084]    1-amino-2,5-dimethylbenzene-4-β-sulfatoethylsulfone,  
           [0085]    1-amino-2-methoxybenzene-4-β-sulfatoethylsulfone,  
           [0086]    1-amino-2-chlorobenzene-4-β-sulfatoethylsulfone,  
           [0087]    1-amino-4-methoxybebzene-5-β-sulfatoethylsulfone,  
           [0088]    2-aminonaphthalene-8-β-sulfatoethylsulfone-6-sulfonic acid,  
           [0089]    2-aminonaphthalene-8-β-sulfatoethylsulfone,  
           [0090]    1-amino-2,5-dimethoxybenzene-4-vinylsulfone,  
           [0091]    1-amino-2-methoxy-5-methylbenzene-4-β-sulfatoethylsulfone,  
           [0092]    2-aminonaphthalene-4,5,6-β-sulfatoethylsulfone,  
           [0093]    2-aminonaphthalene-4,5,7-β-sulfatoethylsulfone,  
           [0094]    1-amino-2-bromobenzene-4-vinylsulfone,  
           [0095]    2-amino-8-sulfonaphthalene-6-β-sulfatoethylsulfone,  
           [0096]    2-aminonaphthalene-8-β-phhosphatoethylsulfone-6-sulfonic acid,  
           [0097]    2-aminonaphthalene-8-vinylsulfone-6-sulfonic acid,  
           [0098]    1-amino-2-methoxy-5-methylbenzene-4-μ-chloroethylsulfone,  
           [0099]    1-aminobenzene-2,3-vinylsulfone, 1-aminobenzene-2,4-vinylsulfone,  
           [0100]    1-amino-2-methoxy-5-chlorobenzene-4-β-chloroethylsulfone,  
           [0101]    1-amino-2-methoxy-5-chlorobenzene-4-vinylsulfone,  
           [0102]    1-amino-2-ethoxy-5-chlorobenzene-4-β-chloroethylsulfone,  
           [0103]    1-amino-2-ethoxy-5-chlorobenzene-4-vinylsulfone,  
           [0104]    2-aminonaphthalene-8-β-sulfatoethylsulfone-1-sulfonic acid,  
           [0105]    5-chloroaniline-2-β-sulfatoethylsulfone,  
           [0106]    5-sulfoaniline-2-β-sulfatoethylsulfone, aniline-2-β-phosphatoethylsulfone,  
           [0107]    5-chloroaniline-2-β-phosphatoethylsulfone, 5-chloroaniline-2-vinylsulfone,  
           [0108]    5-sulfoaniline-2-vinylsulfone, aniline-2-β-chloroethylsulfone,  
           [0109]    5-chloroaniline-2-β-chloroethylsulfone,  
           [0110]    5-sulfoaniline-2-β-chloroethylsulfone, aniline-2-β-thiosulfatoethylsulfone,  
           [0111]    5-chloroaniline-2-β-thiosulfatoethylsulfone,  
           [0112]    5-sulfoaniline-2-β-thiosulfatoethylsulfone,  
           [0113]    3-Amino-2′-(2-sulfatoethylsulfonyl)ethylbenzamide,  
           [0114]    4-Amino-2′-(2-sulfatoethylsulfonyl)ethylbenzamide.  
           [0115]    The dyestuffs of the present invention can be produced by the above methods, reaction conditions are fully described in the above description. The dyestuffs of the present invention can be purified by known processes such as spray drying, precipitation, or filtration. They can be in the form of powder, granules, particle or liquid and an auxiliary reagent, for example, retarding agent, leveling agent, assistant agent, surfactant agent, or dispersing agent may be added.  
           [0116]    The dyestuffs of the present invention all contain at least one anionic group, such as a sulfonic acid group. For convenience they are expressed as free acid in the specification. When the dyestuffs of the present invention are manufactured, purified or used, they often exist in the form of water soluble salts, especially the alkaline metal salts, such as the sodium salt, lithium salt, potassium salt or ammonium salt, preferably sodium salt.  
           [0117]    The dyestuffs of formula (I) in accordance with the present invention are fiber-reactive and useful for dyeing or printing hydroxyl group-containing and amide group-containing materials.  
           [0118]    The dyestuffs of formula (I) according to the invention are suitable for dyeing and printing the various materials, such as silk, leather, wool, polyamide fibers and polyurethanes, and in particular all types of fiber materials containing cellulose. Examples of such fiber materials are the natural cellulose fibers, such as cotton, linen and hemp, as well as cellulose and regenerated cellulose. The dyestuffs of formula (I) are also suitable for dyeing or printing fibers which contain hydroxy groups and are contained in blended fabrics, for example mixtures of cotton with polyester fibers or polyamide fibers.  
           [0119]    The dyestuffs according to the invention can be applied to the fiber material and fixed on the fiber in various ways, in particular in the form of aqueous dyestuff solutions and printing pastes. They are suitable both for the exhaust dyeing and for dyeing by the pad-dyeing process, in which the goods are impregnated with aqueous dyestuff solutions, if appropriate containing salts, and the dyestuff is fixed, after an alkali treatment or in the presence of alkali, if appropriate under the action of heat. The dyestuffs according to the invention are particularly suitable for the so-called cold pad-batch process, in which the dyestuff is applied to the padder together with the alkali and is then fixed by storage at room temperature for several hours. After fixing, the dyeings or prints are rinsed thoroughly with cold and hot water, if appropriate with addition of a dispersing agent which promotes diffusion of the non-fixed dye residues.  
           [0120]    The present invention therefore also relates to the use of the compounds of the formula (I) according to the invention for dyeing (including printing) these materials and to processes for dyeing (and printing) such materials by a procedure which is customary per se, in which a compound of the formula (I) is employed as the coloring agent, by applying the compound of formula (I) to the material in an aqueous medium and fixing it on the material by means of heat or by means of an alkali or by means of both.  
           [0121]    The dyestuffs of formula (I) are distinguished by a high reactivity, good fixing capacity and very good build-up capacity. The dyestuffs of the formula (I) can also exhibit excellent color-depth, level-dyeing and wash-off properties and high solubility as well as high exhaustion and fixation percentages. They can therefore be employed by the exhaust dyeing process at low dyeing temperatures and require only short steaming times in the pad-steam process. The degrees of fixing are high and the non-fixed portions can easily be washed out, the difference between the degree of exhaustion and the degree of fixing being remarkably small, i.e. the soaping loss is very low. The dyestuffs of formula (I) are also particularly suitable for printing, above all on cotton, and similarly also for printing nitrogen-containing fibers, for example wool or silk or blended fabrics which contain wool or silk.  
           [0122]    The dyeings and prints produced on cellulose fiber materials with the dyestuffs according to the invention have a good depth of color and a high fiber-dyestuff bonding stability both in the acid and in the alkaline range, and furthermore good light-fastness, good perspiration-light fastness and very good wet-fastness properties, such as fastnesses to washing, water, seawater, cross-dyeing and perspiration, as well as a good fastness to pleating, fastness to ironing and fastness to rubbing.  
           [0123]    The Examples that follow serve to illustrate the invention, which are only illustrative, but not limiting. The compounds are depicted in the formulae are shown in the form of free acids; in general, they are prepared and isolated in the form of their alkali metal salts and used for dyeing in the form of their salts. In the same way it is possible to use the starting compounds and components mentioned in the form of free acids in the examples below in particular the Table of examples, in the synthesis as such or in the form of their salts, preferably alkali metal salts.  
           [0124]    The Examples that follow serve to illustrate the invention. Parts and percentages are by weight, unless otherwise stated. Parts by weight bear the same relation to parts by volume as the kilogram to the liter.  
           [0125]    The absorption maxima (X max) in the visible region reported for the compounds according to the present invention were determined from aqueous solutions of alkali metal salts. 
       
    
    
     EXAMPLE 1  
       [0126]    A solution containing 4-nitroaniline-2-sulfonic acid (21.8 parts) and a 35% aqueous solution of sodium nitrite (21.7 parts) in water (150 parts) was introduced into a solution containing ice water (300 parts) and concentrated hydrochloric acid (35.5 parts), while controlling the temperature at 0 to 5° C., and the mixture was stirred for 1 hour at this temperature to effect diazotization.  
         [0127]    Successively, after excess nitrous acid had been decomposed, 2-amino-8-hydroxynaphthalene-3,6-disulfonic acid (31.9 parts) was added to the reaction mixture, and the mixture was stirred for 12 hours at room temperature, thereby performing a coupling reaction. Thereafter, the reaction mixture was adjusted to pH 8 to 10, and mixed with sodium sulfide (10.7 parts), and the mixture was heated to 60° C. and stirred for 3 hours at this temperature to effect reduction of the nitro group. Then, the reaction mixture was mixed with sodium chloride (40 parts) to deposit crystals, which were collected on a filter and washed. The resulting wet cake was dissolved in water (400 parts). The solution was mixed with cyanuric chloride (16.7 parts), and the mixture was stirred for 5 hours at 0 to 10° C., while controlling the pH within a range of 4 to 5 using a 20% aqueous solution of sodium carbonate, thereby performing a first condensation compound of formula (1).  
                         
 
       EXAMPLE 2  
       [0128]    To a solution containing the compound of Example 1 was added 27.8 parts of 1-N-ethylaminobenzene-3-β-sulfatoethylsulfone. The mixture was heated to 55° C., and was maintained at pH 4 to 5 for 5 hours.  
         [0129]    To the resulting solution was added sodium chloride to precipitate the desired product of formula (2), (λmax=525 nm),  
                         
 
       EXAMPLE 3 to 33  
       [0130]    The procedure described in Example 2 is repeated, reacting the compound of Example 1 with the following compounds, 3 to 33. As a result, bluish red (525±2 nm) monoazo derivatives are obtained.  
       EXAMPLE  
       [0131]    No. Compound Used  
         [0132]    3 1-N-ethylaminobenzene-4-β-sulfatoethylsulfone  
         [0133]    4 1-N-ethylaminobenzene-2-β-sulfatoethylsulfone  
         [0134]    5 1-N-ethylamino-4-methoxybenzene-3-β-sulfatoethylsulfone  
         [0135]    6 1-N-methylaminobenzene-3-β-sulfatoethylsulfone  
         [0136]    7 1-N-methylaminobenzene-4-β-sulfatoethylsulfone  
         [0137]    8 1-N-methylaminobenzene-2-β-sulfatoethylsulfone  
         [0138]    9 1-N-methylamino-4-methoxybenzene-3-β-sulfatoethylsulfone  
         [0139]    10 1-N-β-carbamoylethylaminobenzene-3-β-sulfatoethylsulfone  
         [0140]    11 1-N-β-carbamoylethylaminobenzene-4-β-sulfatoethylsulfone  
         [0141]    12 1-N-β-carbamoylethylaminobenzene-2-β-sulfatoethylsulfone  
         [0142]    13 1-N-β-carbamoylmethylamino-4-methoxybenzene-3-β-sulfatoethylsulfone  
         [0143]    14 1-N-n-propylaminobenzene-3-β-sulfatoethylsulfone  
         [0144]    15 1-N-n-propylaminobenzene-4-β-sulfatoethylsulfone  
         [0145]    16 1-N-n-propylaminobenzene-2-β-sulfatoethylsulfone  
         [0146]    17 1-N-n-propylamino-4-methoxybenzene-3-β-sulfatoethylsulfone  
         [0147]    18 1-N-β-cyanoethylaminobenzene-3-β-sulfatoethylsulfone  
         [0148]    19 1-N-β-cyanoethylaminobenzene-4-β-sulfatoethylsulfone  
         [0149]    20 1-N-β-cyanoethylaminobenzene-2-β-sulfatoethylsulfone  
         [0150]    21 1-N-β-cyanoethylamino-4-methoxybenzene-3-β-sulfatoethylsulfone  
         [0151]    22 1-N-β-hydroxyethylaminobenzene-3-β-sulfatoethylsulfone  
         [0152]    23 1-N-β-hydroxyethylaminobenzene-4-β-sulfatoethylsulfone  
         [0153]    24 1-N-β-hydroxyethylaminobenzene-2-β-sulfatoethylsulfone  
         [0154]    25 1-N-β-hydroxyethylamino-4-methoxybenzene-3-β-sulfatoethylsulfone  
         [0155]    26 1-N-β-sulfatoethylaminobenzene-3-β-sulfatoethylsulfone  
         [0156]    27 1-N-β-methoxycarbonylethylaminobenzene-3-β-sulfatoethylsulfone  
         [0157]    28 1-N-ethylamino-2-methoxybenzene-5-β-sulfatoethylsulfone  
         [0158]    29 1-N-ethylamino-2,4-dimethylbenzene-5-β-sulfatoethylsulfone  
         [0159]    30 1-N-ethylamino-2-methoxy-5-methylbenzene-3-β-sulfatoethylsulfone  
         [0160]    31 1-N-ethylaminonaphthalene-6-β-sulfatoethylsulfone  
         [0161]    32 1-N-ethylamino-8-sulfonaphthalene-6-β-sulfatoethylsulfone  
         [0162]    33 1-N-methylaminonaphthalene-8-β-sulfatoethylsulfone  
       EXAMPLE 34  
       [0163]    To a solution containing the compound of Example 1 was added an aqueous solution of 3.78 parts of cyanamide in about 100 parts of water, and the mixture is heated to 40˜60° C. and maintained at a pH 8 to 10 by means of a 20% aqueous solution of sodium carbonate until the reaction has ended, after 6 to 7 hours to give the monochlorotriazine of formula (34):  
                         
 
       EXAMPLE 35  
       [0164]    To a solution containing the product of Example 34 are added 25.3 parts of 1-aminobenzeze-3-β-sulfatoethylsulfone. The mixture is heated to 55° C., and is maintained at pH 4 to 6 for 4 hours.  
         [0165]    To the resulting solution is added sodium chloride to precipitate the desired product of formula (35), (λmax=525 nm).  
                         
 
       EXAMPLE 36 to 76  
       [0166]    A procedure similar to that described in Example 35 is repeated; a solution containing the product of Example 34 is reacted with compound listed below (Examples 36 to 76)  
       EXAMPLE  
       [0167]    No. Compound Used  
         [0168]    36 1-N-ethylaminobenzene-4-β-sulfatoethylsulfone  
         [0169]    37 1-N-ethylaminobenzene-2-β-sulfatoethylsulfone  
         [0170]    38 1-N-ethylamino-4-methoxybenzene-3-β-sulfatoethylsulfone  
         [0171]    39 1-N-methylaminobenzene-3-β-sulfatoethylsulfone  
         [0172]    40 1-N-methylaminobenzene-4-β-sulfatoethylsulfone  
         [0173]    41 1-N-methylaminobenzene-2-β-sulfatoethylsulfone  
         [0174]    42 1-N-methylamino-4-methoxybenzene-3-β-sulfatoethylsulfone  
         [0175]    43 1-N-β-carbamoylethylaminobenzene-3-β-sulfatoethylsulfone  
         [0176]    44 1-N-β-carbamoylethylaminobenzene-4-β-sulfatoethylsulfone  
         [0177]    45 1-N-β-carbamoylethylaminobenzene-2-β-sulfatoethylsulfone  
         [0178]    46 1-N-β-carbamoylmethylamino-4-methoxybenzene-3-β-sulfatoethylsulfone  
         [0179]    47 1-N-n-propylaminobenzene-3-β-sulfatoethylsulfone  
         [0180]    48 1-N-n-propylaminobenzene-4-β-sulfatoethylsulfone  
         [0181]    49 1-N-n-propylaminobenzene-2-β-sulfatoethylsulfone  
         [0182]    50 1-N-n-propylamino-4-methoxybenzene-3-β-sulfatoethylsulfone  
         [0183]    51 1-N-β-cyanoethylaminobenzene-3-β-sulfatoethylsulfone  
         [0184]    52 1-N-β-cyanoethylaminobenzene-4-β-sulfatoethylsulfone  
         [0185]    53 1-N-β-cyanoethylaminobenzene-2-β-sulfatoethylsulfone  
         [0186]    54 1-N-β-cyanoethylamino-4-methoxybenzene-3-β-sulfatoethylsulfone  
         [0187]    55 1-N-β-hydroxyethylaminobenzene-3-β-sulfatoethylsulfone  
         [0188]    56 1-N-β-hydroxyethylaminobenzene-4-β-sulfatoethylsulfone  
         [0189]    57 1-N-β-hydroxyethylaminobenzene-2-β-sulfatoethylsulfone  
         [0190]    58 1-N-β-hydroxyethylamino-4-methoxybenzene-3-β-sulfatoethylsulfone  
         [0191]    59 1-N-β-sulfatoethylaminobenzene-3-β-sulfatoethylsulfone  
         [0192]    60 1-N-β-methoxycarbonylethylaminobenzene-3-β-sulfatoethylsulfone  
         [0193]    61 1-N-ethylamino-2-methoxybenzene-5-β-sulfatoethylsulfone  
         [0194]    62 1-N-ethylamino-2,4-dimethylbenzene-5-β-sulfatoethylsulfone  
         [0195]    63 1-N-ethylamino-2-methoxy-5-methylbenzene-3-β-sulfatoethylsulfone  
         [0196]    64 1-N-ethylaminonaphthalene-6-β-sulfatoethylsulfone  
         [0197]    65 1-N-ethylamino-8-sulfonaphthalene-6-β-sulfatoethylsulfone  
         [0198]    66 1-N-methylaminonaphthalene-8-β-sulfatoethylsulfone  
         [0199]    67 1-aminobenzene-4-β-sulfatoethylsulfone  
         [0200]    68 1-aminobenzene-2-β-sulfatoethylsulfone  
         [0201]    69 1-N-ethylaminobenzene-3-β-sulfatoethylsulfone  
         [0202]    70 1-amino-4-methoxybenzene-3-β-sulfatoethylsulfone  
         [0203]    71 1-amino-2-methoxybenzene-5-β-sulfatoethylsulfone  
         [0204]    72 1-amino-2-methoxy-5-methylbenzene-4-β-sulfatoethylsulfone  
         [0205]    73 1-amino-2,4-dimethylbenzene-5-β-sulfatoethylsulfone  
         [0206]    74 1-aminonaphthalene-6-β-sulfatoethylsulfone  
         [0207]    75 1-amino-8-sulfonaphthalene-6-β-sulfatoethylsulfone  
         [0208]    76 1-aminonaphthalene-8-β-sulfatoethylsulfone  
       EXAMPLE 77  
       [0209]    To a solution containing the compound of Example 1 was added 25.3 parts of 1-aminobenzene-3-β-sulfatoethylsulfone. The mixture was heated to 55° C., and maintained at pH 4 to 5 for 5 hours. To this reaction mixture was added 18.5 parts of 3-carboxypyridine, and the mixture is heated to 85˜90° C., and is maintained at pH 4 to 5 for 12 hours.  
         [0210]    To the resulting solution is added sodium chloride to precipitate the desired product of formula (77), (λmax=528 nm),  
                         
 
       EXAMPLE 78˜118  
       [0211]    A procedure similar to that described in Example 77 is repeated using the substituents listed in examples 78 to 118 instead of 1-aminobenzene-3-β-sulfatoethylsulfone that used in Examples 77. As a result, bluish red (528±2 nm) monoazo derivatives are obtained.  
       EXAMPLE  
       [0212]    No. Compound Used  
         [0213]    78 1-N-ethylaminobenzene-4-β-sulfatoethylsulfone  
         [0214]    79 1-N-ethylaminobenzene-2-β-sulfatoethylsulfone  
         [0215]    80 1-N-ethylamino-4-methoxybenzene-3-β-sulfatoethylsulfone  
         [0216]    81 1-N-methylaminobenzene-3-β-sulfatoethylsulfone  
         [0217]    82 1-N-methylaminobenzene-4-β-sulfatoethylsulfone  
         [0218]    83 1-N-methylaminobenzene-2-β-sulfatoethylsulfone  
         [0219]    84 1-N-methylamino-4-methoxybenzene-3-β-sulfatoethylsulfone  
         [0220]    85 1-N-β-carbamoylethylaminobenzene-3-β-sulfatoethylsulfone  
         [0221]    86 1-N-β-carbamoylethylaminobenzene-4-β-sulfatoethylsulfone  
         [0222]    87 1-N-β-carbamoylethylaminobenzene-2-β-sulfatoethylsulfone  
         [0223]    88 1-N-β-carbamoylmethylamino-4-methoxybenzene-3-β-sulfatoethylsulfone  
         [0224]    89 1-N-n-propylaminobenzene-3-β-sulfatoethylsulfone  
         [0225]    90 1-N-n-propylaminobenzene-4-β-sulfatoethylsulfone  
         [0226]    91 1-N-n-propylaminobenzene-2-β-sulfatoethylsulfone  
         [0227]    92 1-N-n-propylamino-4-methoxybenzene-3-β-sulfatoethylsulfone  
         [0228]    93 1-N-β-cyanoethylaminobenzene-3-β-sulfatoethylsulfone  
         [0229]    94 1-N-β-cyanoethylaminobenzene-4-β-sulfatoethylsulfone  
         [0230]    95 1-N-β-cyanoethylaminobenzene-2-β-sulfatoethylsulfone  
         [0231]    96 1-N-β-cyanoethylamino-4-methoxybenzene-3-β-sulfatoethylsulfone  
         [0232]    97 1-N-β-hydroxyethylaminobenzene-3-β-sulfatoethylsulfone  
         [0233]    98 1-N-β-hydroxyethylaminobenzene-4-β-sulfatoethylsulfone  
         [0234]    99 1-N-β-hydroxyethylaminobenzene-2-β-sulfatoethylsulfone  
         [0235]    100 1-N-β-hydroxyethylamino-4-methoxybenzene-3-β-sulfatoethylsulfone  
         [0236]    101 1-N-β-sulfatoethylaminobenzene-3-β-sulfatoethylsulfone  
         [0237]    102 1-N-β-methoxycarbonylethylaminobenzene-3-β-sulfatoethylsulfone  
         [0238]    103 1-N-ethylamino-2-methoxybenzene-5-β-sulfatoethylsulfone  
         [0239]    104 1-N-ethylamino-2,4-dimethylbenzene-5-β-sulfatoethylsulfone  
         [0240]    105 1-N-ethylamino-2-methoxy-5-methylbenzene-3-β-sulfatoethylsulfone  
         [0241]    106 1-N-ethylaminonaphthalene-6-β-sulfatoethylsulfone  
         [0242]    107 1-N-ethylamino-8-sulfonaphthalene-6-β-sulfatoethylsulfone  
         [0243]    108 1-N-methylaminonaphthalene-8-β-sulfatoethylsulfone  
         [0244]    109 1-aminobenzene-4-β-sulfatoethylsulfone  
         [0245]    110 1-aminobenzene-2-β-sulfatoethylsulfone  
         [0246]    111 1-N-ethylaminobenzene-3-β-sulfatoethylsulfone  
         [0247]    112 1-amino-4-methoxybenzene-3-β-sulfatoethylsulfone  
         [0248]    113 1-amino-2-methoxybenzene-5-β-sulfatoethylsulfone  
         [0249]    114 1-amino-2-methoxy-5-methylbenzene-4-β-sulfatoethylsulfone  
         [0250]    115 1-amino-2,4-dimethylbenzene-5-β-sulfatoethylsulfone  
         [0251]    116 1-aminonaphthalene-6-β-sulfatoethylsulfone  
         [0252]    117 1-amino-8-sulfonaphthalene-6-β-sulfatoethylsulfone  
         [0253]    118 1-aminonaphthalene-8-3-sulfatoethylsulfone  
       EXAMPLE 119  
       [0254]    A solution containing 4-nitroaniline-2-sulfonic acid (21.8 parts) and a 35% aqueous solution of sodium nitrite (21.7 parts) in water (150 parts) was introduced into a solution containing ice water (300 parts) and concentrated hydrochloric acid (35.5 parts), while controlling the temperature at 0 to 5° C., and the mixture was stirred for 1 hour at this temperature to effect diazotization.  
         [0255]    Successively, after excess nitrous acid had been decomposed, 2-N-methylamino-8-hydroxynaphthalene-3,6-disulfonic acid (33.3 parts) was added to the reaction mixture, and the mixture was stirred for 12 hours at room temperature, thereby performing a coupling reaction. Thereafter, the reaction mixture was adjusted to pH 8 to 10, and mixed with sodium sulfide (10.7 parts), and the mixture was heated to 60° C. and stirred for 3 hours at this temperature to effect reduction of the nitro group. Then, the reaction mixture was mixed with sodium chloride (40 parts) to deposit crystals, which were collected and washed. The resulting wet cake was dissolved in water (400 parts). The solution was mixed with cyanuric chloride (16.7 parts), and the mixture was stirred for 5 hours at 0 to 10C., while controlling the pH within a range of 4 to 5 using a 20% aqueous solution of sodium carbonate, thereby performing a first condensation. To this reaction mixture was added an aqueous solution of 3.78 parts of cyanamide in about 100 parts of water, and the mixture is heated to 40˜60° C. and maintained at a pH 8.0 to 10.0 by means of a 20% aqueous solution of sodium carbonate until the reaction has ended after 6 to 7 hours, thereby performing a second condensation.  
         [0256]    25.3 parts of 1-aminobenzeze-3-β-sulfatoethylsulfone were added to the above reaction mixture, and the resulting mixture was heated to 55° C., and maintained at pH 4 to 6 for 4 hours. To the resulting solution was added sodium chloride to precipitate the desired product of formula (119), (λmax=530 nm).  
                         
 
       EXAMPLE 120 to 193  
       [0257]    In similar manner compounds (120) to (193) were prepared. Each naphthol compound of formula(XI) shown in a second column of the following table was used in place of 2-N-methylamino-8-hydroxynaphalene-3,6-disulfonic acid, and each compound of the formula (X) shown in a third column in place of 4-nitroaniline-2-sulfonic acid, cyanamide as shown in a fourth column, and each aromatic amine compound of the formula(VIII) shown in a fifth column in place of 1 -aminobenzeze-3-β-sulfatoethylsulfone, thereby obtaining the desired corresponding monoazo compound.  
                                                             Ex.   Compound of   Compound of       No.   Formula (V)   Formula (IX)               120                                                                           121                                                                           122                                                                           123                                                                           124                                                                           125                                                                           126                                                                           127                                                                           128                                                                           129                                                                           130                                                                           131                                                                           132                                                                           133                                                                           134                                                                           135                                                                           136                                                                           137                                                                           138                                                                           139                                                                           140                                                                           141                                                                           142                                                                           143                                                                           144                                                                           145                                                                           146                                                                           147                                                                           148                                                                           149                                                                           150                                                                           151                                                                           152                                                                           153                                                                           154                                                                           155                                                                           156                                                                           157                                                                           158                                                                           159                                                                           160                                                                           161                                                                           162                                                                           163                                                                           164                                                                           165                                                                           166                                                                           167                                                                           168                                                                           169                                                                           170                                                                           171                                                                           172                                                                           173                                                                           174                                                                           175                                                                           176                                                                           177                                                                           178                                                                           179                                                                           180                                                                           181                                                                           182                                                                           183                                                                           184                                                                           185                                                                           186                                                                           187                                                                           188                                                                           189                                                                           190                                                                           191                                                                           192                                                                           193                                                                                Ex.   Cyana-   Compound of           No.   mide   Formula (III)   Shade               120   NH 2 CN                                 Bluish red               121   NH 2 CN                                 Bluish red               122   NH 2 CN                                 Bluish red               123   NH 2 CN                                 Bluish red               124   NH 2 CN                                 Bluish red               125   NH 2 CN                                 Bluish red               126   NH 2 CN                                 Bluish red               127   NH 2 CN                                 Bluish red               128   NH 2 CN                                 Bluish red               129   NH 2 CN                                 Bluish red               130   NH 2 CN                                 Bluish red               131   NH 2 CN                                 Bluish red               132   NH 2 CN                                 Bluish red               133   NH 2 CN                                 Bluish red               134   NH 2 CN                                 Bluish red               135   NH 2 CN                                 Bluish red               136   NH 2 CN                                 Bluish red               137   NH 2 CN                                 Bluish red               138   NH 2 CN                                 Bluish red               139   NH 2 CN                                 Bluish red               140   NH 2 CN                                 Bluish red               141   NH 2 CN                                 Bluish red               142   NH 2 CN                                 Bluish red               143   NH 2 CN                                 Bluish red               144   NH 2 CN                                 Bluish red               145   NH 2 CN                                 Bluish red               146   NH 2 CN                                 Bluish red               147   NH 2 CN                                 Bluish red               148   NH 2 CN                                 Bluish red               149   NH 2 CN                                 Bluish red               150   NH 2 CN                                 Bluish red               151   NH 2 CN                                 Bluish red               152   NH 2 CN                                 Bluish red               153   NH 2 CN                                 Bluish red               154   NH 2 CN                                 Bluish red               155   NH 2 CN                                 Bluish red               156   NH 2 CN                                 Bluish red               157   NH 2 CN                                 Bluish red               158   NH 2 CN                                 Bluish red               159   NH 2 CN                                 Bluish red               160   NH 2 CN                                 Bluish red               161   NH 2 CN                                 Bluish red               162   NH 2 CN                                 Bluish red               163   NH 2 CN                                 Bluish red               164   NH 2 CN                                 Bluish red               165   NH 2 CN                                 Bluish red               166   NH 2 CN                                 Bluish red               167   NH 2 CN                                 Bluish red               168   NH 2 CN                                 Bluish red               169   NH 2 CN                                 Bluish red               170   NH 2 CN                                 Bluish red               171   NH 2 CN                                 Bluish red               172   NH 2 CN                                 Bluish red               173   NH 2 CN                                 Bluish red               174   NH 2 CN                                 Bluish red               175   NH 2 CN                                 Bluish red               176   NH 2 CN                                 Bluish red               177   NH 2 CN                                 Bluish red               178   NH 2 CN                                 Bluish red               179   NH 2 CN                                 Bluish red               180   NH 2 CN                                 Bluish red               181   NH 2 CN                                 Bluish red               182   NH 2 CN                                 Bluish red               183   NH 2 CN                                 Bluish red               184   NH 2 CN                                 Bluish red               185   NH 2 CN                                 Bluish red               186   NH 2 CN                                 Bluish red               187   NH 2 CN                                 Bluish red               188   NH 2 CN                                 Bluish red               189   NH 2 CN                                 Bluish red               190   NH 2 CN                                 Bluish red               191   NH 2 CN                                 Bluish red               192   NH 2 CN                                 Bluish red               193   NH 2 CN                                 Bluish red                  
 
       EXAMPLE 194  
       [0258]    To an aqueous mixture of the dichloro triazine described in example 119 was added 1-aminobenzeze-3-β-sulfatoethylsulfone (25.3 parts), and the mixture is heated to 55° C. and maintained at a pH 4 to 5 by means of a 20% aqueous solution of sodium carbonate until the reaction was complete after 3 to 5 hours.  
         [0259]    18.5 parts of 3-carboxypyridine were added to the above reaction mixture, and the resulting mixture was heated to 85˜90° C. at pH 4 to 5 for 12 hours. To the resulting solution was added sodium chloride to precipitate the desired product of formula (194), (λmax=535 nm).  
                         
 
       EXAMPLE 195 to 268  
       [0260]    In a similar manner compounds (195) to (268) were prepared. Each naphthol compound of formula (XI) shown in a second column of the following table was used in place of 2-N-methylamino-8-hydroxynaphthalene-3,6-disulfonic acid, and each compound of the formula (X) shown in a third column in place of 4-nitroaniline-2-sulfonic acid, 3-carboxypyridine as shown in a fourth column, and each aromatic amine compound of the formula(VIII) shown in a fifth column in place of 1-aminobenzeze-3-β-sulfatoethylsulfone, thereby obtaining the desired corresponding monoazo compound.  
                                                             Ex.   Compound of   Compound of       No.   Formula (XI)   Formula (X)               195                                                                           196                                                                           197                                                                           198                                                                           199                                                                           200                                                                           201                                                                           202                                                                           203                                                                           204                                                                           205                                                                           206                                                                           207                                                                           208                                                                           209                                                                           210                                                                           211                                                                           212                                                                           213                                                                           214                                                                           215                                                                           216                                                                           217                                                                           218                                                                           219                                                                           220                                                                           221                                                                           222                                                                           223                                                                           224                                                                           225                                                                           226                                                                           227                                                                           228                                                                           229                                                                           230                                                                           231                                                                           232                                                                           233                                                                           234                                                                           235                                                                           236                                                                           237                                                                           238                                                                           239                                                                           240                                                                           241                                                                           242                                                                           243                                                                           244                                                                           245                                                                           246                                                                           247                                                                           248                                                                           249                                                                           250                                                                           251                                                                           252                                                                           253                                                                           254                                                                           255                                                                           256                                                                           257                                                                           258                                                                           259                                                                           260                                                                           261                                                                           262                                                                           263                                                                           264                                                                           265                                                                           266                                                                           267                                                                           268                                                                                Ex.   3-Carboxy   Compound of           No.   pyridine   Formula (VIII)   Shade               195                                                               Bluish red               196                                                               Bluish red               197                                                               Bluish red               198                                                               Bluish red               199                                                               Bluish red               200                                                               Bluish red               201                                                               Bluish red               202                                                               Bluish red               203                                                               Bluish red               204                                                               Bluish red               205                                                               Bluish red               206                                                               Bluish red               207                                                               Bluish red               208                                                               Bluish red               209                                                               Bluish red               210                                                               Bluish red               211                                                               Bluish red               212                                                               Bluish red               213                                                               Bluish red               214                                                               Bluish red               215                                                               Bluish red               216                                                               Bluish red               217                                                               Bluish red               218                                                               Bluish red               219                                                               Bluish red               220                                                               Bluish red               221                                                               Bluish red               222                                                               Bluish red               223                                                               Bluish red               224                                                               Bluish red               225                                                               Bluish red               226                                                               Bluish red               227                                                               Bluish red               228                                                               Bluish red               229                                                               Bluish red               230                                                               Bluish red               231                                                               Bluish red               232                                                               Bluish red               233                                                               Bluish red               234                                                               Bluish red               235                                                               Bluish red               236                                                               Bluish red               237                                                               Bluish red               238                                                               Bluish red               239                                                               Bluish red               240                                                               Bluish red               241                                                               Bluish red               242                                                               Bluish red               243                                                               Bluish red               244                                                               Bluish red               245                                                               Bluish red               246                                                               Bluish red               247                                                               Bluish red               248                                                               Bluish red               249                                                               Bluish red               250                                                               Bluish red               251                                                               Bluish red               252                                                               Bluish red               253                                                               Bluish red               254                                                               Bluish red               255                                                               Bluish red               256                                                               Bluish red               257                                                               Bluish red               258                                                               Bluish red               259                                                               Bluish red               260                                                               Bluish red               261                                                               Bluish red               262                                                               Bluish red               263                                                               Bluish red               264                                                               Bluish red               265                                                               Bluish red               266                                                               Bluish red               267                                                               Bluish red               268                                                               Bluish red                  
 
       EXAMPLE 269  
       [0261]    2-Amino-8-hydroxynaphthalene-6-disulfonic acid (23.8 parts) was added to 4-nitro-2-sulphobenzene diazonium chloride prepared as in Example 1, and the mixture was stirred for 12 hours at room temperature, to effect coupling. The reaction mixture was then adjusted to pH 8 to 10, and mixed with sodium sulfide (10.7 parts), and the mixture was heated to 60.° C. and stirred for 3 hours at this temperature to reduce the nitro group. Then, the reaction mixture was mixed with sodium chloride (40 parts) to deposit a solid, which was collected and washed. The resulting wet cake was dissolved in water (400 parts). The solution was mixed with cyanuric chloride (16.7 parts), and the mixture was stirred for 5 hours at 0 to 10° C., while controlling the pH within a range of 4 to 5 using a 20% aqueous solution of sodium carbonate, thereby performing a first condensation. To this reaction mixture was added 1-N-ethylaminobenzene-3-β-sulfatoethylsulfone (27.8 parts), and the mixture is heated to 55° C. and maintained at a pH 4 to 5 by means of a 20% aqueous solution of sodium carbonate until the reaction has ended after 3 to 5 hours.  
         [0262]    To the resulting solution is added sodium chloride to precipitate the desired product of formula (269), (λmax=518 nm),  
                         
 
       EXAMPLE 270 to 295  
       [0263]    By a similar procedure compounds of examples 270 to 295 were prepared. Each naphthol compound of formula (XI) shown in a second column of the following table was used in place of 2-amino-8-hydroxynaphthalene-6-disulfonic acid, and each compound of the formula (X) shown in a third column in place of 4-nitroaniline-2-sulfonic acid, cyanuric chloride or cyanuric fluoride as shown in a fourth column in which Cl and F denote cyanuric chloride and cyanuric fluoride, and each aromatic amine compound of the formula (VIII) shown in a fifth column in place of 1-N-ethylaminobenzene-3-β-sulfatoethylsulfone, thereby obtaining the desired corresponding monoazo compound.  
                                                               Cyanuric                           chloride or       Ex.   Compound of   Compound of   Cyanuric   Compound of       No.   Formula (XI)   Formula (X)   fluoride   Formula (VIII)   Shade                                               270                                                               Cl                                 Bluish red       271                                                               Cl                                 Bluish red       272                                                               Cl                                 Bluish red       273                                                               Cl                                 Bluish red       274                                                               Cl                                 Bluish red       275                                                               Cl                                 Bluish red       276                                                               Cl                                 Bluish red       277                                                               Cl                                 Bluish red       278                                                               F                                 Bluish red       279                                                               F                                 Bluish red       280                                                               F                                 Bluish red       281                                                               F                                 Bluish red       282                                                               F                                 Bluish red       283                                                               F                                 Bluish red       284                                                               F                                 Bluish red       285                                                               F                                 Bluish red       286                                                               F                                 Bluish red       287                                                               F                                 Bluish red       288                                                               F                                 Bluish red       289                                                               F                                 Bluish red       290                                                               F                                 Bluish red       291                                                               F                                 Bluish red       292                                                               F                                 Bluish red       293                                                               F                                 Bluish red       294                                                               F                                 Bluish red       295                                                               F                                 Bluish red                  
 
       EXAMPLE 296  
       [0264]    Urea 100 parts, m-nitrobenzene sulfonic acid sodium salt, 10 parts, sodium bicarbonate, 20 parts, sodium alginate, 55 parts, warm water, 815 parts, were stirred in a vessel to give a completely homogeneous printing paste.  
         [0265]    Dyestuff of formula (2) (prepared as in example 2), 3 parts, and the above printing paste, 100 parts, were mixed together to make a homogeneous colored paste. A 100 mesh printing screen covering an adequate sized piece of cotton fabric was painted with this colored paste on printing screen to give a colored fabric.  
         [0266]    The colored fabric was placed in an oven at 65° C. to dry for 5 minutes then taken out, and put into a steam oven using saturated steam for 10 minutes at 102-105° C.  
         [0267]    The colored fabric was washed with cold water, hot water, and soap then dried to obtain a bluish red fabric with good build-up, light fastness, wet fastness and wash fastness.  
       EXAMPLE 297  
       [0268]    Dyestuff of formula (2) (prepared from the example 2), 3 parts was dissolved in 100 parts of water to give a padding liquor. 25 ml of alkali solution (NaOH (38° Be′) 15 ml/l Glauber&#39;s salt 30 parts/l) were added to the padding liquor. The resultant solution was put into a pad roller machine. The cotton fabric was padded by the roller pad machine, then was batched for 4 hours. The padded fabric was washed with cold water, hot water, and soap solution then dried to obtain a bluish red fabric with good build-up, light fastness, wet fastness and wash fastness.  
       EXAMPLE 298  
       [0269]    Dyestuff of formula (2) (prepared from the example 2), 0.25 parts was dissolved in 250 parts of water. To 40 ml of this solution, in a dyeing bottle, was added cotton fabric, Glauber&#39;s salt,2.4 parts, and 32% alkali solution, 2.5 parts. The dyeing bottle was shaken at 60° C. for 60 minutes. The colored fabric was washed with cold water, hot water, and soap solution then dried to obtain a bluish red fabric with good build-up, light fastness, wet fastness and wash fastness.  
       EXAMPLE 299  
       [0270]    Dyestuff of the formula (35), (prepared as described in Example 35) 0.25 parts was dissolved in 250 parts of water. To 40 ml of this solution, in a dyeing bottle, was added cotton fabric, Glauber&#39;s salt,2.4 parts, and 32% alkali solution, 2.5 parts. The dyeing bottle was shaken at 60° C. for 60 minutes. The colored fabric was washed with cold water, hot water, and soap solution then dried to obtain a bluish red fabric with good build-up, light fastness, wet fastness and wash fastness.  
       EXAMPLE 300  
       [0271]    Dyestuff of the formula (77), (prepared as described in Example 77) 0.25 parts was dissolved in 250 parts of water. To 40 ml of this solution, in a dyeing bottle, was added cotton fabric, Glauber&#39;s salt,2.4 parts, and 32% alkali solution, 2.5 parts. The dyeing bottle was shaken at 60° C. for 60 minutes. The colored fabric was washed with cold water, hot water, and soap solution then dried to obtain a bluish red fabric with good build-up, light fastness, wet fastness and wash fastness.  
       EXAMPLE 301  
       [0272]    Dyestuff of the formula (119), (prepared as described in Example 119)0.25 parts was dissolved in 250 parts of water. To 40 ml of this solution, in a dyeing bottle, was added cotton fabric, Glauber&#39;s salt, 2.4 parts, and 32 % alkali solution, 2.5 parts. The dyeing bottle was shaken at 60° C. for 60 minutes. The colored fabric was washed with cold water, hot water, and soap solution then dried to obtain a bluish red fabric with good build-up, light fastness, wet fastness and wash fastness.  
       EXAMPLE 302  
       [0273]    Dyestuff of the formula (194), (prepared as described in Example 194) 0.25 parts was dissolved in 250 parts of water. To 40 ml of this solution, in a dyeing bottle, was added cotton fabric, Glauber&#39;s salt, 2.4 parts, and 32 % alkali solution, 2.5 parts. The dyeing bottle was shaken at 60° C. for 60 minutes. The colored fabric was washed with cold water, hot water, and soap solution then dried to obtain a bluish red fabric with good build-up, light fastness, wet fastness and wash fastness.  
       EXAMPLE 303  
       [0274]    Dyestuff of the formula (269), (prepared as described in Example 269) 0.25 parts was dissolved in 250 parts of water. To 40 ml of this solution, in a dyeing bottle, was added cotton fabric, Glauber&#39;s salt, 2.4 parts, and 32 % alkali solution, 2.5 parts. The dyeing bottle was shaken at 60° C. for 60 minutes. The colored fabric was washed with cold water, hot water, and soap solution then dried to obtain a bluish red fabric with good build-up, light fastness, wet fastness and wash fastness.  
         [0275]    Although the present invention has been explained in relation to its preferred embodiment, it is to be understood that many other possible modifications and variations can be made without departing from the spirit and scope of the invention as hereinafter claimed.