Monoazo reactive red dyestuff

Abstract

A monoazo reactive red dyestuff of the formula (I), 1

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: 2

[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), 3

[0008] wherein:

[0009] X is —NHCN, —OH, —SCH2COOH, —NHSO2CH3, 3-carboxypyridinium, 4

[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, C1-4 alkyl, C1-4 alkoxyl, nitro, amino, hydroxyl, carboxyl, phosphonic acid and sulfo group; preferably D is phenyl having 0 to 3 substituent groups;

[0012]  Z is —SO2—CH═CH2 or SO2—CH2—CH2—U; U is —OSO3H, Cl, Br, —OPO3H2, —SSO3H or 5

[0013]  preferably Z is ‘3SO2CH═CH2 or —SO2—CH2—CH2—OSO3H;

[0014]  R2 is sulfo, carboxy, halogen or C1-4 alkoxy; preferably R2 is sulfo or carboxy;

[0015]  n is 0 or 1, and preferably n is 1;

[0016]  when X is a halogen atom, R1 is limited to a hydrogen atom and R3 is limited to C1-4 alkyl or C1-4 alkyl having at least one substituent; preferably when X is fluorine atom or chlorine atom, R1 is hydrogen atom and R3 is C1-4 alkyl;

[0017]  when X is —NHCN, —OH, —SCH2COOH, —NHSO2CH3, 3-carboxypyridinium or 6

[0018]  R1 and R3 independently can be any group selected from hydrogen atom, C1-4 alkyl, phenyl, 7

[0019]  or C1-4alkyl having one or more substituent group selected from hydroxyl, carboxyl, sulfo, carbamoyl or methoxy carbonyl; preferably R1 and R3 is hydrogen atom or C1-4 alkyl.

[0020] The dyestuffs of the present invention is preferably represented by the following formula (Ia), 8

[0021] wherein:

[0022] X is —NHCN, —OH, —SCH2COOH, —NHSO2CH3, 3-carboxypyridinium, 9

[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, C1-4 alkyl, C1-4 alkoxyl, nitro, amino, hydroxyl, carboxyl, phosphonic acid and sulfo group;

[0025]  preferably D is phenyl having 0 to 3 substituent groups;

[0026]  Z is —SO2—CH═CH2 or SO2—CH2—CH2—U; U is —OSO3H, Cl, Br, —OPO3H2, —SSO3H or 10

[0027]  preferably Z is —SO2CH═CH2 or —SO2—CH2—CH2—OSO3H;

[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 R3 is limited to C1-4 alkyl or C1-4 alkyl having at least one substituent; preferably when X is fluorine atom or chlorine atom, R1 I is hydrogen atom and R3 is C1-4 alkyl;

[0030]  when X is —NHCN, —OH, —SCH2COOH, —NHSO2CH3, 3-carboxypyridinium or 11

[0031]  R1 and R3 independently can be any group selected from hydrogen atom, C1-4 alkyl, phenyl, 12

[0032]  or C1-4 alkyl having one or more substituent group selected from hydroxyl, carboxyl, sulfo, carbamoyl or methoxy carbonyl; preferably R1 and R3 is hydrogen atom or C1-4 alkyl.

[0033] The formula (I) dyestuff of the present invention is also preferably represented by the following formula (Ib), 13

[0034] wherein:

[0035] X is —NHCN, —OH, —SCH2COOH, —NHSO2CH3, 3-carboxypyridinium, 14

[0036]  halogen; preferably X is —NHCN, 3-carboxypyridinium, chlorine or fluorine;

[0037]  Z is —SO2—CH═CH2 or SO2—CH2—CH2—U ; U is —OSO3H, Cl or Br; preferably

[0038]  Z is —SO2—CH2—CH2—OSO3H;

[0039]  n is 0 or 1, and preferably n is 1;

[0040]  when X is a chlorine atom or fluorine atom, R1 is limited to a hydrogen atom and R3 is limited to C1-4 alkyl; preferably R1 is hydrogen atom and R3 is methyl or ethyl;

[0041]  when X is —NHCN, —OH, —SCH2COOH, —NHSO2CH3, 3-carboxypyridinium or 15

[0042]  R1 and R3 independently can be any group selected from hydrogen atom, C1-4 alkyl, or C1-4 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, R1 and R3 is hydrogen atom, methyl, or ethyl.

[0044] The formula (Ib) dyestuff is preferably the following formula (I-1) dyestuff: 16

[0045] The formula (Ib) dyestuff is preferably the following formula (I-2) dyestuff: 17

[0046] The formula (Ib) dyestuff is preferably the following formula (I-3) dyestuff: 18

[0047] The formula (Ib) dyestuff is preferably the following formula (I-4) dyestuff: 19

[0048] The formula (Ib) dyestuff is preferably the following formula (I-1) dyestuff: 20

[0049] The formula (Ib) dyestuff is preferably the following formula (I-6) dyestuff 21

[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), 22

[0055] wherein Hal is —F, —Cl, —Br; R1, R2, 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), 23

[0058] wherein Hal is —F, —Cl, —Br; X is —NHCN, —OH, —SCH2COOH, —NHSO2CH3, 3-carboxypyridinium, 24

[0059] R1, R2, 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), 25

[0062] wherein R3, 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 R3, 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. 26

[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: 272829

[0072] The above compounds of formula (VIII) can be synthesised by reacting the compound of formula (XIII) with an alkylating agent.

H2N—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). 30

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), 31

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): 32

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). 33

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), 34

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). 35

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	36	37
121	38	39
122	40	41
123	42	43
124	44	45
125	46	47
126	48	49
127	50	51
128	52	53
129	54	55
130	56	57
131	58	59
132	60	61
133	62	63
134	64	65
135	66	67
136	68	69
137	70	71
138	72	73
139	74	75
140	76	77
141	78	79
142	80	81
143	82	83
144	84	85
145	86	87
146	88	89
147	90	91
148	92	93
149	94	95
150	96	97
151	98	99
152	100	101
153	102	103
154	104	105
155	106	107
156	108	109
157	110	111
158	112	113
159	114	115
160	116	117
161	118	119
162	120	121
163	122	123
164	124	125
165	126	127
166	128	129
167	130	131
168	132	133
169	134	135
170	136	137
171	138	139
172	140	141
173	142	143
174	144	145
175	146	147
176	148	149
177	150	151
178	152	153
179	154	155
180	156	157
181	158	159
182	160	161
183	162	163
184	164	165
185	166	167
186	168	169
187	170	171
188	172	173
189	174	175
190	176	177
191	178	179
192	180	181
193	182	183
Ex.	Cyana-	Compound of
No.	mide	Formula (III)	Shade
120	NH2CN	184	Bluish red
121	NH2CN	185	Bluish red
122	NH2CN	186	Bluish red
123	NH2CN	187	Bluish red
124	NH2CN	188	Bluish red
125	NH2CN	189	Bluish red
126	NH2CN	190	Bluish red
127	NH2CN	191	Bluish red
128	NH2CN	192	Bluish red
129	NH2CN	193	Bluish red
130	NH2CN	194	Bluish red
131	NH2CN	195	Bluish red
132	NH2CN	196	Bluish red
133	NH2CN	197	Bluish red
134	NH2CN	198	Bluish red
135	NH2CN	199	Bluish red
136	NH2CN	200	Bluish red
137	NH2CN	201	Bluish red
138	NH2CN	202	Bluish red
139	NH2CN	203	Bluish red
140	NH2CN	204	Bluish red
141	NH2CN	205	Bluish red
142	NH2CN	206	Bluish red
143	NH2CN	207	Bluish red
144	NH2CN	208	Bluish red
145	NH2CN	209	Bluish red
146	NH2CN	210	Bluish red
147	NH2CN	211	Bluish red
148	NH2CN	212	Bluish red
149	NH2CN	213	Bluish red
150	NH2CN	214	Bluish red
151	NH2CN	215	Bluish red
152	NH2CN	216	Bluish red
153	NH2CN	217	Bluish red
154	NH2CN	218	Bluish red
155	NH2CN	219	Bluish red
156	NH2CN	220	Bluish red
157	NH2CN	221	Bluish red
158	NH2CN	222	Bluish red
159	NH2CN	223	Bluish red
160	NH2CN	224	Bluish red
161	NH2CN	225	Bluish red
162	NH2CN	226	Bluish red
163	NH2CN	227	Bluish red
164	NH2CN	228	Bluish red
165	NH2CN	229	Bluish red
166	NH2CN	230	Bluish red
167	NH2CN	231	Bluish red
168	NH2CN	232	Bluish red
169	NH2CN	233	Bluish red
170	NH2CN	234	Bluish red
171	NH2CN	235	Bluish red
172	NH2CN	236	Bluish red
173	NH2CN	237	Bluish red
174	NH2CN	238	Bluish red
175	NH2CN	239	Bluish red
176	NH2CN	240	Bluish red
177	NH2CN	241	Bluish red
178	NH2CN	242	Bluish red
179	NH2CN	243	Bluish red
180	NH2CN	244	Bluish red
181	NH2CN	245	Bluish red
182	NH2CN	246	Bluish red
183	NH2CN	247	Bluish red
184	NH2CN	248	Bluish red
185	NH2CN	249	Bluish red
186	NH2CN	250	Bluish red
187	NH2CN	251	Bluish red
188	NH2CN	252	Bluish red
189	NH2CN	253	Bluish red
190	NH2CN	254	Bluish red
191	NH2CN	255	Bluish red
192	NH2CN	256	Bluish red
193	NH2CN	257	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). 258

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	259	260
196	261	262
197	263	264
198	265	266
199	267	268
200	269	270
201	271	272
202	273	274
203	275	276
204	277	278
205	279	280
206	281	282
207	283	284
208	285	286
209	287	288
210	289	290
211	291	292
212	293	294
213	295	296
214	297	298
215	299	300
216	301	302
217	303	304
218	305	306
219	307	308
220	309	310
221	311	312
222	313	314
223	315	316
224	317	318
225	319	320
226	321	322
227	323	324
228	325	326
229	327	328
230	329	330
231	331	332
232	333	334
233	335	336
234	337	338
235	339	340
236	341	342
237	343	344
238	345	346
239	347	348
240	349	350
241	351	352
242	353	354
243	355	356
244	357	358
245	359	360
246	361	362
247	363	364
248	365	366
249	367	368
250	369	370
251	371	372
252	373	374
253	375	376
254	377	378
255	379	380
256	381	382
257	383	384
258	385	386
259	387	388
260	389	390
261	391	392
262	393	394
263	395	396
264	397	398
265	399	400
266	401	402
267	403	404
268	405	406
Ex.	3-Carboxy	Compound of
No.	pyridine	Formula (VIII)	Shade
195	407	408	Bluish red
196	409	410	Bluish red
197	411	412	Bluish red
198	413	414	Bluish red
199	415	416	Bluish red
200	417	418	Bluish red
201	419	420	Bluish red
202	421	422	Bluish red
203	423	424	Bluish red
204	425	426	Bluish red
205	427	428	Bluish red
206	429	430	Bluish red
207	431	432	Bluish red
208	433	434	Bluish red
209	435	436	Bluish red
210	437	438	Bluish red
211	439	440	Bluish red
212	441	442	Bluish red
213	443	444	Bluish red
214	445	446	Bluish red
215	447	448	Bluish red
216	449	450	Bluish red
217	451	452	Bluish red
218	453	454	Bluish red
219	455	456	Bluish red
220	457	458	Bluish red
221	459	460	Bluish red
222	461	462	Bluish red
223	463	464	Bluish red
224	465	466	Bluish red
225	467	468	Bluish red
226	469	470	Bluish red
227	471	472	Bluish red
228	473	474	Bluish red
229	475	476	Bluish red
230	477	478	Bluish red
231	479	480	Bluish red
232	481	482	Bluish red
233	483	484	Bluish red
234	485	486	Bluish red
235	487	488	Bluish red
236	489	490	Bluish red
237	491	492	Bluish red
238	493	494	Bluish red
239	495	496	Bluish red
240	497	498	Bluish red
241	499	500	Bluish red
242	501	502	Bluish red
243	503	504	Bluish red
244	505	506	Bluish red
245	507	508	Bluish red
246	509	510	Bluish red
247	511	512	Bluish red
248	513	514	Bluish red
249	515	516	Bluish red
250	517	518	Bluish red
251	519	520	Bluish red
252	521	522	Bluish red
253	523	524	Bluish red
254	525	526	Bluish red
255	527	528	Bluish red
256	529	530	Bluish red
257	531	532	Bluish red
258	533	534	Bluish red
259	535	536	Bluish red
260	537	538	Bluish red
261	539	540	Bluish red
262	541	542	Bluish red
263	543	544	Bluish red
264	545	546	Bluish red
265	547	548	Bluish red
266	549	550	Bluish red
267	551	552	Bluish red
268	553	554	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), 555

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	556	557	Cl	558	Bluish red
271	559	560	Cl	561	Bluish red
272	562	563	Cl	564	Bluish red
273	565	566	Cl	567	Bluish red
274	568	569	Cl	570	Bluish red
275	571	572	Cl	573	Bluish red
276	574	575	Cl	576	Bluish red
277	577	578	Cl	579	Bluish red
278	580	581	F	582	Bluish red
279	583	584	F	585	Bluish red
280	586	587	F	588	Bluish red
281	589	590	F	591	Bluish red
282	592	593	F	594	Bluish red
283	595	596	F	597	Bluish red
284	598	599	F	600	Bluish red
285	601	602	F	603	Bluish red
286	604	605	F	606	Bluish red
287	607	608	F	609	Bluish red
288	610	611	F	612	Bluish red
289	613	614	F	615	Bluish red
290	616	617	F	618	Bluish red
291	619	620	F	621	Bluish red
292	622	623	F	624	Bluish red
293	625	626	F	627	Bluish red
294	628	629	F	630	Bluish red
295	631	632	F	633	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'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'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'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'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'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'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'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.

Claims

1. A monoazo reactive red dyestuff of formula (I),

2. The monoazo reactive red dyestuff of claim 1, wherein X is —NHCN, 3-carboxypyridinium, chlorine or fluorine.

3. The monoazo reactive red dyestuff of claim 1, wherein D is phenyl having 0 to 3 substituent groups.

4. The monoazo reactive red dyestuff of claim 1, wherein Z is —SO2—CH═CH2, or —SO2—CH2—CH2—OSO3H.

5. The monoazo reactive red dyestuff of claim 1, wherein R2 is sulfo or carboxy.

6. The monoazo reactive red dyestuff of claim 1, wherein n is 1.

7. The monoazo reactive red dyestuff of claim 1, wherein while X is chlorine atom or fluorine atom, R1 is hydrogen atom and R3 is C1-4 alkyl.

8. The monoazo reactive red dyestuff of claim 1, wherein while X is —NHCN, —OH, —SCH2COOH, —NHSO2CH3, 3-carboxypyridinium or

9. The monoazo reactive red dyestuff of claim 1, wherein dyestuff of formula (I) is the following formula (Ia),

10. The monoazo reactive red dyestuff of claim 9, wherein X is is —NHCN, 3-carboxypyridinium, chlorine or fluorine.

11. The monoazo reactive red dyestuff of claim 9, wherein D is phenyl having 0 to 3 substituent groups.

12. The monoazo reactive red dyestuff of claim 9, wherein Z is —SO2—CH═CH2, or —SO2—CH2—CH2—OSO3H.

13. The monoazo reactive red dyestuff of claim 9, wherein n is 1.

14. The monoazo reactive red dyestuff of claim 9, wherein while the X is chlorine atom or fluorine atom, the R1 is hydrogen atom and the R3 is C1-4alkyl.

15. The monoazo reactive red dyestuff of claim 9, wherein while the X is —NHCN, —OH, —SCH2COOH, —NHSO2CH3, 3-carboxypyridinium or

16. The monoazo reactive red dyestuff of claim 1, wherein formula (I) dyestuff is the following formula (Ib) dyestuff,

17. The monoazo reactive red dyestuff of claim 16, wherein X is is —NHCN, 3-carboxypyridinium, chlorine or fluorine.

18. The monoazo reactive red dyestuff of claim 16, wherein Z is —SO2—CH2—CH2—OSO3H.

19. The monoazo reactive red dyestuff of claim 16, wherein n is 1.

20. The monoazo reactive red dyestuff of claim 16, wherein while X is chlorine atom or fluorine atom, R1 is hydrogen atom and R3 is methyl, or ethyl.

21. The monoazo reactive red dyestuff of claim 16, wherein while the X is —NHCN, —OH, —SCH2COOH, —NHSO2CH3, 3-carboxypyridinium or

22. The monoazo reactive red dyestuff of claim 16, wherein said formula (Ib) dyestuff is the following formula (I-1) dyestuff.

23. The monoazo reactive red dyestuff of claim 16, wherein said formula (Ib) dyestuff is the following formula (I-2) dyestuff.

24. The monoazo reactive red dyestuff of claim 16, wherein said formula (Ib) dyestuff is the following formula (I-3) dyestuff.

25. The monoazo reactive red dyestuff of claim 16, wherein said formula (Ib) dyestuff is the following formula (I-4) dyestuff.

26. The monoazo reactive red dyestuff of claim 16, wherein said formula (Ib) dyestuff is the following formula (I-5) dyestuff.

27. The monoazo reactive red dyestuff of claim 16, wherein said formula (Ib) dyestuff is the following formula (I-6) dyestuff.

28. A process for dyeing and printing a material containing hydroxyl or amide groups, particularly cellulosic fiber materials, which comprises treating the fiber materials with a dye of the formula (I) according to claim 1 in aqueous solution.

29. The process of claim 28, wherein the cellulosic fiber materials is cotton.