JPS5946991B2 - Method for producing reactive azine dyes - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel water-soluble reactive dyes, and more particularly to azine-based water-soluble reactive dyes.

According to the present invention, the formula (1):
HQ (wherein Q is a sulfatoethylsulfonyl group, or an acyl group of acrylic acid, cyclobutane, cyclobutene, or a 6-membered heterocyclic carboxylic acid or sulfonic acid containing 2 or 3 ring nitrogen atoms) , it has a cellulose-reactive substituent, or Q is a heterocycle having a cellulose-reactive substituent and one or two six-membered heterocycles having two or three nitrogen atoms in each ring. (wherein the cellulose-reactive substituent is selected from F, Ct, Br or SO3H) represents a benzene nucleus V or W or an anilino group or a N (lower alkino(ha)benzylamino group) A reactive azine dye is obtained which is present in Am and the dye as a whole also contains at least one more sulfonic acid group.

Q is an unsaturated bond or a substituent that reacts with the hydroxyl group of the cellulose molecule in the presence of an alkaline substance and is capable of covalently attaching the dye molecule.

Examples of Q include a vinyl sulfone group and an aliphatic sulfone group having a halogen atom or a sulfuric acid ester group at the β-position relative to the sulfur atom, such as β-chloroethyl or β-sulfatoethylsulfone and β- sulfatoethylsulfonylamino groups, α,β-monounsaturated acyl groups of aliphatic carboxylic acids such as acrylic acid, α-chloroacrylic acid, propiolic acid, maleic acid and mono- and dichloromaleic acids; likewise alkali Acyl groups of acids with substituents which react with cellulose in the presence of halogenated aliphatic acids such as chloroacetic acid, β-chloro- and β-bromo-
Mention may be made of the acyl groups of propionic acid and α,β-dichloro- and dibromo-propionic acid.

Other examples of Q are tetrafluorocyclobutylcarbonyl,
trifluorocyclobutenylcarbonyl, tetrafluorocyclobutylethenylcarbonyl, trifluorocyclobutenylethenylcarbonyl, and heterocycles having 2 or 3 nitrogen atoms in the ring and at least 1 nitrogen atom on the ring carbon atom. It is a heterocyclic group having 4 cellulose-reactive substituents.
Examples of such heterocyclic groups include, for example: 2,3-dichloro-quinoxaline-5- or -6
-Sulfonyl, 2,3-dichloro-quinoxaline-5-1 or -6-carbonyl, 2,4-dichloro-quinazoline-5-1 or -J-meth[sulfonyl, 2,4,6-trichloro-quinazoline-J-meth] or -8-sulfonyl, 2,4,7
1- or 2,4,8-trichloro-quinazoline-6-sulfonyl, 2,4-dichloro-quinazoline-6-carbonyl 1,4-dichlorofuthalazine-6-carbonyl, 4
, 5-dichloropyridazon-1-yl, 2,4-dichloro-pyrimidine-5-carbonyl, 4-(4',5'
-dichloroupyridaz-6'-one-1'-ino (c)
Benzoyl, 4-(4',5'-dichloropyridaz-6'-one-1'-yl)phenylsulfonyl, 5-chloro-2-methylsulfonyl-6-methyl-pyrido-4
-yl 2,4-difluoro-5-chloropyrimide-6
-yl, and more particularly aryloxy or aryl radicals having a bromine or preferably chlorine atom, a sulfonic acid group, a thiocyanate group, an electronegative substituent on at least one of the remaining 2, 4-1 and 6-1 positions. groups such as sulfophenoxy, sulfophenylthio, nitrosulfophenoxy, disulfophenoxy and sulfonaphthoxy, or of the formula:
[In the formula, Y1 represents a group of atoms necessary to form a 5- or 6-membered heterocycle which may have a substituent or to form a part of a fused ring system]; or or a pyridinium group of formula: or a group of the formula: [wherein R3 and R4 may be the same or different and each represents a hydrogen atom or an alkyl, aryl or anorealkyl group] s-triazin-2-yl and pyrimidin-2-yl or -4
-yl group.

If the pyrimidine or triazine ring has only one such reactive substituent, said ring may have non-reactive substituents on the remaining carbon atoms.

A non-reactive substituent is a group bonded by a covalent bond to a carbon atom of the triazine or pyrimidine nucleus; examples of such substituents used in reactive dye applications include, for example, primary amino acids. and hydroxyl groups, as well as - or disubstituted amino groups, etherified hydroxyls and etherified mercapto groups; in the case of substituted amino groups, this group includes, for example, mono- and di-alkylamino groups (in which the alkyl groups preferably has at most 4 carbon atoms, and it can likewise contain substituents, such as hydroxyl or alkoxy groups, and phenylamino, preferably sulfonated phenylamino (which can also contain on the nucleus, for example CH3, OCH3, CO2H or on the N atom, e.g. CH3, C2
H5, optionally substituted by hydroxyethyl or sulfomethyl), and naphthylamino groups, preferably sulfonated naphthylamino with up to 3 sulfonic acid substituents); etherified hydroxyl and mercapto groups In the case of
and phenoxy, phenylthio, naphthoxy or naphthylthio groups; specific examples of all these groups include, for example, methylamino, ethylamino, diethylylamino, β-hydroxyethylamino, di-(β-hydroxyethyl)amino,
β-chloroethylamino, cyclohexylamino, anilino, o-, m- and p-sulfoanilino, 2,4-,
2,5- and 3,5-disulfoanilino, N-methylsulfoanilino, N-β-hydroxyethylsulfoanilino, mono-, di- and trisulfonaphthyl-amino, 4
- and 5-sulfo- o -tolylamino, o-, m-
and p-carboxyanilino, 4- and 5-sulfo-2
-carboxyanilino, N-ω-sulfomethylanilino, methoxy, ethoxy, and butoxy, phenoxy, p
-sulfophenoxy, o-chlorophenoxy and phenylthio groups. Chlorine atoms or cyano, nitro, carboxy and carbalkoxy groups in the 5-position of the pyrimidyl group fall within the scope of non-reactive substituents. If desired, Q can be of the form: [wherein Ht is a cellulose-reactive Ct or Br atom 111-
ku, ゛ ,′ ＋k−＾? 18 T, 1,} ding TIL
and Q1 are a diamine group bonded by two amino groups, and Q1 represents the same as Q, and is a sulfatoethylsulfonyl group, acrylic acid, or cyclobutane, cyclobutene, or a ring nitrogen atom 2 or a 6-membered heterocyclic ring containing 3 or 6-membered heterocyclic carboxylic or sulfonic acid acyl groups containing 2 or 3 nitrogen atoms in each ring; a heterocyclic group having one or two rings and a cellulose-reactive substituent].

If the symbol Q1 represents an s-triazine ring with a Ct atom and a non-reactive substituent, the latter may be a group of colored amines, for example of the azo, anthraquinone or phthalocyanine type, but more particularly of the formula (1). The dye as a whole may therefore have two groups of the formula (formula) linked by chloro-s-triazine groups or two chloro-s-triazine groups and a diamine group. It has two groups of formula (1). The present invention also provides a method for producing a new dye, which has the formula (1'): (alkyl)benzylamino group] present in Am), carbyl sulfate, an acid chloride of acrylic acid, carboxylic acid, or sulfonic acid as described above, or a halogen atom and 2 or 2 nitrogen atoms in each ring. 1 or 2 6-membered heterocycles containing 3 and at least 1
The reaction components are characterized in that both reactants together have at least two sulfonic acid groups.

The above method involves stirring the reactants in an aqueous medium, optionally in the presence of a water-soluble organic solvent, within the range of 0 to 100°C. It can be advantageously implemented by.

Examples of acid chlorides or heterocyclic compounds that may be used include, for example, acid halides of α,β monounsaturated aliphatic acids;
Acid chlorides of halogenated aliphatic acids, such as chloromaleic anhydride, propiolyl chloride and acryloyl chloride, such as chloroacetyl chloride, sulfochloroacetyl chloride, β-bromo- and β-chloro-propionyl chloride and α,β-dichloride. - and dibromo-propionyl chloride, 2,2,3,3-tetrafluorocyclobutylcarbonyl chloride, β-(2,2,3,3
-tetrafluorocyclobutyl)acryloyl chloride, 2,3,3-trifluorocyclobut-1-enylcarbonyl chloride, β-(2,3,3-trifluorocyclobut-1-enyl)acryloyl chloride, and hetero Heterocyclic compounds having at least two nitrogen atoms in the ring and two or more halogens, especially chlorine atoms, in the position ortho to the nitrogen atoms, such as 2,3-dichloro-
Quinoxaline-5- and -6-carbonyl chloride, 2
, 3-dichloroquinoxaline-51 and -6-sulfonyl chloride, 2,4-dichloroquinazoline-5-1 and -J me[sulfonyl chloride, 2,4,6-trichloroquinazoline-J me[and -8 -sulfonyl chloride, 2,
4,7-2 and 2,4,8-trichloroquinazoline-6-sulfonyl chloride, 2,4-dichloroquinazoline-6-carbonyl chloride, 1,4-dichlorofuthalazine-6-carbonyl chloride, 2, 4-dichloro-pyrimidine-5-carbonylchloride, β-(4
,5-dichloropyridazonyl-1-)-propionyl chloride, 1-(4'-chlorocarbonylphenyl)-
4,5-dichloro-6-pyridazone, 1-l-chlorosulfonylphenyl-4,5-dichloro-6-pyridazone, 2,4,56-tribromo- and trichloro-pyrimidine, 2,4,5,6 -tetrachlorpyrimidine, 5-
Methyl-2,4,6-trichloropyrimidine, 5-nitro-2,4,6-trichloropyrimidine, 2,4-dichloro-5-nitro-6-metal loopy, 2,4
-dichloro-5-nitropyrimidine, 2,4,6-trichlor-5-cyanopyrimidine, 5-ethoxycarbonyl-2,4-dichloro-pyrimidine, 2,4-dichloropyrimidine-5-carbonyl chloride, 4,5 - 2-methylsulfonyl-6-methylpyrimidine, 2
, 4,6-trifluoro-5-chloropyrimidine, cyanuric bromide, cyanuric chloride; cyanuric bromide or cyanuric chloride with ammonia, alkali metal sulfites or thiocyanates or organic mercaptans, hydroxy compounds or organic primary or secondary amines, e.g. , methanol, ethanol, iso-propanol, phenol o-, m- and p-chlorophenol o-, m- and p-cresol o-, m- and p-sulfophenol, thiophenol, thioglycolic acid, dimethyldithiocarbamic acid , mercaptobenzate azole, thioacetamide, methyl-, dimethyl-, ethyl-, diethyl-, n-propyl-, iso-propyl-, butyl-, hexyl- and cyclohexylamine, toluidine, piperidine, morpholine, methoxyethylamine, ethanol Amine, diethanolamine, aminoacetic acid, aniline-2,4-,2,
5- and 3,5-disulfonic acid, ortanilic acid, metanilic acid and sulfanilic acid, 2-, 3- and 4-aminobenzoic acid, 4- and 5-sulfo-2-aminobenzoic acid, 4
1- and 5-sulfo-0-toluidine, 5-amino-2-
hydroxybenzoic acid, 2-amino-ethanesulfonic acid,
Primary condensation products with amino-naphthalene mono-, di- and trisulfozoic acids and amino- and N-methylamino-ethanesulfonic acids; likewise with cyanuric chloride, alkali metal sulfites, alkali metal thiocyanates, electronegative substituents and secondary condensation products with compounds of the formula: S in which Yl, Rl, R2, R3 and R4 are as defined above.

Of the compounds of formula (1Y) used in the above method, some are known and others are new.

Generally they are obtained in one of the following ways: (a)
1,3-Dianilinonaphthalene-8-sulfonic acid is reacted in particular with 4,4'-diaminodiphenylamine containing one or two sulfonic acid groups. (b) especially 1 or 2
4-nitro-4'-aminodiphenylamine or 4-nitrophenyl-4'- containing sulfonic acid groups
Aminonaphth-l'-ylamine sulfonated aniline and N-(lower alkyl)-N-(sulfobenzyl)
React with aniline in the presence of an oxidizing agent and reduce the product.

(c) in particular reacting sulfonated β-phenylnaphthylamine with p-nitrozone(lower alkynole)aniline, treating the product with an alkali metal bisulfite to introduce sulfonic acid groups and producing a product is reacted with phenylenediamine sulfonic acid.

Cellulose-reactive dyes of the formula (1) [wherein Q is an s-triazine nucleus substituted with a chlorine or bromine atom and an amino group or a substituted amino group] can also be used with phenazine compounds (where IY is cyanuric chloride or odor It is obtained by reacting with cyanuric acid to form a cellulose-reactive dye of formula (1) containing a dichloro- or dibromo-s-triazine group and reacting this with ammonia or an amine.

Advantageously, the process comprises combining the reaction components in an aqueous medium at a temperature of 30 DEG to 60 DEG C., optionally in the presence of a water-soluble organic solvent and an acid binder, in particular in order to neutralize the hydrogen halides formed during the reaction. This can be carried out by stirring while maintaining the pH at 5 to 8 by adding .

Suitable acid binders are alkali metal hydroxides, alkali metal carbonates and alkali metal bicarbonates or one of the reactants.
Excess ammonia or aliphatic amine.

As amine, any of those listed above can be used.

Furthermore, when diamine is used in a ratio of 1 mole to 2 moles of dichloro-s-triazine dye, the resulting product is such that the dye as a whole has 2 chloro-s-triazine groups.
Group 2 of formula (1) bonded via one diamine group and one diamine group
of the above-mentioned type containing the following.

In this connection, it is possible to use, for example, any of the following: piperazine, aliphatic diamines such as alkylene diamines and other α
, ω-diaminoaliphatic compounds such as ethylene diamine, 1,2- and 1,3-propylene diamine, 1,6-
hexylene diamine, triethylenetetramine, di-(β-aminoethyl)ether, aromatic diamines of the benzene or naphthalene series, especially those containing one or two SO3H groups, such as m- and p-phenylene diamine, 1,3-phenylenediamine-4-sulfonic acid and -4
, 6-disulfonic acid, 1,4-phenylenediamine
2-sulfonic acid and -2,5-disulfonic acid, 2,
6-naphthylenediamine-4-sulfonic acid and -4,
8-disulfonic acid, 1,5-naphthylenediamine-2
- and -4-sulfonic acid and -3,7-disulfonic acid, 4,4'-diaminodiphenyl-2-sulfonic acid and -2,2'-disulfonic acid, 4,4'-diaminosulfene-2, 2'-disulfonic acid, 4,4'-diaminodiphenylurea-2,2'- and -3,3'-disulfonic acid, 4,4'-diaminodiphenylamine-2,
2'-disulfonic acid, 4,4'-diaminodiphenoxyethane-2,2'-disulfonic acid, 4,4'-diaminodiphenylmethane-2,2'-disulfonic acid, 4,4'
-diaminoazobenzene-2-sulfonic acid and -2
, 2'-disulfonic acid, N-methyl- and N-ethyl-
1,4-phenylenediamine-12-sulfonic acid, N
-(β-hydroxyethyl)ethylenediamine.

Optionally, by reacting with equimolar ratios of diamines, the resulting product contains free amino groups.

Carbyl sulfate or aliphatic, isocyclic, or 6-membered multi-ring system containing 2 or 3 nitrogen atoms in the ring containing a cellulose-reactive substituent or carboxylic acid or sulfonic acid. an acid chloride or a halogen atom and one or two 6-membered heterocycles containing two or three nitrogen atoms in each ring bonded to a carbon atom of the ring and at least one cellulose-reactive substitution The resulting dye contains Q of the formula (5) (wherein Ht represents a 2-chloro-4,6-s-triazinylene group). . Q is SO3H, a quaternary ammonium group, or the formula (
s- substituted by groups 2), (3) and (4)
Cellulose-reactive dyes of formula (1), which are triazine cores, are likewise dyes of formula (1) containing an s-triazine group substituted by at least one chlorine or bromine atom, by any method described above. It is obtained by forming cellulose-reactive dyes and reacting them with sulphites, tertiary amines or alkali metal salts of compounds of formulas (6), (7) and (8).

This new dye can be used for dyeing various materials, such as natural and synthetic polyamide materials, such as wool and nylon, and in particular natural or man-made cellulose materials, such as cotton, linen and viscose rayon. When dyed or printed in the presence of alkali, bright blue and reddish blue tones are obtained which have excellent fastness to washing.

Generally, commercially available blue reactive dyes rely on anthraquinone chromophores or copper azo chromophores.

The present dyes are superior to the former when very high chromaticities on a molar basis are to be obtained and present the advantage of very good fastness to wet fading compared to the latter.
Next, the present invention will be explained in detail with reference to examples.

Note that "part" means "part by weight" and "W/V" means "g/l". Example 1 15.6 parts of 1,3-diphenylaminonaphthalene-8-sulfonic acid, 2 parts of 4,4'-diaminodiphenylamine
- 11.4 parts of sulfonic acid and 9.5 parts of sodium carbonate are stirred in a mixture of 100 parts of water and 100 parts of ethyl alcohol.

Next, 10 parts of water and ammonia solution (specific gravity 0.890)
A solution of 1.5 parts of copper borate pentahydrate in 15 parts is added and a slow stream of air is bubbled through the mixture and the mixture is heated to 3.
Stir at 5-40°C for 24 hours. The precipitated aminophenazine of the formula: (estimated) [wherein X, Y and Z all represent H] is filtered off, washed with cold water and dried.

1-Aminobenzene-3-sulfonic acid in 50 parts of water 1.
9 parts of the neutral solution are added to a suspension of 1.9 parts of cyanuric chloride in 100 parts of water at 0-5°C.

The mixture is stirred for 1 hour at 0-5°C, during which time the pH is reduced to 2.
Maintained at 6-7 by addition of N-sodium carbonate solution. Thereafter, a solution of 2,4-dichloro-s-triazinylaminobenzene-3-sulfonic acid was added to a suspension of 6.6 parts of aminophenazine in 500 parts of water and the mixture was
Stir at ˜40° C. for 6 hours, keeping the pH at 6-7 by addition of 2N sodium monocarbonate solution. Thereafter, the solution is screened and sodium chloride is added to the lachrymal fluid at 10% W/V. Precipitate the dye in a centrifuge for 20
00rPI! Separate by l. After decanting the liquid, the dyestuff is dried at 40°C. When applied to cotton or viscose fiber materials, the dye produces a deep blue shade with good fastness to washing treatments and moderate fastness to light.

According to the invention, other examples are listed in the table, where X, Y and Z relate to formula (9) and 1 equivalent of the compound in column 1 is condensed with 1 equivalent of acylating agent in column 1.

In the first column, (Dct)ba-2,4-dichloro-
Represents s-triazine''. The tone of all these dyes on cotton is light blue. These examples are of the class of dyes that can be represented by formula (9), except that one hydrogen atom of the NH2 group is replaced by Q in formula (1). .

Example 66 A mixture of 27.5 parts of 4-amino-4'-nitrodiphenylamine-2'-sulfonic acid and 29.1 parts of N-ethyl-N-3'-sulfobenzylaniline in 750 parts of water
Stir at H6-7 and O<0>C.

A solution of 37.8 parts of sodium dichromate dihydrate in 200 parts of water and 18.6 parts of sulfuric acid is added rapidly at 0° C. and the mixture is stirred for 15 minutes. 10 of 15.5 parts of 4-aminobenzenesulfonic acid in 150 parts of water and pH 6-7
Add the solution. The mixture is then stirred at 15° C. for 15 minutes, heated to 40° C., stirred for a further 15 minutes, then rapidly heated to 80° C. and 5.5 parts of sodium carbonate are added. The mixture is allowed to cool to 70° C. for 10 minutes. 25 parts of needle dust are added and the mixture is stirred at 70-75°C for 75 minutes. The mixture is filtered at 70° C. and the residue is extracted with 1500 parts of water at 70° C. and filtered again. Add sodium chloride to the combined solution at 20% w/v and allow to cool. Formula (guess): [In the formula, X1=SO3H, X2, X3, Y=H, Rl=C
The precipitated aminophenadine of 2H5, R2 = m-sulfobenzyl] is filtered off, washed with 20% brine and dried at 40°C.

7.4 parts of aminophenazine in 200 parts of water, 0-5°C
and cyanuric chloride 2 in 150 parts of water with a pH of 6-7.
．． Add to 0 parts of suspension at 0-5°C.

The mixture is stirred for 1 hour at 0 to 5°C, with the exception that P
H is kept at 6-7 by addition of 2N sodium carbon solution. Screen the solution and add sodium chloride to the bottom solution at 10% w/v. The precipitated dye is filtered out,
Mix with 0.8 parts of a mixture of 1 part of disodium hydrogen phosphate and 2 parts of potassium dihydrogen phosphate and dry under vacuum. When applied to cotton or viscose fiber materials, the dyes produce deep bright red-blue shades with good fastness to washing and moderate fastness to light.

The following table lists a number of other compounds according to the invention obtained by condensing compounds of the formula σ0), in which Xl, X2, X3, Y, Rl and R2 represent those in column 1, with the compounds listed in column 1. Post the dye.

The term (Dct) represents 2,4-dichloro-s-triazine. All products give rise to a reddish-blue color.

In general, good dyes have the formula σ0) [where Y is H,
CH3y. represents 0CH3, R1 is an alkyl group with up to 4 carbon atoms, R2 is a benzyl group or a sulfobenzyl group, one of Xl, X2 and X3 is a sulfo group and the other is H It can be obtained from amines according to These dyes have one hydrogen atom of the NH2 group replaced by Q (representing any of the above). Such dyes have a high tonality, giving very bright reddish-blue tones, very good fastness to washing and moderately high fastness to light, as well as dyes of the same color. Has much better resistance to wet fading than copper azo dyes. Example 85 22 parts of phenyl-β-naphthylamine and 3-sulfo-4
- The mixture with 24.5 parts of the sodium salt of diethylaminoaniline is stirred and brought to reflux.

45 parts of acetic acid are added, followed by a solution of 31 parts of sodium dichromate in 50 parts of water. Stir the mixture and add 1
Reflux for 5 minutes, cool to 20°C and dilute with 100 parts of water. The precipitated phenazine of formula: is filtered off and dried.

25 parts of sodium sulfite in 1000 parts of water, pH 7.

The solution of No. 5 is stirred at 70-80° C. and 25 parts of phenazine are added over the course of 1 hour.

After the addition is complete, the mixture is heated for an additional 5 hours at 75 to
Stir at 80°C. Filter the solution and add 100 parts of sodium chloride to the cooled sap. The disulfonated phenazine of formula: is separated and dried.

5.4 parts of disulfonated phenazine in 100 parts of water and 1
, 4-phenylenediamine-2,5-disulfonic acid 4.
A solution of 0 parts of PH7O is stirred and refluxed for 7 hours.

Cool the solution and add 5 parts of sodium chloride. The precipitated phenazine of the formula: is filtered off and dried.

Aminophenazine 7.3 as prepared above in 400 parts of water
PH7. A solution of O is added to a suspension of 2.0 parts of cyanuric chloride in 100 parts of water.

The mixture is stirred for 3 hours at 0-5° C. while maintaining the pH at 6-7 by simultaneously adding the required amount of 2N sodium carbonate solution.

The solution is filtered and 50 parts of sodium chloride are added to the filter solution. The precipitated dye is filtered off, mixed very well with 1 part of anhydrous disodium hydrogen phosphate and 1.9 parts of anhydrous potassium dihydrogen phosphate and dried at a temperature of 20 DEG to 30 DEG C. When the resulting dye is applied to cellulose fiber products, it produces a blue color that is fast to wet processing.

This is a class of dyes of the formula: where R1 represents an alkyl group having up to 4 carbon atoms.

Example 86 A solution of 9.25 parts of the dichlorotriazine dye prepared in Example 40 in 200 parts of water was prepared at a pH of 7. Stir at O and temperature 20°C.

1.1 parts of aniline are added and the mixture is stirred at 35-40° C. for 6 hours, maintaining the pH at 6-7 by simultaneously adding the required amount of 2N sodium carbonate solution. The dye is precipitated by adding sodium chloride, filtered and dried at 40°C.

When applied to cellulose fiber products, it gives a bright blue color with good fastness to washing and moderate fastness to light.

The examples in the following table are obtained in a similar manner to Example 86 by condensing aminophenazine with cyanuric chloride and reacting the product with ammonia or an amine.

Aminophenazine is indicated in column... by providing the number of the formula used in the above example; amines based on formulas (9) and (au) give a bright blue color and are
Based on amines, they produce bright reddish-blue colors.

Example 134 A solution of 9.25 parts of the dye obtained in Example 29 was added to 2 parts of water.
00 parts at a temperature of 20°C and a pH of 70.

4,47-diaminodiphenylurea-2 in 50 parts of water,
pH of 2.0 parts of 2'-disulfonic acid: 7. The mixture is stirred at 35-40° C. for 8 hours while the pH is maintained at 6-7 by adding the required amount of 2N sodium carbonate solution at the same time. The dye is precipitated by adding potassium chloride, filtered and dried at 40°C. When applied to cotton textile products, it produces a reddish-blue color with good fastness to washing and moderate fastness to light.

゜In place of 2.0 parts of 4,4'-diaminodiphenylamine-2,2'-disulfonic acid used in the above example,
Similar dyes are obtained if equal amounts of any of the following diamines are used: Example 139 A solution of 8.8 parts of the dye prepared in Example 66 is dissolved in 2 parts of water.
00 parts at pH 6-7 and temperature 20°C.

A solution of PH7O of 1.7 parts of 1,3-phenylenediamine-4-sulfonic acid in 50 parts of water is added, and the pH is adjusted by simultaneously adding the required amount of 2N sodium carbonate solution. Heat the mixture to 35-40°C while maintaining at 6-7
Stir for 6 hours. The solution is then cooled to 0-5° C. and a solution of 1.9 parts of cyanuric chloride in 25 parts of acetone is added. The mixture is then stirred for 5 hours at 0-5° C. while maintaining the pH at 6-7 by adding the required amount of 2N sodium carbonate solution. Then water 50
pH of 1.8 parts of 1-aminobenzene-3-sulfonic acid in 7. The mixture is stirred for a further 5 hours at 35-40° C. while maintaining the pH at 6-7 by adding the required amount of 2N sodium carbonate solution. The dye is precipitated by adding sodium chloride, filtered and dried.

In the analysis, 2 hydrolyzable chlorine per dye molecule
．． It is proven that 0 atoms are contained. When applied to cellulose fiber products in the presence of an acid binder, it produces a bright reddish-blue color that is fast to wash.

Further examples of the invention are shown in the table below, in which the dyes prepared in the examples indicated in column
It is first condensed with the diamine in column No. 1, then reacted with the compound of column V, and finally with the compound of column V.

The resulting shades are indicated in the column. Example 146 To the solution of the dye obtained as described in Example 119, 3 parts of pyridine and 2 parts of sodium sulfite are added.

The solution is stirred at 60° C. until sulfification is complete as judged by the amount of sodium chloride liberated. The solution is evaporated to dryness under vacuum at 40°C. When applied to cellulose fiber products, it produces a bright reddish color with good fastness to washing and moderate fastness to light.

Example 147 To a solution of the dye obtained as described in Example 119, 3 parts of trimethylamine in 10 parts of water are added.

Claims (1)

[Claims] 1 Formula (1): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) [In the formula, Am represents an anilino group, a di(lower alkyl)amino group, or an N(lower alkyl)benzylamino group] Represented by NHQ (in the formula Q
is a sulfatoethylsulfonyl group, or an acyl group of acrylic acid or cyclobutane, cyclobutene, or a 6-membered heterocyclic carboxylic acid or sulfonic acid containing 2 or 3 ring nitrogen atoms; or Q is a cellulose-reactive substituent and a 6-membered heterocycle containing 2 or 3 nitrogen atoms in each ring.
or 2 groups, in which the cellulose-reactive substituents are selected from F, Cl, Br or SO_3H) groups are benzene nuclei V or W or anilino groups or N (lower alkyl ) is present in Am representing a benzylamino group, and the dye as a whole also has at least one more sulfonic acid group], the formula (1'): ▲mathematical formula, chemical formula, There are tables etc.▼(1') [In the formula, Am represents the above and NH_2
group present in the benzene nucleus V or W or Am representing an anilino group or N (lower alkyl)benzylamino group] is converted into a phenazine compound of carbyl sulfate, an acid chloride of an acrylic acid or a carboxylic acid or a sulfonic acid as described above. or with a heterocyclic compound having a halogen atom and at least one cellulose-reactive substituent and one or two six-membered heterocycles containing two or three nitrogen atoms in each ring. A process for producing reactive azines, characterized in that the cellulose-reactive substituent is as described above and both reactive components together have a total of at least two sulfonic acid groups. 2 Formula (1): ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) Q
is an s-triazine nucleus substituted by a chlorine or bromine atom and an amino or substituted amino group) group is present in the benzene nucleus V or W or Am representing an anilino group or an N (lower alkyl)benzylamino group, and the dye as a whole also contains at least one more sulfonic acid group], in order to prepare a reactive azine dye of the formula (1'):
▲There are mathematical formulas, chemical formulas, tables, etc.▼(1') [Am in the formula
represents the above and the NH_2 group is present in Am representing the benzene nucleus V or W or anilino group or N(lower alkyl)benzylamino group] is reacted with cyanuric chloride or cyanuric bromide to form dichloro- or a process for the preparation of reactive azine dyes according to claim 1, characterized in that a cellulose-reactive dye of the above formula having dibromo-s-triazine groups is formed and this is reacted with ammonia or an amine. . 3 Formula (1): ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) Q
is the formula: Ht-Dm-Q_1 {where Ht represents a 2-chloro-4,6-s-triazinylene group, and Dm represents Ht and Q by two amino groups.
_1 represents a diamine group bonding Q_1, and Q_1 is a sulfatoethylsulfonyl group, or acrylic acid, or cyclobutane, cyclobutene, or a 6-membered heterocyclic carboxylic acid containing 2 or 3 ring nitrogen atoms. or an acyl group of a sulfonic acid, which has a cellulose-reactive substituent, or Q is a cellulose-reactive substituent and a six-membered heterocycle containing two or three nitrogen atoms in each ring. 1 or 2 heterocyclic groups, in which the cellulose-reactive substituents are selected from F, Cl, Br or SO_3H) groups have a benzene nucleus V or W or an anilino group or In order to produce a reactive azine dye of the formula (1'): , chemical formulas, tables, etc. ▼ (1') [In the formula, Am represents the above and the NH_2 group is present in Am representing the benzene nucleus V or W or anilino group or N (lower alkyl) benzylamino group] is reacted with cyanuric chloride to form a cellulose-reactive dye of the above formula having dichloro-s-triazine groups, and this compound is further reacted with diamine H.
1 mole of Dm.H and the resulting product is reacted with carbyl sulfate, an acid chloride of an acrylic acid or a carboxylic acid or a sulfonic acid as described above, or a halogen atom and at least one cellulose-reactive substituent. and a heterocyclic compound having one or two 6-membered heterocycles containing two or three nitrogen atoms in each ring, in which the cellulose-reactive substituent is as described above. A process for preparing reactive azine dyes according to claim 1, characterized in that both reactive components together have a total of at least two sulfonic acid groups. 4 Formula (1) having an s-triazine group substituted with at least one Cl or Br atom by any method according to claims 1 to 3 above: ▲ Numerical formula, chemical formula, table, etc. ▼ (1) [In the formula, Am is anilino group, di(lower alkyl)amino group, or N(lower alkyl)
represents a benzylamino group, NHQ (wherein Q is a sulfatoethylsulfonyl group, or acrylic acid, or cyclobutane, cyclobutene, or a 6-membered heterocyclic carboxylic acid containing 2 or 3 ring nitrogen atoms; an acyl group of a sulfonic acid that has a cellulose-reactive substituent, or Q is a cellulose-reactive substituent and a 6-membered heterocycle containing 2 or 3 nitrogen atoms in each ring; or 2 groups, in which the cellulose-reactive substituents are selected from F, Cl, Br or SO_3H) groups are benzene nuclei V or W or anilino groups or N (lower alkyl ) present in Am representing a benzylamino group, and the dye as a whole also contains at least one more sulfonic acid group], and this product is then treated with an alkali metal salt of sulfite, a tertiary Amine, formula: ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ (6) [In the formula, Y^1 is used to form a 5- or 6-membered heterocycle that may have a substituent, or to form part of a fused ring system. [Representing the atomic group necessary for the purpose of represents an aryl or aralkyl group, or R^1 and R^2 together with the nitrogen atom form a 5- or 6-membered heterocycle; or a compound of the formula: ▲ mathematical formula, chemical formula, table etc. ▼ (8) A patent claim characterized by reacting with a compound of [wherein R^3 and R^4 are the same or different and each represents a hydrogen atom or an alkyl, aryl or aralkyl group] A method for producing a reactive azine dye according to any one of the ranges 1 to 3.