KR850001354B1 - A process for manufacturing of reactive dyes - Google Patents

Abstract

Reactive dyestuffs of the formula Q-N(R)-E1-N=N-D-N=N-E2 are new. In the formula, Q is a cellulose-rective gp.; R is H or a C1-4 alkyl gp., opt. substd. by OH, CN, SO3H or OSO3H; E1 is an opt. substd. 1,4-phenylene or 1,4-naphthylene gp.; D is a 2,5-disulfo-1,4- phenylene gp.; and E2 is an opt. substd. 1-N-phenylaminonaphthyl gp. The disazo dyes are used for cellulosic fabrics, having high tinctorial power and good general fastness.

Description

Preparation of Reactive Dye

The present invention relates to a method for producing a reactive dye. In particular the invention relates to a process for the preparation of disazo dyes containing 2,5-disulfo-1,4-phenylene groups.

British Patent No. 1093354 describes dyes containing cellulose reactive groups and 2,5-disulfo-1,4-phenylene groups, and in Federal Republic of Germany Patent No. 1085629, Disulfo-1,3- Various types of disazo reactive dyes containing phenylene groups have been described. The new type of reactive dyes containing 2,5-disulfo-1,4-phenylene groups are known to have excellent properties such as higher dyeing strength and better light fastness than other dyes of similar structure.

In this invention, the reactive dye of following General formula (1) is provided:

QN (R) -E ₁ -NDN = NE ₂ . … … … … … … … … … … … (One)

In the above formula,

Q is a cellulose reactive group;

R is C _1-4 alkyl group optionally substituted with OH, CN, SO ₃ H or OSO ₃ H or is H;

E ₁ is an optionally substituted 1,4-phenylene or 1,4-naphthylene group;

D is a 2,5-disulfo-1,4-phenylene group; And

E ₂ represents an optionally substituted 1-N-phenylaminonaphthyl group.

The cellulose reactive group represented by Q may be any group capable of forming a covalent bond with the cellulosic material. These may be any conventional cellulose reactive group described in British Patent No. 1440948.

Examples of cellulose reactive groups include α, β-unsaturated acyl radicals of aliphatic carboxylic acids such as acrylic acid, α-chloroacrylic acid, α-bromoacrylic acid, propionic acid, maleic acid and mono- and dichloromaleic acid, and β-sulfatoethyl Like sulfonyl groups, there may be mentioned aliphatic sulfonyl groups in which sulfate ester groups are located at the β-position of the sulfur atom. Also acyl radicals of acids having substituents that react with cellulose in the presence of alkalis are examples of cellulose reactive groups, including chloroacetic acid, β-chloro and β-bromopropionic acid and α, β-cyclolo and di Radicals of halogens and aliphatic acids, such as bromopropanoic acid, or radicals of vinylsulfonyl- or β-chloroethylsulfonyl- or β-sulfatoethylsulfonyl-endo-methylene cyclohexane carboxylic acid. Still other examples of cellulose reactive groups include tetrafluorocyclobutyl carbonyl, trifluorocyclobutenylcarbonyl, tetrafluorocyclo-butylethenylcarbonyl, trifluorocyclobutenyledenyl carbonyl-activated halogenated Example of 1,3-dicyanobenzene:

2,4-dicyano-3,5-difluoro-6-chlorophenyl, 2,4-dicyano-3,5-difluoro-6-nitrophenyl, -2, 4-dicyano-3, 5,6-trifluorophenyl, 2,4-dicyano-3,5,6-trichlorophenyl, 2,4,6-tricyano-3,5-difluorophenyl, 2,4,6- Tricyano-3,5-dichlorophenyl and heterocycle rings are heterocycle radicals having 1,2 or 3 nitrogen atoms and having at least one cellulose reactive substituent on the carbon atom of the heterocycle ring.

Many reactive groups can be defined as heterocycles or acyl groups because they consist of acyl groups with heterocycle substituents. If there are cellulose reactive substituents on the heterocycle ring, these are referred to herein as heterocycle reactive groups for convenience.

Examples of heterocycle radicals above are:

2: 3-dicloquinoxaline-5-or-6-sulfonyl,

2: 3-dichloroquinoxaline-5-or-6-carbonyl,

2: 4-dichloroquinazolin-6-or-6-sulfonyl,

2: 4: 6-trichloroquinazolin-7- or-8-sulfonyl,

2: 3: 7-or 2: 4: 8-trichloroquinoxaline-6-sulfonyl,

2: 4-dichloroquinazolin-6-carbonyl,

1: 4-dichlorotalazine-6-carbonyl,

4- (4 ': 5'-dichloropyridaz-6'-one-1'-yl) benzoyl,

2-chlorobenzthiazole-6-carbonyl,

3,6-dichloropyrazine-4-carbonyl,

4- (4 ': 5'-dichloropyridaz-6'-one-1'-yl) phenylsulfonyl,

And activating 4,6-dihalopyridin-2-yl and 2,6-dihalopyridin-4-yl groups (e.g. 3,4,5,6-tetrafluoro pyridin-2-yl, 2,3, 5,6-tetrafluoropyridin-4-yl, 2,5,6-trifluoro-3-cyanopyridin-4-yl, 2,5,6-trichloro-3-cyanopyridine-4- Work,

2,6-difluoro-3-cyano-5-chloropyridin-4-yl,

2,6-difluoro-3,5-dichloropyridin-4-yl) and especially triazinyl or pyrimidinyl groups.

Examples of pyriminyl groups include pyrimidin-2-yl or -4-yl groups having cellulose reactive atoms or groups, in particular C 1, Br or F in at least one position of the remaining 2-, 4- and 6-positions. to be. The 5-position from above is not usually cellulose reactive on its own but can enhance the reactivity of substituents at other positions of the pyrimidine ring. Several substituents may be located, such as C1 or CN. Examples of such pyrimidinyl groups are as follows:

2,6-dichloropyrimidin-4-yl; 4,6-dichloropyrimidin-2-yl: 2,5,6-trichloropyrimidin-4-yl: 4, 5, 6-trichloropyrimidin-2-yl: 5-chloro-2-methylsul Phenyl-6-methylpyrimidin-4-yl: 2,6-dichloro-5-cyanopyrimidin-4-yl: 4,6-dichloro-5-cyanopyrimidin-2-yl: 2,6 -Difluoro-5-chloropyriminyl-4-yl: 4,6-dichloro-5-chloropyrimidin-2-yl: 2,6-difluoro-5-cyanopyrimidine-4- Day: and 4,6-difluoro-5-cyanopyrimidin-2-yl.

Examples of triazinyl groups include triazin-2-yl groups having cellulose reactive atoms or groups in one or both of the 4- and 6-positions. In this case, a wide range of cellulose reactive atoms or groups are useful, for example several groups bonded via activated alkoxy or sulfur atoms (eg SO ₃ H) and preferably F, Br particularly preferably C1: Quaternary ammonium groups such as tri-lower alkylammonium, (CH ₃ ) ₃ N ⁺ -] and pyridinium groups, in particular those derived from pyridine carboxylic acids or nicotinic acid.

Triazinyl groups having only one reactive atom or group in the nucleus of the 4- or 6-position may have non-reactive substituents on cellulose in the remaining 4- or 6-position.

Such non-reactive substituents include alkyl or attylthio, alkoxy or attyloxy groups and optionally substituted amino groups.

More preferred examples of these are:

C _1-4 alkoxy (e.g. methoxy, ethoxy, n-propoxy and isopropoxy, butoxy), and lower alkoxy lower alkoxy (e.g. β-methoxy-ethoxy, β-ethoxyethoxy, Phenoxy and sulfophenoxy): amino: lower alkylamino] eg methylamino, ethylamino, butylamino, di (loweralkyl) amino (dimethylamino, diethylamino, methylethylamino, dibutylamino)] and OH Β-hydroxyethylamino, di (β-hydroxyethylamino, β-cyanoethylamino, di (β-cyanoethyl) amino, β-sulfo, substituted by an alkyl group by CN or SO ₃ H Ethylamino, β-hydroxy propylamino, (β-hydroxybutyl) ethylamino and (β-hydroxyethyl) methylamino: cycloalkylamino (e.g. cyclohexylamino): cyclic amino (e.g. morpholino or blood piperazino) naphthyl optionally substituted amino and optionally substituted with 1, 2 or ₃ H group 2SO Carbonyl-amino group.

Particularly preferred as an optionally substituted phenylamino group is a group represented by the following general formula (2):

Wherein G is toil, methyl, ethyl ω-sulfomethyl, β-carboxy-, β-hydroxy or β-cyanoethyl; Z and X are each independently H, COOH, SO ₃ H, CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , Cl, Br, CN, NO ₂ , NHCOCH ₃ and β-sulfatoethylsulfone It is selected from among the poly.

Specific examples of these groups are as follows:

Anilino: o-, m- and p-sulfonanilino; o-, m- and p-carboxycyanilino; 4- and 5-sulfo-2-carboxycyanilino; 4- and-5-sulfo-o-tolylamino; 2,4-, 2,5- and 3,5-disulfoanilide; 2,4-dicarboxycyanilino; 4- and 5-sulfo-2-methoxyanilino; N-methyl-o-, m- and p-sulfonanilino; N-ω-sulfomethylanilino; N- (β-hydroxyethyl) -3-sulfoanilino.

The cellulose reactive group Q, if necessary, may take the form of the general formula:

-Ht-Dm-Q '

In the above formula, Ht is an S-triazine nucleus containing a cellulose reactive atom or group; Dm is a diamine residue which connects Ht and Q 'by 2 amino groups; Q 'is a cellulose reactive group with the same meaning as in Q above.

In particular, it is usually preferred that the cellulose reactive atoms or groups on Ht are F, Br or preferably Cl, and Q 'is an S-triazine residue having the same meaning as for Q above.

In addition, the cellulose reactive group Q may be in the form of the following general formula.

-Ht'-Dm-Q '

In the above formula, Dm and Q 'have the same meaning as above, and Ht' is a S-triazine nucleus without cellulose reactive atoms or groups (e.g. 2,4-S- with an amino group optionally substituted at the 6-position). Triazinyl).

When Q represents an S-triazine ring containing a halogen atom and a non-reactive substituent, the non-reactive substituent thereof may be a residue of a colored amine (eg azo, anthraquinone or phthalocyanine series).

Examples of diamine DmH ₂ which may provide the residue Dm are as follows:

Heterocycle diamines (eg pyrazine): aliphatic diamines such as alkylene-, hydroxy alkylene- or sulfatoalkylene diamines, especially aliphatic diamines having 2 to 6 carbon atoms (eg ethylene diamine, 1,2- And 1,3-propylenediamine, 1,6-diaminohexane, β-hydroxy ethylamino ethylamine, 2-hydroxy-1,3-diaminopropane, 2-sulfato-1,3-diamino Propine) other α-, ω-diaminoaliphatic compounds (e.g. triethylenetetramine, di- (β-diaminoethyl ether), naphthalene diamine sulfonic acid (e.g. 2,6-diaminonaphthalene-4,8- Disulfonic acids, 1,5-diaminonaphthalene-3,7-disulfonic acids; diamine derivatives of benzene-based mono- and di-cycle compounds such as phenylene diamine and mono- and disulfonic acids thereof (e.g. m-and p-phenylenediamine, 1,3-phenylenediamine-5-sulfone and 4,6-disulfonic acid, 1,4-phenylenediamine-2-sulfone and 2,5-disulfonic acid);

Diamine represented by the following general formula (3):

Where p and q are each 0 or 1 and E is a direct bond or a group selected from SO ₂ , O, CH ₂ , C ₂ H ₂ , C ₂ H ₄ , NH, and NHCONH, etc. '-Diaminostilben-2,2'-disulfonic acid, benzinin-2-sulfone and 2,2'-disulfonic acid, 3,3'- and 4,4'-diamino diphenylurea, 4,4 '-Diaminodiphenylurea-2,2'- and 3,3'-disulfonic acid, 4,4'-diaminodiphenylamine-2-sulfonic acid 4,4'-diaminodiphenylmethane, 4,4 '-Diaminodiphenylmethine-2,2'-disulfonic acid, 4,4'-diaminodiphenylether, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylethane-2 , 2'-disulfonic acid) and N-lower alkyl and N, N'-di (lower alkyl) derivatives of said amines, such as 4-methylamino and 4-ethylaminoaniline-3-sulfonic acid, N, N ' -Dimethyl-4,4-diaminodiphenylamine-2-sulfonic acid).

Examples of optionally substituted alkyl group R include n-propyl, isopropyl, n-butyl, hydroxymethyl, hydroxypropyl, cyanoethyl, sulfatoethyl and sulfoethyl, with ethyl being preferred and methyl More preferred.

E, an example of a group is as follows.

1,4-phenylene: 2,5-dimethoxy-1,4-phenylene:

2-ureido-1,4-phenylene: 2-carboxy-1,4-phenylene:

2-acetylamino-1,4-phenylene: 2-methoxy-1,4-phenylene:

2-methyl-1,4-phenylene: 3-methoxy-1,4-phenylene:

2-methyl-5-methoxy-1,4-phenylene: 6,7- and 8-sulfo-1,4-naphthalene:

2,5-dimethyl-1,4-phenylene: 6,8-disulfo-1,4-naphthylene: and

3-methyl-1,4-phenylene: 2-dichlorotriazinylamino-1,4-phenylene

In the above example, the azo group is assumed to be bound to the position of E ₁ .

And an example of a group of E ₂ is as follows:

1-hydroxy-8-N-phenylamino-5-sulfonaf-2-yl:

1-hydroxy-5-N-phenylamino-3-sulfonaf-2-yl:

4-N-phenylamino (6-or-7-)-sulfonaf-1-yl:

4-N-phenylamino-5-sulfonaf-1-yl:

4-N-phenylamino-5,7-disulfonaf-1-yl:

1-hydroxy-8-N-phenylamino-3-sulfonaf-2-yl:

1-hydroxy-8-N-phenylamino-3-5-disulfonaf-2-yl:

1-hydroxy-8-N-phenylamino-3,6-disulfonaf-2-yl:

1-hydroxy-8--3'-methylphenylamino-3,6-disulfonaf-2-yl:

1-hydroxy-8-N-2'-methylphenylamino-3-6-disulfonaf-2-yl:

1-hydroxy-8-N-2 ', 5'-dimethylphenylamino-3,6-disulfonaf-2-yl:

1-hydroxy-8-N-3'-methylphenylamino-3,5-disulfonaf-2-yl:

1-hydroxy-8-N-4'-methoxyphenylamino-3,6-disulfonaf-2-yl:

1-hydroxy-8-N-3'-methoxyphenylamino-3,5-disulfonaf-2-yl:

1-hydroxy-8-N-2 ', 5'-dimethylphenylamino-3,5-disulfonaf-2-yl:

1-hydroxy-5-N-4'-methylphenylamino-3-sulfonaf-2-yl:

1-hydroxy-5-N-3'-methylphenylamino-3-sulfonaf-2-yl:

1-hydroxy-8-N-phenylamino-5-sulfonaf-2-yl:

1-hydroxy-8-N-3'-sulfophenylamino-3,6-disulfonaf-2-yl:

1-hydroxy-8-N-4'-sulfophenylamino-3,6-disulfonaf-2-yl:

1-hydroxy-8-N-3'-carboxyphenylamino-3,6-disulfonaf-2-yl:

1-hydroxy-8-N-3'-sulfophenylamino-3,5-disulfonaf-2-yl:

1-hydroxy-8-N-2 ', 5'-dimethylphenylamino-3-sulfonaf-2-yl:

1-hydroxy-8-N-phenylamino-3-sulfonaf-2-yl:

1-hydroxy-8-3'-carboxyphenylamino-3,5-3,6-disulfonaf-2-yl:

1-hydroxy-8-N-2 ', 5-dimethoxyphenylamino-3,6-disulfonaf-2-yl:

1-hydroxy-8-N-4'-aminophenylamino-3,6-disulfonaf-2-yl:

1-hydroxy-8-N-3'-aminophenylamino 3,6-disulfonaf-2-yl:

1-hydroxy-8-N-3'-2``, 4 ''-dichloro-S-triazin-6-ylaminophenylamino-3,6-disulfonaf-2-yl:

1-hydroxydi-8-N-4'-2``, 4 ''-chlorot-S-lyazine-6 ''-ylaminophenylamino-3,6-disulfonaf-2-yl:

1-hydroxy-8-N-4'-2 ''-chloro-4 ''-3 '' '-sulfophenylamino-S-triazine-6' '-ylaminophenylamino-3,6-disulfide Phonaft-2-day:

1-hydroxy-8-N-4'-2``-chloro-4 ''-4 '' '-sulfophenylamino-S-triazine-6' '-ylaminophenylamino-3,6-disulfide Phonaft-2-day:

1-hydroxy-8-4'-2 '', 4 ''-dichloro-S-triazin-6 ''-ylaminophenylamino-3,5-disulfonaf-2-yl:

4-N-4'-sulfophenylamino-5-sulfonaf-1-yl:

4-N-4'-aminophenylamino-5-sulfonaf-1-yl:

4-N-4'-2 '', 4 ''-dichloro-S-triazin-6 ''-ylamino phenylamino-5-sulfonaf-1-yl:

4-N-4'-2 ''-chloro-4 ''-3 '' '-sulfophenylamino-S-triazine-6' '-ylaminophenylamino-5-sulfonaf-1-yl:

4-N-3'-aminophenylamino-5-sulfonaf-1-yl:

4-N-4'-methethylylamino-5-sulfonaf-1-yl:

4-N-2 ', 5'-dimethylphenylamino-5-sulfonaf-1-yl:

4-N-2'-methylphenylamino-7-sulfonaf-1-yl:

4-N-3′-methylphenylamino-6-sulfonaf-1-yl:

4-N-4'-methylphenylamino-5,7-disulfonaf-1-yl:

4-N-4'-methoxyphenylamino-5-sulfonaf-1-yl:

4-N-4'-sulfophenylamino-5-sulfonaf-1-yl:

4-N-4'-amino-3'-sulfophenylamino-5-sulfonaf-1-yl:

4-N-4'-sulfophenylamino-7-sulfonaf-1-yl.

It can be seen from the examples of the E ₂ groups listed above that it contains substituents such as cellulose reactive dichlorotriazinyl amino. Therefore, in this example, the dye of general formula (1) has a second cellulose reactive group in addition to that defined by Q.

Preferable examples of the dye of the general formula (1) include the following characteristics;

(1) Q is a triazinyl or pyrimidinyl group,

(2) R is ethyl, methyl or especially hydrogen,

(여기서 ×는 H, CH₃, OCH₃, NH₂, NHCOCH₃, NHCONH₂, 또는 NHCOOC₂H₅이며 Y는 H, CH₃, OCH₃, 또는 COOH임)이거나,(3) E ₁ is

(Where × is H, CH ₃ , OCH ₃ , NH ₂ , NHCOCH ₃ , NHCONH ₂ , or NHCOOC ₂ H ₅ and Y is H, CH ₃ , OCH ₃ , or COOH), or

And

(4) E ₂ is

Or

1 or 2 (where ring A is

Amino, substituted amino, or in particular 0 to 2 substituents each selected from CH ₃ , OCH ₃ Cl, COOH or SO ₃ H, wherein NH is linked to the 1- or 4-position of the naphthalene nucleus)

Particularly preferred examples of E ₂ are as follows:

In the above formula, Ring A is as defined above, one of B ₁ and B ₂ is SO ₃ H and the other is H.

The dye of the general formula (1) according to the present invention comprises a dye base of the following general formula (6): a sulfate or a general formula Qhal (where Q is a cellulose reactive group except β-sulfato ethylsulphone and hal is a halogen) It can be prepared by reacting with a compound:

H · N (R) -E ₁ -N = NDN = NE ₂ . … … … … … … … (6)

In the above formula, R and D are the same as defined above.

The reaction of the carbic sulphate with an amino group forms a β-sulfato ethylsulfonyl group.

The above reaction may be carried out conventionally in an aqueous medium in the presence of an acid-binding agent (e.g. sodium carbonate, sodium bicarbonate, or sodium hydroxide) at a temperature suitable for the reactivity of the compound Qhal (i.e. 0 to 100 ° C). .

Specific examples of the compound Qhal can be seen from the specific examples of Q given above. It is generally preferred that hal is chlorine, for example Qhal, such as β-chloropropionyl chloride, cyanuric chloride, methoxydichloro-S-triazine, and 2,4,5,6-tetrachloro pyri There is midine. However, in some cases when hal is a cellulose reactive substituent present in Q, it may be another halogen, F, wherein Qhal is 2,4 for introducing a difluoro-5-chloropyrimidinyl group , 6-trifluoro-5-chloropyrimidine.

When the reactive group Q is -Ht-Dm-Q ', as defined above, the reactant Qhal used in the above reaction is of the general formula hal-Ht-Dm-Q', where hal, Ht, Dm and Q 'are as defined above. Is equal to).

Such compounds include diamine DmH ₂ in 1 mole carbyl sulfate or Qhal (where Q and hal are as defined above) and 1 mole S-triazine compound

Where hal is a halogen atom,

Y is a cellulose reactive substituent). Where Ht is a chloro-S-triazinyl group, then Y is preferably Cl. That is, the above S-triazine compound is cyanuric chloride.

The dye base of formula (6) is mono-acetylated with the amine of formula (5), diazotized and coupled with 1-N-phenylaminonaphthalene coupling component E ₂ H, followed by hydrolysis to acetyl It can be prepared by removing the group:

In the above formula, R is the same as defined above. Therefore, the production route of the general formula (1) can be specifically divided into two steps. That is, it can be divided into two stages, acetylation and hydrolysis. However, the dye base of general formula (6) first diazotizes one amino group of 1,4-phenylenediamine-2,5-disulfonic acid, and the 1-N-phenyleneamino-naphthalene coupling component E ₂ H Coupling to paracoupling amine HE ₁ N (R) H (where E ₁ and R are as defined above), followed by diazotization of the second amino group of the 1,4-phenylenediamine residue. It can be obtained conventionally. In addition, 4-acetylaminoaniline-2,5-disulfonic acid may be coupled to diazotization and E ₂ H, and the acetyl group may be diazotized-1,4-phenylenediamine-2,5 as E ₂ H. If in any case the coupling of disulfonic acid turns out to be excessively slow, it can be removed by hydrolysis.

Reactive dyes of formula (1) wherein the cellulose reactive group Q is an S-triazine nucleus substituted by a Cl, Br or F atom and an amino or substituted amino group and also Q is chloro, bromo or difluoro-S-tri The reactive dye of the general formula (1), which is a azine group, may be prepared by reacting with ammonia or amine.

This process is carried out at a temperature of 30-60 ° C., in an aqueous medium, optionally in the presence of a water-soluble organic solvent, and with the addition of an acid binder to keep the pH at 5-8, while stirring the reaction while neutralizing the hydrogen halides produced during the reaction. Can be achieved. Suitable acid binders are alkali metal hydroxides, carbonates and bicarbonates, or excess ammonia or aliphatic amines.

In addition, the product obtained by using 1 mole of diamine with respect to 2 moles of the dichloro-dibromo- or difluoro-S-triazinyl dyes, the dyes are two chloro-, bromo-, or fluoro-S- It is one of the above-mentioned kinds which contains two groups of general formula (1) of low Q connected via a triazine group and a diamine radical. In the above method, any of the diamines DmH ₂ already mentioned can also be used.

The product produced by reacting a dichloro-, dibromo- or difluoro-S-triazine dye with an equivalent amount of diamine DmH ₂ may contain free amino groups, which are compounds of Qhal or carbyl sulfate as defined above By reacting with, the dye thus obtained may contain cellulose reactive groups of the general formula-Ht-Dm-Q ', wherein Ht is chloro-, bromo- or fluoro triazinyl, as defined above.

Also dyes of this kind can be prepared by first reacting diman with 1 mole of carbyl sulfate or Qhal and then reacting the resulting monoamine with a dichloro-, dibromo-, or difluoro-S-triazine dye. .

In the above reaction, when 1 mole of diamine is reacted with carbyl sulfate or 1 mole or with dichloro-, dibromo- or difluoro-S-triazinyl groups, from 1 mole of diamine and 2 moles of other reactants In order to minimize the formation of undesirable reaction products, it is preferred that the diamines have amino groups of different reactivity.

A dye wherein Q is -Ht'-Dm-Q 'as defined above is reacted with a dichloro-, dibromo- or difluoro-S-triazine dye with an equivalent amount of diamine DmH ₂ , followed by a triazine nucleus phase. In order to displace the residual halogen of, it can be prepared by reacting with a non-reactive group of cellulose, ie ammonia or amine, and finally with carbyl sulfate or Qhal as defined above.

When Q is a triazinyl group carrying quaternary ammonium or pyridinium substituents as cellulose reactive substituents, these dyes react the corresponding chloro-, bromo-, or fluor-triazinyl dyes with the appropriate tertiary amine or pyridine compound You can get it by Generally this reaction proceeds in an aqueous medium under a temperature of 30 to 100 ° C.

When Q is a triazinyl group having a SO ₃ H substituent as the cellulose reactive substituent, the corresponding chloro-, bromo- or fluorotriazinyl dye is added to the alkali metal sulfide in an aqueous medium at a temperature of 30 to 100 ° C. Can be obtained by reacting with a fight.

The dyes prepared according to the above method can be separated by conventional methods such as dry spraying or precipitation and filtration. The dyes according to the invention have sulfonic acid groups which impart water solubility and can also be separated in free acid form. However, it is more convenient to separate the dyes in the form of alkali metal salts, in particular sodium metal salts.

The dyes according to the invention can be used to dye various fabrics with hydroxyl or amino groups.

The dyes according to the invention are also important reactive dyes for cellulose. It provides very good washing and daylight fastness and has the property of deepening color penetration.

The present invention will be described in more detail with reference to the following examples, where all parts are based on weight and% (x / v) is based on g / 100 millimeters.

Example 1

14.3 parts of the sodium salt of 4-amino-4'-N-methylamino-2,5-disulfo-l, 1'- azobenzel and 16.7 parts of 2N sodium nitrite aqueous solution at 0-5 degreeC in the solution of 250 minutes of water. After addition, concentrated hydrochloric acid is added to maintain the pH at 1. The resulting mixture is stirred for 30 minutes at 0-5 ° C. and then sulfamic acid is added to remove excess nitrous acid. The diazonium mixture was added to 27.1 parts of sodium salt of 1-N-phenylamino-8-niphthol-3.6-disulfonic acid and 200 parts of water in a neutral solution of 2N sodium carbonate to maintain a pH of 6.5 to 7, Stir at 0-10 ° C. for 2 hours.

Sodium chloride (20% w / v) is added and the resulting mixture is filtered, then the residue on the filter is dried under pressure. A neutral solution of 8.31 parts of N- (methylamino disazo compound tetrasodium salt and 800 parts of water is added to a mixture of cyanuric chloride 1.75 parts, 20 parts of acetone and 40 parts of ice / water, and then 2N aqueous sodium carbonate solution is added. The pH is adjusted to 6.5-7 and the resulting mixture is stirred at 0-10 ° C. for 3 hours.

Sodium chloride (10 gw / v) is added and the resulting mixture is filtered, and the residue on the filter is kneaded and dried with 0.66 parts of a mixture consisting of 1 part of 2 sodium monohydrogen phosphates and 2 parts of potassium dihydrogen phosphate.

The dye composition obtained here contains one hydrolyzable chlorine for each azo group present. When the above salts were used in cellulose fabrics with acid-binding agents, they appeared black.

31.2 parts of diazonium salt of the 2-sodium salt of 4-aminoaniline-2,5-disulfonic acid in a neutral solution of 44.3 parts of disodium 1-N-phenylamino-8-naphthol-3,6-disulfonic acid and 300 parts of water is 3N. The pH is maintained at 6.5--7 by addition with aqueous sodium carbonate solution, and the resulting mixture is stirred at 0-5 ° C. for 5 hours. A portion (0.05 g mol) of the above 1-N-phenylamino-7-4'-amino-2 ', 5-disulfophenylazo-8-naphthol-3,6-disulfonic acid solution at 0 to 5 ° C Concentrated hydrochloric acid is added to diazotize to pH 2, and then 5N sodium nitrite aqueous solution is added.

After adding 6.9 parts of 2-methoxy-5-methylaniline to 10 parts of concentrated hydrochloric acid and dissolving in 40 parts of water, the resulting solution was cooled to 0 to 5 DEG C, and then the pH was adjusted to 5-5 by adding an aqueous 3N sodium carbonate solution. The above diazonium mixture is added with 3N aqueous sodium carbonate solution to adjust the pH to 5-5-5, and the resulting mixture is stirred for 6 hours until the coupling reaction is completed. A solution of 11.1 parts of cyanuric chloride and 75 parts of acetone was added to the solution of the aminodisazo compound together with an aqueous solution of 3N sodium carbonate to adjust the pH of the mixture to 6 to 6.5 and stirred at 0 to 5 ° C. for a time.

21 parts of ammonia solution (specific gravity 0.88) are added and the resulting mixture is stirred at 30 ° C. for 3 hours. Sodium chloride (15% w / v) is added and the resulting mixture is filtered, then the residue on the filter is dried.

The following table shows an example of a new dye of the present invention prepared according to Example 3. The aminomono azo compound of paragraph (II) is prepared by coupling the diazotized 4-aminoaniline-2,5-disulfonic acid to phenylaminonaphthylene. Its aminomonoazo compound is diazotized and coupled to paracouplingamine (III) term. The amino disazo compound obtained here is condensed with the heterocycle compound of the item (IV). The amines of (V) are reacted with the reaction products of the substances of (II), (III) and (IV) or continuously with the heterocycle compounds of (IV) and of the substances of (II) and (III). React with the reaction product.

The color tone of the dye on the cellulose is shown in section (IV).

Example 55

2 of 4-2 ', 4'-dichloro-S-triazine-6'-ylamino-4'-amino-2,5-dimethoxy-2', 5'-disulfo-1,1'-azobenzene To a solution of 12,48 parts of sodium salt and 300 parts of water, 9.52 parts of disodium salt of 4,4'-diamino-2,5-dimethoxy-2 ', 5'-disulfo-1,1'-azobenzene and water A solution of 250 is added and the reaction mixture is heated to 40-45 [deg.] C. for 3 hours, then aqueous 2N sodium carbonate solution is added to maintain the pH at 7. The solution is cooled to 0-5 [deg.] C., 2.76 parts of sodium nitrite are added, and then the pH is adjusted to 1.8 by addition of 36% hydrochloric acid. The tetraazolation mixture is stirred at 0-10 ° C. with excess nitrous acid present for 1 hour and then sulfamic acid is added to remove excess nitrous acid. The above mixture was added to the solution by stirring in a solution of 18 parts (2 mol) of 1-N-phenylamino-8-naphthol-3,6-disulfonic acid and 700 parts of water at 0 to 10 DEG C, and a pH of 6.5 was added by adding an aqueous 2N sodium carbonate solution. To 7

The coupling mixture is stirred for 3 h at 0-10 ° C., sodium chloride (18% w / v) is added and then filtered.

The dye composition obtained here had a number of 0.25 hydrolyzable chlorine atoms per azo group, and when it was added to the cellulose fabric with an acid-binding agent, black color was very excellent in washing and light fastness.

Example 56

4-2 ', 4'-dichloro-S-triazine-6'-ylamino-4'-amino-2,5-dimethoxy-2', 5'-disulfo-1 used in Example 55 above 12.48 parts of disodium salt of, 1'-azobenzene and 9.52 parts of disodium salt of 4,4'-diamino-2,5-dimethoxy-2 ', 5'-disulfo-1,1'-azobenzene are equivalent thereto Replace the dye with an amount of 4-2 '4'-dichloro-S-triazine-6'-ylamino-4'-amino-2-methyl-2', 5'-disulfo 1,1'-azobenzene Manufacture.

Example 57

The sodium salt of 4,4'-diamino-2-methyl-2,5'-disulfo-1,1'-azobenzene used in Example 55 above was equivalent to 4,4'-diamino-2. Dye is prepared by replacing with -methyl-5-methoxy-2 ', 5'-disulfo-1,1'-azobenzene.

Claims (1)

The dye base of formula (6) is reacted with carbyl sulfate or Qhal (where Q is a cellulose reactive group except β-sulfato ethylsulfone and hal is halogen) to produce a reactive dye of formula (1) How to : QN (R) -E ₁ -N = NDN = NE ₂ . … … … … … … (One) H · N (R) -E ₁ -N = NDN = NE ₂ . … … … … … … (6) In the above, Q is a cellulose reactive group; R is hydrogen or C _1-4 alkyl group optionally substituted by OH, CN, SO ₃ H or OSO ₃ H; E ₁ is an optionally substituted 1,4-phenylene or 1,4-naphthylem group; D is a 2,5-disulfo-1,4-phenylene group; E ₂ is an optionally substituted 1-N-phenylaminonaphthyl group.