JPS6029747B2 - Fiber-reactive azo dye and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a compound of the formula [wherein K is unsubstituted or a sulfo group,
Alkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, alkanoylamino group having 1 to 6 carbon atoms, benzoylamino group, -NH2, methylamino group, ethylamino group, ureido group, hydroxyl group, a carboxyl group, or a 1,4-phenylene group or a 1,4 naphthylene group substituted with a halogen; R and R2 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms; X is hydrogen, an alkyl group having 1 to 4 carbon atoms, hexyl group, methoxyethyl group, ethoxyethyl group, methoxypropyl group, chloroethyl group, hydroxyethyl group, hydroxypropyl group, 8-sulfoethyl group, 8-sulfate group; thyl group, benzyl group, cyclohexyl group, unsubstituted phenyl group, methyl group, chlorine, acetylamino group,
Nitro group, hydroxyl group, methoxy group, ethoxy group,
phenyl, unsubstituted naphthyl, or naphthyl, pyridyl, benzthiazolyl, chi/lyl, or pyrimidyl substituted by carboxyl or sulfo groups; Or, N(R2X) forms a morpholino group, a piberidino group, or a piperazino group.

R is hydrogen, halogen, nitro group, -NH2, alkylamino group having 1 to 4 carbon atoms, hexylamino group, hydroxyethylamino group, benzylamino group, cyclohexylamino group, phenylamino group, 4-nitro Phenylamino group, dimethylamino group, diethylamine/group,
Dibenzylamino/group, N-methyl-N-phenylamino group, acetylamino group, propionylamino group, benzoylamino group, alkoxy group having 1 to 4 carbon atoms, fiber-reactive group, unsubstituted 1', 2' ,4,5
naphthylene triazolyl group, or 1',2,4,5 naphthylene triazolyl group substituted by a sulfo group, 3-methyl- or 3-carboxy-4-phenyl (or mono-4-naphthyl)a Zopyrazolone-5-yl'1' group (this phenyl group or naphthyl group is K
or a benzene residue, a naphthalene residue, which can be substituted by the substituents defined for K), or the formula AN=N-'21, where A can be substituted by the substituents defined for K. , which is also a pyrazolone residue).

The group K is especially an aryl group, such as a benzene or naphthalene residue.

R, and R2 are considered to be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a te-butyl group as an alkyl group having 1 to 4 carbon atoms. .

X includes, for example, a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s as an aliphatic group.
ec-butyl group, and tert-butyl group, hexyl group, methoxyethyl group, ethoxyethyl group, methoxypropyl group, chloroethyl group, hydroxyethyl group, hydroxybropyl group, 3-sulfoethyl group, 8-sulfaethyl group, benzyl group , chlorohexyl group, phenyl group as aromatic group, 2-, 3- or 4-methylphenyl group, 2,3-, 2,4-, 2,5-, 2,6-, 3,
4- or 2,5-dimethylphenyl group, 2- or 4-chlorophenyl group, 3- or 4-acetylaminophenyl group, 2-, 3- or 4-nitrophenyl group, 2-, 3- or 4-chlorophenyl group 1- or 4-hydroxyphenyl group, 2-methyl-4-nitrophenyl group, 2-methyl-5-nitrophenyl group, 3-methyl-4-nitrophenyl group, 2-nitro-4-methyl-phenyl group, 3-nitro 1-4-methyl-phenyl group, 2-, 3- or 4-aminophenyl group, 3-amino-4-methyl-phenyl group,
3-methyl-4-aminophenyl group, 2-amino-4
-Methyl-phenyl group, 2-, 3- or 4-methoxy-phenyl group, naphthyl-'1) group, naphthyl-'2}
group, 4-aminonaphthyl [1} group, 5-aminonaphthyl {1} group, 1-hydroxynaphthyl ■ group,
4-hydroxynaphthyl'1} group, 8-hydroxynaphthyl'11 group, 7-hydroxynaphthyl group [
1) group, 2-, 3- or 4-sulfophenyl group, 2,
4- or 2,5-disulfophenyl group, 2-1, 3- or 4-carboxyphenyl group, 3-carboxy-4
monohydroxyphenyl group, 3-sulfo-4-carboxyphenyl group, 2-carboxy5-sulfophenyl group, 2-sulfo-5-carboxyphenyl group, 2-,
3-, 4-, 5-, 6-, 7- or 8-sulfonaphthyl {11 groups, 1-, 4-, 5-, 6-, 7- or 8-sulfonaphthyl-'21 groups, 2,4-, 2,5-, 2,7-2,8-, 3,5-, 3,6-, 3,7-,
3,8-, 4,6-, 4,7-, 4,8-1 or 5,8
- Di-sulfonaphthyl (1' group, 1,5-1, 1,6
1, 1, 7 1, 3, 6-, 3, 7-, 4, 7-, 4, 8
-, 5,7- or 6,8-di-sulfonaphthyl■
Group, 2,4,6-, 2,4,7-, 2,5,7-, 3,
5,7-, 3,6,8- or 4,6,8 trisulfonaphthyl {11 groups, 13 7-, 1,5,7-, 3
, 5, 7-, 3, 6, 7-, 3, 6, 8- or 4, 6
, 8-trisulfonaphthyl-■ group, polycyclic groups include 2-, 3- or 4-pyridyl group, 2-benzothiazolyl group, 5-, 6- or 8-quinolyl group, 2-pyrimidyl group , or a group in which X and R2 form a ring and the nitrogen atom to which .

For example, R can be a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom, and an optionally substituted amino group can be a -N group, a methylamino group, an ethylamino group, a propylamino group, or an isopropylamino group. group, butylamino group, isobutylamino group, sec-butylamino group, ten-butylamino group, hexylamino group, hydroxylamine group, benzylamino group, cyclohexylamino group, phenylamine group, 4-nitrophenylamine group, dimethylamino group / group, jetylamino group, dibenzylamino group, N-methyl-N-phenylamino group, and also as acylamino group, acetylamino group, propionylamino group, benzoylamino group and especially acylamino group, in which the acyl group is fiber-reactive, e.g. Chloropropionylamino group, Q,8-dibromopropionylamino group, acryloamino group, 2-halogenobenzothiazole-6-carbonylamino group, 4,5-dic.

Ropyridazone-[6]-propionylamino group, 1,4
-dichlorophthalazine-6-carbonylamino group, 2,
3-dichloroquinoxaline-6- or -5-carbonylamino group, 3,5,6-trichloropyridazinyl-{4}-amino group, 2,6-di- or 2,5,6-trichloropyrimidyl group [4}-Amino group, 5-chloro-6-methyl-2-methylsulfonylpyrimidyl[
4' monoamino group, 2,4-dichloropyrimidine-5-
carbonylamino group, 5-chloro(bromo or fluoro)-[41-amino group], 2,4-dichloro(bromo or fluoro)-Striazine-6-yl-amino group, and 2-chloro(bromo or fluoro)-4- The NH2 (alkylamino, arylamino, alkoxy, aryloxy, alkylthio or arylthio)-S triazin-6-ylamino group is considered.

1', 2', optionally substituted with a sulfonic group;
The 4,5-naphthylenetriazolyl group is, for example, a 5-sulfo-2naphthylene-(1',2',4,5)-triazolyl group or a 6,8-disulfo-2naphthylene-(1
',2',4,5)-triazolyl group. Examples of the 4-arylazopyrazolon-5-yl-'1} group substituted at the 3-position include 3-methyl (or carboxy)-4-arylazopyrazolone-5-yl'
There are 11 possible.

An arylazo group is especially a phenylazo group or a naphthylazo group. Group A is inter alia a benzene radical, a naphthalene residue or a pyrazolone residue.

The arylazo group in the groups A and K as well as 4-arylazopyrazolon-5-yl substituted in the 3-1 position {11 contains, inter alia, a sulfone group as a substituent. Examples of substituents other than the S03 group include the following groups. Alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, and propyl groups, 1 to 4 carbon atoms;
alkoxy groups with 4 carbon atoms, such as methoxy, ethoxy, propoxy and isopropyloxy groups, acylamino groups with 1 to 6 carbon atoms, such as acetylamino, propionylamino and pennzoylamino groups, ami/groups For example, monoNH2 groups, methylamino and ethylamino groups, ureido groups, hydroxyl groups, carpoxy groups and halogen atoms such as fluorine, chlorine and bromine atoms. K is optionally a sulfonic group, a chlorine atom, a 1,4-phenyl group with 1 to 4 carbon atoms substituted by an alkyl group and an alkoxy group and an acetylamine group, or optionally a sulfonic group; is a 1,4 naphthylene group, R, and R
2 is a hydrogen atom, R is a hydrogen atom, a chlorine atom, a bromine atom, a nitro group, an amino group, an acetylamino group, or 6
, 8-disulfo-(1',2,4,5)-naphthylenetriazolyl group, and the fiber-reactive azo dye represented by the formula {1} in which x has the meaning described in the formula {1} is preferable.

K and R, and R2 and is the basis,
Of particular interest are fiber-reactive azo dyes of the formula '1', in which Y is a hydrogen atom, an aliphatic group, an aromatic group or a dicyclic group.

Among these, K is optionally a sulfone group, a chlorine atom, a 1,4-phenylene group having 1 to 4 carbon atoms substituted with an alkyl group, an alkoxy group, and an acetylamino group, or a 1,4 naphthylene group substituted with a sulfonic group, in which R and R2 are hydrogen atoms or optionally a phenyl group substituted with a sulfonic group, a carboxy group or a methyl group, or optionally It is a naphthyl group substituted with a sulfone group, and R is an acylamino group represented by formula '31 (in this formula, R3 and R4 are hydrogen atoms, and Y has the same meaning as X). Fiber-reactive azo dyes represented by 1' form a preferred group.

The azo dye of formula m exhibits fiber reactivity since it contains a fluorine atom which can be split into an S-triazine group.

A fiber-reactive compound is a compound that can react with the hydroxyl groups of cellulose or the amino groups of natural or synthetic polyamides to form covalent chemical bonds.

The fiber-reactive azo dye represented by the formula '1} is a 2,4,6-trifluoro-S-triazine represented by the formula,
An azo compound represented by the formula [In these formulas, K, R, R, R2, and × are the formula {1}
An amine represented by the formula {
It is made by condensation with a fiber-reactive azo dye represented by 1'.

As a starting material, a 2,4,6-trifluoro S triazine represented by the formula There is 1
, 4-phenylene group, or a 1,4-naphthylene group optionally substituted with a sulfone group, R
, is a hydrogen atom, and R is a hydrogen atom, a chlorine atom, a bromine atom, a nitro group, an amino group, an acetylamide group, or 6,
An azo compound represented by the formula (51) which is an 8-disulfo-(1',2',4,5)naphthylene triazolyl group, R2 is a hydrogen atom, and X has the meaning described in formula [1} Amines represented by the formula side are preferred.

K and R, R2 and X have the meanings described in formula {1},
R is the formula (in this formula, R3 and R4 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Y
is a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group.The production of the fiber-reactive dye represented by the formula '1' involves the use of 2,4,6-trifluoro-S triazine represented by the formula [4}. , K and R have the meanings described in formula [1'], and R is an amino group represented by formula (in this formula, R3 has the above meaning), an azo compound represented by formula '5} and an amine represented by the formula [6} [in which R2 and X have the meanings described in formula 1] and a formula (in which R
4 and Y have the above-mentioned meanings).

Starting materials are in particular 2,4,6-trifluoroS-triazines of the formula K optionally substituted with sulfonic groups, chlorine atoms, 1 to 4 carbon atoms with alkyl and alkoxy groups and acetylamino groups. 1,4-phenylene group or optionally substituted with a sulfonic group
- an azo compound represented by the formula ■, which is a naphthylene group, R and R3 are hydrogen atoms; An amine represented by the formula which is a substituted phenyl group or, in some cases, a naphthyl group directly substituted with a sulfone group, R4 is a hydrogen atom, and Y has the same meaning as x. An amine represented by the formula (2) is preferred.

Different methods of deformation are possible, since the individual oak layers mentioned can be applied in the order of type or, if appropriate, even simultaneously.

The starting materials to be applied for each partial reaction become clear from formula '1'. Generally, the reaction is carried out step by step, in which case the formulas {4', [5} and [6l or ■ and ■ and '6} and '8
The order of the simple condensation between the individual reaction components represented by 1 and 1 can be chosen freely. An important process variant is 'a) condensing the 2,4,6-trifluoro-S-triazine of formula (4) with an azo compound of formula The minoazo compound is condensed with an amine of formula '6) to obtain a monofluoro-S-triazinylaminoazo dye of formula {11.

'b} 2,4,6-trifluoro-S represented by formula ■
Triazine is first condensed with an amine represented by formula '6-, and the resulting difluoro-S-triazylamino compound is condensed with an azo compound represented by formula '5- to form formula '1}.
A monofluoro S triazinylaminoazo dye represented by is obtained.

A similar method can be used to produce a fiber-reactive azo dye represented by formula m in which R is an acylamino group represented by formula '3'.

In such a case, of course, many more variations are possible. If the group -N(R2)- A first condensation product is prepared from the amine represented by the formula '7}, and this is condensed with an azo compound represented by the formula (5') in a molar ratio of 2:1, where R is an amino group represented by the formula '7}, or First, an azo compound represented by the formula [5' in which R is an amino group represented by the formula {7} is condensed with 2 moles of 2,4,6-trifluoro-S triazine represented by the formula 1 The condensation product is further condensed with 2 moles of an amine of the formula {61 (or '8'). The azo compounds of the formula {5} which are applied as starting materials are known.

According to the relative position of the azo group to the stilbene Fuji group,
You can obtain them in various ways. Compounds in which K is an aryl group include 4-aminostilbene-2,2-disulfonic acid substituted at the 4'-position with a group represented by R, such as 4'-nitro-4-aminostilbene-2,2
-disulfonic acid, 4'-(5-sulfo-2-naphthylene-(1',2,4,5)-triazolyl)-4-aminostilbene-2,2-disulfonic acid, 4'-acetylamino-4-amino stilbene-2,2-disulfonic acid,
4'-penzoylamino-4-aminostilbene-2,
2-disulfonic acid, 4'-chloro-4-amino/stilbene-2,2-disulfonic acid, 4'-bromo-4-aminostilbene-2,2'-disulfonic acid, 4'-dimethylamino-4-aminostilbene-2, 2'-disulfonic acid, 4'-anilino-4-aminostilbene-2,2-
Diazotization from disulfonic acid or 4'-dibenzylamine/14-aminostilbene-2,2'-disulfonic acid and the resulting diazonium compound as an arylamine or alkylarylamine such as aniline (in the form of the -methanesulfonate), m -toluidine, 2-methoxy5-methylaniline, 1-naphthylamine-6-sulfonic acid, 0-anisidine, 2,5-dimethoxyaniline,
Obtained by coupling with m-anisidine, 1-naphthylamine-7-sulfonic acid, Q-naphthylamine, monomethylaniline, monoethylaniline, monobutylaniline and anthranilic acid (in the form of the -methanesulfonic acid salt).

A series of compounds which may be used as starting materials can thus be obtained by applying benzene-based primary aromatic amines as coupling components, the resulting products being 4
Corresponding to 4′-1(4″-aminophenylazo)-stilbene-2,2′-disulfonic acid substituted at the 1-position,
Other parts of this series have substituents on the benzene ring of the aminophenylazo group.

Another method for preparing this group of compounds is to convert 4'-nitrostilbene-2,2-disulfonic acid substituted in the 4-position, such as 4,4'-dinitrostilbene-2-2-disulfonic acid, into p-phenylenediamine. It consists of treating in the presence of alkali. Suitable p-phenylenediamines include, for example, 1,4-phenylenediamine-2-sulfonic acid, 2
-methyl-1,4-phenylenediamine, 2-methoxy-1,4-phenylenediamine and especially p-phenylenediamine itself. diazotizing the resulting product itself when the applied coupling component contains an unsubstituted amino group bonded to the aromatic nucleus;
The nitro group can be reacted with a coupling component before being reduced.

In this way, a polyazo group can be obtained in the group represented by R. When an amino group or a monoalkylamino group is introduced into the molecule together with a coupling component, the introduced group is transferred to a group that does not react with trifluoro-S triazine, for example by acylation, before the nitro group is reduced. is self-evident. In this way a wide variety of coupling components can be used.

For example, phenols, naphthols, pyrazolones, 81-ketoacetarylides, arylamines, acylaminonaphthols and sulfonic acids derived therefrom may be applied. Particular examples of coupling components that can be applied in this way include phenol, Q-naphthol, 8-naphthol, 1-naphthol-4-sulfonic acid, 1-naphthol-5-sulfonic acid, 2-naphthol-1-sulfonic acid, 2-naphthol-4-sulfonic acid, 6-sulfonic acid, 2-naphthol-7-sulfonic acid, 2-naphthol-3,6-disulfonic acid, 1-naphthol-3,6-disulfonic acid, 1-naphthol-3,8-disulfonic acid, 1-naphthol-3
, 6,8-trisulfonic acid, 3-methyl-pyrazolone-
5,1-phenyl-3-methyl-pyrazolone-5,1-(2',5'-dichloro4'-sulfophenyl)-3
-Methyl-pyrazolone-5,1-(2'-chloroysulfophenyl)-3-methyl-pyrazolone-5,1-
(2'-chloroo-5'-sulfophenyl)-3-methyl-pyrazolone-5, 1-(3'-sulfophenyl)-3
-Methyl-pyrazolone-5,1-(4'-sulfophenyl)-3-methyl-pyrazolone-5,1-(2'-sulfophenyl)-3-methyl-pyrazolone-5,1-(4
'-chlorophenyl)-3-methyl-pyrazolone-5,
1-(2-chlorophenyl)-13-methyl-pyrazolone-5,1-(2,5-dichlorophenyl)-13-methyl-pyrazolone-5,1-(2'-chloro6'-methylphenyl)-13- Methyl-pyrazolone-5,11 (2'
-methylphenyl)-3-methyl-pyrazolone-5,1
-(3'-chloro-6-carboxyphenyl)-13-methyl-pyrazolone-5,1 -(3-carboxyphenyl)-13-methyl-pyrazolone-5,1-(Z-carboxyphenyl)-3 -Methyl-pyrazolone-5,1-(2
',6'-dimethylphenyl)-13-methyl-pyrazolone-5,1-(2'-ethylphenyl)-13-methyl-pyrazolone-5,2-chloro4-sulfoacetoacetanilide, 4-sulfoacetane Acetanilide, 2-chloroacetoacetanilide, acetoacetanilide, acetoaceto 0-anisidine, 5-sulfoacetoacetone 0
-anisidine, 3-methyl-4-chloro-6-methoxyacetoacetanilide, 4-chloro-2,5-dimethoxyacetoacetanilide, aniline, m-toluidine,
5-methyl-2-methoxyaniline, m-chloroaniline, m-anisidine, 0-anisidine, 2,5-dimethoxyaniline, 1-naphthylamine-6- and -7-sulfonic acid, 1-acetylamino- and 1-penzoylamino-8-naphthol-3 , 6-disulfonic acid, 1
-acetylamino- and 1-penzoylamino-8-naphthol-4,6-disulfonic acid, 1-acetylamino- and 1-benzoylamino-8-naphthol-2
, 4-disulfonic acid, 2-acetylamino- and 2-benzoylamino-8-naphthol-6-sulfonic acid,
2-acetylamino and 2-penzoylamino 8
-naphthol-6-sulfonic acid, 2-acetylamino and 2-penzoylamino-8 naphthol-3,6
-disulfonic acid, 1-acetylamino- and 1-penzoylamino-8-naphthol-4-sulfonic acid.

Other suitable compounds are, for example, aromatic primary amines such as aniline-2,5-disulfonic acid, m- and p-nitroaniline, 4-nitroaniline.

Aniline-2-sulfonic acid, 3-nitroaniline-4-sulfonic acid, m- and p-aminoacetanilide, 4-
Aminoacetanilide 3-sulfonic acid, 3-aminoacetanilide 4-sulfonic acid, or 4-amino-2-acetotolide 5-sulfonic acid is diazotized, and the resulting diazo compound is substituted at the 31-position. 4-amino-4'-(3-carboxypyrazolone-5-yl-1)-stilbenedisulfonic acid e.g. 4-amino-4'-(3-carboxypyrazolone-5-yl)-stilbene-2,2
It can be obtained by coupling with '-disulfonic acid or 4-amino-(3-methylpyrazolone-5-yl-1)-stilbene-2,2'-disulfonic acid.

The process is carried out in particular at temperatures below 100°. A preferred reaction medium is water, although it may contain aqueous organic solvents such as acetone or dioxane. Optionally, acid-binding agents such as sodium carbonate or sodium bicarbonate can be added. The diazotization is usually carried out at low temperatures under the action of nitrous acid in an aqueous-mineral acid solution, and the coupling is carried out at weakly acidic, neutral to slightly alkaline pH values.

The following starting materials for producing the fiber-reactive azo dye represented by formula [1} can be mentioned. 2,4,6-trifluoro-S-triazine (cyanyl fluoride) represented by formula [4].

Azo compound represented by formula (5} 4-(4″-aminophenylazo)-4-nitrostilbene-2,2′-disulfonic acid, 4-(4″-aminophenylazo)-14′-ami/ Stilbene-2,2'-disulfonic acid, 4-amino-4'-(6,8-disulfo-2-naphthylene-(1
',2,4,5)triazolyl)-stilbene-2,
2-disulfonic acid → 2-methoxy-5-methyl-5-aniline, 4-amino-4'-(6,8-sulfo-2-naphthylene-(1',2,4,5)-triazolyl)-stilbene-2,2-disulfonic acid →Aniline, 4-amino-4-(5-sulfo-2-naphthylene-(1',2,
4,5)-Triazolyl)-stilbene-2,2-disulfonic acid → 1-naphthylamine-6-sulfonic acid, 4-
Amino-4'-(5-sulfo-2-naphthylene-(1')
,2',4,5)triazolyl)-stilbene-2,
2-disulfonic acid → aniline, 4-amino-4'-(7
-Sulfo-2-naphthylene-(1',2,4,5)triazolyl)-stilbene-2,2'-disulfonic acid→
m-toluidine, 4-(2″-methoxyphenylazo)
-4'-Aminostilbene-2,2-disulfonic acid→
1-Naphthylamine-7-sulfonic acid, 4-(4″-methylaminophenylazo)-4′-aminostilbene-2,2-disulfonic acid, 4-(4″-methylaminophenylazo)-4′,8 -Chloropropionylaminostilbene-2,2'-disulfonic acid, 4-(4''-N-
methylaminophenylazo)-4'-(2''',3'
″)-dichloroquinoxaline-6″)-carbonylaminostilbene-2,2′-disulfonic acid, 4-(4″-
N-methylaminomethylphenylazo)-4'-aminostilbene-2,2'-disulfonic acid, 4-(4
″-N-ethylaminophenylazo)-4-aminostilbene-2,2′-disulfonic acid, 4-(4″-N,8
-hydroxyethylaminophenylazo)-4'-aminostilbene-2,2-disulfonic acid, 4-(4''-amino-2''-monomethyl-phenylazo)-4'-benzoylaminostilbene-2,2'-disulfonic acid , 41 (
4″-aminomemethyl-phenylazo)-stilbene-2,2′-disulfonic acid, 4-(4″-methylaminophenylazo)-4-nitrostilbene-2,2-disulfonic acid, 4-(4″- Amino-2''-ureidophenylazo)-4'-aminostilbeso-2,2-disulfonic acid, 4-(4''-amino-nasulfonaphthyl(r)-azo)-14'-methoxystilbene-2, 2
-disulfonic acid, 4-(4″-amino-3″-toxyphenylazo)-4′-aminostilbene-2,2′
-disulfonic acid, 4-(4″-amino-3″-methoxypousulfonaphthyl-(r)-azo)-4-aminostilbene-2,2-disulfonic acid, 4-(4″-aminophenylazo)-4′-bromo Stilbene-2,2-disulfonic acid, 4-(4″-aminophenylazo)-4′
[3-methyl-4-(2,5'-disulfophenylazo)-5-pyrazolonyl(1)-]-stilbene-2,
2'-disulfonic acid, 4-(4''-amino-2''-methylphenylazo)-4'-aminostilbene-2,2-
Disulfonic acid, 4-(4″-amino-2″,5″-dimethylphenylazo)-4′-aminostilbene-2,2
'-disulfonic acid, 4-(4''-amino-2''-methyl-5''-methoxyphenylazo)-4'-aminostilbene-2,2-disulfonic acid, 4-(4''-amino-6''-sulfonaphthi) Ru(r)-azo)-4'-aminostilbene-2,2'-disulfonic acid, 4-(4''-amino-8''-sulfonaphthyl-(r)-azo)-4-aminostilbene-2,2'-disulfone Acid, 4-(4″
-aminome acetylaminophenylazo)-4'
-Aminostilbene-2,Z-disulfonic acid, 4-(4
″-aminophenylazo)-4′-acetylaminostilbene-2,2′-disulfonic acid, 4-(4″-amino-bosulfonaphthyl-(r)-azo)-4′-aminostilbene-2,2 -disulfonic acid, 4-(4″-aminophenylazo)-4′-00-stilbene-2,
2-Disulfonic acid, 4-(4″-N-acetylaminophenylazo)-4-bromo-stilbene-2,2-disulfonic acid, 4-(4″-N-butylaminophenylazo)-4 '-Benzoylaminostilbene-2,2
'-disulfonic acid, 4-(4''-amino-mechlorophenylazo)-4'-1N,N-dimethylaminostilbene-2,2'-disulfonic acid, 4-nitro-4'-aminostilbene-2,2 '-disulfonic acid → N-methylaniline (then reduces the nitro group), 4-nitro 4'-aminostilbene-2,2'-disulfonic acid →
N-methyl-m-toluidine (then reduces the nitro group)
, 4-nitroaminostilbene-2,2-disulfonic acid → 1-naphthylamino-8-sulfonic acid (then reducing the nitro group), 4-nitro-4-aminostilbene-2,2-disulfonic acid → 1-naphthylamine -7-sulfonic acid (then reducing the nitro group), 4-nitro 4'
-Aminostilbene-2,2-disulfonic acid→1-naphthylamino-6-sulfonic acid.

Formula {6 Armpit, is the amine represented by the foot methylamine, dimethylamine, ethylamine, diethylamine, propylamine, isof.

Lopylamine, butylamine, dibutylamine, isobutylamine, sec-butylamine, te-butylamine, hexylamine, methoxyethylamine, ethoxyethylamine, methoxypropylamine, chloroethylamine, hydroxyethylamine, dihydroxyethylamine, hydroxybropylamine, aminoethane Sulfonic acid, B-sulfatoethylamine, benzylamine, cyclohexylamine, aniline, o-, m- and p-toluidine, 2,3-, 2,4-, 2,5-, 2
,6-,3,4- and 3,5-dimethylaniline, o
1,m- and p-chloroaniline, N-methylaniline, N-ethylaniline, 3- or 4-acetylaminoaniline, 01,m- and p-nitroaniline, o
-, m- and p-aminophenol, 2-methyl-4
Nitroaniline, 2-methyl-5-nitroaniline, 2,5-dimethylaniliso, 2,5-dimethoxyaniline, 3-methyl-4-nitroaniline, 2-nitro-4-methyl-aniline, 3-nitroaniline 14-methyl-aniline, 3-nitro 4-methyl-aniline, o1, m
- and p-phenylenediamine, 3-amino-4-methyl-aniline, 4-amino-3-methyl-aniline,
2-amino-4-methyl-aniline, o-, m- and p-anisidine, o-, m- and p-phenetidine,
naphthylamine-'1}, naphthylamine-{21, 1
, 4-diaminonaphthylaniliso, 1,5-diaminonaphthalene, 2-amino-1-hydroxynaphthalene,
1-Amino-4-hydroxynaphthalene, 1-amino/
1-8-hydroxynaphthalene, 1-amino-2-hydroxynaphthalene, 1-amino-7-hydroxynaphthalene, orthanilic acid, metanilic acid, sulfanilic acid, aniline-2,4-disulfonic acid, aniline-2,5
-disulfonic acid, anthranilic acid, m- and p-amino-benzoic acid, 2-aminotoluene-4-sulfonic acid,
2-aminotoluene-5-sulfonic acid, p-aminosalicylic acid, 1-amino-4-carboxybenzene-3-sulfonic acid, 1-amino-2-carboxybenzene-5-sulfonic acid, 1-amino-5-carboxybenzene-2-sulfonic acid , 1-naphthylamine-21, -3
1, 141, 15-, 161, 7- and -8-sulfonic acid, 2-naphthylamine-11, 141, 151,
61,171 and -8-sulfonic acid, 1naphthylamine-2,41,12,51,2,7-,12,8-,
-3,5-, -3,6-, -3,7-, -3,8-, -4,6, -4,7-, -4,8- and -5,8-disulfonic acids, -2- Naphthylamine-1,5-,-1,6-
, -1,7-, -3,6, -3,7-, -4,7-, -4,8-, -5,7- and -6,8-disulfonic acids,
1 naphthylamine-2,4,6-,-2,4,7-,
-2,5,7-, -3,5,7-, -3,6,8- and -4,6,8-trisulfonic acid, 2-naphthylamine-1,3,7-, -1,5,7- , 13, 5, 7, 13,
6,7-, -3,6,8- and 4,6,8-trisulfonic acid, 2-, 3- and 4-aminopyridine, 2-aminobenzothiazole, 5-, 6- and 8-aminoquinoline, 2-amino Pyrimidine, morpholine, piverizine, piverazine.

A 2,4,6-trifluoro-S triazine represented by the formula {41, an azo compound represented by the formula {51] and a formula {6
} and the amine of '81 is carried out in particular in aqueous solution or suspension at reduced temperatures and at slightly acidic, neutral to slightly alkaline pH values.

The hydrogen fluoride liberated in the condensation is neutralized by continuous addition of aqueous alkali hydroxide, carbonate, or bicarbonate. The fiber-reactive azo dye represented by formula '1} is.

It is characterized by high reactivity and high adhesion rate. They are suitable for dyeing and printing a variety of materials, such as silk, leather, wool, polyamide fibers and polyurethane fibers, but especially cellulose-containing materials of fibrous structure, such as flax, cellulose, regenerated cellulose and, above all, cotton.

They include the exhaust method as well as the padding process in which the article is impregnated with an aqueous and sometimes salt-containing dye solution and the dye is fixed by alkaline treatment or in the presence of an alkali, sometimes under the action of heating. Suitable for dyeing by method. They are also suitable for printing, in particular on cotton, but also on printing bromine-containing fibers such as wool, silk or wool-containing mixed fabrics.

It is preferable to thoroughly rinse the dyeings and prints with cold and hot water, optionally with the addition of agents which have a dispersing effect and promote the diffusion of unfixed parts.

In the following examples, parts mean parts by weight.

Example 1 1 part aminobenzene-2,5-disulfonic acid in 30 parts water
Add 1 part of toluene to 2.65 parts of an ice-cold neutral solution within 10 minutes.
A solution of 7.4 parts of cyanuryl chloride in the eaves was added dropwise, and at the same time an IN-sodium hydroxide solution was added dropwise to adjust the pH of the solution.
Keep it between 6 and 7.

After complete acylation, the solution of the first condensation product obtained was diluted with 4
-(4''-Methylaminophenylazo)-14'-aminostilbene-2,2-disulfonic acid in 11.85 parts of neutral solution and warmed to room temperature. By dropwise addition of IN-sodium hydroxide solution. The pH of the reaction mixture is maintained between 7 and 8. After the subsequent acylation of both aminos/groups, the dyestuff is separated by addition of a mixture of sodium chloride and potassium chloride and filtered out. It is mixed with a concentrated aqueous solution of 2 parts of disodium hydrogen and dried in vacuum at 50° C. The dyestuff thus obtained dyes cotton in a yellow shade. The max of this dyestuff is 38 orbital m. To an ice-cold neutral solution of 8.65 parts of orthanilic acid in 200 parts of water was added dropwise over 15 minutes a solution of 7.4 parts of cyanuryl fluoride in 1 part of toluene, and at the same time a solution of IN sodium hydroxide was added. Keep the pH of the dropwise solution between 6 and 7.

The condensation product obtained after complete acylation is made into a neutral suspension of 25.2 parts of 4-(4''-aminophenylazo)-enitrostilbene-2,2'-disulfonic acid in 50 g of water. Pour and flood to 25 qC and keep the pH of the reaction mixture at 7-8 by dropwise addition of IN sodium hydroxide.

The dye formed is separated using potassium chloride and heated.
The dye paste is mixed with a concentrated aqueous solution of 2 parts of disodium hydrogen phosphate and dried in vacuo for 5 to 0 minutes. The resulting dye dyes cotton in a yellow shade. The amount of this dye is max
is 394mm. Water 30 Amino/group-containing stilbentriazole 16 represented by the formula
．． A solution of 3 parts of cyanuryl fluoride in 5 parts of toluene is added dropwise over 10 minutes to 6 parts of an ice-cold neutral solution, and the pH of the reaction mixture is kept between 6 and 7 by addition of IN sodium hydroxide solution dropwise.

After the subsequent acylation, a neutral solution of 3.46 parts of methanic acid in 50 parts of water was added to the first condensation product for 30 to 3 y.
During the second condensation, the pH is kept between 6 and 7 using IN sodium hydroxide solution. The resulting dye is precipitated with sodium chloride, furnaced and dried at 50 oo in vacuo using 2 parts of disodium hydrogen phosphate as a buffer. The dye thus obtained dyes cotton in a golden yellow shade. The max of this dye is 38 nodes m. A similar dye is obtained by reacting sulfanilic acid with the difluorotriazine dye instead of methanic acid.

Example 4 In 30 parts of water, 15 amide/group-containing stilbentriazoles represented by the formula
．． 7. A solution of 3 parts of cyanuryl fluoride in 5 parts of toluene is added dropwise to the ice-cold neutral solution of Moribe over 15 minutes, keeping the axis of the reaction mixture between 6 and 7 using IN-sodium hydroxide solution.

After the subsequent acylation, 2.14 parts of 0-toluidine are added to the first condensation product, the reaction mixture is flooded to 35-40°C and the pH is brought to 7-8 by dropwise addition of IN-sodium hydroxide solution. Keep in between. After separation, it is mixed with 2 parts of disodium hydrogen phosphate and dried in vacuo at 50 qo. The dye thus obtained dyes cotton in a yellow shade. The total max of this dye is 7 nm. Reaction of the difluorotriazine dyes with ammonia in a corresponding manner gives similar dyes.

By monoacylating or diacylating the stilbene dyes listed in column 1 of the table below with difluorotriazine derivatives of the amines listed in column 2, other dyes are obtained which dye cotton in the shades listed in column 3. .

Dyeing Example 1 2 parts of the dye obtained according to Example 1 are dissolved in 100 parts of water with the addition of 0.5 part of sodium m-nitrobenzenesulfonate.

A cotton fabric is impregnated with the resulting solution to absorb 75% by weight and dried. The fabric was then impregnated with a solution flooded to 20oC containing 5 parts of sodium hydroxide and 300 parts of sodium chloride per night, absorbing 7 parts per night.
Pressed to 5% by weight, the dyeing is steamed at 100 DEG -101 DEG C. for 3 cycles, soaped for 1/4 hour in a 0.3% boiling solution of an ion-free detergent, rinsed and dried.

Dyeing Example 2 2 parts of the dye obtained according to Example 1 are dissolved in 100 parts of water.

Add 190 parts of cold water to this solution, add 6 parts of sodium chloride, and add 100 parts of cotton fabric to the dye.

The temperature is raised to 40° C. and after 3 minutes there, 4 parts of bran soda and a further 6 parts of sodium chloride are added.

The temperature is kept at 40 DEG C. during the 3 powder days, rinsed, and the dyeing is then soaped for 15 minutes in a 0.3% boiling solution of an ion-free detergent, rinsed and dried.

Claims (1)

[Claims] 1 Formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, K is unsubstituted or a sulfo group, an alkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms an alkoxy group having 1 to 6 carbon atoms, an alkanoylamino group having 1 to 6 carbon atoms, a benzoylamino group, -NH
_2 is a methylamino group, ethylalumino group, ureido group, hydroxyl group, carboxyl group, or halogen-substituted 1,4-phenylene group or 1,4-naphthylene group; R_1 and R_2 are each independently is hydrogen or an alkyl group having 1 to 4 carbon atoms; Ethyl group, hydroxypropyl group, β-sulfoethyl group,
β-sulfatoethyl group, benzyl group, cyclohexyl group, unsubstituted phenyl group, methyl group, chlorine,
a phenyl group substituted by an acetylamino group, a nitro group, a hydroxyl group, a methoxy group, an ethoxy group, a carboxyl group, or a sulfo group, an unsubstituted naphthyl group, or a hydroxyl group, or a sulfo group substituted is a naphthyl group, pyridyl group, benzthiazolyl group, monolyl group, or pyrimidyl group, and N(R_2X) is a morpholino group, piperidino group,
It also forms a piperazino group. R is hydrogen, halogen, nitro group, -NH_2, alkylamino group having 1 to 4 carbon atoms, hexylamino group, hydroxyethylamino group, benzylamino group, cyclohexylamino group, phenylamino group, 4-nitrophenylamino group group, dimethylamino group, diethylamino group, dibenzylamino group, N-methyl-N-phenylamino group, acetylamino group, propionylamino group, benzoylamino group, alkoxy group having 1 to 4 carbon atoms, fiber-reactive group, 1', 2', 4 not substituted
, 5-naphthylene triazolyl group, or 1',2',4,5-naphthylene triazolyl group substituted by a sulfo group, 3-methyl- or 3-carboxy-4
- a phenyl (or -4-naphthyl)azo-pyrazolon-5-yl-(1) group, which phenyl or naphthyl group can be substituted by the substituents defined for K, or of the formula A- N=N- (2) where A is a benzene residue, a naphthalene residue, or a pyrazolone residue which can be substituted by the substituents defined for K. Fiber-reactive azo dye. 2 K is an unsubstituted 1,4-phenylene group, or a 1,4-phenylene group substituted with a sulfo group, chlorine, an alkyl group or alkoxyl group having 1 to 4 carbon atoms, or an acetylamino group or an unsubstituted 1,4-naphthylene group, or a 1,4-naphthylene group substituted by a sulfo group,
R_1 and R_2 are each independently hydrogen or a methyl group, and R is hydrogen, chlorine, bromine, nitro group, amino group, acetylamino group, benzoylamino group, methoxy group, 6,8-disulfo-(1',2',4,5)-naphthylenetriazolyl, or 3-methyl-4-(2',
5'-disulfophenylazo)-5-pyrazolonyl-(
1) a group, such that X has the meaning given in claim 1, and fiber-reactive azo dyes according to claim 1. 3 K, R_1, R_2 and is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Y
The fiber-reactive azo dye according to claim 1, wherein X is a fiber-reactive acylamino group represented by X independently having the meaning of X defined in claim 1. 4 K is an unsubstituted 1,4-phenylene group, a sulfo group, chlorine, an alkyl group or alkoxyl group having 1 to 4 carbon atoms, or a 1,4-phenylene group substituted with an acetylamino group , an unsubstituted 1,4-naphthylene group, or a 1,4-naphthylene group substituted by a sulfo group, and R_1 and R_
2 are each independently hydrogen or a methyl group, and
is hydrogen, an unsubstituted phenyl group, a phenyl group substituted by a sulfo group, a carboxyl group, a methyl group, an unsubstituted naphthyl group, or a naphthyl group substituted by a sulfo group, Claim 1 in which R is a fiber-reactive acylamino group of formula (3), R_3 and R_4 are each independently hydrogen or a methyl group, and Y has the same meaning as X. Fiber-reactive azo dyes as described. 5. The fiber-reactive azo dye according to claim 1, which is represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 6 2,4,6-trifluoro-S-triazine represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, and an azo compound represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. , chemical formulas, tables, etc.▼ [In these formulas, K is unsubstituted or a sulfo group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a carbon atom 1 to 6
Alkanoylamino group, benzoylamino group,
-NH_2, methylamino group, ethylamino group, ureido group, hydroxyl group, carboxyl group, or halogen-substituted 1,4-phenylene group or 1,4
- Naphthylene group; R_1 and R_2 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms; X is hydrogen, an alkyl group having 1 to 4 carbon atoms, hexyl group, methoxyethyl group, ethoxyethyl group, methoxypropyl group, chloroethyl group, hydroxyethyl group, hydroxypropyl group, β-sulfoethyl group, β-sulfatoethyl group, benzyl group, cyclohexyl group,
unsubstituted phenyl group, methyl group, chlorine, acetylamino group, nitro group, hydroxyl group, methoxy group,
Phenyl, unsubstituted naphthyl, substituted by ethoxy, carboxyl or sulfo, or naphthyl, pyridyl, benzthiazolyl, quinolyl substituted by hydroxyl or sulfo , or pyrimidyl group, or N
(R_2X) forms a morpholino group, a piperidino group, or a piperazino group. R is hydrogen, halogen, nitro group, -NH_2, alkylamino group having 1 to 4 carbon atoms, hexylamino group, hydroxyethylamino group, benzylamino group, cyclohexylamino group, phenylamino group, 4-nitrophenyl Amino group, dimethylamino group, diethylamino group, dibenzylamino group, N-methyl-N-phenylamino group, acetylamino group, propionylamino group, benzoylamino group, alkoxy group having 1 to 4 carbon atoms, fiber reactivity group, unsubstituted 1', 2', 4
, 5-naphthylene triazolyl group, or 1',2',4,5-naphthylene triazolyl group substituted by a sulfo group, 3-methyl- or 3-carboxy-4
- a phenyl (or -4-naphthyl)azo-pyrazolon-5-yl-(1) group, which phenyl or naphthyl group can be substituted by the substituents defined for K, or of the formula A- N=N- (2) where A is a benzene residue, a naphthalene residue, or a pyrazolone residue which can be substituted by the substituents defined for K. There are formulas, mathematical formulas, chemical formulas, tables, etc. that are condensed with amines to obtain the fiber-reactive azo dye represented by formula (1). (In this formula, K, R_1, R_2, X, and R are A manufacturing method for fiber-reactive azo dyes. 7 2,4,6-trifluoro- represented by formula (4)
S-triazine and the formula (5) [In this formula, K is unsubstituted or a sulfo group, a chlorine atom, 1 to 4 carbon atoms]
a 1,4-phenylene group substituted with an alkyl group, an alkoxy group, and an acetylamino group,
or a 1,4-naphthylene group that is unsubstituted or substituted with a sulfo group, R_1 is a hydrogen atom, and R is a hydrogen atom, a chlorine atom, a bromine atom, a nitro group, an amino group, an acetylamino group or 6,8-disulfo-(1
',2',4,5-naphthylene triazolyl group]
An azo compound represented by the formula (6) [in this formula, R_
2 is a hydrogen atom, and X has the meaning as defined in claim 6] as a starting material. 8 2,4,6-trifluoro- represented by formula (4)
S-triazine is represented by the formula (5) [In this formula, K and R_1 have the meanings described in claim 6, and R is represented by the formula ▲
There are mathematical formulas, chemical formulas, tables, etc.▼ (In this formula, R_3 is a hydrogen atom or a carbon atom of 1 to 4
an azo compound represented by formula (6) [in which R_2 and X have the meanings given in claim 6]; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In this formula, R_
4 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Y is a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. Formula (1) [In this formula, K, R_1, R_2 and and R_4 and Y are an acylamino group having the above-mentioned meanings).The method according to claim 6, for producing a fiber-reactive dye represented by the following formula. 9 2,4,6-trifluoro-S-triazine represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and 2,4,6-trifluoro-S-triazine, which is represented by the formula 1, which is free or substituted with a sulfo group, a chlorine atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, and an acetylamino group;
a 4-phenylene group, or a 1,4-naphthylene group that is unsubstituted or substituted with a sulfo group, and R_1 and R_2 are hydrogen atoms], and an azo compound represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc.▼ (In this formula, R_2 is a hydrogen atom, and or unsubstituted or substituted with a sulfol group);
9. The method according to claim 8, wherein an amine represented by the formula (in this formula, R_4 is a hydrogen atom and Y has the same meaning as X) is used as a starting material. 10 The reactions are carried out one after another, in which case formulas (4) and (5
) and (6) or (4) and (5) and (6) and (8) in which the order of simple condensation between the individual reaction components can be freely selected. The method according to any one of Items 9 to 9. 11 2,4,6-trifluoro-S-triazine represented by formula (4) is condensed with an azo compound represented by formula (5), and then the obtained difluoro-S-triazinylamino-azo compound is The method according to claim 6 or 7, wherein the monofluoro-S-triazinylamino-azo dye represented by formula (1) is obtained by condensation with an amine represented by formula (6). 12 First, 2,4,6-trifluoro-S-triazine represented by formula (4) is condensed with an amine represented by formula (6), and the resulting difluoro-S-triazinylamino compound is expressed as formula (5). Claim 6 or 7 to obtain a monofluoro-S-triazinylamino-azo dye represented by formula (1) by condensation with an azo compound represented by formula (1).
The method described in section. 13 First, a first condensation product from 2,4,6-trifluoro-S-triazine represented by formula (4) and an amine represented by formula (6) [or (8)] is produced; and an azo compound represented by formula (5) [in this formula, R is an amino group represented by formula (7)] in a molar ratio of 2:1.
10. The method according to claim 8 or 9, wherein the method is condensed with 14 First, an azo compound represented by the formula (5) [in this formula, R is an amino group represented by the formula (7)] is converted to the azo compound represented by the formula (
4), and the resulting di-first condensation product is condensed with 2 moles of an amine represented by formula (6) [or (8)]. The method according to claim 8 or 9. 15 2,4,6-trifluoro-S-triazine represented by formula (4) is condensed with aminobenzene-2,5-disulfonic acid, and the resulting first condensation product is 4-(4
″-aminophenylazo)-4′-aminostilbene-
2. The method according to claim 8 or 10, in which the fiber-reactive azo dye is condensed with 2'-disulfonic acid in a molar ratio of 2:1 to a fiber-reactive azo dye represented by the formula: .