JPS603108B2 - Production method of fiber-reactive phthalocyanine-azo dye - Google Patents

Description

Detailed Description of the Invention The present invention relates to the following general formula (1) [wherein A is a fiber-reactive residue and B is an optionally substituted mononuclear or dinuclear aromatic or araliphatic carbonized Residues of hydrogen (the alkylene chain is -do-
A), R7 Pc is a metal-containing or metal-free phthalocyanine residue;
ar is an optionally substituted mononuclear or dinuclear aromatic or araliphatic hydrocarbon residue (the alkyl-S02--
N-ren chain is attached to the blind group), R3R
, represents a hydrogen atom, an optionally substituted alkyl group (having 1 to 6 carbon atoms), a phenalkyl- or naphthalkyl-group containing 1 to 3 carbon atoms in the aliphatic chain, a phenyl group or a naphthyl group (of which R2 is a hydrogen atom, an optionally substituted alkyl group (having 1 to 6 carbon atoms) or an unsubstituted alkyl group (having 1 to 6 carbon atoms); 7 to 2 rigid, R3 is a hydrogen atom, an optionally substituted alkyl group (1 to 6 carbon atoms), R4 is a hydrogen atom or an optionally substituted alkyl group (1 to 6 carbon atoms) or an unsubstituted alkyl group (having 7 to 1 carbon atoms), R7 means a hydrogen atom or an optionally substituted alkyl group (having 1 to 4 carbon atoms), and k is 0, 1, 2, or 3, 1 represents 0, 1 or 2, m represents 1, 2, 3 or 4, and the sum of k, 1 and m is 3 or 4.

The method of the present invention relates to a method for producing a valuable water-soluble, fiber-reactive green phthalocyanine-azo dye represented by (In the formula, Pc, ar,
R,, R2, R3, k, 1 and m have the meanings given above,
The amino group is attached to the aromatic carbon atom of residue ar.

) by diazotizing the phthalocyanine amine shown by
The aqueous soot center axis 3 to 8 has the following formula (M) [wherein R'4 is an optionally substituted alkyl group (having 1 to 6 carbon atoms) or an unsubstituted alkyl group (having 7 to 1 carbon atoms)]
R5 is an optionally directly substituted alkyl group (having 1 to 6 carbon atoms) or a non-human alkyl group (having 7 to 1 carbon atoms), Z is a hydrogen atom, and R5 is an optionally substituted alkyl group (carbon Fujiko number: 1 to 1q hard), an optionally substituted phenyl group, or an alkoxycarbonyl group having 2 to 6 carbon atoms.

] to obtain the following formula (W) (wherein, Pc, ar, R,, R2, R3
, R4, R5, k, 1 and m have the meanings given above.

) is converted into a pyrazolone compound represented by the following general formula (V) by the action of an alkali, and this compound is converted into the following general formula (W) (where B, R7 and A have the above-mentioned meanings.

) or by coupling the amine represented by the following general formula (W) with a diazonium compound (wherein E is a group that can be converted into a group of the formula by a known method) means.

) is coupled with a diazonium compound, and then the group E is converted into a group of the formula by a conventional method.

In the phthalocyanine amine of the general formula (0) to be used according to the invention, Pc is a scale group of a metal-containing phthalocyanine, and ar is a mononuclear or dinuclear group optionally substituted with a -S03 group. Aromatic or araliphatic carbon-hydrogen residues (which have one carbon atom per nucleus)
~4 alkoxy groups, one SQ& or even one SQH, or one or two identical R, 'or' different, halogen roniko, -S.

may be substituted by a substitution rhombus from the group consisting of state<R2' and -COO date. ), or in some cases -SQ
The phenylene radicals R and R', which may be substituted by H radicals and additionally by 1 to 3 identical or different C1-C4 alkyl radicals, are independently of one another:
Hydrogen atom, methyl group, carboxymethyl group, sulfomethyl group, optionally CI, orbital, OH, alkoxy group having 1 to 6 carbon atoms, alkanoylamino group having 1 to 6 carbon atoms, preferably acetylamino alkyl groups of 2 to 6 carbon atoms substituted by a group, a penzoylamino group, an alkanoyloxy group of 1 to 6 carbon atoms, preferably an acetyloxy group, 1COO or -S03,
phenalkyl- containing 1 to 3 carbon atoms in the aliphatic chain
or naphthoalkyl group, phenyl group or naphthyl group, in which case the aromatic nucleus is CI, Br, OH, carbon number 1-6
alkyl and/or alkoxy groups, alkanoylamino groups having 1 to 6 carbon atoms, one COO day or -
SQH), R2 and R2 are independently a hydrogen atom, a methyl group, a carboxymethyl group, a sulfomethyl group, optionally CI, B
OH, alkoxy group having 1 to 6 carbon atoms, alkanoylamine group having 1 to 6 carbon atoms, benzoylamino group, alkanoyloxy group having 1 to 6 carbon atoms, one COO day or -S03H' Therefore, an imitation alkyl group having 2 to 6 carbon atoms, or a solid non-converted alkyl group having 7 to 2 carbon atoms, R3 is a hydrogen atom, a methyl group, a carboxymethyl group, a sulfomethyl group, optionally CI,B
OH, alkoxy group having 1 to 6 carbon atoms, alkanoylamino group having 1 to 6 carbon atoms, benzoylamino group, alkanoyloxy group having 1 to 6 carbon atoms, one COO day or one According to the SQ rule, the number of carbon atoms substituted is 2
~6 alkyl groups, R5 is a methyl group, a carpoxymethyl group, an alkyl group having 2 to 3 carbon atoms, a benzyl group, or a phenyl group (in which case, the aromatic nucleus is one or two times 1COO
day or -S03 day).

In this case, the symbol k represents the number 0, 1, 2, or 3, and 1 represents 0.
, 1 or 2, m represents a number 1, 2, 3 or 4, and the sum of k, 1 and m is 3 or 4.

Among the amines of the general formula (0) to be used according to the invention, particularly advantageous are the radicals of the general formula (0) in which Pc is a residue of a metal-containing phthalocyanine, for example a monocobalt or monocopper phthalocyanine, but especially This is a compound that represents the residue of nickel phthalocyanine.

Aroaliphatic residues denoted by a[ always have an aromatic nucleus of N
It is bonded to the Q group.

The mononuclear aromatic or araliphatic residue represented by ar is an optionally substituted phenylene group and an optionally substituted general formula shown below (where n means an integer of 1 to 10).

) is a mono or polymethylene-phenylene group. The aromatic or araliphatic group represented by ar is an optionally substituted naphthylene group and an optionally substituted general formula (wherein n means an integer of 1 to 3).

) and optionally substituted groups represented by the following formulas and.

Examples of the mononuclear or dinuclear aromatic or araliphatic hydrocarbon group that can be represented by ar in the amine represented by the general formula (0) include the following: Phenylene (1 .4), phenylene 1, 3), 2-sulfophenylene (1.4), 3-sulfophenylene (1, 4)
), 4- or 5-sulfophenylene (1.3), 2-carboxyphenylene (1.4), 3-carboxyphenylene (1.4), 4-, 5- or 6-carboxyphenylene (1・3), 2-carboxy-5-sulfophenylene (1.4), 2-carboxy-6-sulfophenylene (1.4), 3-carboxy-6-sulfophenylene (
1,4), 6-hydroxy-4-sulfophenylene (1
・3), 5-ruboxy-2-sulfophenylene (1・
3), 2,5-dicarboxyphenylene (1,4), 4
・6-dicarpoxyphenylene (1.3), 2-chloro-5-sulfophenylene (1.4), 2-chloro-6-sulfophenylene (1.4), 3-chloro-6-sulfophenylene (1. 4), 6-chloro-4-sulfophenylene (1,3), 2-chloro-5-carpoxyphenylene (1,4), 2,6-disulfophenylene (1,4)
), 2,5-disulfophenylene (1.4), 4,6-disulfophenylene (1,3), 3-chloro-6-carpoxyphenylene (1,4), 6-chloro-4-carboxyphenylene Nylene (1,3), 4-chloro-5-carboxyphenylene (1,3), 2-methyl-5-carboxyphenylene (1,4), 2-ethyl-6-carboxyphenylene (1)・4), 3-ethyl-6-sulfophenylene (1.4), 6-ethyl-4-carboxyphenylene (1.3), 6-propylene-4-sulfophenylene (1.3), 5-isopropyl-4- Sulfophenylene (1,3), 5-isopropyl-6-carboxyphenylene (1,3), 41-n-butyl-6-sulfophenylene (1,3), 3-n-butyl-6-sulfophenylene (1,4) ), 4-tert-butyl-6-sulfophenylene (
1,3), 3-isobutyl-6-sulfophenylene (1
・4), 2,5-diisopropyl-6-sulfophenylene (1,4), 2,4-diethyl-5-hydroxyphenylene (1,-3), 2,4,6-trimethyl-5-sulfophenylene (1.3), 2-cyan-phenylene (
1,4), 4-cyan-phenylene (1,3), 2-cyan-5-sulfophenylene (1,4), 2-trifluoromethyl-phenylene (1,4), 2-methylsulfonylphenylene Ren (1.4), 2-ethylsulfonyluenylene (114), 4-sulfonaphthylene (1.5)
, 8-sulfonaphthylene (1.5), 4-sulfonaphthylene (2.6), 2-carboxynaphthylene (1.4)
, 2-ruboxynaphthylene (1,5), 5-ruboxynaphthylene (1,4), 3-ruboxynaphthylene (1,8), 3-ruboxynaphthylene (1,5) ), 4
-Lupoxynaphthylene (2,6), 4-carboxynaphthalene (2,7), 1-sulfonaphthylene (2,6)
, 8-sulfonaphthylene (1,3), 4,8-disulfonaphthylene (2,6), 3,7-disulfonaphthylene (
1.5), 1-sulfo-4-chlornaphthylene (216
), 1-chloro-5-sulfonaphthylene (2.6), 1
-chloro-7-sulfonaphthylene (2,6), 2-chloro-6-sulfonaphthylene (1,4), 1-methyl-4
-sulfonaphthylene (2.6), 2-methyl-7-sulfonaphthylene (1.4).

The amino/group is then present in the 11-position of the phenyl nucleus or in the 1-& or 2-position of the naphthalene nucleus.

The following table shows examples of compounds from which other divalent residues represented by ar are derived, and the second column of the table shows the position ( The amines of formula (0) to be used according to the invention: Especially advantageous ar is optionally substituted phenylene, naphthylene, an optionally substituted mono- or di-nuclear aromatic group represented by ar in the amines of formula (0) to be used according to the invention, or Preferably, the araliphatic hydrocarbon group contains at least one sulfo or carboxyl group, but it is also useful to use residues of the general definition of ar, which do not contain any acidic groups that render them acidic. A dye according to the invention is obtained.

Furthermore, ar has one -OH per nucleus, an alkoxy group having 1 to 4 carbon atoms, one CN, one CF3, one SO
It may be substituted by 2R5 or an additional SQH or by one or two identical or different substituents from the group consisting of halogen atoms and -COO.

a [When subtracted from the miphenylene group, this group can be substituted by one to three identical or different alkyl groups (having 1 to 4 carbon atoms) in addition to the optionally present -SQH group. May be replaced. Particularly advantageously used is ar in formula (0) phenylene, or phenylene substituted by one or two carboxyl groups or by one or two sulfo groups, or one or Amines are naphthylene radicals substituted by two sulfo groups or stilbenylene radicals substituted by two sulfo groups, and especially amines in which ar is a residue of the formula:

The bonding positions mentioned here correspond to those in general formula (1). In the amine of formula (0) containing a group in ar, R, and R, A are independently a hydrogen atom, optionally OH, an alkoxy group having 1 to 3 carbon atoms, one COO or a C2 or C3 alkyl group, methyl group, carboxymethyl group or sulfomethyl group replaced by -SQH, and also where R2 and R'2 are, independently of each other, optionally OH ,
Alkoxy group having 1 to 3 carbon atoms, one COO day or -
C2 or C3 alkyl radicals imitated by SQH, or unsubstituted alkyl radicals of 1 to 2 M carbon atoms, but especially hydrogen atoms, methyl radicals, carboxymethyl radicals or optionally OH Number of carbon atoms substituted by 2
or 3 alkyl radicals.

Particularly advantageous values for R and R2 are hydrogen, methyl or 8-hydroxyethyl. Hydrogen, methyl and 3-hydroxyethyl are likewise particularly advantageous meanings of R' and R'2. Particularly advantageous amines of the formula (0) are those which have no other substituents in their divalent residue ar besides carboxylic and sulfonic acid groups.

Other advantageous groups of amines of general formula (0) to be used according to the invention include R3 being a hydrogen atom, a methyl group,
Carboxymethyl group, sulfomethyl group or optionally C
I, OH, alkoxy group having 1 or 2 carbon atoms -CO
It is characterized by denoting an ethyl group, in particular a hydrogen atom or a methyl group, substituted by 0 or 1 SO3.

Among the amines of formula (0) containing -S02-R in ar, convenient are those in which & is a methyl, ethyl, phenyl or carpoxymethyl group. Furthermore, in the amine of the formula (b) to be used according to the present invention, 1
Amines in which k is 0, k is 2 or 3, m is 1 or 2, and the sum of k and m is 4 are particularly advantageous.

The substituent described in formula (0) is 31 and (
or) in the 4-1 position; it is particularly advantageous for the substituent to be in the 3-position.

The 31st position means the 3rd, 3', 3'' and 3rd skin positions of phthalocyanine, and the 41st position also means the 4th and 4th positions.
'・4'' and 4...mean first place.

The amine of the general formula (0) necessary for producing the dye of the general formula (1) according to the present invention is, when 1 is 0,
Phthalocyanine-3- or -4-di,tri- or especially-tetrasulfochloride is represented by the following general formula (X)-KawaN
H2 x) R3 (wherein R3 and ar have the above-mentioned meanings.

) can be obtained by reacting with the amine shown in In place of the amine represented by the above formula (X), a monoacylated amine, such as an acetylated amine represented by the following general formula (Xa), can also be used.

In this case, the resulting condensation product with phthalocyanine sulfochloride is subsequently saponified. When 1 in formula (1) or (N) is 1, the amine of formula (D) is phthalocyanine-3-1 or 1-4-sulfochloride, in any order, represented by the following general formula (X). (wherein R and R2 have the above-mentioned meanings.

) and an amine represented by formula (X). However, from the beginning, the formula (X
) and (phantom) as starting materials.

The reaction of phthalocyanine sulfochloride with the above-mentioned amines can be carried out in the following three ways:
This is carried out by adding the sulfochloride to a concentrated aqueous suspension of the sulfochloride in water or in a mixture of water and a water-miscible organic solvent. However, the reaction can also be carried out exclusively in organic solvents. The temperature of the reaction mixture is maintained at 0 to 35 DEG C., and the monomer value (always in the acidic range during the reaction) is maintained at 4 to IQ, especially 6 to 8, by gradual addition of alkali. As the alkali, conventional substances acting on alkalinity, such as caustic soda solution, soda, potassium carbonate, trisodium phosphate, etc., can be considered. Particularly convenient is caustic soda solution. It is advantageous to add a tertiary amine (for example pyridine) as a catalytic base to accelerate the reaction. It is also possible to further process the amine of formula (0) directly in aqueous solution to obtain the amine, but
- It is generally advantageous to isolate the nuclear amine and thereby eliminate any unreacted amine components of formula (X) and/or formula (X) that may still be present. Formula (phantom) that can be used to produce the amine represented by formula (0)
The following may be mentioned as amines: ammonia, methylamine, dimethylamine, ethylamine, diethylamine, 8-hydroxyethylamine, 8-methoxyethylamine, bis-6-hydroxyethylamine, aminoacetic acid, taurine, N-methyltaurine. , butylamine, caprylamine, laurylamine, aniline, toluidine, chloraniline, aniline-o, m or p-sulfonic acid, aniline-o, m or p-carboxylic acid, N-methylaniline, N-ethylaniline-o, m or p-sulfonic acid, aniline- -methane-sulfonic acid, penzylamine, N-6-hydroxyethylbenzylamine, penzylamine-sulfonic acid, 3-acetylaminoethylamine.

Formula (X
Examples of amines represented by ) include the following: P-phenylenediamine, N-methyl-p-phenylenediamine, N-carboxymethyl-p-phenylenediamine,
-m-phenylenediamine, N-8-hydroxyethyl-m-phenylenediamine,
1,4-phenylenediamine-2-sulfonic acid, 1-amino-4-N-sulfomethylamino-phenylene-2-sulfonic acid, 1,4-phenylenediamine-2,5- or -2,6-disulfonic acid, 1 -Amino-4-N-methylaminophenylene-2,6-disulfonic acid, 1,3
-phenylenediamine-4-sulfonic acid, 1,3-phenylenediamine-4,6-disulfonic acid, 2,4-diaminotoluor-5- or -6-sulfonic acid, 216
-Diaminotoluor-4-sulfonic acid, 2,6-diamino-1,3,5-trimethylbenzole-4-sulfonic acid, 2,6-diamino-1,3-diethylbenzole-4-sulfonic acid, 2,4-diamino-1-chlor Benzol-6 monosulfonic acid, 2,4-diamino-1-tert-butylbenzole-6-sulfonic acid, 2,4-diaminotoluol-5-1 or -6-sulfamide, 2,6-diaminotoluol-4-ethanol -or-diethanol-sulfamide, 1,4-diaminophenylene-2
-dimethylsulfamide, 1,3-diaminophenylene-4-sulfanilide, 1,3-diaminophenylene-4-3-hydroxyethylsulfone, N-ethyl-p-
Phenylene diamine, N-propyl p-phenylene diamine, N-butyl-
p-phenylenediamine, N-benzene-p-phenylenediamine, N-hexyl-p-phenylenediamine, N-8-hydroxy-propyl-p-phenylenediamine, N-G-carboxypropyl-p-phenylenediamine, N-y-chlorooptyl-p-phenylenediamine, N-6-methoxybutyl-p-phenylenediamine, N-6-propoxybutyl-p-phenylenediamine, N-8-acetylaminoethyl-p -phenylenediamine, N-8-butyrylaminoethyl-p-phenylenediamine, N-benzoylaminoethyl-p-phenylenediamine,
1-N-methyl-3-aminobenzole-4-sulfonic acid, 1-N-butyl-4-aminobenzole-3-
Sulfonic acid, 2,4-diaminophenol-6-sulfonic acid, 2,4-diamino-1-methoxybenzole-
5-sulfonic acid, 1,5-diaminonaphthalene, 1,5-diaminonaphthalene-3-sulfonic acid, 1,5
-diaminonaphthalene-4-sulfonic acid, 1,5-diaminonaphthalene-2-sulfonic acid, 1,6-diaminonaphthalene-14-sulfonic acid, 1,4-diaminonaphthalene-2-sulfonic acid, 1,4-diaminonaphthalene 15
-sulfonic acid, 1,4-diaminonaphthalene-7-sulfonic acid, 1,8-diaminonaphthalene-4-sulfonic acid, 2,6-diaminonaphthalene-8-sulfonic acid, 2.
6-diaminonaphthalene-4,8-disulfonic acid, 1.
5-diaminonaphthalene-3,7-disulfonic acid, 1.
4-diaminonaphthalene-5-carboxylic acid, 1,4-diaminonaphthalene-2-carboxylic acid, 1,8-diaminonaphthalene-13-carboxylic acid, 4,4'-diami/-diphenyl, 2,2'-dimethyl-4,4 '-diaminodipheni', 3,3'-dichloro-4,4'-diaminodipheni'
4,4'-diaminodiphenylated-2,2-disulfonic acid, 3,3-dimethoxy4,4'-diaminodiphenylated, 1-amino-4-aminomethyl-benzole,
1-amino-4-aminomethyl-benzole-3-sulfonic acid, 1-amino-4-8-aminomethyl-benzole-2-sulfonic acid, 1-amino-4-aminobropy-benzole-3-sulfonic acid, 2 -Amino 5m
Aminomethylnaphthalene-1-sulfonic acid, 4,4'
-diaminodiphenylmethane-2,2-disulfonic acid, 4,4'-diaminodiphenylethane-2,2-disulfonic acid, 4,4'-diaminodiphenylethane-mono-sulfamide, 4,4 '-diaminodiphenylethane-disulfamide, 4,4'-diaminostilbene-2,2-disulfonic acid, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane-3 -Hydroxyethylsulfamide, 4,4'-diaminodiphenylamine-3-sulfonic acid, 3,4
'-diamino-6-methoxydiphenylamine-2'
Monosulfonic acid, 3,4-diamino-4-methyl-diphenylamine-2-sulfonic acid, 3,3'-diaminobenzophenone-5,6-disulfonic acid, 3,4'-diami/penzophenone-3'-sulfonic acid, 4・4'-diaminodiphenylsulfone, 4,4'-dichloro-3・
3'-diami/-diphenylsulfone, 3,3'-diamino-4-methyl-diphenylsulfone-5-sulfonic acid, 3,3'-diamino-diphenylsulfone-4,4
'-disulfonic acid.

When producing the dye represented by the general formula (1) according to the present invention, first the following general formula (0) (wherein Pc, ar,
R,, R2, R3, k, 1 and m have the meanings given above,
The free amino stalk is attached to the aromatic carbon atom of residue ar.

) by diazotizing the phthalocyanine amine shown by
In an aqueous medium at pH 3 to 8, the following formula (m) (wherein R'4 and R5 have the above-mentioned meanings, Z is a hydrogen atom, optionally an alkoxy group having 1 to 4 carbon atoms or a carbon atom number) 2-6
a hard alkyl group of 1 to 1 carbon atoms substituted by alkoxycarbonyl groups, optionally CI, Br,
It means a phenyl group directly substituted with an alkyl or alkoxy group having 1 to 4 carbon atoms or an alkoxycarbonyl group having 2 to 6 carbon atoms.

) is coupled with a competitive acid derivative shown in

Convenient silicic acid derivatives of formula (m) include R'4 in which CI
, OH or an alkyl group having 2 to 6 carbon atoms, preferably 2, substituted by an alkoxy group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, or an alkyl group having 1 to 18 carbon atoms, preferably 1 ~6 unsubstituted alkyl groups, R6
is an ethyl group substituted with CI, CH or an alkoxy group having 1 to 2 carbon atoms, or an unsubstituted ethyl group having 1 to 2 carbon atoms
1 refers to an alkyl group, and Z represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group, a methylphenyl group or an alkoxycarbonyl group having 2 or 3 carbon atoms; .

Particularly advantageous are the acid derivatives in which R'4 and R5 are the same in formula (m), meaning a methyl group or an ethyl group, and Z meaning a methyl group.

Diazotization of the amine represented by the general formula (0) is carried out in a known manner by reaction with nitric acid or an agent that eliminates this acid in an aqueous acidic environment.

Salts of nitric acid, especially alkali salts, such as sodium or potassium nitrite, are generally used as agents for removing dust nitric acid. In a convenient embodiment, a solution of sodium nitrite is added in a molar ratio of 1:m to a neutral aqueous solution of 1 mole of the amine of formula (0), and the mixture is then poured over the solution of the amino groups present. At least 2.5 moles, preferably 3 moles, of about 5 to 15% dilute hydrochloric acid are added at -5 to 125°C, preferably -2 to 15°C. The diazo suspension thus obtained is then reacted with a competitive acid converter represented by the formula (m) at a speckle value of 3 to 8, preferably 4.5 to 5.5. In this case, for example, a competitive acid derivative is added to an acidic suspension of a diazonium compound and the axis value is then adjusted to an alkali, for example sodium hydroxide.
The desired value is achieved by adding soda, sodium bicarbonate, sodium acetate, potassium carbonate or sodium phosphate. After 1 to 3 hours of incubation, the diazotized amine is no longer visible and the formation of the hydrazone compound is complete.

The product can then be brought out of solution by salting, ie by addition of a neutral water-lacquered salt, such as sodium chloride or potassium chloride. However, it is by no means necessary to precipitate the hydrazone compound for further processing; on the contrary, it is expedient and advantageous to use the reaction solution obtained during the coupling immediately for subsequent processing. The aqueous medium for carrying out the coupling reaction between the diazotized product of the amine represented by formula (0) and the competitive oxidase derivative of formula (m) is an organic solvent miscible with water, especially a lower aliphatic alcohol (e.g. methanol, ethanol or isopropanol).

It is also possible for known coupling promoters to be present in the coupling reaction, such as urea or pyridine. In the second reaction step of the production method according to the present invention, that is, the cyclization of the hydrazone compound (W) to the pyrazolone compound (V), an aqueous solution of the hydrazone compound represented by the formula (W) is heated at a temperature of 0 to 100 °C, especially 15-30℃, shame value 8-1
4 and 50 days of alcohol withdrawal is quite easily carried out by alkali treatment.

This cyclization can involve saponification of the group COOR4 of the resulting pyrazolone to generate a free carboxyl group. For this purpose, near the upper limit of the above-mentioned axis value, for example, the fence - value 10
It is only necessary to operate in ~14. It is also preferred that this moating is carried out directly in the reaction solution of the hydrazone compound of formula (N) obtained during the coupling by raising the bait value to 10-14. In this case, room temperature is generally sufficient. After cooling the solution of the pyrazolone compound (V) obtained in this manner to 15 to 135°C, preferably 15 to 120°C, without adding the compound alone, the solution is expressed by the following formula (W). It is preferable to add a diazo solution of the amine to be added and stir the mixture at a temperature of -5 to 125° C., preferably 15 to 115° C., with cooling if necessary, until the coupling reaction is completed.

During the course of the coupling reaction (which generally ends within a few minutes) the speckle value is kept at 3-8, especially 5-6, by successive additions of buffer substances or alkalis. In the amine of the formula (machi) used as the diazo component according to the present invention, A is a fiber-reactive group, and the fiber-reactive group here refers to a group that can be separated as an anion or neutrally, or contains activated double bonds that can undergo an addition reaction with the hydroxyl groups of cellulose or superpolyamide when the dye is applied onto the cellulose material in the presence of an acid binder and/or under the action of heat. It is a group that, when applied to a fiber (for example, wool), can react with the nucleophilic center of the fiber while forming a covalent bond.

Groups that can be separated by nucleophilic reactions are groups that have strong electron-withdrawing properties based on their position in the periodic system and/or based on positively charged centers. The activated double bond is, for example, one in a conjugated state with a polar double bond (eg, a carbonyl group). Many such fiber-reactive groups are known from the literature. Examples of known fiber-reactive groups A include: Q.8 monounsaturated residues, such as acrylic acid, Q-chloroacrylic acid, Q-bromoacrylic acid, bropiolic acid, etc. An acid that produces a residue of a Q.8 monounsaturated acid by removing an acid group containing a substituent that can be easily nucleophilically substituted (e.g., a halogen atom), or a neutral or anionic group. Qianji, or vinyl sulfone or 8-
Residues of acids containing halogenalkyl- or 8-sulfatoalkyl-sulfonic groups, such as chloroacetic acid, 3-chloropropionic acid, 8-phenylsulfonylpropionic acid, 8-pyridiniumpropionic acid, B-sulfato Bropionic acid or 8-sulfatophethanesulfonic acid, -(
3-chloroethylsulfonyl) monobutyric acid, 4-B-chloroethylsulfonylbenzoic acid, and other residues.

Residues of carboxylic or sulfonic acids of the metacyclic group, such as 2,3-dichloroquinoxaline-5, which are easily substituted during application by coagulating groups of cellulose or by nucleophilic groups of wool or polyamide. - or mono-6-sulfonic acid, 2.3
-dichloroquinoxaline-5- or -6-carboxylic acid,
2,4-dichloroquinazoline-6-or-17-sulfonic acid, 2,4-dichloroquinazoline-6-carboxylic acid, 1
・4-dichlorophthalazine-6-carboxylic acid and the corresponding dibromo-, monohalogen-monomethyl-sulfonyl or monohalogen-monoethylsulfonyl derivatives, 3,6-dichloropyridazine-4-carboxylic acid or 2,4- Dichlororu, 2,4-dibromo or 2,4-
Residues such as difluoropyrimidine-5- or 16-carboxylic acid or the corresponding monohalogen-monomethyl- or monohalogen-monoethylsulfonyl derivatives and 2-chlorobenzthiazole-carboxylic acid or -sulfonic acid.

a 6-membered heterocyclic residue containing 2 or 3 nitrogen atoms,
For example, s-triazine-2-yl group and pyridine-2
-yl- or -4-yl group having at least one nucleophilically easily substitutable substituent in at least one of the remaining 21-, 4- or 6-positions.

Substituents which can easily be nucleophilically substituted on the rear ring include, for example, halogen atoms (CI, Br or F), tertiary and quaternary amines (including hydrazinium), sulfonyl, especially optionally substituted and optionally substituted phenylsulfonyl, rhodan, sulfinic acid and sulfonic acid.

If a pyrimidine or triazine ring has only one such labile substituent, these rings may contain one non-labile substituent on the remaining carbon atoms or several non-labile substituents. substituents bonded to the remaining carbon atoms. As non-labile pupil substituents, groups which are bonded covalently to a carbon atom of a triazine or pyrimidine ring are to be understood. This covalent bond is then not cleaved under the conditions applied for using the reactive dye. Examples of such non-labile substituents include amino groups and mono- or di-substituted amino groups, etherified hydroxyl and mercapto groups.

Substituted amino groups, which can be present as non-labile substituents of the double ring, are in particular mono- and di-alkyl amino groups containing 1 to 4 carbon atoms in the optionally substituted alkyl group. phenylamino group, which has no substituents or contains one or two preferably sulfonic acid groups, but which may also contain other substituents customary and common in dye chemistry. and a naphthylamino group. Amines that can serve as non-labile substituents are, for example: ammonia, methylamine, dimethylamine, ethylamine, benzylamine, hexylamine, diethylamine, n-propylamine, i-bropylamine, di-i-propylamine, 8 -hydroxyethylamine, y-aminopropanol/8-ethoxyethylamine, 8-propoxyethylamine, 8-methoxyethylamine, bis-8-methoxyethylamine, bis-6-hydroxyethylamine, ethylethanolamine, cyclohexylamine, N-1. Methylcyclohexylamine, aminoacetic acid, 8-sulfatopropylamine, taurine, N-methyltaurine, n-butylamine, i-butylamine, dimethylaminopropylamine, piveridine, morpholine, aniline, o, m or p-toluidine, o, m or p-chloroaniline, aniline-o, m or p-sulfonic acid, aniline-2,4- or -2,5-disulfonic acid, aniline-o, m or p-carboxylic acid, 4-aminotoluol-2- or mono-3-sulfonic acid. , 4
-Methylaniline, N-ethylaniline-o, m or p-sulfonic acid, aniline-methane-sulfonic acid, penzylamine, N-B-hydroxyethylbenzylamine, penzylamine-sulfonic acid, 8-acetylaminoethylamine .

Etherified hydroxyl and mercapto groups include in particular the following: optionally substituted alkoxy and alkylthio groups (up to 4 carbon atoms) in the alkyl group, preferably sulfonic acid groups. phenoxy and phenylthio groups which have the same substituents as are customary and known in dye chemistry and which can also carry the phenyl groups.

A chloro atom, a cya/group, a nitro group or a carpoxyl group at the 51-position of the pyrimidinyl group also falls into the category of substituents that are not unstable.

The same applies to one of the two chloro atoms in the 2,3-dichloroquinoxaline group, the 2,4-dichloroquinazoline group, or the 1,4-dichlorofuthalazine group.

Hydroxy or thio compounds that can serve to introduce non-reactive substituents include, for example: methanol, ethanol, propanol,
i-propanol, butanol, i-butanol, ethylene glycol, ethylene glycol-mono-methyl ether, ethylene glycol-monoethyl ether,
Diethylene glycol-monomethyl ether, phe/
alkylphenols containing 1 to 9 carbon atoms in the alkyl chain, phenolic o-, m- or p-sulfonic acids, methyl mercaptan, thiophenol, 8-hydroxyethyl mercaptan.

An important group of non-labile substituted amino groups are those which themselves additionally carry reactive groups.

Denoting this additional reactive group by 8, this group of non-labile substituents of residue A has the following general formula: H
In the above formula, Het and Het'' are independently an oxygen atom or a sulfur atom, preferably an optionally substituted -NH- group, and the crosslinking agent BR is a divalent aliphatic,
An aromatic or araliphatic residue, A' being one of the groups already mentioned for A, which no longer contains reactive groups among the optionally present non-labile groups. Not included.

Considering the above-mentioned preferred meaning of tin combination for Het and Het', the group -Het-BR-Het'- is preferably derived from an aliphatic or aromatic diamine.

Suitable aliphatic diamines include alkyl chains containing 2 to 6 carbon atoms or cycloalkyl chains containing 5 or 6 carbon atoms. In this case, the two cycloalkyl chains can also be linked by a hydrocarbon group containing 1 to 3 carbon atoms. The alkyl or cycloalkyl group may be substituted, but generally does not contain any substituents other than the two amide/stem. In addition, those in which the alkyl chain is interposed by a secondary or tertiary nitrogen atom, and those in which one or both nitrogen atoms of the diamine are formed by an alkyl chain, and furthermore, an alkyl group having 1 to 6 carbon atoms or carbon atoms. Number 5
Alternatively, those substituted with 6 cycloalkyl groups are also suitable. Particularly advantageous is ethylenediamine. Other examples include:1.
3-diaminopro/gun, 112-propylene diamine, 3-methylamino-propylamine, bis(3-aminopropyl)-methylamine, dipropylene triamine, 2-aminomethylcyclobentylamine, 3-amino-
1-Cyclohexylaminopro/gun, 4,4'-diaminodicyclohexylmethane, 1,3-bis(ethylamino)-propane, 2,2-bis(4-aminocyclohexyl)-propane/1,4-diaminoptan, 1,6 - Diaminohexane.

Suitable aromatic or araliphatic diamines include optionally substituted mononuclear or dinuclear aromatics of the benzene, alkylbenzole, naphthalene, alkylnaphthalene, biphenyl or diphenyl series as hydrocarbon radicals. residues such as benzole, sulfobenzole, disulfobenzole, naphthalene, sulfonaphthalene, disulfonaphthalene, dimethylbiphenyl, disulfobiphenyl, diphenylmethane, diphenylethane, sulfodiphenylmethane, sulfodiphenylamine, sulfodiphenyl Contains residues such as ethers.

Conveniently, benzene and its mono- and di-sulfonic acid residues, such as phenylene(1.4)-, phenylene(1.3)-,2-sulfophenylene(1.4)-1,3-sulfophenylene(1. 4) 1,4- or 5-sulfophenylene (1.3) 1,2,6-disulfophenylene (1.4)-,2,5-disulfophenylene (1.
4) 1,4,6-disulfophenylene (1,3)-group, etc. Listed below are also mononuclear or dinuclear aromatic residues useful as cross-linking agents: 2-carboxyphenylene (1.4), 3-carboxyphenylene (1
・4), 4-, 5- or 6-lupoxyphenylene (1
・3), 2-carpoxy 6-sulfophenylene (1.
4), 2,5-dicarboxyphenylene (1,4), 4
-sulfonaphthylene (1.5), 4-sulfonaphthylene (2.6), 2-sulfonaphthylene (1.5), 1
-sulfonaphthylene (2.6), 4.8-disulfonaphthylene (2.6), 3.7-disulfonaphthylene (1.
5).

Other useful crosslinking agents are derived from the hydrocarbons listed below.

In this case, the first number listed in brackets after the chemical name represents the bonding position to the chemical group Het, and the second number represents the bonding position to the chemical group Het'. Yes: 2,2-dimethyl-diphenyl (
4,4′), 3,3-dimethoxydiphenyl (4,4
'), 2,2-disulfobiphenyl (4,4'), diphenyl-ethane (4,4'), diphenylmethane (4,
・4′), 2,2-disulfodiphenylmethane (4
・4'), 3,3-disulfodiphenyl-ethane (4
・4'), 2,2-disulfodiphenylene ether (
4,4'), stilbene-2,2-disulfonic acid (4,
4'), methyl-phenyl (4.), 1-methyl-phenyl-3-sulfonic acid (4.), 5-methylnaphthalene-1-sulfonic acid (2.), diphenylamine (4.4). '), 2-sulfodiphenylamine (4,4'
), 6-methoxydiphenylamine-2-sulfonic acid (3.4'). Convenient residues A and A' are especially s-
It is a descendant of a 6-membered compound ring derived from triazine.

B is in particular a residue of a mono- or di-nuclear aromatic or araliphatic hydrocarbon, optionally replaced by -S03, which residue has from 1 to 1 carbon atoms in the nucleus. by 4 alkoxy groups, -SO2R6 or even one SQH, or by 1 or 2 identical or different halogen atoms, and -COO, or by 1 to 3 substituents from the group consisting of
It may be substituted with the same or different alkyl groups having 1 to 4 carbon atoms.

In this case, R'' is a hydrogen atom, a methyl group, a carpoxymethyl group, a sulfomethyl group, and in some cases CI, Br, OH
, alkoxy group having 1 to 6 carbon atoms, 1 to 6 carbon atoms
6 alkanoylamino groups, preferably acetylamino groups, benzoylamino groups, alkanoyloxy groups having 1 to 6 carbon atoms, preferably acetyloxy groups, one C
Number of carbon atoms replaced by OO day or -S03 day 2
~6 alkyl groups, 7e:soalkyl or naphthoalkyl groups, phenyl groups or naphthyl groups containing 1 to 3 carbon atoms in the aliphatic chain, in which case the aromatic nucleus is CI
, orbital, OH, alkyl and/or alkoxy groups having 1 to 6 carbon atoms, alkanoylamino groups having 1 to 6 carbon atoms, can be substituted by one COO day or one S03 day . Moreover, R″2 is a hydrogen atom, a methyl group,
Carboxymethyl group, sulfomethyl group, optionally CI
, Br, OH, alkoxy group having 1 to 6 carbon atoms, alkanoylamine group having 1 to 6 carbon atoms, benzoylamino group, alkanoyloxy group having 1 to 6 carbon atoms, one COO day or - S03H' thus means a substituted alkyl group having 2 to 6 carbon atoms or a thin unconverted alkyl group having 6 to 2 carbon atoms. Ma also means a methyl group, a carboxymethyl group, an alkyl group having 2 or 3 carbon atoms, a benzyl group or a phenyl group, in which the aromatic nucleus is substituted once or twice by -COO or -S03. It can be done. The araliphatic residue represented by B always has its aromatic nucleus bound to the primary amino group and its alkylene chain bound to the -NR7A group.

The aromatic or araliphatic residue of the wing core which can be represented by B is an optionally substituted phenylene group and an optionally substituted compound of the following general formula (where n means an integer of 1 to 10). do.

) is a mono- or polymethylene-phenylene group. Furthermore, the dinuclear aromatic or araliphatic group which can be represented by B is an optionally substituted naphthylene group and an optionally folded compound of the following general formula (where n' is 1 to 3). ) and optionally substituted residues of the following formulas and.

Examples of mononuclear or dinuclear aromatic or araliphatic hydrocarbon residues which can be represented by 8 in the dyes that can be produced according to the invention include: phenylene (1.4
), phenylene (1,3), 2-sulfophenylene (1
・4), 3-sulfophenylene (1.4), 4- or 5
-sulfophenylene (1.3), 2-carboxyphenylene (1.4), 3-carboxyphenylene (1.4)
, 4-, 5- or 6-carpoxyphenylene (1.3)
, 2-poxy-5-sulfophenylene (1.4),
2-hydroxy-6-sulfophenylene (1.4), 3
-Carboxy-6-sulfophenylene (1.4), 6-carboxy-4-sulfophenylene (1.3), 5-carboxy-2-sulfophenylene (1.3), 2.5-dicarboxyphenylene (1.4), 4. 6-dicarboxyphenylene (1.3), 2-chloro-5-sulfophenylene (1.4), 2-chloro-6-sulfophenylene (1.4), 3-chloro-6-sulfophenylene (1)
・4), 6-chloro-4-sulfophenylene (1.3)
, 2-chloro-5-carboxyphenylene (1.4),
2,6-disulfophenylene (1.4), 2,5-disulfophenylene (1.4), 4,6-disulfophenylene (1.3), 3-chloro-6-carboxyphenylene (1.4), 6-chloro-4-trioxyphenylene (
1,3), 4-chloro-5-carboxyphenylene (1
・3), 2-methyl-5-ruboxyphenylene (1.
4), 2-ethyl-6-carboxyphenylene (1.4
), 3-ethyl-6-sulfophenylene (1.4), 6
-ethyl-4-carboxyphenylene (1.3), 6-
Propyl-4-sulfophenylene (1,3), 5-isopropyl-4-sulfophenylene (1,3), 5-inpropyl-6-carpoxyphenylene (1,3), 4-
n-butyl-6-sulfophenylene (1.3), 3-n
-butyl-6-sulfophenylene (1,4), 4-tert-butyl-6-sulfophenylene (1,3), 3-isobutyl-6-sulfophenylene (1,4), 2,5-diisopropyl-6-sulfophenylene Phenylene (1.4), 2.4
-diethyl-5-carpoxyphenylene (1.3), 2
・4,6-trimethyl-5-sulfophenylene (1.3
), 2-cyan-phenylene (1.4), 4-cyan-phenylene (1.3), 2-cyan-5-sulfophenylene (1.4), 2-trifluoromethyl-phenylene (
1,4), 2-methylsulfonylphenylene (1,4)
), 2-ethylsulfonylphenylene (1.4), 4
1-3-methoxyethylsulfonylphenylene (1.3
), 4-sulfonaphthylene (1.5), 8-sulfonaphthylene (1.5), 4-sulfonaphthylene (2.6),
2-carboxynaphthylene (1.4), 2-carboxynaphthylene (1.5), 5-carboxynaphthylene (
1.4), 3-carboxynaphthylene (1.8), 3
Monocarboxynaphthylene (1.5), 4-carboxynaphthylene (2.6), 4-carboxynaphthylene (2.
7) "1-sulfonaphthylene (2.6), 8-sulfonaphthylene (1.3), 4.8-disulfonaphthylene (2.
・6), 3,7-disulfonaphthylene (1,5), 1-sulfo-4-chlornaphthylene (2,6), 1-chloro-5-sulfonaphthylene (2,6), 1-chloro-7-sulfonaphthylene Naphthylene (2.6), 2-chloro-6-sulfonaphthylene (1.4), 1-methyl-4-sulfonaphthylene (2.6), 2-methyl-7-sulfonaphthylene (
1.4).

The azo group is then present in the 11-position of the phenyl nucleus or in the 11- or 2-position of the naphthalene nucleus.

The following table shows examples of compounds from which other divalent residues represented by B are derived, and the second side of the table shows the position where the divalent rear group is bonded to the azo group ( first number) and t of the -N-dye that can be produced according to the invention
The position (second digit) attached to the group is indicated: for B of the dyes which can be prepared according to the invention, optionally substituted phenylene, naphthylene groups as well as the formula Groups such as

The optionally substituted mononuclear or dinuclear aromatic or araliphatic hydrocarbon group represented by B preferably contains at least one sulfo or carboxyl group, but preferably contains an acidic group to render it water-soluble. Valuable dyes are also obtained for residues of the general definition of B that do not contain.

Particularly advantageous among the dyes which can be prepared according to the invention are those in which B is a phenylene group, or a phenylene stalk substituted by one or two carboxyl groups or by one or two sulfo groups; or a naphthylene group substituted by two sulfo groups, or a stilbenylene group substituted by two sulfo groups, and especially those in which B is a group of the following formula.

In this case, the bonding positions described here correspond to those of the general formula (1). R7 is particularly a hydrogen atom, a methyl group, a carboxymethyl group, a sulfomethyl group, optionally CI, B
r, OH, alkoxy group having 1 to 6 carbon atoms, alkanoylamine group having 1 to 6 carbon atoms, benzoylamino group, alkanoyloxy group having 1 to 6 carbon atoms, one COO day or -S03 means an alkyl group having 2 to 4 carbon atoms which is substituted with zero.

Among the divalent groups B, particularly advantageous are those having no substituents other than the carboxylic acid group and the sulfonic acid group.

Examples of amines represented by the formula (W) are shown in the table below: The amines represented by the formula (W) can be prepared by converting the amines represented by the following formula (skin) into the acyl compound represented by the following formula x A. It is produced by acylation with a curing agent according to the following reaction scheme: In the above formula, X means a group that can be separated by a nucleophilic reaction of a diamine.

Examples of diamines that yield amines of the formula after the reaction according to the above reaction formula include the following:
P-phenylenediamine, N-methyl-p-phenylenediamine, N-carboxymethyl-p-phenylenediamine, m-
phenylenediamine, N-8-hydroxyethyl-m-phenylenediamine,
1,4-phenylenediamine-2-sulfonic acid, 1-amino-4-N-sulfomethylaminophenylene-2-
Sulfonic acid, 1,4-phenylenediamine-2,5- or 12,6-disulfonic acid, 1-amino-4-N-methylaminophenylene-2,6-disulfonic acid, 1,3
-phenylenediamine-4-sulfonic acid, 1,3-phenylenediamine-4,6-disulfonic acid, 2,4-diaminotoluor-5-1 or -6-sulfonic acid, 2,6
-Diaminotoluol-4-sulfonic acid, 2,6-diamino-1,3,5-trimethylbenzole-4-sulfonic acid, 2,6-diamino-1,3-diethylbenzole-4-sulfonic acid, 2,4-diamino- 1-chlorobenzole-6-sulfonic acid, 2,4-diamino-1-tert-butyl-penzole-6-sulfonic acid, 2,4-diaminotoluol-5- or -6-sulfamide, 2.
6-diaminotoluene-4-ethanol or jetanol sulfamide, 1,4-diaminophenylene-2
-dimethylsulfamide, 1,3-diaminophenylene-4-sulfanilide, 1,3-diaminophenylene-4-8-hydroxyethylsulfone, N-ethyl-p-phenylenediamine, N-propyl-p-phenylenediamine, N-butyl-p-phenylenediamine, N-benchyl-p-phenylenediamine, N-hexy-p-phenylenediamine, N-3-hydroxy-propyl-p-phenylenediamine, N-8-hydroxy-propyl-p-phenylenediamine.
Propyl-p-phenylenediamine, N-y-chloro-
Butyl-p-phenylenediamine, N-6-methoxybutyl-p-phenylenediamine, N-6-bropoxybutyl-p-phenylenediamine, N-P-acetylaminoethyl-p-phenylenediamine, N-8-butyrylaminoethyl-p-phenylenediamine, N-benzoylaminoethyl-p-phenylenediamine,
1-N-methyl-3-amino-benzole-3-sulfonic acid, 1-N-butyl-4-amino-benzole-3-sulfonic acid, 2,4-diaminophenol-6-sulfonic acid, 2,4-diamino-1- Methoxybenzole
5-sulfonic acid, 1,5-diaminonaphthalene, 1,5-diaminonaphthalene-3-sulfone, 1,5
-diaminonaphthalene-4-sulfonic acid, 1,5-diaminonaphthalene-2-sulfonic acid, 1,6-diaminonaphthalene-4-sulfonic acid, 1,4-diaminonaphthalene-2-sulfonic acid, 1,4-diaminonaphthalene-2-sulfonic acid −
5-sulfonic acid, 1,4-diaminonaphthalene-7-sulfonic acid, 1,8-diaminonaphthalene-4-sulfonic acid, 2,6-diaminonaphthalene-8-sulfonic acid, 2
・6-diaminonaphthalene-4,8-disulfonic acid, 1
・5-diaminonaphthalene-3,7-disulfonic acid, 1
・4-diaminonaphthalene-5-carboxylic acid, 1,4-
Diaminonaphthalene-2-carboxylic acid, 1,8-diaminonaphthalene-3-carboxylic acid, 4,4'-diaminodiphenyl, 2,2-dimethyl-4,4'-diaminodiphenylene,
3,3-dichloro-4,4'-diaminodiphenyl,'
4,4'-diaminodiphenyl-2,2-disulfonic acid, 3,3-dimethoxy-4,4'-diaminodipheni'
Le, 1-amino-4-aminomethyl-benzole, 1-
Amino-4-aminomethyl-benzole-3-sulfonic acid, 1-amino-4-8-aminoethyl-benzole-
2-sulfonic acid, 1-amino-4-aminopropylbenzole-3-sulfonic acid, 2-amino-5-aminomethylnaphthalene-1-sulfonic acid, 4,4'-diaminodiphenylmethane-2,2 -disulfonic acid, 4
・4'-diaminodiphenylethane-2,2-disulfonic acid, 4,4'-diamino-diphenylethane-monosulfamide, 4,4'-diaminodiphenylethane-disulfamide, 4,4'- Diaminostilbene-2,2'-disulfonic acid, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane-di8-hydroxyethylsulfamide, 4,4-diaminodiphenyl Amine-3-sulfonic acid, 3,4-diamino-6-methoxydiphenylamine-2-sulfonic acid, 3,4'-diamino-4-methyl-diphenylamine-2-sulfonic acid, 3,3'-diaminobenzo Phenone-5,5-disulfonic acid, 3,4'-diami/penzophenone-3-sulfonic acid, 4,4'-diaminodiphenylsulfone, 4,4-dichloro-3,3-diaminodiphenylsulfone, 3 -3-diamino-4-methyl-diphenylsulfone-5-sulfonic acid, 3,3'-diaminodiphenylsulfone-4,4'-disulfonic acid.

By reacting with a diamine according to the above reaction scheme, formula (W) is obtained.
Many examples of acylating agents of the formula xA that can produce amines have been reported in the literature.

The most important representative of all classes are listed below: cyanuric chloride, cyanuric bromide, dihalogen-monoaminotriazine (in which case the amino group can be substituted as a non-reactive substituent according to the above scheme). ), for example, 2,6-dichloro-4-aminotriazine, 2,6-dichloro-4-methylaminotriazine, 2,6-dichloro-4-oxyethylamino-triazine, 2,6-dichloro-4-phenylaminotriazine , 2,6-dichloro-4-(o-, m- or p-sulfophenyl)-aminotriazine, 2,6-dichloro-4-(2,4'- or 2,5-disulfophenyl)-aminotriazine, dihalogen- Alkoxy and -aryloxy-Syn. triazine, e.g. 2
-6-dichloro-4-methoxytriazine, 2,6-dichloro-4-i-propoxytriazine, 2,6-dichloro-4-phenoxytriazine, tetrahalogenpyrimidine, such as tetrachlor-, tetrabromo or tetrafluoropyrimidine, 2,4 -6-trihalogen-pyrimidine, such as 2,4,6-trichlor-, -tribromo or -trifluoropyrimidine, 2,4,6
-trichloro-5 nitro or 5-methyl- or -5
-carbomethoxy- or -5-cyanopyrimidine, 2
・6-difluoro-4-methyl-5-chloropyrimidine, 2,4-difluoro-pyrimidine-5-ethylsulfone, 2,6-difluoro-4-chloropyrimidine, 2
・4.6-trifluoro-5-chlorpyrimidine, 4.
6-difluoro-2,5-dichloro- or -dibromopyrimidine, 2-methylsulfonyl-4-chloro-6-methylpyrimidine, 2,6-bis-methylsulfonyl-4
-5-dichloropyrimidine, 2-methylsulfonyl-4,5-dichloro-6-methyl-pyrimidine, 2-ethylsulfonyl-4,6-dichloropyrimidine, derivatives of heterocyclic carboxylic or sulfonic acids, e.g.・6-dichloropyridazine-4-carboxylic acid chloride, 2.4
-dichloropyrimidine-5-carboxylic acid chloride, 2.
4,6-trichloropyrimidine-5-carboxylic acid chloride, 2-methyl-4-chloropyrimidine-5-carboxylic acid chloride, 2-chloro-4-methylpyrimidine-5-carboxylic acid chloride, 2,6-dichloropyrimidine-4
-carboxylic acid chloride, 2-methylsulfonyl-6-chloropyrimidine-4- or -5-carboxylic acid chloride,
2-ethylsulfonyl-6-chloropyrimidine-4-1- or -5-carboxylic acid chloride, 2,6-bis-(methylsulfonyl)-pyrimidiso-4-carboxylic acid chloride,
2-Methylsulfonyl-6-methyl-4-chloro- or -4-bromopyrimidine-5-carboxylic acid chloride or -bromide, 2,6-bis(methylsulfonyl)-4-chloropyrimidine-5-carboxylic acid chloride, 2- or 3 -monochloroquinoxaline-6-carboxylic acid chloride or -6-sulfonic acid chloride, 2- or 3-monobromoquinoxaline-6-carboxylic acid bromide or -6
-Sulfonic acid bromide, 2,3-dichloroquinoxaline-6-carboxylic acid chloride or -6-sulfonic acid chloride, 2,3-dibromomonoxaline-6-carboxylic acid bromide or -6-sulfonic acid bromide, 1,4 -Dichlorophthalazine-6-carboxylic acid chloride or -6-sulfonic acid chloride and the corresponding brome compound, 2,4-dichloroquinazoline-161- or 17-carboxylic acid chloride or -sulfonic acid chloride and the corresponding brome compound, N- Methyl-N-(2,4-dichlorotriazinyl-6)-aminoacetyl chloride, 2-chlorobenzthiazole-5- or -6-carboxylic acid chloride or-
5-1- or -6-sulfonic acid chloride and the corresponding bromine compounds, 2-methylsulfonyl- or 2-ethylsulfonyl- or 2-phenylsulfonylbenzthiazole-5-1- or -6-sulfonic acid chloride, aliphatic reactive components, e.g. Acrylic acid chloride, mono-, di- or trichloroacrylic acid chloride, 3-chloropropionic acid chloride, 3-phenylsulfonyl-propionic acid chloride, 3-methylsulfonyl-propionic acid chloride, 3-ethylsulfonyl-propionic acid chloride, 3-
Chlorethane sulfochloride, Q-methylsulfonylacrylic acid chloride and Q-bromoacrylic acid chloride.

In order to acylate the diamine represented by the formula (W) with a compound of the formula ×A according to the above-mentioned reaction formula, a Schotten-Baumann reaction method may be used in an aqueous or aqueous-organic or organic solvent by a known method. 0-80℃, preferably 10
Performed at ~25q0.

Preferably, the acid liberated in this case is neutralized or buffered by the addition of an alkali (eg sodium bicarbonate, soda, caustic soda solution or sodium acetate). Suitable organic solvents are, in particular, acetone, chlorinated hydrocarbons such as ethylene chloride or chlorobenzole, or neutral polar solvents such as dimethylformamide. The diazotization of the amine represented by the formula () is carried out by converting the amine into an aqueous soot using an agent 1 which removes nitric acid or nitrous acid.
This is carried out by reacting the amine in the presence of at least 2 equivalents, preferably about 2.5 equivalents, of a strong acid per mole of the amine.

As agents for eliminating nitrous acid, salts of dust nitric acid, especially alkali salts, such as sodium or potassium salts, are generally used in tin-acidic media. In the manufacturing method of the present invention, the formula (W)
When the diazonium compound of the amine is coupled to the pyrazolone compound of the formula (V), the production of the water-soluble, fiber-reactive phthalocyanine-azo dye according to the invention is completed after the coupling reaction has proceeded.

This form of implementation of the method of the invention is particularly advantageous. The phthalocyanine-azo dye thus obtained can then be isolated from the aqueous solution by salting out.

Alternatively, the dye can be obtained as a solid dye product by fog drying the above solution. In addition, when producing a dye according to the present invention, the following formula (W) day 2N-B-E (skin) (in the formula, B has the above-mentioned meaning, and E is the method of the public third phrase※※
N--A means a group that can be changed into a group of the formula l.

) A diazonium compound of the amine represented by R7 can also be coupled to the pyrazolone compound (V).

A suitable group for E is, for example, the following formula (K) This is an acylamino group represented by

Acyl in this case means any aliphatic or aromatic acyl group which can be removed by saponification. The aliphatic acyl group preferably contains 3 or less carbon atoms, preferably 2 carbon atoms, and the aromatic acyl group is preferably a derivative of the penzoyl group, preferably the penzoyl group itself. When E is such an acylamino group, the dye is preferably alkali, e.g. 2-10%
The following formula (la) (in the formula, B, P
c, ar, R, , R2, R3, R4, R7, k, 1 and m have the meanings given above.

) is acylated with an acylating agent of the formula x-A.

For this purpose, the same reaction conditions and compound x-A as already mentioned for the preparation of the amine of formula (W) are suitable. Furthermore, when a dye in which R7 is day is produced according to the present invention, a dye of the formula (W) in which E represents a nitro group is used.
It is also possible to use amines from the skin.

In this case, the phthalocyanine-azo dye obtained in this way is reduced by the method described above, and then the following formula (lb) (where B, Pc, ar, R, , R2, R3 ,
R4, k, 1 and m have the meanings given above.

) is acylated with an acylating agent of the formula x-A by a known method.

In this way, a fiber-reactive dye represented by formula (1) is obtained. The water-soluble, fibre-reactive phthalocyanine dyes which can be prepared according to the invention are very suitable for dyeing or printing cellulosic materials, cellulose-containing materials and natural or synthetic polyamide materials.

The dyestuffs are distinguished by high fixation yields, especially in the printing process and fixation by dry heat, and are also distinguished by the fact that unfixed dyestuffs can be easily washed away, as well as very good light fastness properties; Good wet fastness (e.g. 6000 and 950
Yellow to blue color with high brightness and coloration, exhibiting seawater fastness, sweat fastness (acidic and alkaline), chlorine bath water fastness, peroxide fastness and chimney gas fastness. Produces green staining and printing.
Mixtures of dyes which can be prepared according to the invention, in particular mixtures in which the meanings of k and/or 1 and/or m differ in the individual components, are also very suitable for dyeing or printing cellulose materials. , exhibiting similar advantageous properties as the individual components.

Such mixtures can be prepared, for example, in the production process of the present invention by starting from a mixture of amines of formula (0) in which the individual components differ in the meaning of k and/or 1 and/or m. obtained in case. Mixtures of amines of formula (0), which are generally significantly enriched in one component, are obtained in the preparation of amines of formula (b) by reaction of dilute phthalocyanine-sulfochloride with the amine. Example 1 m-phenylenediamine-sulfonic acid 1 isoyu about 600
190 m of cyanuric chloride dissolved in acetone is added to this solution at 0-5 °C,
At the same time, approximately 100' of melon-caustic soda solution is added to maintain the pH at 6-7.

When phenylenediamine sulfonic acid could no longer be proven, 70 mg of sodium nitrite was added to the neutral solution,
Then, at 0 to 3°C, mix 1 melon with 250 g of hydrochloric acid while stirring. When the diazotization was completed, the diazo suspension was mixed with N-[3-(3-carpoxy-5-hydroxy-1-pyrazol)-4-sulfophenyl]-Ni to which 100 g of bicarbonate had been added beforehand. Add to the solution of trisulfophthalocyanyl sulfonamide. Coupling takes just a few minutes. The green phthalocyanine azo produced
The dye can be isolated by salting out or by fog drying. Phthalocyanine pyrazo required for coupling.

A solution of the compound can be prepared as follows: 3-(3-amino-4-sulfophenyl)-aminosulfonylnickel-thalocyanine-3'.3''
- Trisulfonic acid (produced by combining nickel phthalocyanine sulfochloride with 1,3-diami/benzole-4-sulfonic acid in a conventional manner) 1,060 ml of water with 7,000 ml of water, 1 ml of caustic soda. Add 400 birds of solution and dissolve. To this solution is added 72 parts of sodium nitrite, which is then stirred into a mixture of 2,000 parts of ice and 300 parts of concentrated hydrochloric acid over a period of 30 minutes.
Add another 2,000 ml of ice to maintain the temperature between 0 and 5°C. After a period of time, any excess nitrite present is destroyed by addition of aminosulfonic acid. 21 grams of acetyl dimethyl ester was poured into the diazo suspension thus obtained. Then, first add about 13 hours of soda to maintain the axis value at 5.5, then add about 21 hours of sodium bicarbonate to maintain the value at 5-6. Then, after about an hour, pray. The completion of the reaction is confirmed by the constant value and by the fact that no change in color occurs when a solution of H-acid in young soda solution is added to the sample. Oxalacetic acid dimethyl ester 3-(nickel trisulfophthalocyaninyl sulfonylamino) 6-
Add 350 g of alkaline solution to the solution of sulfophenyl hydrazone, thereby increasing the wind value to 12-13.

Then let it sit at room temperature for several hours, or best overnight. Thus N-[3-(3-carboxy5-hydroxy-1
-pyrazolyl)-4-sulfophenyl]-nickel trisulfophthalocyaninyl sulfonamide is completed. The value is then lowered to 8 with a little hydrochloric acid and the crude solution obtained is used directly for the coupling.
Valuable green reactive dyes are likewise obtained if, in the preparation of the diazo component, cyanuric chloride is replaced by a molar amount of one of the following acylating agents, otherwise the procedure is as described above: 2.4.6 -trisulfo-1,3,5 triazine, 8-chloropropionic acid chloride, Q, 3-dipromopropionic acid chloride, 8-phenylsulfonylpropionic acid chloride, B-pyridinium propionic acid chloride, 8-sulfato Propionic acid chloride, acrylic acid chloride, Q-bromoacrylic acid chloride, 3-8-chloroethylsulfonylbenzoic acid chloride, 4
-vinylsulfonylcyclohexanecarboxylic acid chloride, 4-8-chloroethylsulfonyl-2,5-endomethylene-cyclohexanecarboxylic acid chloride, mono(8
-chloroethylsulfonyl) monobutyric acid chloride, 2,4-dichloropyrimidine-5-butyric acid chloride, 2.
4-dibromopyrimidine-5-carboxylic acid bromide,
2,4-difluoropyrimidine-5-carboxylic acid chloride, 2,6-dichloropyrimidine-4-carboxylic acid chloride, 2,3-dichloroquinoxaline-6-carboxylic acid chloride, 2,3-dichloroquinoxaline-6 −
Sulfonic acid chloride, 1,4-dichlorofuthalazine-6-sulfonic acid chloride, 1,4-dichlorofuthalazine-6-carboxylic acid chloride, 2-methylsulfonyl-6-chloropyrimidine-4-carboxylic acid chloride ,3
-6-dichloropyridazine-4-carboxylic acid.

2-methylsulfonyl-6-chloropyrimidine-5-carboxylic acid chloride, 2,6-bis-(methylsulfonyl)-pyrimidine-5-carboxylic acid chloride.

The condensation product of nickel phthalocyanine sulfochloride and one of the following amines is used instead of the condensation product of nickel phthalocyanine sulfochloride and 1,3-diami/benzolyl sulfonic acid described above to prepare the coupling component. , otherwise when operated as described above, a valuable green reactive dye can be obtained: 1.4
-phenylenediamine-2-sulfonic acid, 1,3-phenylenediamine-4,6-disulfonic acid, 1,4-phenylenediamine-2,5-disulfonic acid, 1,4-phenylenediamine-2,6-disulfone acid, 2,4-diaminotoluol-6-sulfonic acid, 2,6-diaminotoluol-4-sulfonic acid, 2,4-diamino-1,3
・5-trimethylbenzole-6-sulfonic acid, 2.6
-diaminonaphthalene-4,8-disulfonic acid, 1,5
-diaminonaphthalene-2-sulfonic acid, 2,6-diaminonaphthalene-8-sulfonic acid, 1-amino-4-aminomethyl-benzole-3-sulfonic acid, 2-amino/
-5-aminomethylnaphthalene-1-sulfonic acid, 4
・4'-diaminodiphenylamine-3-sulfonic acid, 3,3'-diamino-4-methyl-diphenylsulfone-5-sulfonic acid, 1,3-phenylenediamine (acetyl derivative, followed by saponification), 2,4-diamino Toluol (acetyl derivative, followed by saponification), 1,4-phenylenediamine (acetyl cryptic conductor, followed by saponification), 4.4
'-diaminodiphenylethane-2,2-disulfonic acid, 4,4'-diaminodiphenylethane-monosulfamide, 4,4'-diaminodiphenylethane-disulfamide, 4,4'- Diaminostilbene-2・
2-disulfonic acid, 4,4-diaminodiphenylethane-di-8-hydroxyethylsulfamide, 4,4-
Diaminodiphenylamine-3-sulfonic acid, 3.4
'-diamino-6-methoxy-diphenylamine-mesulfonic acid, 3,4'-diamino-4-methyl-diphenylamine-2-sulfonic acid, 3,3-diaminobenzophenone-5,5-disulfonic acid, 3. 4-diaminobenzophenone-3'-sulfonic acid, 4,4'-diaminodiphenylsulfone, 4,4'-dichloro-3,3'
-diamino-diphenyl sulfone, 3,3-diamino-4-methyl-diphenyl sulfone-5-sulfonic acid, 3
-3-diaminodiphenylsulfone-4-pagesulfonic acid.

Example 2 p-Phenylenediamine-2,6-disulfonic acid 2 is reacted with methoxydichlortriazine 1 in a conventional manner.

After adding 70 m of sodium nitrite, the solution of the condensation product obtained was poured into 1 molar volume and 25 m of hydrochloric acid. The diazo suspension thus obtained was then diluted with 3.3 as described in Example 1.
'-bis[(4-aminophenyl)-aminosulfonyl]nickel phthalocyanine-3''.3-disulfonic acid is added to a solution of a bispyrazolone compound prepared as follows. - value of 7 to 7.2 and the resulting green dye is isolated by salting out or spray drying. The pipirazolone compound used as coupling component was prepared as follows: 3. 3'-pis-[(4-aminophenyl)
-Aminosulfonyl]nickel phthalocyanine-3
``・3 skin-disulfonic acid (This was produced by condensing 0.5 mole of nickel phthalocyanine tetrasulfochloride with 1 mole of acetyl p-phenylene diamine in a conventional manner and saponifying this condensation product) water 350
0. Worship with me, add 1-200 ml of caustic soda solution and dissolve.

Add 70 ml of sodium nitrite to this solution, then approx.
In 0 minutes, mix it into a mixture consisting of 2000 g of ice and 300 g of concentrated hydrochloric acid. A further 100 g of ice is added to maintain the temperature between 0 and 5°C. After about IQ minutes, the slight excess of light nitrate that may be present is then removed with aminosulfonic acid. To the diazo suspension thus obtained is added 135 mg of acetyl ester acid. Approximately 250 g of soda is then used to bring the pH value to approximately 6, and this pH value is maintained until the diazo compound can no longer be evidenced. Thus, the turquoise 3/3′ service-[41(
A solution of 1,2-bis-ethoxycarbonyl-ethylideso)-hydrazinophenyl-aminosulfonyl]-nickel phthalocyanine-3'',3...-disulfonic acid is obtained.This solution is treated as is) by the action of an alkali. In this case, add about 400 g of a 1 ml solution of caustic soda to the solution and let it stand at room temperature for about 4 hours. If you use the ″・4″′ derivative,
The aircraft will yield valuable phthalocyanine hydrazone compounds.

Also, instead of the amine used above as the diazo' parent for the pyrazolone compound step, a condensation product of nickel phthalocyanine-sulfochloride with 2 moles of one of the amines listed in the table below was used, and the others Proceeding as described above, green phthalocyanine-azo dyes are likewise obtained: 1,3-phenylenediamine (acetyl derivative, followed by saponification), 2,4-diaminotoluol (acetyl derivative, followed by saponification). , 2,4-diaminoanisole (acetyl derivative followed by saponification), 1,4-phenylenediamine-2-sulfonic acid, 2,4-diaminotoluol-6-sulfonic acid, 4-aminobenzylamine (4
-acetyl derivative followed by saponification), 4,4'-diaminostilbenzylsulfonic acid, 4,4'-diaminomethanedisulfonic acid, 4,4'-diami/-diphenylamine-3-sulfonic acid.

The process according to the invention to give valuable azophthalocyanine dyes is likewise possible when the acetyl source silic acid diethyl ester used as the coupling component for the pyrazolone compound step is replaced by one of the competing acid derivatives described below. The same is true if one of the following reactive components is used instead of methoxydichlorotriazine in the acylation of p-phenylenediamine-2,6-disulfonic acid. Valuable dyes are obtained: 2-amino-4,6-dichloro-1,3,5-triazine, 2-phenoxy-4,
6-dichloro-1,3,5-triazine, 2-phenylamino-4,6-dichloro-1,3,5-triazine,
2-N-methyl-N-phenylamino-4,6-dichloro-1,3,5-triazine, 2-butylmercapto-4,6-dichloro-1,3,5-triazine, 2-8-methoxyethoxy4,6-dichloro-1, 3,5-triazine, 2-(2-rupoxyphenoxy)-4,6
-dichloro-1,3,5-triazine, 2-carpoxymethylthio-4,6-dichloro-1,3,5-triazine, 2-phenylthio-4,6-dichloro-1,3,5
- triazine, condensation product of 1 mol of cyanuric chloride and 1.3.51 mol of 2-3-aminoethylamino-4-(Z.5-disulfophenylami/)-6-chlorotriazine, cyanuric acid. Chloride and 2-(4'-amino/1-3'-sulfophenyl-amino)-4-(2''-hydroxyphenylamino)-6-chlorotriazine-1
・3.5 Condensation product with 1 mole, cyanuric chloride and 2-(3'-amino-4'-sulfophenylamino)
141n-poxy-6-chlortriazine-1.3.
5 Condensation product with 1 mole, 2,4-disulfo-6-chloro-1,3,5-triazine, tetrachloropyrimidine, 2,4,6-trichloropyrimidine, 5-cyan-2,4,6-trichloropyrimidine, 5-nitro -2,4,6-trechlorpyrimidine, 2,4-difluoro-6-chlorpyrimidine, 2-methylsulfonyl-4-methyl-6-chlorpyrimidine, cyanuric chloride and 2-methoxy-4-B-hydroxyethoxy-
Condensation product of 6-chloro-1,3,5-triazine,
2-methylsulfonyl-4,6-dichloropyrimidine,
2,3-dichloroquinoxaline-5-carboxylic acid chloride, 2,3-dichloroquinoxaline-5-carboxylic acid chloride, 2,3-dichloroquinoxaline-5-sulfonic acid chloride, 2,3-dichloroquinoxaline -6-sulfonic acid chloride, 2,4-dichloroquinazoline-6-carboxylic acid chloride, 2,4-dichloroquinazoline-6-sulfonic acid chloride.

2,4-dichloroquinazoline-7-sulfonic acid chloride, 1,4-dichlorophthalazine-6-carboxylic acid chloride, 3,6-dichloropyridazine-4-carboxylic acid chloride.

2,4-dichloropyrimidine-5-carboxylic acid chloride, 2,4-difluoropyrimidine-6-carboxylic acid chloride.

Example 3 The amine described in Example 1, 3-[(3-amino-4-sulfophenyl)-amino-sulfonyl]-nickel phthalocyanine-3.3".3"' trisulfonic acid, is replaced by the following table: Using a corresponding molar amount of one of the amines and otherwise working as described in Example 1, similarly valuable pyrazolone derivatives of oxalacetic acid methyl ester are obtained.

This can be further processed to give a pyrazolone compound with the corresponding substituent. Example 4 To the dye prepared according to Example 1 is added one of the following compounds containing at least a molar amount of acylatable amino groups and heated to 3, 4, and 50, respectively for 1 hour; Equally valuable green reactive dyes are obtained if the axis value is maintained between 4 and 7 by adding alkali (for example sodium bicarbonate, soda or caustic soda solution).

In this case, if ammonia or aliphatic amines are used, the alkali can be replaced by a first molar amount of amine. Ammonia, methylamine, diethylamine, isopropylamine, ethanolamine, diethanolamine, N・N-dimethylhydrazine, aniline, o, m or p-toluidine, N-methylaniline, aniline-2,3,4-sulfonic acid, 2. 3,4-aminobenzoic acid, aniline-methanesulfonic acid, moorminoethanesulfonic acid, N-methyltaurine, aminoacetic acid, aniline-2,4- or 12,5-disulfonic acid, p-phenylenediamine, cyanuric chloride and aniline-
A condensation product consisting of 3-sulfonic acid, a condensation product consisting of ethylenediamine, cyanuric chloride and aniline-2,4-disulfonic acid, a condensation product consisting of 1,4-phenylenediamine-2,5-disulfonic acid and isopropoxydichlorotriazine. product, a condensation product consisting of 1,3-phenylenediamine-4-sulfonic acid and 8-ethoxyshetoxydichlorotriazine, a condensation product consisting of P-phenylenediaminesulfonic acid and cyanuric chloride, P-phenylenediaminesulfonic acid and a condensation product consisting of p-phenylenediaminesulfonic acid and 2,3-dichloroquinoxaline-carboxylic acid chloride, p-phenylenediaminesulfonic acid and 2,6-dichloro pyrimidine
A condensation product consisting of 4-carboxylic acid chloride, a condensation product consisting of P-phenylenediaminesulfonic acid and 3,6-dichloropyridazine-4-carboxylic acid chloride.

Example 5 The diazo component 2-amino-4-dichlorotriazinylamino-benzole sulfonic acid used in Example 1 was replaced by an equivalent amount of 2-amino-4-acetylamino-benzole sulfonic acid, otherwise Example 1 Proceed as described in .

Next, 1/200 parts of caustic soda solution was added to the resulting solution of green azophthalocyanine dye and stirred at 990°C for 5 hours until the acetyl groups were completely saponified. The dye solution thus obtained is neutralized with about 100 g of hydrochloric acid, and then at 0 DEG -5 DEG C. a solution of 190 g of cyanuric chloride in acetone is added.

At the same time, approximately 80 g of sodium bicarbonate is added in small portions to maintain the temperature value between 5.0 and 6.5. The reaction ends when no diazotizable a-mino groups can be evidenced anymore. The dye thus obtained is identical to that prepared according to Example 1.

Claims (1)

[Claims] 1 The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A is a fiber-reactive residue, B is an optionally substituted mononuclear or dinuclear aromatic Pc is a residue of a metal-containing or metal-free phthalocyanine;
ar is an optionally substituted mononuclear or dinuclear aromatic or araliphatic hydrocarbon residue (the alkylene chain is bonded to a ▲ mathematical formula, chemical formula, table, etc. group), R_1 is Hydrogen atom, optionally substituted alkyl group (
1 to 6 carbon atoms), phenyl or naphthalkyl groups containing 1 to 3 carbon atoms in the aliphatic chain, phenyl or naphthyl groups (in which case the aromatic nucleus optionally carries further substituents). ), R_2 is a hydrogen atom, an optionally substituted alkyl group (having 1 to 6 carbon atoms)
) or unsubstituted alkyl group (7 to 20 carbon atoms)
, R_3 is a hydrogen atom, an optionally substituted alkyl group (1 to 6 carbon atoms), R_4 is a hydrogen atom, an optionally substituted alkyl group (1 to 6 carbon atoms), or an unsubstituted alkyl group (7 to 18 carbon atoms), R_7
means a hydrogen atom or an optionally substituted alkyl group (1 to 4 carbon atoms), k is 0, 1, 2 or 3, l
represents 0, 1 or 2, m represents 1, 2, 3 or 4, k
, l and m are 3 or 4. ] In producing the water-soluble fiber-reactive green phthalocyanine-azo dye and its alkali, ammonium or alkaline earth salt, the following general formula (II) is used:
▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Pc, ar, R_1, R_2, R_3, k, l
and m have the meanings given above, and the amino group is bonded to the aromatic carbon atom of the residue ar. ) by diazotizing the phthalocyanine amine shown by
In an aqueous medium at pH 3 to 8, the following formula (III) ▲ mathematical formula, chemical formula,
There are tables, etc.
18), R_5 is an optionally substituted alkyl group (
(1 to 6 carbon atoms) or unsubstituted alkyl group (7 to 18 carbon atoms), Z is a hydrogen atom, optionally substituted alkyl group (1 to 10 carbon atoms), optionally substituted means a phenyl group or an alkoxycarbonyl group having 2 to 6 carbon atoms. ] The following formula (IV) was obtained by coupling with the succinic acid derivative shown in
4, R_5, k, l and m have the meanings given above. ) by the action of an alkali, the following general formula (V) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, Pc, ar, R_1, R_2, R_3, R_4
, k, l and m have the meanings given above. ), and convert this compound into an amine represented by the following general formula (VI) ▲ Numerical formula, chemical formula, table, etc. ▼ (wherein, B, R_7 and A have the above-mentioned meanings) Coupled with a diazonium compound or the following general formula (VII) H_2N-B-E
(VII) (wherein, E means a group that can be converted into a group of the formula ▲a mathematical formula, a chemical formula, a table, etc.▼ by a known method), and then the group E is coupled with a diazonium compound of the amine represented by the formula. A method for producing the above-mentioned phthalocyanine-azo dye, which is characterized in that by a known method, the phthalocyanine-azo dye is changed into a group having the formula ▲, which has a mathematical formula, chemical formula, table, etc. 2 In the general formula (II) described in claim 1, Pc is a metal-containing or metal-free phthalocyanine residue, and ar is a mononuclear or dinuclear group optionally substituted with a -SO_3H group. after an aromatic or araliphatic hydrocarbon group (this residue can also contain one C1-4 alkoxy group per nucleus, -SO_2R_6 or even -SO_3
or by one or two identical or different halogen atoms; by the -SO_3H group and additionally by 1 to 3 identical or different carbon atoms
A phenylene group optionally substituted by four alkyl groups, R_1 and R'_1 are independently a hydrogen atom, a methyl group, a carboxymethyl group, a sulfomethyl group, and optionally Cl, Br, OH, or a carbon atom. Alkoxy group having 1 to 6 carbon atoms, alkanoylamino group having 1 to 6 carbon atoms, preferably acetylamino group, benzoylamino group, alkanoyloxy group having 1 to 6 carbon atoms, preferably acetyloxy group, - COOH or -SO_3H
an alkyl group having 2 to 6 carbon atoms, substituted by
phenalkyl- containing 1 to 3 carbon atoms in the aliphatic chain
or naphthoalkyl group, phenyl group or naphthyl group (
Aromatics are Cl, Br, OH, alkyl and/or alkoxy groups having 1 to 6 carbon atoms, alkanoylamino groups having 1 to 6 carbon atoms, -COOH or -S
O_3H), R_
2 and R'_2 are each independently a hydrogen atom, a methyl group, a carboxymethyl group, a sulfomethyl group, optionally Cl, Br, OH, an alkoxy group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms. alkanoylamino group, benzoylamino group, alkanoyloxy group having 1 to 6 carbon atoms, alkyl group having 2 to 6 carbon atoms substituted with -COOH or -SO_3H, or 7 to 6 carbon atoms
20 unsubstituted alkyl groups, R_3 is a hydrogen atom, methyl group, carboxymethyl group, sulfomethyl group, optionally Cl, Br, OH, alkoxy group having 1 to 6 carbon atoms, an alkanoylamino group, a benzoylamino group, an alkanoyloxy group having 1 to 6 carbon atoms, an alkyl group having 2 to 6 carbon atoms substituted with -COOH or -SO_3H, R_4 is a methyl group,
Carboxymethyl group, alkyl group having 2 to 3 carbon atoms, benzyl group or (in this case, aromatic nucleus is substituted once or twice -C
(can be substituted by OOH or -SO_3H), k is 0, 1, 2 or 3, l is 0,
1 or 2, m represents 1, 2, 3 or 4, and the sum of k, l and m is 3 or 4. The method described in Scope No. 1. 3. A process according to claim 1 or 2, which comprises diazotizing a phthalocyanine-based amine of formula (II) in which 3Pc is a cobalt-, copper- or nickel-phthalocyanine residue. 4. The method according to any one of claims 1 to 3, which comprises diazotizing a phthalocyanine amine of formula (II) in which Pc represents a residue of nickel phthalocyanine. 5 ar is an optionally substituted phenylene group or an optionally substituted mono- or a poly-methylene-phenylene group, or an optionally substituted naphthylene group, or an optionally substituted general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, n means an integer from 1 to 3) ) mono- or poly-methylene-naphthylene-
Claim 1 consists of diazotizing a phthalocyanine-based amine of formula (II), which is a group or optionally substituted group represented by the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ or the method described in any one of Section 4. 6 A phthalocyanine-based amine of formula (II) in which ar is an optionally substituted phenylene or naphthylene group or an optionally substituted group represented by the following formula ▲ Numerical formula, chemical formula, table, etc. 6. A method according to any one of claims 1 to 5, which comprises: 7 ar is a phenylene group optionally substituted by one or two carboxyl groups or one or two sulfo groups, or a naphthylene group substituted by one or two sulfo groups, or 2 Claims 1 to 3 are obtained by diazotizing a phthalocyanine-based amine of formula (II), which is a naphthylene group substituted with one sulfo group or a stilbenylene group substituted with two sulfo groups. The method described in any one of Section 6. 8. Any one of claims 1 to 7 which consists of diazotizing a phthalocyanine-based amine of formula (II) in which ar is a group represented by the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ The method described in one. 9 R_1 and R'_1 are each independently a hydrogen atom, optionally OH, an alkoxy group having 1 to 3 carbon atoms, an alkyl group having 2 or 3 carbon atoms substituted with -COOH or -SO_3H 9. The method according to any one of claims 1 to 8, which comprises diazotizing a phthalocyanine amine of formula (II) which is a methyl group, a carboxymethyl group or a sulfomethyl group. 10 R_2 and R'_2 are independently a hydrogen atom, a methyl group, a carboxymethyl group, optionally OH,
Alkoxy group having 1 to 3 carbon atoms, -COOH or -
A patent obtained by diazotizing a phthalocyanine-based amine of formula (II) which is an alkyl group having 2 or 3 carbon atoms substituted with SO_3H or an unsubstituted alkyl group having 1 to 20 carbon atoms. Claims 1 to 9
The method described in one of the sections. 11 R_2 and R'_2 are, independently of each other, a hydrogen atom, a methyl group, a carboxymethyl group, or optionally OH
Claims 1 to 10 are obtained by diazotizing a phthalocyanine amine of formula (II) which is an alkyl group having 2 or 3 carbon atoms substituted by Method. 12 A patent claim consisting of diazotizing a phthalocyanine-based amine of formula (II) in which R_1 and R_2 and R'_1 and R'_2 are each independently a hydrogen atom, a methyl group, or a β-hydroxyethyl group. The method according to any one of items 1 to 11. 13 R_3 is a hydrogen atom, a methyl group, a carboxymethyl group, a sulfomethyl group, optionally Cl, OH, an alkoxy group having 1 or 2 carbon atoms, -COOH or -SO_
13. The method according to claim 1, which comprises diazotizing a phthalocyanine amine of formula (II) which is an ethyl group substituted by 3H. 14 l is 0, k is 2 or 3, m is 1 or 2, and k
14. The method according to any one of claims 1 to 13, which comprises diazotizing a phthalocyanine amine of formula (II) in which the sum of m and m is 4. Claims 1 to 14 consist of diazotizing a phthalocyanine-based amine of formula (II) in which the substituent present in the 15 Pc-residue is present at the 3- or 4-position of the phthalocyanine. The method described in one of the following. Any one of claims 1 to 15, which consists of diazotizing a phthalocyanine-based amine of formula (II) in which the substituent present on the 16 Pc-residue is present at the 3-position of the phthalocyanine. The method described in. 17 A diazotized product of the amine of formula (II) having 2 to 6 carbon atoms in which R'_4 and R_5 are substituted with Cl, Br, OH or an alkoxy group having 1 to 4 carbon atoms. or an unsubstituted alkyl group having 1 to 18 carbon atoms, Z is a hydrogen atom, and optionally an alkoxy group having 1 to 4 carbon atoms or an unsubstituted alkyl group having 2 to 6 carbon atoms.
an alkyl group having 1 to 10 carbon atoms substituted by alkoxycarbonyl groups, optionally Cl, Br,
A patent for coupling with a succinic acid derivative of formula (II) which is a phenyl group substituted by an alkyl or alkoxy group having 1 to 4 carbon atoms or an alkoxycarbonyl group having 2 to 6 carbon atoms. A method according to claim 1. 18 A diazotized product of the amine of formula (II) in formula (III) in which R'_4 is substituted with Cl, OH or an alkoxy group having 1 to 2 carbon atoms or an ethyl group having 1 carbon atom
18. The method according to claim 1 or 17, which comprises coupling with a succinic acid derivative of formula (III) which is 6 unsubstituted alkyl groups. 19 A diazotized product of the amine of formula (II) in formula (III) where R_5 is an ethyl group substituted with Cl, OH or an alkoxy group having 1 to 2 carbon atoms, or an ethyl group having 1 to 2 carbon atoms
19. The method according to claim 1 or 17 or 18, which comprises coupling with a succinic acid derivative of formula (III) which is 18 unsubstituted alkyl groups. 20 A diazotized product of the amine of the formula (II) is coupled with a succinic acid derivative of the formula (III) in which R'_4 and R_5 are the same and are a methyl group or an ethyl group. Claims 1 and 17
The method described in any one of Items 1 to 19. 21 A diazotized product of the amine of formula (II) in formula (III) where Z is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group, a methylphenyl group, or an alkoxycarbonyl group having 2 or 3 carbon atoms. 21. A method according to claim 1, which comprises coupling the succinic acid derivative of formula (III) as a group. 22 Claims 1 and 17 to 17 consist of coupling a diazotized product of the amine of the formula (II) with a succinic acid derivative of the formula (III) in which Z is a methyl group. The method described in any one of Section 21. 23 The pyrazolone compound represented by formula (V) has the following general formula (VI) ▲ Numerical formula, chemical formula, table, etc. a fiber-reactive residue containing an activated double bond, B is a mono- or di-nuclear aromatic or araliphatic hydrocarbon residue optionally substituted by -SO_3H (
This residue can be formed by an alkoxy group with 1 to 4 carbon atoms per nucleus, -SO_2R'_6 or even -SO_3H, or by one or two identical or different halogen atoms, ▲
Numerical formulas, chemical formulas, tables, etc. may be substituted by substituents from the group consisting of and - COOH or by 1 to 3 identical or different alkyl groups having 1 to 4 carbon atoms. ), R_7 is a hydrogen atom, a methyl group, a carboxymethyl group, a sulfomethyl group, optionally Cl, Br, OH, an alkoxy group having 1 to 6 carbon atoms, an alkanoylamino group having 1 to 6 carbon atoms, a benzoylamino group , an alkanoyloxy group having 1 to 6 carbon atoms, -COOH or -S
means an alkyl group having 2 to 4 carbon atoms substituted by O_3H, where R″_1 is a hydrogen atom, a methyl group, a carboxymethyl group,
Sulfomethyl group, optionally Cl, Br, OH, alkoxy group having 1 to 6 carbon atoms, alkanoylamino group having 1 to 6 carbon atoms, preferably acetylamino group, benzoylamino group, 1 to 6 carbon atoms alkanoyloxy groups, preferably acetyloxy groups, alkyl groups of 2 to 6 carbon atoms substituted by -COOH or -SO_3H, phenealkyl- or naphthyl groups containing 1 to 3 carbon atoms in the aliphatic chain Alkyl group, phenyl group or naphthyl group (in which aromatic nucleus is Cl, Br, OH, alkyl group and/or alkoxy group having 1 to 6 carbon atoms, alkanoylamino group having 1 to 6 carbon atoms) ,-C
It may be substituted with OOH or -SO_3H. ), R″_2 is a hydrogen atom, a methyl group, a carboxymethyl group, a sulfomethyl group, optionally Cl, Br,
OH, alkoxy group having 1 to 6 carbon atoms, alkanoylamino group having 1 to 6 carbon atoms, benzoylamino group, alkanoyloxy group having 1 to 6 carbon atoms, -CO
2 carbon atoms substituted by OH or -SO_3H
~6 alkyl group or an unsubstituted alkyl group having 6 to 20 carbon atoms, R'_6 is a methyl group, carboxymethyl group, an alkyl group having 2 or 3 carbon atoms, a benzyl group, or It means a phenyl radical, in which the aromatic nucleus may be substituted once or twice by -COOH or -SO_3H. The method according to claim 1, which comprises coupling a diazonium compound of the amine represented by the following. 24 Formula (VI) to the pyrazolone compound represented by Formula (V)
A residue of an aliphatic carboxylic acid or sulfonic acid containing a substituent that can be easily substituted nucleophilically, or a residue of an α/β-unsaturated aliphatic carboxylic acid or sulfonic acid , or a residue of an aliphatic carboxylic acid or sulfonic acid that readily converts into an α/β-unsaturated aliphatic carboxylic acid or sulfonic acid residue upon removal of a neutral or anionic group. (VI)
24. The method according to claim 1 or 23, which comprises coupling a diazonium compound of an amine. 25 Formula (VI) to the pyrazolone compound represented by formula (V)
Formula (VI) in which A is a residue of a heterocyclic carboxylic acid or sulfonic acid containing a substituent that can be easily substituted nucleophilically
24. The method according to claim 1 or 23, which comprises coupling a diazonium compound of an amine. 26 Formula (VI) to the pyrazolone compound represented by formula (V)
of an amine of formula (VI) in which A is the residue of a 6-membered heterocycle having 2 or 3 nitrogen atoms and containing at least one nucleophilically easily substitutable substituent; Claim 1 consisting of coupling a diazonium compound
or the method described in paragraph 23. 27 Formula (VI) to the pyrazolone compound represented by formula (V)
in which A is easily nucleophilically substitutable and additionally non-labile substituents, including fiber-reactive groups as defined in claims 23-26. do not have)
27. The method according to claim 1, 23, or 26, which comprises coupling a diazonium compound of an amine of formula (VI) which is a residue of a six-membered heterocycle containing 28 Formula (VI) to the pyrazolone compound represented by formula (V)
Claims 1, 23, and 26 in which the fiber-reactive group represented by A is coupled with a diazonium compound of an amine represented by formula (VI), which is a residue of an s-triazine compound. The method described in any one of paragraphs 1 and 27. 29 Formula (VI) to the pyrazolone compound represented by formula (V)
in which A can be easily substituted nucleophilically with a substituent and additionally with the following formula -Het-BR-Het'-A' (wherein Het and Het' are, independently of each other, an oxygen atom or a sulfur atom, preferably optionally substituted -
NH- group, BR is a divalent aliphatic, aromatic or araliphatic residue, and A' is defined for A in any one of claims 23 to 28. means a fiber-reactive group. ) Claims 1 or 23 consist of coupling a diazonium compound of an amine represented by formula (VI) which is a residue of a 6-membered heterocycle containing an unstable group represented by or the method described in paragraph 26. 30 Formula (VI) to the pyrazolone compound represented by formula (V)
where B is an optionally substituted phenylene group or an optionally substituted general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, n means an integer from 1 to 10.) A mono- or poly-methylene-phenylene group, or an optionally substituted naphthylene group, or an optionally substituted general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, n is an integer from 1 to 3. ), or the optionally substituted following formula ▲ There is a mathematical formula, chemical formula, table, etc. A method according to any one of claims 1 or 23 to 29, which comprises coupling a diazonium compound of the amine of formula (VI) as a residue. 31 Formula (VI) to the pyrazolone compound represented by formula (V)
where B is an optionally substituted phenylene or naphthylene group, or an optionally substituted group represented by the following formula: A method according to any one of claims 1 and 23 to 30, which comprises coupling a diazonium compound of the amine of formula (VI). 32 Formula (VI) to the pyrazolone compound represented by formula (V)
in which B is 1 or 2 carboxyl groups or 1
a phenylene group substituted with one or two sulfo groups, a naphthylene group substituted with one or two sulfo groups, or a stilbenylene group substituted with two sulfo groups 32. A method according to claim 1, which comprises coupling a diazonium compound of the amine of formula (VI). 33 Formula (VI) to the pyrazolone compound represented by formula (V)
In this case, B is a residue represented by the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ A method according to any one of claims 1 and 23 to 32. 34 The pyrazolone compound represented by formula (V) has the following general formula (VII) H_2N-B-E (VII) (wherein, E means a group represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼), In this case, R_7 has the meaning described in claim 1, and Acyl is an aliphatic acyl group having 1 to 3 carbon atoms, preferably 2, or an optionally substituted benzoyl group, preferably (Means the benzoyl group itself.) Coupling a diazonium compound of the amine shown by ( In the formula, B, Pc, ar, R_1, R_2, R_3, R
_4, R_7, k, l and m have the meanings given in claim 1. 2. A method according to claim 1, which comprises acylating a dye of formula X-A in a known manner with an acylating agent of formula X-A. 35 Formula (VII) is added to the pyrazolone compound represented by formula (V).
A diazonium compound of the amine of the formula (VII) in which E is a nitro group is coupled, and the obtained phthalocyanine azo dye is reduced by a known method to form the following formula (Ib) ▲ Numerical formula, chemical formula, There are tables, etc. ▼ (In the formula, B, Pc, ar, R_1, R_2, R_3, R
_4, k, l, and m have the meanings given in claim 1. 2. A method according to claim 1, which comprises acylating a dye of formula X-A in a known manner with an acylating agent of formula X-A.