JP2002514676A - Water-soluble monoazo dye compound, its production method and use as dye - Google Patents

Abstract

(57) Abstract: A novel monoazo mixture, a method for producing the same, and a method for dyeing a hydroxy- and / or carboxamide-containing fiber material using the same are provided. SOLUTION: A monoazo compound represented by the following general formula (1) (wherein, X is a fiber-reactive group or the like, D is a substituted phenylene group or the like, G is 2-5 having a C number of 5-8. W, s, R ⁰ , r, alk, t, M, m and R, such as a divalent cycloalkyl or bicycloalkyl radical, are each defined in claim 1):

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a water-soluble monoazo dye compound, a method for producing the same, and use as a dye.

US Pat. No. 3,649,615 and European Patent Application No. 0090114 disclose fiber-reactive azo compounds containing a β-carboxyethyl-carbonylamino group or a carboxyacylamino group in the coupling component of sulfonaphthol. ing.

When these azo compounds are used as dyes, for example, they dye cotton in red shades, but are not satisfactory in some properties and, in particular, in some applications lightfast. Sex is not satisfied.

The present invention provides a monoazo compound represented by the following general formula (1). This monoazo compound has improved properties as compared with known dyes, and in particular, a portion that is not fixed to a dyed material having excellent light fastness can be washed off well, The stability in padding liquid is also very good.

[0005]

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In the above general formula (1), M is hydrogen or another metal which forms a colorless salt such as an alkali metal such as sodium, potassium or lithium, or an equivalent of an alkaline earth metal such as calcium. M is 0 or 1 (when m is 0, M is hydrogen); X is a fiber-reactive group or a group containing a fiber-reactive group; W is methylene, ethylene or Alkylene having 1 to 4 carbon atoms such as n-propylene, or alkyl having 1 to 4 carbon atoms such as sulfo, carboxyl, methyl or ethyl; alkoxy having 1 to 4 carbon atoms such as methoxy or ethoxy; and chlorine. Phenylene which may be substituted by one or two selected substituents, or 3-6 carbon atoms interrupted by -O- or -NH- Be alkylene; R ⁰ is hydrogen or alkyl of 1 to 4 carbon atoms, such as methyl or ethyl, or sulfo, methyl, ethyl, methoxy, optionally substitution by ethoxy or chlorine phenyl, preferably hydrogen Alk is an alkylene having 1 to 4 carbon atoms such as methylene or ethylene; r is 0 or 1; s is 0 or 1; t is 0 or 1 D is selected from the group consisting of sulfo, carboxyl, alkyl having 1 to 4 carbons (such as ethyl, especially methyl), alkoxy having 1 to 4 carbons (such as ethoxy, particularly methoxy) and chlorine. R is water, which is phenylene optionally substituted by one or two substituents, or naphthylene optionally substituted by one or two sulfo groups; G is a divalent radical of a cycloalkyl having 5 to 8 carbons or a bivalent alkyl of a bicycloalkyl having 5 to 8 carbons, such as methyl; The free radical may contain an olefinic double bond and / or may be interrupted by a hetero group (such as -O- or -NH-), and may further include a halogen (such as chlorine or bromine), and a hydroxy or carbon. May be substituted with one or two substituents selected from the group of alkyl having 1 to 4 carbon atoms which may be substituted by alkoxy having 1 to 4 carbon atoms (such as methoxy and ethoxy); for, -SO ₃ M is 8-hydroxy - preferably in 3 or position 4 of the naphthalene radical (particularly preferably 3 positions) are arranged, in this case, 8-hydroxy - 1 naphthalene radical Located are bonded preferably -N (R) -CO-G- COOM group, also, -SO ₃ M is 8-hydroxy - when placed in 4 position of the naphthalene radical is -N (R) -CO-G-COOM group is located at position 3 of the 8-hydroxy-naphthalene free radical, and when m is 0, -N (R) -CO-G-COOM group Is preferably located at position 2 or 3 of the 8-hydroxy-naphthalene radical; furthermore, when X is a heterocyclic radical, s is 0 and r is 1.

In the above general formula (1) and a number of general formulas described below, individual elements (symbols) in the formulas may be different from each other even if the designations in the formulas are different or the same. Can have the same or different meanings as long as they fall within the definition of.

[0008] "Sulfo", "thiosulfato", "carboxyl", "phosphato" and "
The term "sulfato" includes not only the acid form, but also the salt form of each group. Accordingly, sulfo groups are groups of the general formula -SO ₃ M, thiosulfato groups,
A group represented by the formula -S-SO ₃ M, a carboxyl group of the general formula -COO
A group represented by M, phosphato groups are groups of the general formula -OPO ₃ M _2, a sulfato group is a group represented by the general formula -OSO ₃ M, M in these respective Is as defined above.

Examples of G are the divalent radicals of cyclopentane, cyclohexane, cyclohexene, cycloheptane and cycloheptene, which are substituted or unsubstituted with 1 to 4 carbon atoms, as specified above for G. May be substituted with alkyl, halogen or alkoxy having 1 to 4 carbon atoms. In these cases, such alicyclic radicals, particularly cyclohexane and cyclohexene radicals, form a bicyclic group by an alkylene bridge such as methylene or ethylene, an oxygen bridge, and an aliphatic bridge containing NH—. May be. These free radicals may be in either cis or trans form.

Examples of G include the following general formulas (2a), (2b), (2c), (2d) or (2e)
).

[0011]

Embedded image In the above general formulas (2a) to (2e), R ¹ is hydrogen, methyl or ethyl, and R ² is hydrogen, methyl, ethyl or chlorine.

The G radicals are, in particular, 1,2-cyclohexylene, 3-methyl or 4-methyl-1,2-cyclohexylene, 1,2-cyclohex-4-enylene, 7-
Oxabicyclo (2,2,1) hept-5-ene-2,3-ylene, endo-norbol-5-ene-2,3-ylene, 1,4-dimethylcyclohex-4-ene-1,2- Irene, 3-methylcyclohex-4-ene-1,2-ylene, methyl-5-norbornene-2,3-ylene or endo-bicyclo (2,2,2) oct-5-ene-2,3- I'm Iren. Each is in cis or trans form. Preferably, G is 1,2-cyclohexylene or 1,2-cyclohex-4
-Enylene.

The fiber-reactive group X or the group X having a fiber-reactive group is, for example, an s-triazine or pyrimidine group substituted with halogen, wherein the halogen substituent is fluorine, chlorine or bromine. , Fluorine or chlorine is preferred. The halogen-substituted s-triazine group may additionally have a substituted or unsubstituted amino group, and in this case, the substituent of the amino group may be phenyl, naphthyl, alkyl having 1 to 4 carbon atoms. It is. These substituents also contain fiber reactive groups of the vinylsulfone series or are, for example, 2,3-dichloro-1,4-phenazine-6-carbonyl free radicals. However, in this case, X is one of these heteroalicyclic radicals.
And s is 0 and r is 1.

Further examples of X include vinylsulfone-based fiber-reactive groups such as, for example, vinylsulfonyl or ethylsulfonyl substituted in the β-position with a substituent which can be eliminated with an alkali.

The fiber-reactive group is, for example, represented by the following general formula (3a), (3b), (3c), (3c)
3d), (3e), (3f), (3g), (3h), or (3j).

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In the above general formulas (3a) to (3j), Y is a substituent which can be eliminated with vinyl or an alkali (for example, chlorine, bromine, sulfato, thiosulfato, phosphato, C 2-5) Ethyl substituted by alkanoyloxy (such as acetyloxy, benzoyloxy, sulfobenzoyloxy or p-toluylsulfonyloxy), especially vinyl, β-chloroethyl or β-sulfatoethyl; Hal is Each has the same or different meaning and is chlorine, bromine or fluorine, particularly preferably chlorine or fluorine; R ^α is hydrogen or Hal as defined above; R ³ is hydrogen or carbon An alkyl having 1 to 4 carbon atoms, wherein the alkyl is hydroxy, alkanoyloxy having 2 to 5 carbon atoms (acetoyl); Carboxymethyl, etc.), sulfatoethyl, phosphato, carboxyl, may be substituted by alkoxy of sulfo or carbonitrides total number 1-4; R ⁴ is hydrogen or alkyl of 1 to 4 carbon atoms, said alkyl, It may be substituted by hydroxy, alkanoyloxy having 2 to 5 carbon atoms (acetooxy, etc.), sulfato, phosphato, carboxyl, sulfo or alkoxy having 1 to 4 carbon atoms, or unsubstituted, methylmonosubstituted or disubstituted From cyclohexyl having 5 to 8 carbon atoms, sulfo, carboxyl, chlorine, alkyl having 1 to 4 carbons (such as ethyl, especially methyl), and alkoxy having 1 to 4 carbons (such as ethoxy, especially methoxy). Phenyl or sulfo optionally substituted with one or two substituents selected from the group consisting of A good naphthyl be, also, R ³ and R ⁴ taken together, the number of carbon atoms which is interrupted or form an alkylene of 5-8 carbon atoms, or -O- or -NH- with R ⁵ is hydrogen or C 1 -C 4 alkyl (methyl), which forms an alkylene of 4 to 6 or a saturated heterocyclic free radical (such as piperidino, morpholino or piperazino) together with nitrogen; Or phenyl optionally substituted with chlorine, sulfo, carboxyl, methyl, ethyl, methoxy or ethoxy; and R ⁶ is represented by the following general formula (4a) or (4b). be that _{group; Y-SO 2 -ALK- Y-} SO 2 -AR- (4a) (4b)

In the above formulas (4a) and (4b), Y is the same as defined above, and ALK is an alkylene having 1 to 4 carbon atoms (methylene, especially ethylene or n-propylene, etc.); Is one or two selected from the group consisting of sulfo, carboxyl, alkoxy having 1 to 4 carbon atoms (ethoxy, especially methoxy, etc.), alkyl having 1 to 4 carbon atoms (ethyl, especially methyl, etc.) and chlorine. R ⁷ is hydrogen or alkyl having 1 to 4 carbons (such as methyl); phenylene which may be substituted by a substituent, or naphthylene which may be substituted by one or two sulfo groups; but preferably rather is hydrogen; R ⁸ have the following general formula (4c) or a group represented by _{(4d); Y-SO 2} -Alk-E-Alk- (4c) Y- _{O 2 - (Alk) p -E-} (Alk) q - (4d)

In the above formulas (4c) and (4d), Y is the same as defined above, Alk is an alkylene having 2 to 4 carbon atoms (preferably ethylene), and E is —O— or —NH—, and p is 0 or 1, provided that (p + q) is 1.

The general formula X- (W) _s- (NR ⁰ ) _r- (alk) _t -included in the general formula (1)
Preferred groups represented by D- are, particularly, the following general formulas (5a), (5b), and (5c)
Or a group represented by (5d).

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In the above formulas (5a) to (5d), Y, M, R ⁰ and m are each as defined above; R ⁹ is hydrogen, sulfo, alkyl having 1 to 4 carbon atoms (ethyl , especially methyl), alkoxy of 1 to 4 carbon atoms (ethoxy, especially methoxy) or halogen (such as chlorine); R ¹⁰ is hydrogen, alkyl of 1 to 4 carbon atoms (ethyl, especially methyl) , or alkoxy having 1 to 4 carbon atoms (ethoxy, especially methoxy) be; R ¹¹ is hydrogen, sulfo, alkyl (ethyl, especially methyl) having 1 to 4 carbon atoms; or an alkoxy of 1 to 4 carbon atoms (Ethoxy, especially methoxy), and V is the above general formula, (3a), (3b), (3c), (3d), (3e), (3f), (3g), or (3h) N is 1, 2 or 3;

Examples of the groups represented by the general formulas (5a) and (5b) are as follows: 4- (β
-Sulfato-ethylsulfonyl) phenyl, 4-vinylsulfonylphenyl,
3- (β-sulfatoethylsulfonyl) -phenyl, 2- (β-sulfatoethylsulfonyl) phenyl, 2-methoxy-5- (β-sulfato-ethylsulfonyl) phenyl, 2-methoxy-5vinylsulfonylphenyl, 2-sulfo-
4- (β-sulfato-ethylsulfonyl) phenyl, 2-methoxy-5-methyl-4- (β-sulfatoethylsulfonyl) phenyl, 2,5-dimethoxy-
4- (β-sulfatoethylsulfonyl) phenyl, 5- (β-sulfatoethylsulfonyl) -naphth-2-yl, 6- (β-sulfatoethylsulfonyl)
Naphth-2-yl, 8- (β-sulfatoethyl-sulfonyl) naphth-2-yl, 1-sulfo-8- (β-sulfatoethylsulfonyl) naphth-2-yl,
4- (β-chloroethylsulfonyl) phenyl, 2-methoxy-4- (β-sulfatoethylsulfonyl) phenyl, 4-methoxy-3- (β-sulfatoethyl-sulfonyl) phenyl, 2-carboxy-4- (Β-sulfatoethylsulfonyl) phenyl, 4- (β-thiosulfato-ethylsulfonyl) phenyl,
4- (β-phosphatoethylsulfonyl) phenyl and 4- (β-acetyloxyethylsulfonyl) phenyl.

Examples of the heterocyclic fiber-reactive groups represented by the general formulas (3a) to (3h) are as follows: 2,4-difluoro-5-chloropyrimidin-6-yl, 4-
Difluoro-pyrimidin-6-yl, 4,6-difluoro-5-chloropyrimidin-6-yl, 4,6-difluorochloropyrimidin-6-yl and the general formula (3
f), (a group represented by 3g) and (3h), wherein R ³ in these formulas, hydrogen, methyl, ethyl, β- hydroxyethyl or β- sulfoethyl, R ⁴
Is hydrogen, methyl, ethyl, β-hydroxyethyl, cyclohexyl, phenyl, 2-sulfophenyl, 3-sulfophenyl, 4-sulfophenyl, 2-carboxyphenyl, 1-naphthyl, 1-sulfo-2-naphthyl, or 1,5-disulfo-2-naphthyl or R ³ R ⁴ N— is morpholino, R ⁵ is hydrogen, R ⁶ is 4- (β-sulfatoethylsulfonyl) phenyl, 3- (β-sulfo Fatoethylsulfonyl) phenyl, 2-methoxy-5- (β-sulfatoethylsulfonyl) -phenyl, 4-vinylsulfonylphenyl, 3-vinylsulfonylphenyl, 2-methoxy-5- (β-sulfatoethylsulfonyl) phenyl , 2,
5-dimethoxy-4- (β-sulfatoethylsulfonyl) -phenyl, 2-methyl-4- (β-sulfatoethylsulfonyl) phenyl, 2-methoxy-5
Methyl-4- (β-sulfatoethylsulfonyl) phenyl, β- (β′-sulfatoethylsulfonyl) ethyl, or γ- (β′-sulfatoethylsulfonyl) propyl, R ⁷ is hydrogen, And R ⁸ is β-[(β ′ (β ″ -chloroethylsulfonyl) ethoxy) ethyl.

The following general formula (6) included in the general formula (5c):

Embedded image Examples of the free radical represented by are: 1,4-phenylene, 1,3-phenylene, 2-sulfo-1,4-phenylene, 4-sulfo-1,3-phenylene,
4,6-disulfo-1,3-phenylene, 2,5-disulfo-1,4-phenylene, 2-methyl-1,4-phenylene, 4-methyl-1,3-phenylene, 4-
Sulfo-6-methyl-1,3-phenylene and 4-sulfo-6-methoxy-1,
3-phenylene.

The following general formula (7) included in the general formula (5d):

Embedded image Examples of the free radical represented by are: 3- (N-methylamino) methyl-
5-sulfo-2,6-dimethylphenyl, 4- (N-methylamino) methyl-3
-Sulfophenyl, 2-aminomethyl-6-sulfo-4-methylphenyl and 5
-Aminomethyl-1-sulfonaphth-2-yl.

Among the monoazo compounds represented by the general formula (1) of the present invention, the following general formula (
Those represented by 1a) and (1a) are particularly emphasized.

Embedded image In the above general formulas (1A) and (1B), M is as defined above; G has the meaning described above, and particularly preferably is 1,2-cyclohexylene or 1,2-cyclohexylene. In formula (1B), the —NH—CO—G-COOM group is bonded to the 2- or 3-position of the 8-hydroxynaphthalene free group; X ⁰ -D ¹ -Is a free radical defined by the above formula (5a), Y is preferably vinyl or β-sulfatoethyl, and R ⁹ and R ¹⁰ are preferably both hydrogen. Or R ⁹ is preferably hydrogen, R ¹⁰ is preferably methyl, ethyl, methoxy or ethoxy, and Y—SO ₂ — is bound meta or para to the free bond of the benzene nucleus; General formula (5b Wherein Y is preferably vinyl or β-sulfatoethyl, M is as defined above, and m is 1, or a group of the above general formula (5c) or ( 5d) wherein R ⁹ is preferably hydrogen, R ¹¹ is preferably hydrogen or sulfo, and V is any of the general formulas (3a), (3b), (3 3g) or (3h), and R ⁰ is preferably hydrogen, methyl or ethyl.

The monoazo compound of the present invention represented by the above general formula (1) can be produced by various methods. For example, aminonaphtholsulfonic acid of the following general formula (9) (where M, m and R in the formula are , Defined above) and

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An anhydride represented by the following general formula (10) (G in the formula is the same as defined above):

Embedded image The compound of the following general formula (11) produced by the reaction in an aqueous suspension, an organic solvent inert to the reaction, or a mixture of the organic solvent and water (wherein M, m, R
And G are the same as defined above. ),

[0028]

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Manufactured by a conventional method represented by the following general formula (12) (where X, W, R ⁰ , alk, D, r, s and t have the same definitions as above). It is produced by coupling with a diazonium salt compound of an amino compound.

Embedded image When producing the monoazo compound of the present invention, wherein X is a heteroalicyclic fiber-reactive group, first, the following general formula (13) (wherein D and R ^{0 in} the formula are , The same as the above definition.) Is converted to H—N (R ⁰ ) —D—NH ₂ (13)

The monoazo compound represented by the following general formula (14) (where each symbol is the same as defined above), which is obtained by coupling with the compound of the above general formula (11) and then formed, ,

Embedded image Reacting with the general formula Hal-X (where Hal is the same as defined above, and X is a free radical of the general formulas (3a) to (3a)), or the general formula (1) Wherein X is a free radical of the general formulas (3a) to (3a), the compound of the above general formula (14) is converted to 2,4,6
-Trihalogeno-1,3,5-triazine (for example, 2,4,6-trifluoro-1,3,5-triazine (cyanuric fluoride) or 2,4,6-trichloro-1,3,5-triazine (Cyanuric acid chloride) and reacting the resulting dihalotriazinylaminoazo compound with a compound of the general formula R ³ R ⁴ NH, R ⁵ R ⁶ NH or R ⁷ R ⁸ NH (where R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same as defined above.) Reaction of the above-mentioned halo-pyrimidine or halo-triazine with an amino compound or aminoazo compound, respectively. Is carried out in an aqueous solution or suspension, as described above, optionally in the presence of an inert organic solvent, which comprises the aminonaphthol of the general formula (9) and the general formula (9) 1 It can also be used in the reaction of 0) with anhydrides, examples of which include dimethylsulfoxide, dimethylformamide and N-methylpyrrolidone.

The reaction between the aminonaphtholsulfonic acid of the general formula (9) and the anhydride of the general formula (10) is preferably carried out as follows. That is, a fine granular or powdery anhydride is added to an aqueous solution of aminonaphtholsulfonic acid while keeping the pH at 2 to 8, preferably 4 to 7, and the temperature is 0 to 30 ° C, preferably 0 to 30 ° C. ~ 25 ° C
The reaction is carried out. The pH is usually adjusted and maintained using alkaline compounds, such as aqueous sodium carbonate, sodium bicarbonate or sodium hydroxide, or the corresponding lithium compounds.

The coupling reaction between the compound of the general formula (11) and the diazonium compound of the amine of the general formula (12) or (13) is carried out by a conventional method in an aqueous solution, for example,
The temperature is from 0 to 25C, preferably from 5 to 20C, and the pH is from 3 to 8, preferably from 4 to 6.
5 is performed. Similarly, the diazotization of the amino compound is carried out in an aqueous solution by a generally used method. For example, using sodium nitrite in a strongly acidic medium such as hydrochloric acid or sulfuric acid at a temperature of -5 ° C to + 20 ° C and a pH of less than 3, preferably less than 2.5.

The starting compound used for producing the compound of the general formula (1) of the present invention is produced by a generally known method or a method similar to these methods. For example,
In the general formula (12), the amino compound wherein X is a heterocyclic free radical is represented by the general formula (13)
) And a compound of the general formula Hal-X as defined above, in an aqueous solution or suspension, optionally in the presence of an inert organic solvent, at a temperature of from 0 to 70 ° C, It is obtained by reacting at a pH of 3-8. These reaction conditions depend on the reactivity of the starting compound, particularly the reactivity of the halogen-substituted heterocyclic compound. These reactions are also well known to those skilled in the art,
Various modifications can be made by well-known means to achieve satisfactory production.

The reaction of the amino compound having the general formula R ³ R ⁴ NH, R ⁵ R ⁶ NH and R ⁷ R ⁸ NH with the above-mentioned dihalo-s-triazylaminoazo compound is carried out by the above-described amine structure and base. Generally, the reaction is carried out at a temperature of 10 to 60 ° C. and a pH of 3 to 9, although it largely depends on the nature. The modifiers and reaction conditions for these reactions are also well known to those skilled in the art from the literature and their technical knowledge.

The starting compounds having the general formula (9) are exemplified below: 1-amino-8-naphthol-3,6-disulfonic acid, 1-amino-8-naphthol-4,6-disulfonic acid, 3-amino-8-naphthol-6-sulfonic acid, 3-methylamino-
8-naphthol-6-sulfonic acid, 2-amino-8-naphthol-6-sulfonic acid, 3-amino-8-naphthol-4,6-disulfonic acid, 1-amino-8-naphthol-6-sulfonic acid, 1-amino-8-naphthol-4-sulfonic acid, 3
-Amino-8-naphthol-4-sulfonic acid and 2-amino-8-naphthol-
3,6-disulfonic acid, in particular, 3-amino-8-naphthol-6-sulfonic acid, 3-methylamino-8-naphthol-6-sulfonic acid, 2-amino-8
-Naphthol-6-sulfonic acid, preferably 1-amino-8-naphthol-3,6-disulfonic acid, 3-amino-8-naphthol-6-sulfonic acid, 3
-Methylamino-8-naphthol-6-sulfonic acid and 2-amino-8-naphthol-6-sulfonic acid.

The starting compounds having the general formula (10) are exemplified below: ie, trans- and cis-cyclohexane-1,2-dicarboxylic anhydride, trans- and cis-4-cyclohexene-1,2. -Dicarboxylic anhydride, trans- and cis-5-norbonene-endo-2,3-dicarboxylic anhydride, trans- and cis-exo-7-oxabicyclo (2.2.1) hept-5-ene- 2,3-dicarboxylic anhydride, trans- and cis-1,4-dimethylcyclohex-4-
Ene-1,2-dicarboxylic anhydride, trans- and cis-3-methylcyclohex-4-ene-1,2-dicarboxylic anhydride, trans- and cis-methyl-
5-norbonene-2,3-dicarboxylic anhydride and trans- and cis-endo-bicyclo (2.2.2) oct-5-ene-2,3-dicarboxylic anhydride.

Having a vinyl sulfone series fiber-reactive group, and in the general formula (12), X is represented by a general formula Y—SO ₂ — group (Y is the same as defined above); preferably examples of amines useful diazo component corresponding to the amine of the general formula Y-SO ₂ -D-NH ₂ is illustrated below: 4- (beta-sulfatoethylsulfonyl) aniline, 4-vinylsulfonyl Aniline, 3- (β-sulfatoethylsulfonyl)
Aniline, 2- (β-sulfatoethyl-sulfonyl) aniline, 2-methoxy-5- (β-sulfatoethylsulfonyl) aniline, 2-methoxy-5-vinylsulfonylaniline, 2-sulfo-4- (β- Sulfatoethylsulfonyl)
Aniline, 2-methoxy-5-methyl-4- (β-sulfatoethylsulfonyl) aniline, 2,5-dimethoxy-4- (β-sulfatoethyl-sulfonyl)
Aniline, 5- (β-sulfatoethylsulfonyl) -2-aminonaphthalene,
6- (β-sulfatoethylsulfonyl) -2-aminonaphthalene, 8- (β-
Sulfatoethylsulfonyl) -2-aminonaphthalene, 1-sulfo-6- (β
-Sulfatoethylsulfonyl) -2-aminonaphthalene, 6-sulfo-8- (
β-sulfatoethylsulfonyl) -2-aminonaphthalene, 4- (β-chloroethyl-sulfonyl) aniline, 2-methoxy-4- (β-sulfatoethylsulfonyl) aniline, 4- (β-sulfatoethylsulfonyl) -N-ethylaniline, 4- (β-sulfatoethylsulfonyl) benzylaniline, 4-methoxy-3- (β-sulfatoethylsulfonyl) aniline, 2-carboxy-4
-(Β-sulfatoethyl-sulfonyl) aniline, 4- (β-thiosulfatoethylsulfonyl) aniline, 4- (β-phosphato-ethylsulfonyl) aniline and 4- (β-acetoxyethylsulfonyl) aniline.

The starting compound having the general formula (13) is exemplified below. 1,4-diaminobenzene, 1,3-diaminobenzene, 2-sulfo-1,4-diaminobenzene, 4-sulfo-1,3-diaminobenzene, 4,6-disulfo-1,3-diaminobenzene, , 5-Disulfo-1,4-diaminobenzene, 2-methyl-1,
4-diaminobenzene, 4-methyl-1,3-diaminobenzene, 4-sulfo-
6-methyl-1,3-diaminobenzene, 4-sulfo-6-methoxy-1,3-
Diaminobenzene, 3-sulfo-2,6-dimethyl-5-[(N-methylamino) methyl] aniline, 2-sulfo-4-methyl-6-aminoethylaniline, 3
-Sulfo-4-[(N-methylamino) methyl] aniline and 1-sulfo-5-
Aminomethyl-2-amino-naphthalene.

Examples of the starting compounds represented by the general formulas (3a) to (3d) are 2,4,6-difluoro-5-chloropyrimidine and 2,4,6-trifluoropyrimidine.

When the monoazo compound of the general formula (1) according to the present invention is produced in an aqueous solution, the separation and isolation from the aqueous solution are carried out by a generally known method for a water-soluble compound. For example, the reaction is performed by a method of precipitating the reaction medium using an electrolyte such as sodium chloride or potassium chloride, or evaporating the reaction solution itself by spray drying or the like. When the evaporation method is selected as the means for isolation, it is often preferable to remove the sulfate in the solution as calcium sulfate and collect it by filtration.

The monoazo compound of the general formula (1) according to the present invention (hereinafter referred to as compound (1)) has fiber reactivity and very useful dyeing properties. Accordingly, this compound (1) can be used for dyeing (including printing) hydroxy- and / or carboxamide-containing materials. For this reason, the solution obtained in the production of compound (1) can be directly used for dyeing as a liquid preparation. In this case, the solution is optionally added with a buffer substance in advance and concentrated.

The present invention provides the use of compounds (1) for dyeing (including printing) hydroxy- and / or carboxamide-containing materials, and more particularly a process for applying these materials. These materials are preferably in the form of fibrous materials, in particular,
Used in the form of textile fibers such as yarns, packages, fabrics, etc. The process for that is
It can be performed in the same manner as a known procedure.

The hydroxy group-containing material is a cellulose fiber material or a regenerated product thereof and a natural or synthetic material such as polyvinyl alcohol. Cotton is preferred as the cellulosic fiber material, but other vegetable fibers such as flax fiber, hemp fiber, jute fiber, and ramie fiber can also be used. Examples of regenerated cellulose fibers are staple viscose and filament viscose.

Carboxamide-containing materials are, for example, synthetic and natural polyamides and polyurethanes, especially in the form of fibers, in particular wool and other animal hair, silk, leather, nylon 66, nylon 6 , Nylon 11 and nylon 4.

The above fiber materials can also be processed and dyed as blends with each other,
Fiber materials having various chemical properties such as polyester can be included. Examples of these include a blend fabric of cellulose fibers and polyester fibers, and a blend fabric of cellulose fibers and polyamide fibers.

When following the procedure of the present invention, compound (1) can fix the above-mentioned materials, in particular the known procedures for water-soluble fiber-reactive dyes, on fiber materials, by applying them. . For example, the compound (1) is applied to a substrate in a dissolved form or mixed in the substrate, and then fixed in the substrate or the substrate by the action of heat, the action of an alkali, or both. . Such methods of dyeing and fixing are widely described in the literature (eg, EP-A-0181585).

Thus, the compound (1) is suitable not only for the exhaust dyeing method but also for the dyeing by the pad dyeing method. By such a method, the fiber material is converted into the compound (1)
), Optionally with an aqueous solution containing an electrolyte salt, resulting in the compound (1)
Is fixed to the fiber material as described above. Compound (1) is particularly useful in cold pad-batch processes, where the dye is a pad-mangle (Pad-
on the manure, together with the alkali, and then fixed by holding at room temperature for several hours. The dyeings and prints obtained after fixing can be sufficiently washed with cold and hot water. At this time, if necessary, washing can be carried out in the presence of an agent having a function of dispersing the unfixed dye and promoting diffusion.

Compound (1) is distinguished by high reactivity, excellent anchoring performance and very good build-up performance. Thus, this compound allows the use of the exhaustion method at low temperatures and requires only very short vapor times in the pad-steam method. The degree of sticking is high, and the unsticked parts can be easily washed away,
The difference between the degree of exhaustion and the degree of fixation is very small. This is because the loss due to cleaning is very small. In addition, the compound (1) is particularly useful when applied on a cellulose fiber material (such as cotton) by a fiber printing method, as well as a carboxamide fiber material (such as wool, silk, or a blend fabric containing wool or silk). It is also useful for textile printing. Further, the compound (1) is extremely useful even when applied to discharge printing and pre-dyeing.

The dyeings and prints obtained using the compounds (1) have a high color strength (especially on cellulose fibrous materials), a high fiber-dye binding stability in the acidic and alkaline regions, Good lightfastness, including very good wetlightfastness, and generally good wetfastness (eg, washing, water, seawater, cross-dying)
It has good resistance to sweat, as well as good resistance to pleating, hot pressing and clocking.

[0050]

【Example】

The following examples are used to illustrate the invention. “Parts” and “percents” are by weight unless otherwise indicated. The relationship between "parts by weight" and "parts by volume" corresponds to the relationship between kilograms and liters.

The compounds represented by the structural formulas in the following examples are described in the form of a free acid, but are generally in the form of an alkali metal salt (such as a lithium, sodium or potassium salt). It is manufactured and isolated and used for staining in salt form. Similarly, in the following examples (especially the examples in the table), the starting compounds and components described in the form of the free acid are used for the production in the described form or a salt thereof (preferably an alkali metal salt). Is done.

The maximum absorption reported in the visible region (λ max) for the compounds of the invention is that measured for aqueous solutions of their alkali metal salts. In the example of the table,
λmax is reported as the wavelength (nm) in parentheses adjacent to the hue.

Example 1 3-amino-6-sulfo-8-naphthol 239 contained in 1500 parts of water
Part of the solution having a pH of 7 at 15 to 20 ° C. with cis-cyclohex-4-ene-1,2.
Mixed with 170 parts of dicarboxylic anhydride and the reaction batch is adjusted to pH 6, temperature 0-5.
C. for about 5 hours. In contrast, 6-sulfo-8- (
A diazonium salt solution of 410 parts of (β-sulfatoethylsulfonyl) -2-amino-naphthalene was added, and a coupling reaction was performed at pH 5 to 6 and at about 15 ° C.

The novel monoazo compounds of the following formula (described in the form of the free acid) were isolated as alkali metal salts by salting out with sodium chloride or by spray drying according to conventional methods.

[0055]

Embedded image This compound has very good fiber-reactive dyeing properties and can be used to dye the above-mentioned fiber materials (eg cotton) by dyeing and printing methods commonly used in the art.
Dyes in brilliant orange shades with good fastness, in particular the fastness to light and to washing is emphasized.

Example 2 A solution of 319 parts of 1-amino-3,6-disulfo-8-naphthol at a pH of 6 to 7 contained in 4000 parts of ice water was added to cis-cyclohex-4-ene-1,2. -The mixture was mixed with 180 parts of dicarboxylic anhydride and reacted at pH 6 at a temperature of 0 to 5 ° C for about 5 hours. On the other hand, a diazonium salt solution of 1-sulfo-6- (β-sulfatoethylsulfonyl) -2-amino-naphthalene 410 produced by a conventional method was added, and the temperature was about 15 ° C. and the pH was 5.5 to 6. The coupling reaction was performed at 0.5.

The novel monoazo compounds of the following formula (described in the form of the free acid) were isolated as alkali metal salts by salting out with sodium chloride or by spray drying according to conventional methods.

[0058]

Embedded image This compound dyes the fiber materials described above (for example cotton) in a brilliant red shade with good fastness, in particular the light and wash fastness is emphasized.

Example 3 A solution of 239 parts of lithium salt of 2-amino-6-sulfo-8-naphthol contained in 2,000 parts of water at pH 7 was heated at 15 to 20 ° C. with cis-cyclohex-4-.
It was mixed with 175 parts of ene-1,2-dicarboxylic anhydride. The reaction batch is additionally stirred at 15-20 ° C. for about 3 hours, during which time p
Held at H6. This was then mixed with a suspension of 281 parts of 4- (β-sulfatoethylsulfonyl) aniline prepared in a conventional manner, in diazonium hydrochloride.
By performing the coupling reaction at a pH of 4 to 5 and a temperature of 5 to 10 ° C, the following formula (
The novel azo compound (described in the form of the free acid) was isolated by spray drying at pH 5.5.

[0060]

Embedded image The compounds have very good fiber-reactive dye properties, for example, cotton can be made with good fastness properties (for example, excellent lightfastness) by dyeing and printing methods customary in the field of fiber-reactive dyestuffs. Dyeing) in a deep orange shade with the same color.

Example 4 A neutral solution of 319 parts of 1-amino-3,6-disulfo-8-naphthol contained in 4000 parts of ice water was treated with cis-cyclohexane-1,2-dicarboxylic acid. It was mixed with 180 parts of anhydride. The batch is then transferred to pH 6, temperature 0
The mixture was further stirred at 5 ° C. for about 5 hours.

According to another batch, a neutral solution of 252 parts of 1-sulfo-5-methylamino-2-aminonaphthalene and 71 parts of sodium nitrite contained in 2500 parts of water at 5 ° C. was mixed with 2000 parts of ice and To a mixture with 300 parts by volume of a concentrated hydrochloric acid aqueous solution, the mixture was gradually and continuously added with sufficient stirring. Stirring was continued for 1 hour and excess nitrite was removed in the usual manner using amidosulfonic acid. Then, the suspension of the diazonium salt was added to the initially prepared coupling component, and the coupling reaction was carried out at pH 7 at a temperature of about 20 ° C. for about 1 hour. Then batch 40
C. and adjusted to pH8. Then, while maintaining the pH at 8 and the temperature at about 40 ° C., 187 parts of 2,4,6-trifluoro-5-chloropyridimine was continuously added under sufficient stirring.

After a reaction time of about 1 hour, the solution was adjusted to pH 7.5, and after cooling the reaction solution, the monoazo compound of the present invention was salted out with sodium chloride. The monoazo compounds of the present invention had the following formula when described in free acid form.

[0064]

Embedded image The compounds can be used, for example, to convert cotton into dark red shades with good fastness properties, in particular the fastness to light and washing, by the dyeing and printing methods customary in the field of fiber-reactive dyes. Stained.

Example 5 239 parts of 3-amino-6-sulfo-8-naphthol and cis-cyclohexyl-
170 parts of 4-ene-1,2-dicarboxylic anhydride were reacted according to the procedure of Example 1. Then, a diazonium salt of 311 parts of 2-methoxy-5- (β-sulfatoethylsulfonyl) aniline was added to the obtained coupling component at pH 5 and a temperature of about 15 ° C. in the same manner as in Example 1. Combined. The resulting monoazo compound of the invention having the following formula (described in free acid form) was then isolated by conventional methods.

[0066]

Embedded image This compound dyes the fiber materials (especially cotton) described in the text in a very vivid orange shade with good fastness properties by dyeing and printing methods customary in the field of fiber-reactive dyes. did.

Example 6 A German patent discloses a solution of 281 parts of 4- (β-sulfatoethylsulfonyl) aniline and 40 parts of sodium fluoride at a pH of 6.5 and 150 parts of cyanuric fluoride contained in 3500 parts of ice water. According to the procedure of Publication No. 2746109, the mixture was gradually mixed and reacted by sufficiently stirring. After the reaction has taken place, the batch is mixed with 180 parts of 1,3-diaminobenzene-4-sulfonic acid, adjusted to pH 6.5 with sodium carbonate, and then the pH and the temperature are brought to 0-10 ° C. While holding, the mixture was further stirred for about 3 hours.

The batch was then cooled to 0 ° C. and the resulting amino compound was diazotized using conventional procedures using sodium nitrite and concentrated hydrochloric acid. The resulting diazonium salt solution was then prepared according to Example 2 of the present invention, 1-amino-3,6
319 parts of disulfo-8-naphthol and cis-cyclohex-4-ene-1,2
To the solution of the coupling component consisting of 180 parts of dicarboxylic anhydride. The coupling reaction was performed at a pH of 5.5 to 6.5 and a temperature of about 15 ° C. The resulting novel monoazo compound having the following formula (described in the form of the free acid) was buffered to pH 7 using a mixture of secondary and primary sodium hydrogen phosphate.

[0069]

Embedded image The monoazo compound of the present invention was then isolated by salting out with sodium chloride. This compound has good fiber-reactive dyeing properties, for example, dyes cotton in a deep red shade with good fastness properties.

Examples 7 to 64 The examples in the tables set forth below describe novel monoazo compounds whose components are represented by the following general formula (A).

Embedded image These compounds are prepared according to the production method described in the present invention, for example, a method similar to any of the above-mentioned examples, and when referring to the general formula (A), starting material compounds which are clear from the examples in the respective tables, For example, diazo compound X ⁰ -D ¹ -NH ₂ or a diamine _{^{H 2 N-D 1 -NH 2}} , halogen heterocyclic compounds substituted with X ⁰ -Hal
, An aminonaphtholsulfonic acid compound and a cyclic anhydride represented by the general formula (10).

These compounds have very good fiber-reactive dyeing properties and can be used to convert the materials described in the text, in particular cellulose fibers (such as cotton), respectively into the examples (cotton dyeing) in the table.
, While maintaining high color density and excellent fastness in the hue reported in (1).

[0072]

[Table 1]

[0073]

[Table 2]

[0074]

[Table 3]

[0075]

[Table 4]

[0076]

[Table 5]

[0077]

[Table 6]

[0078]

[Table 7]

Example 65 A solution of 239 parts of a lithium salt of 2-amino-6-sulfo-8-naphthol at a pH of 7 contained in 2000 parts of water at 15 to 20 ° C. was added to trans-cyclohexyl-
It was mixed with 175 parts of 4-ene-1,2-dicarboxylic anhydride. The reaction batch was additionally stirred at 15-20 ° C. for about 3 hours, while maintaining the pH at 6 using lithium hydroxide. This was then mixed with a suspension of 281 parts of 4- (β-sulfatoethylsulfonyl) aniline prepared in a conventional manner, in diazonium hydrochloride. The novel azo compound having the following formula (described in the form of the free acid) was isolated by performing the coupling reaction at a pH of 4-5 at a temperature of 5-10 ° C. by spray drying at pH 5.5.

[0080]

Embedded image The compounds have very good fiber-reactive dye properties, for example, cotton can be dyed and dyed by the customary dyeing and printing methods used in the field of fiber-reactive dyes, for example by good lightfastness. Dyeing) in a deep orange shade with the same color.

Example 66 A solution of 281 parts of 4- (β-sulfatoethylsulfonyl) aniline and 40 parts of sodium fluoride contained in 3500 parts of ice water at a pH of 6.5 and 150 parts of cyanuric fluoride were mixed with Germany. According to the procedure of Patent Publication No. 2746109, the mixture was gradually mixed and reacted by sufficiently stirring. After the reaction has taken place,
This batch is mixed with 180 parts of 1,3-diaminobenzene-4-sulfonic acid,
The pH is adjusted to 6.5 with sodium carbonate and the pH and temperature are then adjusted to 0-10.
The mixture was stirred for about 3 hours while being kept at ° C.

The batch was then cooled to 0 ° C., and the resulting amino compound was diazotized by conventional procedures using sodium nitrite and concentrated hydrochloric acid. The resulting diazonium salt solution was then treated according to Example 2 of the present invention with 319 parts of 1-amino-3,6-disulfo-8-naphthol and trans-cyclohex-4-ene-1,2-dicarboxylic anhydride. 180 parts and was added to the solution of the coupling component prepared. The coupling reaction was performed at a pH of 5.5 to 6.5 and a temperature of about 15 ° C.

The resulting synthesis solution of the novel monoazo compound having the following formula (described in the form of the free acid) was buffered to pH 7 using a mixture of secondary and primary sodium hydrogen phosphate.

[0084]

Embedded image The monoazo compound of the present invention was then isolated by salting out with sodium chloride. This compound has good fiber-reactive dyeing properties, for example, dyes cotton in dark red shades with good fastness properties.

Example 67 239 parts of 3-amino-6-sulfo-8-naphthol were reacted with 170 parts of trans-cyclohex-4-ene-1,2-dicarboxylic anhydride according to the procedure of Example 1. . Then, a diazonium salt of 311 parts of 2-methoxy-5- (β-sulfatoethylsulfonyl) aniline was added to the obtained coupling component at pH 5 and a temperature of about 15 ° C. in the same manner as in Example 1. Combined. The resulting monoazo compound of the invention having the following formula (described in free acid form) was then isolated by conventional methods.

[0086]

Embedded image This compound dyes the textile materials described in the text (especially cotton) in a very vivid orange shade with good fastness properties by dyeing and printing methods customary in the field of fiber-reactive dyes. .

Example 68 A solution of 239 parts of a lithium salt of 2-amino-6-sulfo-8-naphthol at a pH of 7 contained in 2000 parts of water at 15-20 ° C. was treated with 4-methyl-trans-cyclohexyl. It was mixed with 175 parts of 4-ene-1,2-dicarboxylic anhydride. The reaction batch was additionally stirred at 15-20 ° C. for about 3 hours, while maintaining the pH at 6 using lithium hydroxide. This was then combined with the conventionally produced 4- (
β-Sulfatoethylsulfonyl) aniline was mixed with a suspension of 281 parts of diazonium hydrochloride. The novel azo compound having the following formula (described in the form of a free acid) is obtained by performing the coupling reaction at a pH of 4 to 5 and a temperature of 5 to 10 ° C. to obtain a pH of 5.5.
By spray drying.

[0088]

Embedded image This compound has a very good fiber-reactive dyeing property, for example, cotton can be made by a dyeing and printing method commonly used in the field of fiber-reactive dyes to have good fastness (for example, excellent light fastness). Dyeing) in a deep orange shade with the same color.

Example 69 A solution of 281 parts of 4- (β-sulfatoethylsulfonyl) aniline and 40 parts of sodium fluoride at a pH of 6.5 and 150 parts of cyanuric acid fluoride contained in 3500 parts of ice water are described in a German patent. According to the procedure of Publication No. 2746109, the mixture was gradually mixed and reacted by sufficiently stirring. After the reaction has taken place, the batch is mixed with 180 parts of 1,3-diaminobenzene-4-sulfonic acid, adjusted to pH 6.5 with sodium carbonate, and then the pH and the temperature are brought to 0-10 ° C. While holding, the mixture was stirred for about 3 hours.

The batch was then cooled to 0 ° C. and the resulting amino compound was diazotized using conventional procedures using sodium nitrite and concentrated hydrochloric acid. The resulting diazonium salt solution was then treated according to Example 2 of the present invention with 319 parts of 1-amino-3,6-disulfo-8-naphthol and 4-methyl-trans-cyclohex-4-en-
It was added to the solution of the coupling component prepared from 180 parts of 1,2-dicarboxylic anhydride. The coupling reaction was performed at a pH of 5.5 to 6.5 and a temperature of about 15 ° C.

The resulting synthesis solution of the novel monoazo compound having the following formula (described in the form of the free acid) was buffered to pH 7 using a mixture of secondary and primary sodium hydrogen phosphate.

[0092]

Embedded image The monoazo compound of the present invention was then isolated by salting out with sodium chloride. This compound has good fiber-reactive dyeing properties, for example, dyes cotton in dark red shades with good fastness properties.

Example 70 Example 1 comprises 239 parts of 3-amino-6-sulfo-8-naphthol and 170 parts of 4-methyl-trans-cyclohex-4-ene-1,2-dicarboxylic anhydride.
According to the procedure described in Then, a diazonium salt of 311 parts of 2-methoxy-5- (β-sulfatoethylsulfonyl) aniline was added to the obtained coupling component at pH 5 and a temperature of about 15 ° C. in the same manner as in Example 1. Combined. The resulting monoazo compound of the invention having the following formula (described in free acid form) was then isolated by conventional methods.

[0094]

Embedded image This compound dyes the fiber materials described in the text (especially cotton) in a very vivid orange shade with good fastness properties by the dyeing and printing methods customary in the field of fiber-reactive dyes. .

Claims (10)

[Claims] 1. A monoazo compound represented by the following general formula (1). Embedded image Wherein, in the formula (1), M is hydrogen, an alkali metal or another metal that forms a colorless salt; m is 0 or 1 (when m is 0, M is hydrogen). X is a fiber-reactive group or a group containing a fiber-reactive group; W is alkylene having 1 to 4 carbon atoms, or sulfo, carboxyl, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms; and be one or two which may be-phenylene substituted by a substituent, or -O- or a alkylene of 3 to 6 carbon atoms which is interrupted by -NH- that Bareru selected from the group consisting of chlorine; R ⁰ Is hydrogen or alkyl having 1 to 4 carbons, or phenyl optionally substituted by sulfo, methyl, ethyl, methoxy, ethoxy or chlorine; alk is alkylene having 1 to 4 carbons; r is 0 or 1 S is 0 or 1; t is 0 or 1; D is selected from the group consisting of sulfo, carboxyl, alkyl having 1 to 4 carbons, alkoxyl having 1 to 4 carbons and chlorine. R is hydrogen or alkyl having 1 to 4 carbon atoms, which is phenylene which may be substituted by one or two substituents or naphthylene which may be substituted by one or two sulfo groups; G is a divalent radical of cycloalkyl having 5 to 8 carbon atoms or bicycloalkyl having 5 to 8 carbon atoms, and these alicyclic radicals may contain an olefinic double bond. And / or it can be interrupted by a hetero group and is further substituted by one or two substituents selected from the group consisting of halogen and optionally substituted alkyl having 1 to 4 carbon atoms. Well; When X is a heterocyclic radical, s is 0 and r is 1. 2. The monoazo compound according to claim 1, represented by the following general formula (1B). Embedded image However, in the formula (1B), M and G are each as defined in claim 1, and the -NH-CO-G-COOM group is at the 2 or 3 position of the 8-hydroxynaphthalene free radical. And X ⁰ -D ¹ -is a free radical of the following general formula (5a) or (5b). Embedded image However, in the formula (5a) or (5b), M is hydrogen or an alkali metal, Y is vinyl or ethyl containing a substituent which can be eliminated with an alkali at the β-position, and m is 0 or R ⁹ is hydrogen, sulfo, alkyl having 1 to 4 carbons, alkoxy having 1 to 4 carbons, or halogen; R ¹⁰ is hydrogen, alkyl having 1 to 4 carbons, carbon 1-4 alkoxy. 3. The monoazo compound according to claim 1, represented by the following general formula (1B). Embedded image However, in the formula (1B), M and G are each as defined in claim 1, and the -NH-CO-G-COOM group is located at the 2 or 3 position of the 8-hydroxynaphthalene free radical. X ⁰ -D ¹ -is a free radical of the following general formula (5c) or (5d). Embedded image However, in the formula (5c) or (5d), M is hydrogen or an alkali metal, m is 0 or 1, R ⁰ is hydrogen, methyl or ethyl, and R ⁹ is hydrogen, sulfo. R ¹¹ is hydrogen, sulfo, alkyl having 1 to 4 carbons, or alkoxy having 1 to 4 carbons, alkyl having 1 to 4 carbons, alkoxy having 1 to 4 carbons or halogen. , N is 1, 2 or 3, and V is a group represented by the following general formula (3a), (3b), (3g) or (3h). Embedded image However, in the formulas (3a), (3b), (3g) or (3h), Hal is chlorine or fluorine, and R ⁵ is hydrogen or alkyl having 1 to 4 carbons, or chlorine, sulfo, car Phenyl which can be substituted with boxyl, methyl, ethyl, methoxy or ethoxy, and R ⁶ is a group represented by the following general formula (4a) or (4b). Y—SO ₂ —ALK—Y—SO ₂ —AR— (4a) (4b) In the formula (4a) or (4b), Y represents vinyl or a substituent capable of leaving at the β-position with an alkali. ALK is alkylene having 1 to 4 carbon atoms, and AR is 1 selected from the group consisting of sulfo, carboxyl, alkoxy having 1 to 4 carbons, alkyl having 1 to 4 carbons and chlorine. R ⁷ is hydrogen or alkyl having 1 to 4 carbons, which is phenylene which may be substituted by one or two substituents, or naphthylene which may be substituted by one or two sulfo groups. R ⁸ is a group represented by the following general formula (4c) or (4d): Y—SO ₂ —Alk-E-Alk— (4c) Y—SO ₂ — (Alk) _p -E − (Alk) _q − (4d) where the expression In (4c) or (4d), Y is the same as defined above, Alk is alkylene having 2 to 4 carbon atoms, E is -O- or -NH- group, and p is 0 Or 1, and q is 0 or 1, provided that (p + q) is 1. 4. V is a free radical represented by the above general formula (3g),
hal is the same as defined therein, R ⁵ is hydrogen and R ⁶ is a free radical of the general formula (4b) as defined and defined therein. Monoazo compounds. 5. The method according to claim 1, wherein X is a free radical represented by the following general formula (3g).
The monoazo compound according to the above. Embedded image However, in the formula (3g), Hal is chlorine or fluorine, and R ⁵ may be substituted with alkyl having 1 to 4 carbon atoms, or chlorine, sulfo, carboxyl, methyl, ethyl, methoxy or ethoxy. Phenyl and R ⁶ is a group represented by the following general formula (4a) or (4b). Y—SO ₂ —ALK—Y—SO ₂ —AR— (4a) (4b) In the formula (4a) or (4b), Y is vinyl or a substituent capable of leaving at the β-position with an alkali. ALK is alkylene having 1 to 4 carbon atoms, and AR is 1 selected from the group consisting of sulfo, carboxyl, alkoxy having 1 to 4 carbon atoms, alkyl having 1 to 4 carbon atoms and chlorine. Phenylene which may be substituted by one or two substituents; or naphthylene which may be substituted by one or two sulfo groups. 6. G is the following general formula (2a), (2b), (2c), (2d)
Or the monoazo compound according to at least one of claims 1 to 5, which is a free radical represented by (2e). Embedded image However, in the formulas (2a), (2b), (2c), (2d) and (2e), R ¹ is hydrogen, methyl or ethyl, and R ² is hydrogen, methyl, ethyl or chlorine. . 7. G is 1,2-cyclohexylene or 1,2-cyclohexyl-
The monoazo compound according to at least one of claims 1 to 5, which is 4-enylene. 8. X is a free radical represented by the formula Y-SO ₂ — (Y is vinyl, β-sulfatoethyl or β-chloroethyl, or X is a radical represented by the formula Y—SO ₂ —. The monoazo compound according to claim 1, which contains a free radical (Y is the same as described above). 9. A method for producing a monoazo compound represented by the general formula (1) as defined and defined in claim 1, comprising an aminonaphthosulfonic acid represented by the following general formula (9): Wherein each of M, m and R is as defined in claim 1); An anhydride represented by the following general formula (10) (G in the formula is defined in claim 1) in an aqueous suspension, or in a reaction-inactive organic solvent or with the organic solvent: Reacting in a mixture with water, Then, a compound represented by the following general formula (11) (M, m,
R and G are both defined in claim 1. ) To A diazonium salt compound of an amino compound represented by the following general formula (12) (X, WR ⁰ , alk, D, r, s and t in the formula are all defined in claim 1).
) Or Alternatively, in the production of a monoazo compound represented by the above general formula (1), wherein X is a heterocyclic fiber-reactive group, first, a compound represented by the following general formula (13) A diazonium salt (wherein D and R ⁰ are both defined in claim 1) is represented by the formula: H—N (R ⁰ ) —D—NH ₂ (13) Then, the resulting monoazo compound represented by the following general formula (14) (each symbol in the formula is defined by claim 1) is then converted to a compound represented by the following formula: A compound represented by the general formula Hal-X, wherein Hal is defined in claim 1,
X is a free radical represented by the general formulas (3a) to (3h) described above. Or a monoazo compound represented by the above general formula (1), wherein X is the above general formula (
In the production of the compound having a free radical represented by 3f) to (3h), the compound of the above general formula (14) is reacted with 2,4,6-trihalo 1,3,5-triazine. The resulting dihalotriazinylaminoazo compound is represented by the general formula R ³ R ⁴ NH:
Amines represented by R ⁵ R ⁶ NH or R ⁷ R ⁸ NH (R ³ , R ⁴ , R ⁵ , R ⁶ ,
R ⁷ and R ⁸ are defined above. ). 10. A method of using the monoazo compound according to claim 1 or the monoazo compound prepared according to claim 9 for dyeing hydroxy and / or carboxamide materials, particularly preferably those fiber materials.