JPH0539431A - Unsymmetrical dioxazine compound and dyeing or printing fibrous material using the same compound - Google Patents

Abstract

PURPOSE:To obtain a new compound useful for dyeing cellulosic fiber, polyamide fiber, polyurethane fiber, leather, etc., in blue, having excellent solubility, build-up properties and excellent fastness to light and washing and fastness to chlorine. CONSTITUTION:A compound shown by formula I [R is sulfo, halogen or alkoxy; R1 and R2 are H, (substituted)alkyl or acyl; R3 is H or (substituted)alkyl or acyl; X1 and X2 are H, halogen, alkyl, alkoxy or phenoxy; Z is group shown by formula II] such as compound shown by formula III. The compound shown by formula I is obtained by condensing an unsymmetrical dioxazine intermediate shown by formula TV with a compound shown by the formula X-Z (X is halogen) in the presence of an acid eliminator.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is useful for dyeing and printing materials containing hydroxyl groups and / or amide groups, especially cellulose fibers, natural or synthetic polyamide fibers, polyurethane fibers or leather, as well as blended fibers thereof. It relates to improved novel asymmetric dioxazine compounds which enable suitable, lightfast, wetfast and chlorinefast dyeings, as well as their applications.

[0002]

2. Description of the Related Art Reactive dyes having a dioxazine skeleton in the dye molecular structure are known, but they are unsatisfactory in terms of dyeing performance, for example, levelness, build-up property, dyeing speed, or fastness, particularly chlorine fastness. It is sufficient, and further improvement is desired.

[0003]

PROBLEM TO BE SOLVED BY THE INVENTION Hydroxyl group and / or
Alternatively, the fastness of dyeing or printing of a material containing an amide group, especially chlorine fastness is not at a satisfactory level particularly in the case of a hydroxyl group-containing fiber, and the present inventors diligently tried to increase this level. At the same time, as a result of pursuing a compound having excellent build-up property or dyeing reproducibility, an asymmetric dioxazine compound that can solve the above problems was found.

[0004]

The present invention provides a compound represented by the following general formula (I) in the form of a free acid.

[0005]

[Chemical 7]

[In the formula, R is a sulfo group, a halogen or an alkoxy group, R ₁ and R ₂ are each independently hydrogen or an alkyl group which may be substituted, and R ₃ is hydrogen, an alkyl group which may be substituted. Or an acyl group, X ₁ and X ₂
Each independently represent hydrogen, halogen, an alkyl group, an alkoxy group, or a phenoxy group, and Z is the following formula

[0007]

[Chemical 8]

[Wherein R ₄ is hydrogen or an optionally substituted alkyl group, R ₅ is hydrogen or an optionally substituted alkyl, phenyl or naphthyl group, and R ₆ is hydrogen or an optionally substituted Represents an alkyl group, B ₁ is an optionally substituted phenylene, alkylene or naphthylene group, Z ₁ is —SO ₂ CH═CH ₂ or —SO ₂ CH ₂
CH ₂ Y ₁ (Y ₁ represents a group capable of leaving by the action of an alkali.) Q ₁ represents halogen, an optionally substituted pyridinio or alkoxy group, —N (R ₇ ) (R ₈ ) (R ₇ ，
R ₈ is independently of each other hydrogen or optionally substituted alkyl, phenyl, Optionally substituted phenylene, alkylene or naphthylene group, R ₉ is hydrogen or an optionally substituted alkyl group, Z ₂ is —SO ₂ CH═CH ₂ or —SO ₂ CH ₂ C.
H ₂ Y ₂ (Y ₂ represents a group that is eliminated by the action of an alkali)], and W is

[0009]

[Chemical 9]

A divalent cross-linking group represented by and Z'represents a fiber-reactive group. } The asymmetric dioxazine compound shown by these, and the method of dyeing or printing the fiber material characterized by using it.

In the general formula (I), X ₁ and X ₂
Examples of the group represented by are chlorine, bromine, an alkoxy group having 4 or less carbon atoms and an alkyl group, and among them, chlorine and bromine are preferable.

The fiber-reactive group represented by Z is represented by the following formula

[0013]

[Chemical 10]

The group represented by the formula (wherein Q ₁ , W and Z ′ have the above-mentioned meanings) is preferable in terms of dyeing properties.

The fiber-reactive group represented by Z'is a group capable of reacting with -OH, -NH- or -NH ₂ groups of the fiber to form a covalent bond under dyeing conditions.

Specific examples of the fiber-reactive group represented by Z'include the following.

5- or 6-membered aromatic-heterocyclic rings, for example monoazine, diazine or triazine rings, especially pyridine, pyrimidine, pyridazine, pyrazine, thiazine, oxazine or asymmetric or symmetrical triazines. On a ring or on one or more fused aromatic groups
Carbocyclic rings, such as those containing at least one reactive substituent attached to the quinoline, phthalazine, shinoline, quinazoline, quinoxaline, acridine, phenazine or phenanthridine ring system, aliphatic reactions Examples of the functional group include those which are optionally bonded with a suitable linking group.

The reactive substituents on the plural rings and on the carbocycle include halogen (Cl, Br or F) hydrazinium-containing ammonium, sulfonium, sulfonyl, azide (-N ₃ ), thiocyanato, thio, thiol ether, Examples include oxyether, sulfino and sulfo.

The heterocyclic ring system and carbocyclic ring system fiber reactive groups include 2,4-difluorotriazin-6-yl, 2,4-dichlorotriazin-6-yl, monohalo-s-triazinyl group, In particular, monochlorotriazinyl and monofluorotriazinyl groups substituted by alkyl, aryl, amino, monoalkylamino, dialkylamino, aralkylamino, arylamino, alkoxy, aryloxy, alkylthio or arylthio, for example 2-amino. -4-Fluorotriazin-6-yl, 2-methylamino-4-fluorotriazin-6-yl, 2-ethylamino-4-fluorotriazin-6-yl, 2-isopropylamino-4-fluorotriazine-6- Il, 2-dimethylamino-4
-Fluorotriazin-6-yl, 2-diethylamino-4-fluorotriazin-6-yl, 2-β-methoxyethylamino-4-fluorotriazin-6-yl,
2-β-hydroxyethylamino-4-fluorotriazin-6-yl, 2-di- (β-hydroxyethylamino) -4-fluorotriazin-6-yl, 2-β-sulfoethylamino-4-fluorotriazine -6-yl, 2-β-sulfoethylmethylamino-4-fluorotriazin-6-yl, 2-carboxymethylamino-
4-fluorotriazin-6-yl, 2-di- (carboxymethylamino) -4-fluorotriazin-6-yl, 2-sulfomethyl-methylamino-4-fluorotriazin-6-yl, 2-β-cyanoethylamino -4
-Fluorotriazin-6-yl, 2-benzylamino-4-fluorotriazin-6-yl, 2-β-phenylethylamino-4-fluorotriazin-6-yl,
2-benzylmethylamino-4-fluorotriazine-
6-yl, 2- (4-sulfobenzyl) -amino-4-
Fluorotriazin-6-yl, 2-cyclohexylamino-4-fluorotriazin-6-yl, 2- (o
-, M-, p-methylphenyl) -amino-4-fluorotriazin-6-yl, 2- (o-, m-, p-sulfophenyl) -amino-4-fluorotriazine-6-
2- (2 ', 5'-disulfophenyl) -amino-4-fluorotriazin-6-yl, 2- (o-, m
-, P-chlorophenyl) -amino-4-fluorotriazin-6-yl, 2- (o-, m-, p-methoxyphenyl) -4-fluorotriazin-6-yl, 2-
(2'-Methyl-4'-sulfophenyl) -amino-4
-Fluorotriazin-6-yl, 2- (2'-methyl-5'-sulfophenyl) -amino-4-fluorotriazin-6-yl, 2- (2'-chloro-4'-sulfophenyl) -amino -4-Fluorotriazin-6-yl, 2- (2'-chloro-5'-sulfophenyl) -amino-4-fluorotriazin-6-yl, 2- (2 '
-Methoxy-4'-sulfophenyl) -amino-4-fluorotriazin-6-yl, 2- (o-, m-, p-
Carboxyphenyl) -amino-4-fluorotriazin-6-yl, 2- (2 ', 4'-disulfophenyl)
-Amino-4-fluorotriazin-6-yl, 2-
(3 ', 5'-Disulfophenyl) -amino-4-fluorotriazin-6-yl, 2- (2'-carboxy-
4'-sulfophenyl) -amino-4-fluorotriazin-6-yl, 2- (2'-carboxy-5'-sulfophenyl) -amino-4-fluorotriazine-6-
2- (6′-sulfophenyl-2′-yl) -amino-4-fluorotriazin-6-yl, 2-
(4 ', 8'-Disulfonaphthy-2'-yl) -amino-4-fluorotriazin-6-yl, 2- (6',
8'-disulfonaphthy-2'-yl) -amino-4-fluorotriazin-6-yl, 2- (N-methylphenyl) -amino-4-fluorotriazin-6-yl, 2
-(N-Ethylphenyl) -amino-4-fluorotriazin-6-yl, 2- (N-β-hydroxyethylphenyl) -amino-4-fluorotriazin-6-yl, 2- (N-isopropylphenyl) -Amino-4-
Fluorotriazin-6-yl, 2-morpholino-4-
Fluorotriazin-6-yl, 2-piperidino-4-
Fluorotriazin-6-yl, 2- (4 ', 6',
8'-trisulfonaphth-2'-yl) -4-fluorotriazin-6-yl, 2- (3 ', 6', 8'-trisulfonaphth-2'-yl) -4-fluorotriazin-6-yl, 2 -(3 ', 6'-disulfonaphthyl-1'
-Yl) -4-fluorotriazin-6-yl, N-methyl-N- (2,4-dichlorotriazin-6-yl)
-Carbamyl, N-methyl-N- (2-methylamino-
4-chlorotriazin-6-yl) -carbamyl, N-
Methyl-N- (2-dimethylamino-4-chlorotriazin-6-yl) -carbamyl, N-methyl- or N-ethyl-N- (2,4-dichlorotriazine-6-
Yl) -Aminoacetyl, 2-methoxy-4-fluorotriazin-6-yl, 2-ethoxy-4-fluorotriazin-6-yl, 2-phenoxy-4-fluorotriazin-6-yl, 2- (o- , M-, or p-
Sulfophenoxy) -4-fluorotriazin-6-yl, 2- (o-, m-, or p-methyl or -methoxyphenyl) -4-fluorotriazin-6-yl, 2-β-hydroxyethylmercapto-4 -Fluorotriazin-6-yl, 2-phenylmercapto-4
-Fluorotriazin-6-yl, 2- (4'-methylphenyl) -mercapto-4-fluorotriazinyl,
2- (2 ', 4'-dinitrophenyl) -mercapto-
4-fluorotriazin-6-yl, 2-methyl-4-
Fluorotriazin-6-yl, 2-phenyl-4-fluorotriazin-6-yl, and the corresponding 4-chloro- or 4-bromo-triazinyl groups, as well as tertiary bases by halogen exchange such as trimethylamine,
Triethylamine, dimethyl-β-hydroxyethylamine, triethanolamine, N, N-dimethylhydrazine, pyridine or picoline, nicotinic acid or isonicotinic acid, the sulfinates, in particular benzene-sulfinic acid or the corresponding corresponding obtained with hydrogen sulfite. Groups, mono-, di- or trihalopyrimidinyl groups, such as 2,4-dichloropyrimidin-6-yl,
2,3,5-trichloropyrimidin-6-yl, 2,4
-Dichloro-5-nitro- or -5-methyl- or -5-carboxymethyl- or -5-carboxy- or -5-cyano- or -5-vinyl- or -5
Sulfo- or -5-mono-, -di- or -trichloromethyl- or -5-carboalkoxy-pyrimidin-6-yl, 2,6-dichloropyrimidine-4-carbonyl, 2,4-dichloropyrimidine-5-carbonyl , 2-chloro-4-methylpyrimidine-5-carbonyl, 2-methyl-4-chloropyrimidine-5-carbonyl, 2-methylthio-4-fluoropyrimidine-5-carbonyl, 6-methyl-2,4-dichloropyrimidine −
5-carbonyl, 2,4,6-trichloropyrimidine-
5-carbonyl, 2,4-dichloropyrimidine-5-sulfonyl, or 2-chloro-quinoxaline-3-carbonyl, 2- or 3-monochloroquinoxaline-6-
Carbonyl, 2- or 3-monochloroquinoxaline-6-sulfonyl, 2,3-dichloroquinoxaline-6
-Carbonyl, 2,3-dichloroquinoxaline-6-sulfonyl, 1,4-dichlorophthalazine-6-sulfonyl or -6-carbonyl, 2,4-dichloroquinazoline-7- or -6-sulfonyl or -6-carbonyl , 2- or 3- or 4- (4 ', 5'-dichloropyridazo-6'-one-1'-yl) phenylsulfonyl or -carbonyl, β- (4', 5'-dichloropyridazo-6'-one- 1′-yl) ethylcarbonyl, N-methyl-N- (2,3-dichloroquinoxaline-6-sulfonyl) -aminoacetyl, N-methyl-
N- (2,3-dichloroquinoxaline-6-carbonyl) -aminoacetyl, and the corresponding bromine and fluorine derivatives of the above chlorine-substituted heterocyclic groups, such as 2-fluoro-4-pyrimidinyl, 2 , 6-Difluoro-4-pyrimidinyl, 2,6-difluoro-5-chloro-4-pyrimidinyl, 2-fluoro-5,6-dichloro-4-pyrimidinyl, 2,6-difluoro-5-methyl-4-pyrimidinyl , 2-fluoro-5-methyl-6
-Chloro-4-pyrimidinyl, 2-fluoro-5-nitro-6-chloro-4-pyrimidinyl, 5-bromo-2-
Fluoro-4-pyrimidinyl, 2-fluoro-5-cyano-4-pyrimidinyl, 2-fluoro-5-methyl-4
-Pyrimidinyl, 2,5,6-trifluoro-4-pyrimidinyl, 5-chloro-6-chloromethyl-2-fluoro-4-pyrimidinyl, 5-chloro-6-dichloromethyl-2-fluoro-4-pyrimidinyl, 5-chloro-6
-Trichloromethyl-2-fluoro-4-pyrimidinyl, 5-chloro-2-chloromethyl-6-fluoro-4
-Pyrimidinyl, 5-chloro-2-dichloromethyl-6
-Fluoro-4-pyrimidinyl, 5-chloro-2-trichloromethyl-6-fluoro-4-pyrimidinyl, 5-
Chloro-2-fluorodichloromethyl-6-fluoro-
4-pyrimidinyl, 2,6-difluoro-5-bromo-
4-pyrimidinyl, 2-fluoro-5-bromo-6-methyl-4-pyrimidinyl, 2-fluoro-5-bromo-
6-chloromethyl-4-pyrimidinyl, 2,6-difluoro-5-chloromethyl-4-pyrimidinyl, 2,6-
Difluoro-5-nitro-4-pyrimidinyl, 2-fluoro-6-methyl-4-pyrimidinyl, 2-fluoro-
5-chloro-6-methyl-4-pyrimidinyl, 2-fluoro-5-chloro-4-pyrimidinyl, 2-fluoro-
6-chloro-4-pyrimidinyl, 6-trifluoromethyl-5-chloro-2-fluoro-4-pyrimidinyl, 6
-Trifluoromethyl-2-fluoro-4-pyrimidinyl, 2-fluoro-5-nitro-4-pyrimidinyl, 2
-Fluoro-5-trifluoromethyl-4-pyrimidinyl, 2-fluoro-5-phenyl- or -5-methylsulfonylmethyl-4-pyrimidinyl, 2-fluoro-
5-carboxamido-4-pyrimidinyl, 2-fluoro-5-carbomethoxy-4-pyrimidinyl, 2-fluoro-5-bromo-6-trifluoromethyl-4-pyrimidinyl, 2-fluoro-6-carboxamido-4-pyrimidinyl , 2-Fluoro-6-carbomethoxy-4-pyrimidinyl, 2-Fluoro-6-phenyl-4-pyrimidinyl, 2-Fluoro-6-cyano-4-pyrimidinyl, 2-Fluoro-4-dichloromethyl-5-chloro. Pyrimidin-6-yl, 2-fluoro-5-chloropyrimidin-4-yl, 2-methyl-4-fluoro-5-methylsulfonylpyrimidin-6-yl, 2,6-difluoro-5-methylsulfonyl-4- Pyrimidinyl, 2,6
-Dichloro-5-methylsulfonyl-4-pyrimidinyl, 2-fluoro-5-sulfonamido-4-pyrimidinyl, 2-fluoro-5-chloro-6-carbomethoxy-4-pyrimidinyl, 2,6-difluoro-5- Trifluoromethyl-4-pyrimidinyl, sulfonyl-containing triazine groups such as 2,4-bis- (phenylsulfonyl) -triazin-6-yl, 2- (3'-carboxyphenyl) -sulfonyl-4-chlorotriazine- 6
-Yl, 2- (3'-sulfophenyl) -sulfonyl-
4-chlorotriazin-6-yl, 2,4-bis-
(3'-Carboxyphenylsulfonyl) -triazin-6-yl, sulfonyl-containing pyrimidine rings such as 2-carboxymethylsulfonyl-pyrimidin-4-yl, 2-methylsulfonyl-6-methylpyrimidin-4.
-Yl, 2-methylsulfonyl-6-ethylpyrimidin-4-yl, 2-phenylsulfonyl-5-chloro-6
-Methyl-pyrimidin-4-yl, 2,6-bis-methylsulfonyl-pyrimidin-4-yl, 2,6-bis-
Methylsulfonyl-5-chloro-pyrimidin-4-yl, 2,4-bis-methylsulfonyl-pyrimidin-5
-Sulfonyl, 2-methylsulfonyl-pyrimidine-4
-Yl, 2-phenylsulfonyl-pyrimidin-4-yl, 2-trichloromethylsulfonyl-6-methyl-pyrimidin-4-yl, 2-methylsulfonyl-5-chloro-6-methyl-pyrimidin-4-yl, 2 -Methylsulfonyl-5-bromo-6-methyl-pyrimidine-4-
2-methylsulfonyl-5-chloro-6-ethyl-pyrimidin-4-yl, 2-methylsulfonyl-5-yl
Chloro-6-chloromethyl-pyrimidin-4-yl, 2
-Methylsulfonyl-4-chloro-6-methylpyrimidin-5-sulfonyl, 2-methylsulfonyl-5-nitro-6-methylpyrimidin-4-yl, 2,5,6-tris-methylsulfonyl-pyrimidin-4- Ill, 2-
Methylsulfonyl-5,6-dimethyl-pyrimidine-4
-Yl, 2-ethylsulfonyl-5-chloro-6-methyl-pyrimidin-4-yl, 2-methylsulfonyl-6
-Chloropyrimidin-4-yl, 2,6-bis-methylsulfonyl-5-chloro-pyrimidin-4-yl, 2-
Methylsulfonyl-6-carboxypyrimidin-4-yl, 2-methylsulfonyl-5-sulfopyrimidin-4
-Yl, 2-methylsulfonyl-6-carbomethoxypyrimidin-4-yl, 2-methylsulfonyl-5-carboxypyrimidin-4-yl, 2-methylsulfonyl-
5-cyano-6-methoxypyrimidin-4-yl, 2-
Methylsulfonyl-5-chloropyrimidin-4-yl,
2-sulfoethylsulfonyl-6-methylpyrimidine-
4-yl, 2-methylsulfonyl-5-bromopyrimidin-4-yl, 2-phenylsulfonyl-5-chloropyrimidin-4-yl, 2-carboxymethylsulfonyl-5-chloro-6-methylpyrimidin-4-yl , 2-
Methylsulfonyl-6-chloropyrimidine-4- and-5-carbonyl, 2,6-bis- (methylsulfonyl) -pyrimidine-4- or-5-carbonyl, 2
-Ethylsulfonyl-6-chloropyrimidine-5-sulfonyl, 2,4-bis- (methylsulfonyl) -pyrimidine-5-sulfonyl, 2-methylsulfonyl-4-chloro-6-methylpyrimidine-5-sulfonyl or-
Carbonyl, 2-chlorobenzothiazole-5- or -6-carbonyl or -5- or -6-sulfonyl, 2-arylsulfonyl- or -alkylsulfonyl-benzothiazole-5- or -6-carbonyl or -carbonyl, 2 -Phenylsulfonylbenzothiazole-5- or -6-carbonyl or-
Contains 5- or -6-sulfonyl, such as 2-methylsulfonyl- or 2-ethylsulfonyl-benzothiazole-5- or -6-sulfonyl or -5- or -6-carbonyl, and a sulfo group in the fused benzene ring The corresponding 2-sulfonylbenzothiazole-5- or -6-carbonyl or -sulfonyl derivatives, 2-chloro-benzoxazole-5- or -6-carbonyl or -sulfonyl, 2-chloro-benzimidazole- 5- or -6-carbonyl or -sulfonyl, 2-chloro-1-methylbenzimidazole-5- or -6-carbonyl or -sulfonyl, 2-chloro-4-methyl-1,3-thiazole-5-carbonyl or -4- or -5-sulfonyl, 4-chloro Or 4-nitro - quinolin-5
Carbonyl N-oxide and the like can be mentioned.

As the aliphatic fiber-reactive group, acryloyl, mono-, di- or trichloroacryloyl, for example, -CO-CH = CH-Cl, -CO-CCl.
_{= CH 2, -CO-CCl =} CH-CH 3, -CO-C
Cl = CH-COOH, -CO-CH = CCl-COO
H, β-chloropropionyl, 3-phenylsulfonylpropionyl, 3-methylsulfonylpropionyl, 2
-Fluoro-2-chloro-3,3-difluorocyclobutane-1-carbonyl, 2,2,3,3-tetrafluorocyclobutane-1-carbonyl or -1-sulfonyl, β- (2,2,3,3- Tetrafluorocyclobutyl) -aryloxy, α- or β-bromoacryloyl, α- or β-alkyl- or aryl-
Examples thereof include a sulfoacryloyl group, for example, α- or β-methylsulfonylacryloyl, chloroacetyl, vinylsulfonyl, —SO ₂ CH ₂ CH ₂ Z ₁ (Z ₁ represents a group capable of leaving by the action of an alkali) and the like.

The preferred fiber-reactive group Z'is represented by the following formula:

[0022]

[Chemical 11]

[Wherein R ₁₀ is hydrogen or an optionally substituted alkyl group, R ₁₁ is hydrogen or an optionally substituted alkyl, phenyl or naphthyl group, and R ₁₂ is hydrogen or an optionally substituted. Represents an alkyl group, B ₃ is an optionally substituted phenylene, alkylene or naphthylene group, Z ₃ is —SO ₂ CH═CH ₂ , or —SO ₂ C
H ₂ CH ₂ Y ₃ (Y ₃ represents a group capable of leaving by the action of an alkali) Q ₂ is a halogen, an optionally substituted pyridinio or alkoxy group, —N (R ₁₃ ) (R ₁₄ ).
(R ₁₃ and R ₁₄ are each independently hydrogen or optionally substituted alkylphenyl, Optionally a phenylene, alkylene or naphthylene group, R ₁₅ is hydrogen or an optionally substituted alkyl group,
Z ₄ is -SO ₂ CH = CH _2, or -SO ₂ CH ₂ CH
₂ Y ₄ (Y ₄ represents a group capable of leaving by the action of an alkali)]. ] The group shown by these is mentioned.

The optionally substituted alkylene group represented by B ₁ , B ₂ , B ₃ and B ₄ is-(C
_{H 2) 2 -, - (} CH 2) 3 -, - (CH 2) 2 O (C
H ₂ ) ₂ − and the like are exemplified. The phenylene group or naphthylene group which may be substituted is preferably phenylene which may be substituted by 1 or 2 substituents selected from the group consisting of methyl, ethyl, methoxy, ethoxy, chlorine, bromine and sulfo. A naphthylene group which may be substituted with one group or one sulfo group, and examples thereof include the following.

[0025]

[Chemical formula 12]

[0026]

[Chemical 13]

[0027] Represents a bond. )

Examples of the group capable of leaving by the action of an alkali represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ include sulfuric acid ester, thiosulfuric acid ester, phosphoric acid ester, acetic acid ester, halogen and the like. Among them, sulfate ester is preferable.

The optionally substituted alkyl group represented by R ₁ , R ₂ , R ₃ , R ₆ , R ₉ , R ₁₂ and R ₁₅ is, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, 2-hydroxyethyl, 2-hydroxypropyl,
3-hydroxypropyl, 2-hydroxybutyl, 3-
Hydroxybutyl, 4-hydroxybutyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, cyanomethyl, 2-cyanoethyl, 3-cyanopropyl,
Methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-
Ethoxypropyl, 2-hydroxy-3-methoxypropyl, chloromethyl, bromomethyl, 2-chloroethyl, 2-bromoethyl, 3-chloropropyl, 3-promopropyl, 4-chlorobutyl, 4-bromobutyl, carboxymethyl, 2-carboxyethyl. , 3-carboxypropyl, 4-carboxybutyl, 1,2-dicarboxyethyl, carbamoylmethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 4-carbamoylbutyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, 2-methoxycarbonylethyl , 2-ethoxycarbonylethyl, 3-methoxycarbonylpropyl,
3-ethoxycarbonylpropyl, 4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl, methylcarbonyloxymethyl, ethylcarbonyloxymethyl, 2-methylcarbonyloxyethyl, 2-ethylcarbonyloxyethyl, 3-methylcarbonyloxypropyl, 3 -Ethylcarbonyloxypropyl, 4-methylcarbonyloxybutyl, 4-ethylcarbonyloxybutyl, sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, sulfamoylmethyl, 2-sulfamoylethyl, 3-sulfate Famoylpropyl and 4-sulfamoylbutyl can be mentioned, and particularly preferably hydrogen, methyl and ethyl. Hydrogen is more preferable as R ₁ , R ₂ and R ₃ .

R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R
_The optionally substituted alkyl group represented by ₁₃ and R ₁₄ is, for example, 1 or 2 selected from the group consisting of alkoxy having 1 to 4 carbon atoms, sulfo, carboxy, hydroxy, chloro, phenyl and sulfate. Alkyl groups having 1 to 4 carbon atoms which may be substituted by the substituents of are preferred.

Of these, methyl, ethyl, and
n-propyl, iso-propyl, n-butyl, iso
-Butyl, sec-butyl, β-hydroxyethyl, β
-Sulfatoethyl, β-sulfoethyl, β-methoxyethyl, β-carboxyethyl and the like.

R ₅ , R ₇ , R ₈ , R ₁₁ , R ₁₃ , and R ₁₄
The optionally substituted phenyl group represented by
For example, alkyl having 1 to 4 carbon atoms, 1 to 4
A phenyl group optionally substituted by 1 or 2 substituents selected from the group of alkoxy, sulfo, carboxy, chloro and bromo having 4 carbon atoms is preferred.

Of these, phenyl, 2-, and
3- or 4-sulfophenyl, 2,4- or 2,5-disulfophenyl, 2-, 3- or 4-carboxyphenyl, 2-, 3- or 4-chlorophenyl, 2-, 3- or 4- Methylphenyl and 2-, 3- or 4-methoxyphenyl etc. are mentioned.

R ₅ , R ₇ , R ₈ , R ₁₁ , R ₁₃ , and R ₁₄
As the optionally substituted naphthyl group represented by,
For example substituted by 1, 2 or 3 substituents selected from the group of hydroxy, carboxy, sulfo, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms and chloro. The naphthyl group which may be present is preferable.

Of these, particularly preferred are 2-, 3-, 4
-, 5-, 6-, 7- or 8-sulfo-1-naphthyl,
1-, 5-, 6-, 7- or 8-sulfo-2-naphthyl, 1,5-, 5,7-, 6,8-, 4,8-, 4,7
-, 3,8-, 4,6-, 3,7- or 3,6-disulfo-2-naphthyl, 4,6,8-, 2,4,7- or 3,6,8-trisulfo-1 -Naphthyl, 1,5,7
-, 4,6,8- or 3,6,8-trisulfo-2-naphthyl and the like can be mentioned.

The optionally substituted benzyl group represented by R ₇ , R ₈ , R ₁₃ and R ₁₄ is, for example, 1 to 4
Preferred is a benzyl group optionally substituted by 1 or 2 substituents selected from the group consisting of alkyl having 1 carbon atom, alkoxy having 1 to 4 carbon atoms, sulfo and chloro.

Of these, particularly preferred are benzyl, 2-,
3- or 4-sulfobenzyl etc. are mentioned.

In the present invention, one of R ₇ and R ₈ is hydrogen, methyl or ethyl, and the other is C _1- .
₄ alkyl, C ₁ ~ ₄ alkoxy, sulfo, phenyl optionally substituted by carboxy or halogeno, or C ₁ ~ ₄ alkoxy, sulfo, carboxy, hydroxy, chloro or sulfa, - optionally substituted with preparative C ₁ ~ ₄ alkyl, or R ₇ and R ₈
It is particularly preferable that both are hydrogen in terms of dye characteristics. R
_{Also for 13} and R ₁₄ , a combination corresponding to R ₇ and R ₈ shown above is preferable in terms of dye characteristics.

In the above formula, -N (R ₄ ) (R ₅ ) -N (R
_{7) (R 8) -N (} R 10) (R 11) and -N (R ₁₃₎
HNR ₄ R ₅ , HNR ₇ R ₈ , HNR ₁₀ R ₁₁ and H used to form a group represented by (R ₁₄ ), respectively.
Examples of the compound represented by NR ₁₃ R ₁₄ include ammonia or 1-aminobenzene, 1-amino-2-,
-3- or -4-methyl-benzene, 1-amino-3,
4- or -3,5-dimethylbenzene, 1-amino-2
-, -3- or -4-ethylbenzene, 1-amino-2
-, -3- or -4-methoxybenzene, 1-amino-
2-, -3- or -4-ethoxybenzene, 1-amino-2-, -3- or -4-chlorobenzene, 3- or 4
-Amino-phenylmethanesulfonic acid, 2-, 3- or 4-aminobenzenesulfonic acid, 3-methylaminobenzenesulfonic acid, 3-ethylaminobenzenesulfonic acid, 4-methylaminobenzenesulfonic acid, 4-ethylaminobenzene Sulfonic acid, 5-aminobenzene-1,
3-disulfonic acid, 6-aminobenzene-1,3-disulfonic acid, 6-aminobenzene-1,4-disulfonic acid, 4-aminobenzene-1,2-disulfonic acid, 4-
Amino-5-methylbenzene-1,2-disulfonic acid,
2-, 3- or 4-aminobenzoic acid, 5-aminobenzene-1,3-dicarboxylic acid, 5-amino-2-hydroxybenzenesulfonic acid, 4-amino-2-hydroxybenzenesulfonic acid, 5-amino- 2-ethoxybenzenesulfonic acid, N-methylaminobenzene, N-ethylaminobenzene, 1-methylamino-3- or -4-methylbenzene, 1-ethylamino-4-chlorobenzene,
1-ethylamino-3- or -4-methylbenzene, 1
-(2-Hydroxyethyl) -amino-3-methylbenzene, 3- or 4-methylaminobenzoic acid, 3- or 4
-Methylaminobenzenesulfonic acid, 2-aminonaphthalene-1-sulfonic acid, 4-aminonaphthalene-1-sulfonic acid, 5-aminonaphthalene-1-sulfonic acid, 6
-Aminonaphthalene-1-sulfonic acid, 7-aminonaphthalene-1-sulfonic acid, 8-aminonaphthalene-1-
Sulfonic acid, 1-aminonaphthalene-2-sulfonic acid,
4-aminonaphthalene-2-sulfonic acid, 5-aminonaphthalene-2-sulfonic acid, 6-aminonaphthalene-2
-Sulfonic acid, 7-aminonaphthalene-2-sulfonic acid, 7-methylaminonaphthalene-2-sulfonic acid, 7
-Ethylaminonaphthalene-2-sulfonic acid, 7-butylaminonaphthalene-2-sulfonic acid, 7-isobutylaminonaphthalene-2-sulfonic acid, 8-aminonaphthalene-2-sulfonic acid, 4-aminonaphthalene-1,3
-Disulfonic acid, 5-aminonaphthalene-1,3-disulfonic acid, 6-aminonaphthalene-1,3-disulfonic acid, 7-aminonaphthalene-1,3-disulfonic acid, 8
-Aminonaphthalene-1,3-disulfonic acid, 2-aminonaphthalene-1,5-disulfonic acid, 3-aminonaphthalene-1,5-disulfonic acid, 4-aminonaphthalene-1,5-disulfonic acid, 4-amino Naphthalene-1,
6-disulfonic acid, 8-aminonaphthalene-1,6-disulfonic acid, 4-aminonaphthalene-1,7-disulfonic acid, 3-aminonaphthalene-2,6-disulfonic acid,
4-aminonaphthalene-2,6-disulfonic acid, 3-aminonaphthalene-2,7-disulfonic acid, 4-aminonaphthalene-2,7-disulfonic acid, 6-aminonaphthalene-1,3,5-trisulfonic acid , 7-aminonaphthalene-1,3,5-trisulfonic acid, 4-aminonaphthalene-1,3,6-trisulfonic acid, 7-aminonaphthalene-1,3,6-trisulfonic acid, 8-aminonaphthalene Aromatic amines such as -1,3,6-trisulfonic acid and 4-aminonaphthalene-1,3,7-trisulfonic acid, or methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, Isobutylamine, sec-butylamine, dimethylamine, diethylamine, methylethylamine, allylamine, 2-chloroethyl Min, 2-methoxyethylamine, 2-aminoethanol, 2-methylaminoethanol, bis- (2-hydroxyethyl) amine, 2-acetylaminoethylamine, 1-amino-2-propanol, 3-methoxypropylamine, 1- Amino-3-dimethylaminopropane, 2-aminoethanesulfonic acid,
Aminomethanesulfonic acid, 2-methylaminoethanesulfonic acid, 3-amino-1-propanesulfonic acid, 2-sulfatoethylamine, aminoacetic acid, methylaminoacetic acid, ε-aminocaproic acid, benzylamine, 2-3
-Or 4-chlorobenzylamine, 4-methylbenzylamine, N-methylbenzylamine, 2-, 3- or 4-sulfobenzylamine, 2-phenylethylamine, 1-phenylethylamine, 1-phenyl-2
Mention may be made of aliphatic amines such as propylamine.

Among them, particularly preferable compounds are, for example, ammonia, ethylamine, taurine, N-methyltaurine, methylamine, n-propylamine, monoethanolamine, β-alanine, 2-chloroethylamine, 2-sulfatoethylamine, aniline. , Aniline-2-,-3- or -4-sulfonic acid, 2-, 3- or 4-carboxyaniline, N-methylaniline, N-
Ethylaniline, N-ethyl-2-,-3- or -4-
Chloroaniline, aniline-2,4- or -2,5-disulfonic acid, 2-, 3- or 4-chloroaniline, 2
-, 3- or 4-methylaniline, 3- or 4-methylaminobenzenesulfonic acid, etc. can be mentioned.

The halogen atom represented by Q ₁ and Q ₂ is preferably chlorine or fluorine.

The optionally substituted alkoxy represented by Q ₁ and Q ₂ includes phenyl, hydroxy, sulfo, carboxy, chloro, sulfate, methoxy,
Examples thereof include ethoxy or alkoxy having 4 or less carbon atoms which may be substituted with allyloxy. Of these, methoxy and ethoxy are preferable.

The optionally substituted pyridinio group represented by Q ₁ and Q ₂ is carboxy, carbamoyl, sulfo, halogeno or substituted or unsubstituted 1 to 4
Examples thereof include a pyridinio group which may be substituted with an alkyl having 4 carbon atoms, and examples of the substituted alkyl include β-hydroxyethyl, β-sulfoethyl and the like. A carboxy or carbamoyl-substituted pyridinio group is preferred,
Of these, a carboxypyridinio group is preferable in terms of dye characteristics.

Examples of R include a sulfo group, chlorine, bromine, methoxy and ethoxy, and among them, a sulfo group is particularly preferable. Examples of the acyl group represented by R ₃ include alkyl, alkenyl or arylcarbonyl groups such as acetyl group, propionyl group, maleinyl group and benzoyl group, alkyl or arylsulfonyl groups such as p-toluenesulfonyl group and the like. To be done.

The compound of the present invention may be present in the form of a free acid, but is preferably an alkali metal salt or an alkaline earth metal salt such as sodium salt and potassium salt.

The compound of the present invention can be produced, for example, as follows. The following general formula (II)

[0047]

[Chemical 14]

(Wherein R ₁ , R ₂ , R ₃ , R, X ₁ and X ₂ have the above-mentioned meanings) and an asymmetric dioxazine intermediate represented by the following general formula (III) XZ ( III)

(Wherein X represents a halogen atom and Z has the above-mentioned meaning) and can be produced by a conventional method. That is, the asymmetric dioxazine compound represented by the general formula (I) or a salt thereof can be obtained by condensing the compound of the formula (II) and the compound of the formula (III) by a known method in the presence of a deoxidizing agent.

The asymmetric dioxazine intermediate represented by the formula (II) is synthesized by a method known per se,
For example, it can be synthesized as follows.

The following general formula (IV) obtained by condensing the corresponding aniline compound and chloranil

[0052]

[Chemical 15]

The asymmetric dianilide represented by the formula (wherein R ₁ , R ₂ , R ₃ and R have the above-mentioned meanings) is optionally cyclized in the presence of an oxidizing agent to give a compound of the general formula (II) The asymmetric dioxazine intermediate of is obtained.

The compound of the present invention has fiber reactivity and can be used for dyeing or printing a hydroxy group-containing or carbonamide group-containing material. The material is preferably used in the form of a fibrous material or of a blended material thereof.

Hydroxy group-containing materials are natural or synthetic hydroxy group-containing materials such as cellulosic fiber materials or regenerated products thereof and polyvinyl alcohol. The cellulosic fiber material is preferably cotton, as well as other vegetable fibers such as linen, hemp, jute and ramie fibers. Regenerated cellulosic fibers are, for example, viscose staples and filament viscose.

Carbonamide group-containing materials are, for example, synthetic and natural polyamides and polyurethanes, especially in the form of fibers, such as wool and other animal hair, silk, leather, polyamide-6,6, polyamide-6, polyamide-11 and Polyamide-4.

The compounds of the present invention can be prepared on the above-mentioned materials, in particular on the above-mentioned fibrous materials, by a method depending on physical and chemical properties.
It can be dyed or printed.

For example, when performing exhaustion dyeing on cellulose fibers, an acid binder such as sodium carbonate, sodium triphosphate, caustic soda, sodium bicarbonate or the like is added in the presence of a neutral salt such as Glauber's salt or salt, and if desired, , A solubilizing agent, a penetrating agent, or a leveling agent in combination, and is performed at a temperature of 100 ° C. or lower. The neutral salt that accelerates the exhaustion of the dye can be added in portions in some cases.

When dyeing cellulose fibers according to the padding method, after padding at room temperature or elevated temperature and drying,
It can be fixed by steaming or dry heat.

When performing printing on cellulose fibers,
Printing in one phase, for example with a printing paste containing baking soda or other acid binder, and then steaming at 100-160 ° C., or in two phases, for example with a neutral or weakly acidic printing paste, It can be carried out by passing it through a hot electrolyte-containing alkaline bath, or by over-padging with an alkaline electrolyte-containing padding solution, and steaming or dry heat treatment. Alternatively, a paste or emulsifier such as starch ether is optionally used in combination as a conventional printing aid and / or dispersant such as urea.

The acid binder suitable for fixing the compound of the present invention on the cellulose fiber is, for example, a water-soluble basic salt of an alkali metal or alkaline earth metal with an inorganic or organic acid or a compound capable of releasing an alkali under heating. is there. In particular, alkali metal hydroxides and alkali metal salts of weak to medium-strength inorganic or organic acids are mentioned, of which soda salts and potassium salts are particularly preferable. Examples of such an acid binder include caustic soda, caustic potash, baking soda, sodium carbonate, sodium formate, potassium carbonate, sodium dibasic or tribasic phosphate, sodium silicate, sodium trichloroacetate and the like.

Dyeing of synthetic and natural polyamide and polyurethane fibers is carried out by first dyeing from acidic to slightly acidic dyeing to pH.
It can be carried out by changing the pH value to neutral and, in some cases, alkaline so as to cause exhaustion under controlled value and then to fix. Dyeing is usually carried out at a temperature of 60 to 120 ° C., but in order to achieve level dyeing, a common leveling agent, for example, a condensation product of cyanuric chloride and 3-fold molar aminobenzenesulfonic acid or aminonaphthalenesulfonic acid, or For example, an addition product of stearylamine and ethylene oxide can be used.

The compound of the present invention is characterized in that it exhibits excellent performance in dyeing and printing on fiber materials. It is particularly suitable for dyeing cellulose fiber materials, and has good fastness to light and sweat, excellent fastness to wet, such as fastness to washing, fastness to peroxidation, fastness to sweat, acid hydrolysis fastness and alkali. It has fastness, good chlorine fastness, rubbing fastness and iron fastness.

Further, it has excellent build-up property, level dyeing property and wash-off property, good solubility and exhaustion / fixing property, and is of stable quality which is hardly affected by the variation of dyeing temperature and dyeing bath ratio. It is characterized in that a dyed product is obtained.

Further, the dyed product obtained is characterized by little discoloration at the time of fixing treatment or resin processing, and little change due to contact with a basic substance during storage.

[0066]

The present invention will be described in detail below with reference to examples. In the examples, parts and% represent parts by weight, respectively. Example 1

[0067]

[Chemical 16]

19.3 parts of the asymmetric dioxazine intermediate represented by the above structural formula in the form of a free acid was added to 200 parts of water, 5.5 parts of cyanuric chloride was added thereto, and the pH was adjusted to 5 to 6 to 10 to 20 ° C.
The mixture was stirred until the reaction was completed. After completion of the reaction, salting out with potassium chloride yielded an asymmetric dioxazine compound represented by the following structural formula in the released form.

[0069]

[Chemical 17]

Example 2 Instead of the dioxazine intermediate and cyanuric chloride used in Example 1, compounds shown in columns 2 and 3 of the table below were respectively synthesized in the same manner as in Example 1, and the corresponding compounds were obtained. An asymmetric dioxazine compound was obtained. These compounds were dyed to give dyeings of the color tone shown in the fourth column of the table below.

[0071]

[Table 1]

[0072]

[Table 2]

[0073]

[Table 3]

[0074]

[Table 4]

Example 3 19.3 parts of the dioxazine intermediate used in Example 1 was treated with 20 parts of water.
In addition to 0 parts, 5.5 parts of cyanuric chloride was added to the solution to adjust the pH to 5
After reacting at ~ 6,10 ~ 20 ℃, taurine 3.7
Double addition was carried out to carry out further condensation reaction at pH 5 to 8 and 20 to 50 ° C. After completion of the reaction, salting out with potassium chloride gave an asymmetric dioxazine compound represented by the following structural formula in the form of a free acid.

[0076]

[Chemical 18]

Example 4 19.3 parts of the dioxazine intermediate used in Example 1 was added to 20 parts of water.
In addition to 0 parts, 5.5 parts of cyanuric chloride was added to it, and the pH was adjusted to 5
After the reaction at -6 to 10 to 20 ° C, 8.4 parts of 1-aminobenzene-3-β-sulfatoethylsulfone was further added, and the condensation reaction was further carried out at the same temperature and the same pH. After completion of the reaction, 3.7 parts of 3-carboxypyridine was added to the reaction solution and a substitution reaction was carried out at 40 to 80 ° C to obtain an asymmetric dioxazine compound represented by the following structural formula in the form of a free acid.

[0078]

[Chemical 19]

Example 5 Synthesis was carried out in the same manner as in Example 3 except that the dioxazine intermediates, cyanuric chloride and taurine used in Example 3 were replaced with the compounds shown in columns 2, 3 and 4 of the table below. Were carried out to obtain corresponding asymmetric dioxazine compounds. These compounds were dyed to give dyeings of the color tone shown in the fifth column of the table below.

[0080]

[Table 5]

[0081]

[Table 6]

[0082]

[Table 7]

[0083]

[Table 8]

[0084]

[Table 9]

[0085]

[Table 10]

Example 6 The dioxazine intermediate used in Example 4, 1-aminobenzene-3-β-sulfatoethyl sulfone and 3-
Instead of carboxypyridine, the second column in the table below,
Synthesis was carried out in the same manner as in Example 4 using the compounds in columns 3 and 4 to obtain corresponding asymmetric dioxazine compounds. These compounds were dyed to give dyeings having the color tone shown in the fifth column of the table.

[0087]

[Table 11]

[0088]

[Table 12]

[0089]

[Table 13]

[0090]

[Table 14]

[0091]

[Table 15]

Example 7 Reaction of 3-carboxypyridine in Example 4 using the following pyridine and 6 derivatives thereof for each of the 25 asymmetric dioxazine compounds obtained in Examples 3 and 5. The operation and conditions were similarly applied to obtain the corresponding asymmetric dioxazine compound.

[0093]

[Chemical 20]

Example 8

[0095]

[Chemical 21]

17.9 parts of the asymmetric dioxazine intermediate represented by the above structural formula in the form of a free acid was added to 350 parts of water, and 5.5 parts of cyanuric chloride was added thereto to adjust the pH to 5 to 7, 10 to 20.
The mixture was stirred at ℃ until the reaction was completed. After the reaction is over, 1,3
-Add diaminobenzene-4-sulfonic acid 5.6 parts and add
After the condensation, 1-aminobenzene-3-β-
Add 8.4 parts of sulfate ethyl sulfone, pH 3-5
Third condensation was carried out at 60-80 ° C. By further adding 5.5 parts of cyanuric chloride to this reaction solution and conducting a condensation reaction, an asymmetric dioxazine compound represented by the following structural formula in the form of a free acid was obtained.

[0097]

[Chemical formula 22]

Example 9 The dioxazine intermediate used in Example 8, cyanuric chloride, 1,3-diaminobenzene-4-sulfonic acid, 1-
Instead of aminobenzene-3-β-sulfatoethylsulfone and cyanuric chloride (showing the one used in the last condensation), columns 2, 3 and 4, respectively, in the table below.
Synthesis was carried out in the same manner as in Example 8 using the compounds in the columns, columns 5 and 6 to obtain the corresponding asymmetric dioxazine compounds. These compounds were dyed to give dyeings of the color tone shown in column 7 of the table below.

[0099]

[Table 16]

[0100]

[Table 17]

[0101]

[Table 18]

[0102]

[Table 19]

Example 10 38.5 parts of the asymmetric dioxazine compound obtained in Example 8 was dissolved in 300 parts of water, and 1-aminobenzene- was added to this solution.
Add 8.4 parts of 3-β-sulfatoethyl sulfone, p
The reaction is carried out at H4-6, 30-60 ° C. After the reaction,
Salting out with potassium chloride gave an asymmetric dioxazine compound represented by the following structural formula in the form of a free acid.

[0104]

[Chemical formula 23]

Example 11 Instead of the asymmetric dioxazine compound used in Example 10, 14 kinds of compounds obtained in Nos. 1, 6, 7 to 18 in Example 9 were used, and the following compounds were prepared for each of them. (1) ~
The corresponding asymmetric dioxazine compound was obtained by reacting the amine shown in (14) with 1-aminobenzene-3-β-sulfatoethylsulfone in Example 10.

[0106]

[Chemical formula 24]

Example 12 19.3 parts of the asymmetric dioxazine intermediate used in Example 1 was dissolved in 200 parts of water, 5.5 parts of cyanuric chloride was added to the solution to carry out a reaction, and then 1,3-diaminobenzene-
A condensation reaction was carried out by adding 5.6 parts of 4-sulfonic acid. To the reaction solution, 5.5 parts of cyanuric chloride was added again, and the pH was adjusted to 5-6,10.
The reaction is carried out at ~ 30 ° C and finally 1-aminobenzene-
The reaction was carried out by adding 8.4 parts of 4-β-sulfatoethyl sulfone. Potassium chloride was added to the reaction solution and salted out to obtain an asymmetric dioxazine compound represented by the following structural formula in the form of a free acid.

[0108]

[Chemical 25]

Example 13 The dioxazine intermediate used in Example 12, cyanuric chloride, 1,3-diaminobenzene-4-sulfonic acid, cyanuric chloride (indicating the one used for the second time), 1-aminobenzene. Instead of -3-β-sulfatoethyl sulfone, the second column, the third column, the fourth column, and the fifth column in the table below respectively.
Synthesis was carried out in the same manner as in Example 12 using the compounds in the columns and 6th column to obtain the corresponding asymmetric dioxazine compounds. These compounds were dyed to give dyeings of the color tone shown in column 7 of the table below.

[0110]

[Table 20]

[0111]

[Table 21]

[0112]

[Table 22]

[0113]

[Table 23]

Example 14 40.0 parts of the asymmetric dioxazine compound obtained in Example 12 was dissolved in 300 parts of water, and 3-carboxypyridine was added thereto.
8.0 parts was added and the reaction was carried out at pH 3 to 6, 40 to 80 ° C. By salting out the reaction solution with potassium chloride,
An asymmetric dioxazine compound represented by the following structural formula was obtained in the form of a free acid.

[0115]

[Chemical formula 26]

Example 15 The 16 kinds of compounds obtained in Example 13 were used in place of the asymmetric dioxazine compound used in Example 14, and each of them was shown in the following (1) to (10). The corresponding asymmetric dioxazine compound was obtained by reacting the amine in the same manner as in 3-carboxypyridine in Example 14.

[0117]

[Chemical 27]

Dyeing Example 1 0.1, 0.3, and 0.6 parts of each asymmetric dioxazine compound obtained in Examples 1 and 2 were dissolved in 200 parts of water,
10 parts of Glauber's salt and 10 parts of cotton were added, the temperature was raised to 50 ° C., 4 parts of sodium carbonate was added, and dyeing was carried out for 1 hour. Washing, soaping,
After washing with water and drying, a blue dyed product having excellent fastnesses, particularly chlorine fastness, and good build-up properties was obtained.

Dyeing Example 2 Using the asymmetric dioxazine compounds 0.1, 0.3, and 0.6 parts obtained in Examples 3 and 5, respectively, as in Dyeing Example 1,
However, dyeing was carried out at a dyeing temperature of 80 ° C., and similarly, a blue dyed product having excellent various fastnesses and good build-up properties was obtained.

Dyeing Example 3 Dyeing was performed in the same manner as Dyeing Example 1 except that 0.1, 0.3, and 0.6 parts of the asymmetric dioxazine compounds obtained in Examples 4 and 6 to 15 were used, except that the dyeing temperature was 60 ° C. Similarly, a blue dyed product having various fastnesses and good build-up properties was obtained.

Dyeing Example 4 Using each of the asymmetric dioxazine compounds obtained in Examples 1 to 15, a color paste having the following composition was prepared. Asymmetric dioxazine compound 5 parts Urine 5 parts Sodium alginate (5%) Original glue 50 parts Hot water 25 parts Baking soda 2 parts Balance 13 parts This color paste is printed on mercerized cotton broad cloth, and after intermediate drying at 100 ° C Steaming was carried out for 5 minutes, followed by hot water washing, soaping, hot water washing, and drying. The obtained dyed product was excellent in various fastnesses, particularly chlorine fastness, and had good build-up properties.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yutaka Kakine 3-98 Kasugade, Konohana-ku, Osaka City, Osaka Prefecture Sumitomo Chemical Co., Ltd. (72) Inventor Shigeru Kawabata Kasuga, Konohana-ku, Osaka City, Osaka Prefecture Izumi 3-1,98 Sumitomo Chemical Co., Ltd. (72) Inventor Naoki Harada Izumi 3-3-198 Kasuga, Konohana-ku, Osaka City Osaka Prefecture Sumitomo Chemical Co., Ltd.

Claims (8)

[Claims] 1. The following general formula (I) in the form of a free acid:{Wherein R is a sulfo group, a halogen or an alkoxy group, R
₁And R₂Are each independently hydrogen or substituted
Good alkyl group, R₃Is hydrogen, which may be substituted
Alkyl group or acyl group, X₁And X₂Each is German
Vertically hydrogen, halogen, alkyl group, alkoxy group, or
Represents a phenoxy group, and Z is represented by the following formula:[In the formula, R_FourIs hydrogen or optionally substituted alkyl
Group, R_FiveIs hydrogen or optionally substituted alkyl,
Phenyl or naphthyl group, R₆Is hydrogen or substituted
Is a good alkyl group, B₁May be replaced
Phenylene, alkylene or naphthylene group, Z₁Is -S
O₂CH = CH₂Or-SO₂CH₂CH ₂Y₁(Y₁
Represents a group capable of leaving by the action of an alkali. ) Q₁Is ha
Rogen, optionally substituted pyridinio or alkoxy
Si group, -N (R₇) (R₈) (R₇, R₈Are independent of each other
To hydrogen or optionally substituted alkyl, phenyl,
NaphthOptionally phenylene, alkylene or naphthylene group, R
₉Is hydrogen or an optionally substituted alkyl group, Z₂Is
-SO₂CH = CH₂Or-SO₂CH₂CH₂Y
₂(Y₂Represents a group capable of leaving by the action of an alkali. ))
The fiber-reactive group represented by, W isRepresents a divalent crosslinking group, and Z'represents a fiber-reactive group.
You } The asymmetric dioxazine compound shown by these. 2. Z is represented by the following formula: {Wherein Q ₁ and W have the meanings defined in claim 1 and Z ′
Is the following formula: [In the formula, R ₁₀ represents hydrogen or an optionally substituted alkyl group, R ₁₁ represents hydrogen or an optionally substituted alkyl, phenyl or naphthyl group, and R ₁₂ represents hydrogen or an optionally substituted alkyl group. , B ₃ is an optionally substituted phenylene, alkylene or naphthylene group, Z ₃ is —S
O ₂ CH = CH _2, or _{-SO 2 CH 2 CH 2 Y 3} (Y
₃ represents a group capable of leaving by the action of alkali. ), Q ₂ is halogen, an optionally substituted pyridinio or alkoxy group, —N (R ₁₃ ) (R ₁₄ ) (R ₁₃ and R ₁₄ are each independently hydrogen or optionally substituted alkyl, phenyl, Na Optionally substituted phenylene, alkylene or naphthylene group, R ₁₅ is hydrogen or an optionally substituted alkyl group, Z ₄ is —SO ₂ CH═CH ₂ or —SO ₂ CH ₂ C.
H ₂ Y ₄ (Y ₄ represents a group capable of leaving by the action of an alkali)]]. ] Represents the fiber reactive group. } The asymmetric dioxazine compound according to claim 1, which is a fiber-reactive group represented by the following formula. 3. The compound according to claim _1, wherein X ₁ and X ₂ are chloro or bromo. 4. The compound according to claim 1, wherein R is a sulfo group. 5. R ₁ , R ₂ and R ₃ are hydrogen.
5. The compound according to any one of to 4. 6. A divalent bridging group represented by W is The compound according to any one of claims 1 to 5, which is 7. B ₁ , B ₂ , B ₃ and B ₄ are substituted by 1 or 2 substituents selected from the group of methyl, ethyl, methoxy, ethoxy, chlorine, bromine and sulfo groups. Optionally a phenylene group or a naphthylene group optionally substituted with a sulfo group.
The compound according to any one of 1. 8. A method for dyeing or printing a fiber material, which comprises using the asymmetric dioxazine compound according to any one of claims 1 to 7.