JPH0322426B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is in the industrial field of water-soluble disazo dyes having fiber reactivity. The present invention is based on the general formula (1) This invention relates to a novel water-soluble disazo compound. In the above formula, Y has the following meaning: Y is a vinyl group or a group of the formula -CH ₂ -CH ₂ -Z (wherein Z
is an organic or inorganic residue or hydroxyl group that can be eliminated under alkaline conditions, n is a number of zero, 1 or 2, and D is a phenyl residue, which is lower alkyl, lower can be substituted with one or two substituents selected from the group consisting of alkoxy, lower alkanoylamino, benzoylamino, chlorine, bromine, fluorine, carboxy and/or with one sulfo group, or D is a naphthylene residue, which is one selected from the group consisting of lower alkyl, lower alkoxy, lower alkanoylamino, benzoylamino, chlorine, bromine, fluorine, carboxy, and sulfo.
or can be substituted with two substituents, E is a 1,4-phenylene residue selected from the group consisting of lower alkyl, lower alkoxy, ureido, lower alkanoylaminocarboxy and sulfo. A is a 1,4-naphthylene residue which can be substituted by one or two substituents or is substituted by sulfo, A is an ethylene residue of the formula _-CH2 - _CH2 or an ethylene residue of the formula - CH ₂
-CH ₂ -O- ethyleneoxy residue or formula -CH ₂
−CH ₂ −CH ₂ −,

【formula】,

[Formula] or

[Formula] (wherein X represents a hydroxy group or a lower alkanoyloxy group, such as an acetoxy or propionyloxy group, or a halogen atom, preferably a chlorine or bromine atom, or a sulfato or phosphate group) or expression

Residue or formula of [formula]

M is a residue of the formula, where M is a hydrogen atom of a metal, preferably an alkali metal or an alkaline earth metal, such as especially a sodium salt;
Potassium or calcium equivalent, R ¹ is a hydrogen atom, a lower alkyl group, a lower alkenyl group or a lower alkyl group substituted by phenyl and/or hydroxy, where the phenyl residue is substituted by methyl, methoxy and/or chlorine. - such as especially benzyl or phenethyl groups and 2 to 4 C-
Hydroxyalkyl groups having atoms or acid-esterified hydroxyalkyl groups having 2 to 4 carbon atoms in the alkyl residue, such as acetoxyalkyl, propionyloxyalkyl or phenylsulfonyloxyalkyl groups, alkyl groups cyanalkyl groups having 2 to 4 C atoms in the alkyl or carboxyalkylene, carbonamidoalkylene or carbonalkoxyalkylene groups each having 1 to 4 C atoms in the alkyl or alkylene residue; or a halogenalkyl radical having 3 C-atoms, in particular a chloralkyl radical or a lower halogenalkenyl radical, in which halogen is in particular chlorine or bromine, or a formula as defined above;
A-SO ₃ M group, R ² is a hydrogen atom, a lower alkyl group, especially a methyl group, a lower alkoxy group, which can be hydroxy, acetoxy, carboxy, carbonamide, cyanide or a halogen such as chlorine and bromine. or a halogen atom, such as a chlorine, bromine or fluorine atom, in particular a chlorine atom or a trifluoromethyl group, or an alkanoylamino group, such as an acetylamino group or a ureido group. and R ³ is a hydrogen atom, a lower alkyl group, especially a methyl group, or a lower alkoxy group, which can be substituted by hydroxy, acetoxy, cyanide or a halogen such as chlorine or bromine, or a halogen Atoms such as chlorine, bromine or fluorine atoms, especially chlorine atoms. The formula members R ² and R ³ may have the same or different meanings. Here, the term "lower" refers to the alkyl group contained in the group as shown below.
or alkylene- or alkenyl residues are 1 to 6
or 2 to 6 C atoms, especially 1 to 4 or 2 to 4 C atoms. Alkaline-removable groups Z are, for example, halogen atoms, such as chlorine, bromine or fluorine atoms, organic carboxylic acids and ester groups of sulfonic acids, such as lower alkanoyloxy residues, such as acetoxy residues or aromatic carbonyls or acyloxy of sulfonic acids. residues such as benzoyloxy, sulfobenzoyloxy, benzenesulfonyloxy or toluenesulfonyloxy residues, furthermore lower alkylsulfonylamino and arylsulfonylamino groups, phenoxy groups, alkyl groups each having 1 to 4 C atoms; dialkylamino groups such as dimethylamino or diethylamino groups and monoester groups such as thiosulfate, phosphoric acid and especially sulfuric acid. The novel disazo compounds can exist both in the form of the free acid and in the form of its salts. The compounds are preferably in the form of salts, especially alkali and alkaline earth metal salts, especially the sodium, potassium and calcium salts. It is particularly useful in the form of its salts as hydroxy and/or dyes.
Or used for dyeing and printing carbonamide group-containing fibers or leather. The disazo compound of general formula (1) according to the present invention is produced by the following method. That is, this method is
General formula (2) Y-SO ₂ -(CH ₂ ) _o -D-N=N-E-NH ₂ (2) (in the formula, D, E, Y and n have the above meanings)
Disazotization is performed with a compound of formula (3) by a method known per se, and the reaction product is expressed by the general formula (3). (In the formula, M, A, R ¹ , R ² and R ³ have the above meanings.) By coupling with the coupling component of the general formula (1)
and optionally Y is β
-Hydroxyethyl- group, use a sulfating agent to convert Y into the corresponding disazo compound of general formula (1) showing β-sulfatoethyl group, or use a phosphorylating agent to convert Y to β-phosphatoethyl group. It consists of changing to the corresponding compound of general formula (1) which shows - group. Suitable sulphating agents are, for example, 90-100% sulfuric acid, chlorosulfonic acid, amidosulfonic acid or other sulfur trioxide-imparting compounds. Suitable phosphorylating agents are, for example, phosphoric acid, pyrophosphoric acid, metaphosphoric acid or polyphosphoric acid, as well as polyphosphoric acid alkyl esters, phosphorus oxychloride or mixtures of phosphoric acid and phosphorus(V) oxide. The aminoazo compound of the general formula (2) can be prepared by the general formula (4) Y-SO ₂ -(CH ₂ ) _o -D-NH ₂ (4) (where D, Y and n have the above-mentioned meanings) by a method known per se. It can be produced by coupling a diazotized amine (having) with a coupling compound of general formula (5) H-E-NH ₂ (5) (wherein E has the above-mentioned meaning). General formula (1) of this aminoazo compound of general formula (2)
The subsequent reaction to the disazo compound (diazo compound and coupling) can be carried out after its preparation without intermediate isolation. For example, this subsequent reaction can be carried out in the same reaction mixture. Aromatic amines of the general formula (4) which are used as diazo component for preparing the compounds according to the invention are, for example, in particular: 4-β-sulfatoethylsulfonyl-aniline, 4-β-chloro Ethylsulfonyl-aniline, 4-β-phosphatoethylsulfonyl-aniline, 4-vinylsulfonyl-aniline, 4-β
-thiosulfatoethylsulfonyl-aniline,
2-Sulfo-4-β-sulfatoethylsulfonyl-aniline, 2-bromo-4-β-sulfatoethylsulfonyl-aniline, 2-chloro-4-
β-sulfatoethylsulfonyl-aniline, 2
-Chlor-5-β-chloroethylsulfonyl-aniline, 3-β-sulfatoethylsulfonylaniline, 2-bromo-5-β-sulfatoethylsulfonyl-aniline, 2,6-dichloro-4-
β-sulfatoethylsulfonyl-aniline,
2,6-dibromo-4-β-sulfatoethylsulfonyl-aniline, 2,5-dichloro-4-β
-sulfatoethylsulfonyl-aniline, 2-
Methyl-5-β-sulfatoethylsulfonyl-
Aniline, 2-methoxy-5-β-sulfatoethylsulfonyl-aniline, 2-methoxy-4-
β-sulfatoethylsulfonyl-aniline, 2
-Methyl-6-chloro-4-β-sulfatoethylsulfonyl-aniline, 2,6-dimethyl-4-β-sulfatoethylsulfonyl-aniline, 2,6-dimethyl-3-β-sulfato Ethylsulfonyl-aniline, 2,5-dimethoxy-4-β-sulfatoethylsulfonyl-
Aniline, 2-methoxy-5-methyl-4-β-
Sulfatoethylsulfonyl-aniline, 2-nitro-4-β-sulfatoethylsulfonyl-aniline, 4-nitro-2-β-sulfatoethylsulfonyl-aniline, 6-β-sulfatoethylsulfonyl- 2-naphthyl-amine, 1-sulfo-6-β-sulfatoethylsulfonyl-2-
Naphthylamine, 8-β-sulfatoethylsulfonyl-2-naphthylamine, 6-sulfo-8-
β-Sulfatoethylsulfonyl-2-naphthylamine, 6-vinylsulfonyl-2-aminobenzothiazole, 6-β-sulfatoethylsulfonyl-2-aminobenzothiazole, 4-ω-
(β-sulfatoethylsulfonyl)-tolylamine, 6-ω-(β-sulfatoethylsulfonyl)
-tolylamine, 6-methoxy-3-ω-(β-
sulfatoethylsulfonyl)-tolylamine,
4-methoxy-3-ω-(β-sulfatoethylsulfonyl)-tolylamine, 4-ω-(β-sulfatoethylsulfonyl)-ethyl-aniline,
3-ω-(β-sulfatoethylsulfonyl)-ethyl-aniline, 5-(β-sulfatoethylsulfonyl-methyl)-1-naphthylamine and its β-hydroxyethylsulfonyl derivatives. Compounds of formula (4) are known and can be prepared by methods often described in the literature. Preferred compounds of formula (4) containing, for example, a β-sulfatoethylsulfonyl group can be prepared by esterification from the corresponding β-hydroxyethylsulfonyl compound, e.g. Introduction of equimolar amounts of ethylsulfonyl-aniline and -naphthylamine into 60% sulfuric acid and German patent specification no.
1150163, or by subsequent heating, e.g. at room temperature, β-hydroxyethylsulfonylaniline or -
By dissolving naphthylamine in excess concentrated sulfuric acid or 100% sulfuric acid (monohydrate)
It is obtained by reaction with amidosulfonic acid in the presence of pyridine or pyridine base in a similar manner to the esterification method described in No. 1443877.
In this way, β-sulfatoethylsulfonyl-
Aniline and naphthylamine can also be used in non-isolated form in the form of reaction mixtures obtained from esters for use in the process according to the invention. The aromatic amines of the general formula (5) used as coupling components for preparing the aminoazo compounds of the general formula (2) are likewise generally known. Among these, the following may be mentioned in particular: aniline, o-toluidine, m-toluidine, o-anisidine,
m-anisidine, anthralic acid, cresidine,
2,5-xylidine, 2,5-dimethoxy-aniline, 3-amino-acetanilide, 3-amino-acetanilide-4-carboxylic acid, 3-amine-acetanilide-4-sulfonic acid, 3-aminophenyl urea, 3-aminophenyl -Urea-4-
Sulfonic acid, 1-naphthylamine-6-sulfonic acid, 1-naphthylamine-7-sulfonic acid and 2
-Ethoxy-1-naphthylamine-6-sulfonic acid. The residue R ¹ is in particular a hydrogen atom or 2 to 4 C
- an alkyl group with atoms, which can be substituted by a phenyl residue, a hydroxy group, an acetoxy-propionyloxy-cyan- or a carbonamido group, or has 2 or 3 C-atoms; It is a chloralkyl group or a group of the formula -A- _SO3M as defined above. Furthermore, R ² is in particular a hydrogen atom, a methyl or ethyl group,
Methoxy or ethoxy groups, which can be substituted by hydroxy, acetoxy or cyan groups or chlorine, or in particular chlorine or bromine atoms. Similarly, the residue R ³ is in particular a hydrogen atom or a methyl or ethyl, methoxy or ethoxy group, which is substituted by a hydroxy, acetoxy, carboxy, carbonamide or cyan group or a chlorine atom. I can be there. R ³ is likewise especially a chlorine or bromine atom. In the compound according to the present invention of the general formula (1), the residue D is a 1,4-phenylene residue or a 1,4-naphthylene residue, and both residues are methyl, methoxy, chlorine, bromine, carboxy and Preference is given to compounds which can be substituted with one or two substituents of the sulfo group. Similarly, E is a 1,4-phenylene residue,
This can be achieved by one or two lower alkyl groups, such as in particular methyl or ethyl groups, by one or two lower alkoxy groups, such as in particular methoxy and ethoxy groups, by one carboxy group or by one lower alkanoylamino group, e.g. In particular, it may be substituted by an acetylamino or propionylamino group or by one ureido group or by one lower alkanoylnaphthyle group and one sulfo group or by one ureido group and one sulfo group. Alternatively, E is a 1,4-naphthylene residue substituted by a sulfo group or by lower alkoxy groups such as methoxy and especially ethoxy and sulfo groups. Compounds of general formula (1) are preferred. The sulfoalkylanilines of the general formula (3) used as coupling components in the synthesis of the compounds of the general formula (1) are likewise known in known manner, for example from German Patent Application No. 1481831 and/or 1493636. By further methods, RBWagner und, H.
D. Zock, Syntic Organic Chemistry, John
Wiley u. Sons, Inc., New York, 1953, No. 812
- by the method described on page 819, furthermore by the reaction of α,α'-dichlorohydrin with sodium sulfite according to German Patent Specification No. 258 473 and for example by the reaction formula It can be produced by condensation of the above reaction product with an aromatic amine or by reaction of propane sultone with an aromatic amine. β-Sulfoethylaniline-derivatives can also be obtained by the reaction of β-chloroethanesulfonic acid or its salts with aromatic amines – for example JW James, Journal.Prakt.
It can be produced by the method described in Chem [2] 31, 413 (1885). However, the derivatives can also be prepared in very good purity, for example by addition of vinylsulfonyl fluoride to the aniline derivative and subsequent alkaline hydrolysis of the sulfofluoride group. Formula containing β-sulfatoethylamino group
The coupling component of (3) is, for example, written by KHSaunders.
J.Chem.Soc. (London) 121, 2667, 2675 (1922)
It can be manufactured by the method described in . Furthermore, this β-hydroxylethyl-aniline-
They can be prepared by esterification of the derivatives, for example by reaction with sulfuric acid - for example in the presence of cross-sulfonic acids in 100% sulfuric acid or in sulfuric acid (oleum) containing sulfur trioxide. The coupling component of formula (3) esterified in this way can also be used in the non-isolated form of the reaction mixture resulting from the esterification for use in the process according to the invention. Compounds of the general formula (3) which are used as coupling components in the preparation of the compounds according to the invention are, for example: N-β-sulfoethyl-aniline, N-β-sulfoethyl-2-chloroaniline, N-β -Sulfoethyl-3-chloroaniline, N-β-sulfoethyl-2-methylaniline, N-β-sulfoethyl-2-methoxyaniline, N-β-sulfoethyl-2-methyl-5-chloroaniline, N-β
-Sulfoethyl-2-methoxy-5-chloroaniline, N-β-sulfoethyl-2-chloro-5-
Methoxyaniline, N-β-sulfoethyl-2,
5-dichloroaniline, N-β-sulfoethyl-
N-methyl-aniline, N-β-sulfoethyl-
N-ethyl-aniline, N-β-sulfoethyl-
N-ethyl-3-methyl-aniline, N-β-sulfoethyl-N-ethyl-chloroaniline, N-
β-sulfoethyl-N-allyl-aniline, N-
β-sulfoethyl-N-benzyl-aniline, N
-β-sulfoethyl-N-phenethyl-aniline, N-β-sulfoethyl-N-β-carbonamidoethyl-aniline, N-β-sulfoethyl-
N-β-carboxyethyl-aniline, N-β-
Sulfoethyl-N-β-cyanoethyl-aniline, N-β-sulfoethyl-N-β-acetoxyethyl-aniline, N-β-sulfoethyl-N-
β-Hydroxyethyl-aniline, N-β-sulfoethyl-N-ethyl-2-methoxy-5-chloroaniline, N-β-sulfoethyl-N-β-hydroxyethyl-2-methoxy-5-chloroaniline, N- β-Sulfoethyl-N-β-hydroxyethyl-3-chloroaniline, N-β-sulfoethyl-N-β-carboxyethyl-3-chloroaniline, N,N-bis-(β-sulfoethyl)-
Aniline, N,N-bis-(β-sulfoethyl)-
3-Methyl-aniline, N,N-bis-(β-sulfoethyl)-3-chloroaniline, N-γ-sulfopropyl-aniline, N-γ-sulfopropyl-3-chloroaniline, N-γ-sulfopropyl -2-methyl-5-chloroaniline, N-(γ
-sulfo-β-hydroxypropyl)-2-methoxy-chloroaniline, N-(γ-sulfo-β-
hydroxypropyl)-2-chloroaniline, N
-(γ-sulfo-β-hydroxypropyl)2,
5-dichloroaniline, N-(γ-sulfo-β-
hydroxypropyl)-N-ethylaniline, N
-(γ-sulfo-β-sulfatopropyl)-N-
Ethyl-3-methylaniline, N-(γ-sulfo-β-sulfatopropyl)-N-β-sulfatoethyl-aniline, N-(γ-sulfo-β-hydroxypropyl, .N-phenethyl-aniline,
N-(γ-sulfo-β-hydroxypropyl-(β
-hydroxyethyl)-2-methoxy-5-chloroaniline, N-(γ-sulfo-β-hydroxypropyl)-aniline, N-(γ-sulfo-β-hydroxypropyl)-2-chloro-3-methyl-
Aniline, N-(γ-sulfopropyl)-N-ethyl-3-methylaniline, N-(γ-sulfo-β
-hydroxypropyl)-N-β-carboxyethyl-3-chloroaniline, N-(β-sulfo-
α-Methyl-ethyl)-aniline, N-(β-sulfo-α-methyl-ethyl)-2-methoxy-5-
Chloraniline, N,N-bis-(γ-sulfo-
β-hydroxypropyl)-3-chloroaniline,
N-(γ-sulfopropyl)2,5-dichloroaniline, N-β-sulfatoethylaniline, N
-β-sulfatoethyl-N-ethyl-aniline, N-β-sulfatoethyl-N-methyl-aniline, N-β-sulfatoethyl-N-n-butyl-aniline, N-β-sulfatoethyl-N
-ethyl-3-methyl-aniline, N-β-sulfatoethyl-N-ethyl-3-chloroaniline, N-β-sulfatoethyl-N-β-hydroxyethyl-3-chloroaniline, N,N-di-
β-sulfatoethyl-aniline, N,N-di-
β-sulfatoethyl-3-chloro-aniline,
N-β-sulfatoethyl-N-promalyl-
Aniline, N-β-sulfatoethyl-N-2-
Chlorallyl-aniline, N-β-sulfatoethyl-N-benzyl-aniline, N-β-sulfatoethyl-N-β-carbonamidoethyl-aniline, N-β-sulfatoethyl-N-β-carboxyethyl-aniline, N- (4'-sulfophenethyl)-aniline, N-(β-(cyanoethyl)
-N-(4'-sulfophenethyl)-aniline, N-
β-sulfatoethyl-N-β-carboethoxyethyl-aniline, N-β-sulfatoethyl-
β-Cyanethyl-aniline, N-β-sulfatoethyl-N-β-acetoxyethyl-aniline, N-β-sulfatoethyl-N-β-cyanoethyl-3-methyl-aniline, N-β-sulfatoethyl-N-β -Hydroxyethyl-aniline. The diazotization of amines of the general formula (2) can be carried out in generally known manner, for example by the action of alkali nitrous acid and organic acids such as hydrochloric acid, sulfuric acid or phosphoric acid, or with nitrosylmagnetic acid. The coupling reaction with the coupling component of the general formula (3) can likewise be carried out in a manner known per se in a neutral to acidic medium, preferably in a pH range of 1 to 7 and -5°C to +25°C.
It can be carried out at a temperature of 0.degree. C. optionally in the presence of sodium acetate or the like, buffer substances which influence the coupling rate or catalysts such as dimethylformamide or pyridine. The compounds of formula (1) prepared according to the invention can be prepared by salting out with electrolytes such as sodium chloride or potassium chloride, preferably at a pH value of 3.5 to 3.5.
After adjusting to 7.0, it can be separated from the reaction solution, filtered, and then dried. Furthermore, the compounds according to the invention can be isolated from their synthetic mixtures by evaporation or spray drying. If there are large amounts of sulfate ions in the resulting reaction solution, it is recommended to precipitate the sulfate ions as sparingly soluble salts, such as calcium sulfate, before spray drying. It is also possible to use the solution of the compound of formula (1) obtained after synthesis as a liquid preparation for staining, optionally immediately after addition of buffer substances. The novel compounds of the formula (1) are suitable as dyes, in particular as fiber-reactive dyes, and can be applied and fixed fast by methods known for use in reactive dyes, in particular on the substrates described below. The subject of the present invention is therefore also the use of the compounds of formula (1) as dyes, in particular for the dyeing or printing of cellulose fibers and natural or synthetic polyamide fibers or leather. Preferred cellulosic fiber materials are cotton and regenerated cellulose such as viscose rayon and hemp, hemp and jute. Suitable polyamide fiber materials are in particular wool and other animal hair and silk,
Among synthetic polyamides, especially polyamide-6,6,
Polyamide-6, polyamide-11 or polyamide-4. For example, dyeings with very good dyeing yields can be obtained using the diazo compounds according to the invention on cellulose fibers by the exhaust process from long baths using the most alkaline additives. With similarly excellent dyeing yields, the compounds can be used to dye cellulose fibers by the known padding method, in which case the compound of formula (1) can be fixed with an alkali by residence at room temperature, by steaming or by drying. . The printing process is likewise a customary phase process in which the printing paste is carried out in the presence of an acid binder or alkali-imparting agent, such as sodium bicarbonate, sodium carbonate or sodium trichloroacetate, followed by steaming (e.g. 100-103
°C) - or a two-phase process using neutral or weakly acidic printing pastes - in which case after printing the textile material is passed through a hot electrolyte-containing alkaline bath or at the same time an alkaline electrolyte-containing padding liquid. It is possible to use padding, followed by fixation of the compound of formula (1) by steaming or dry heat. This method gives highly colored prints with a good level of contour and a uniform white background. The quality of the print is practically unaffected by changing fixing conditions and the print therefore exhibits satisfactory shade reproduction. The dyeings or prints obtained with the compounds of formula (1) on cellulose fiber materials have considerable fastness properties, of which the most important production and use fastnesses such as sunlight fastness, wash fastness - e.g. °C or 95
-, acid and alkali fullness fastness, water fastness, seawater fastness, acid cross-dye fastness, alkaline and acid sweat fastness and pleat-, ironing- and rub fastness at ℃ are emphasized. Ru. Natural and synthetic polyamide fiber materials are dyed with the new compounds of formula (1), in particular from acidic water-soluble dyebaths or acidic aqueous dye liquors. Preferably, the desired pH value of the dyebath or liquor is adjusted with acetic acid or acetic acid and ammonium acetate or sodium acetate. In order to achieve good uniformity of the dyeing or to improve its uniformity, customary leveling aids such as reaction products of fatty amines such as stearylamine with alkylene oxides such as ethylene oxide and/or cyanuric chloride and approx. It is advantageous to use double molar amounts of the reaction product with aminobenzenesulfonic acid and/or aminonaphthalenesulfonic acid in the dyebath or liquor. Dyeing can normally be carried out at temperatures of 60 DEG -105 DEG C., preferably by the exhaust method, in particular at the boiling temperature of the dyebath or in a printing apparatus at temperatures up to 120 DEG C. The invention is illustrated by the following examples. Unless otherwise stated, the parts mentioned therein are parts by weight and the percentages mentioned relate to % by weight. Parts by volume to parts by weight are the same as liters to grams. Example 1 36.1 parts of 4-β-sulfatoethylsulfonyl-aniline-2-sulfonic acid are dissolved in 200 parts of warm water by addition of sodium bicarbonate under stirring to give an aqueous 5N
- Add 20 parts by volume of sodium nitrite solution and pour the whole onto 200 parts of ice. Next, 31% aqueous hydrochloric acid is gradually introduced while stirring. This is followed by further stirring for another 30 minutes at about 5°C. Excess nitrite is destroyed with some amidosulfonic acid. To this diazonium salt solution was added an acidic solution containing 10.7 parts of 3-methylaniline in 60 parts of water and the coupling was carried out first in the strongly acidic range and later by gradual addition of sodium bicarbonate.
Perform in the PH-range of 3.5 to 3.5. After the coupling is finished, a pH value of 6.5 is adjusted by adding sodium bicarbonate, 20 parts by volume of an aqueous solution of 5N sodium nitrite are added and the mixture is poured gradually into a mixture consisting of 300 parts of ice and 35 parts of 31% hydrochloric acid. . After stirring the diazotization mixture for 2 to 3 hours at about 5° C., excess nitrous acid is destroyed with some amidosulfonic acid. To this is added a solution containing 41.9 parts of the disodium salt of NN-bis-(β-sulfatoethyl)-3-chloroaniline in 150 parts of water and coupling is carried out first in the strongly acidic range and then by addition of sodium bicarbonate. It is carried out at a pH value of 4 to 5. After the coupling has ended, a pH value of 5.5 to 6 is set and the disazo compound according to the invention prepared is isolated by spray drying by salting out with sodium chloride salt. In addition to electrolytes, the formula A dark brown powder is obtained containing the sodium salt of the compound. It has very good dyeing properties and has very good resistance to washing treatments on the aforementioned textile materials such as cotton and wool by the usual and known application and fixing methods for fiber-reactive dyes. Gives yellow-brown dyeing and printing with very good tinting strength. Examples 2 to 13 The method of Example 1 is carried out to prepare disazo compounds according to the invention, with the exception that in this case the N,N-bis-
The disodium salt of (β-sulfoethyl)-3-chloroaniline is replaced in equivalent amounts by one of the coupling components corresponding to general formula (3) described in the following table example. In addition to this, the disazo compounds according to the invention corresponding to the general formula (1) described are likewise obtained in good yields. These fiber-reactive disazo compounds according to the invention likewise exhibit very good dyestuff properties with very good technical properties of use, which make them suitable for fiber-reactive dyes on the aforementioned textile materials, in particular on cellulosic fiber materials and on wool. The very customary application and fixing methods give dyeings and prints with good to very good fastness properties in the shades specified in the respective table examples. The formula member M present in the compounds described by the formula has the meaning given above and is preferably an alkali metal, especially sodium. The formula residue D ₁ described for the compounds according to the invention is of the formula (In the formula, M has the above meaning.)

【table】

Table Example 14 36.1 parts of 4-β-sulfatoethylsulfonyl-aniline-2-sulfonic acid are diazotized as described in Example 1. A neutralizing solution containing 22.3 parts of 1-naphthylamine-6-sulfonic acid in 150 parts of water is added to the diazonium salt solution and the coupling is terminated at a pH value of 4 by gradual addition of sodium bicarbonate. A pH value of 6.5 is then reached, 20 volumes of 5N aqueous sodium nitrite solution are added and the solution is poured slowly into a mixture consisting of 400 parts of ice and 35 parts of 31% hydrochloric acid. Stirring is continued for about 2 hours at about 5° C., and the excess nitrous acid is subsequently destroyed with some amidosulfonic acid. Next, in 180 parts of water, N-(β-sulfoethyl)
An aqueous solution containing 27.5 parts of the disodium salt of 3-chloroaniline is added and the PH value is kept between 4 and 5 by withdrawal of sodium carbonate. The resulting disazo compound is isolated from the coupling mixture by salting out with sodium chloride or by spray drying. In addition to electrolytes, the formula A dark brown powder is obtained containing the sodium salt of the compound. This compound is very well suited as a dye and gives very dark brown dyeings and prints with good fastness properties on cotton and wool with the usual application and fixation for fiber-reactive dyes. Examples 15 to 30 To prepare disazo compounds according to the invention, the method of Example 14 is carried out, except that the sodium salt of N-(β-sulfoethyl)-3-chloroaniline used as coupling component is An equivalent amount of one of the coupling components corresponding to the general formula (3) described in the table example is substituted. In addition to this, the disazo compounds according to the invention corresponding to the general formula (1) described are likewise obtained in good yields. These fiber-reactive disazo compounds according to the invention likewise exhibit very good dyestuff properties with very good technical properties of use, which make them suitable for fiber-reactive dyes on the aforementioned textile materials, in particular on cellulosic fiber materials and on wool. The very customary application and fixing methods give dyeings and prints with good to fastness properties in the shades specified in the respective table examples. The formula member M present in the compounds described by the formula has the meaning given above and is preferably an alkali metal, especially sodium. The formula residue D ₂ described for the compounds according to the invention is of the formula (wherein M has the above meaning).

【table】

【table】

[Table] Example 31 formula 59.4 parts of the aminoazo compound of were diazotized as described in Example 14 and then N-(β-sulfoethyl)-N
A cold aqueous solution of 26.5 parts of ethyl-3-methyl-aniline is coupled to the disazo compound. Conventional post-treatment by spray drying or salting out An alkali metal salt of the compound is obtained, which has very good dye properties. The dyestuffs give very intense blueish-violet dyeings and prints of good fastness on cotton and wool by the application methods customary for fiber-reactive dyes. Example 32 4-β-sulfatoethylsulfonyl)-3′,
49.3 parts of 6'-dimethyl-4'-aminoazobenzene-2-sulfonic acid are adjusted to a pH value of 6 with sodium bicarbonate in 300 parts of water and 20 parts by volume of 5N aqueous sodium nitrite salt solution are added to the solution. Add. This mixture is slowly added to a mixture of 200 parts of ice and 35 parts of 31% aqueous hydrochloric acid to initiate the diazotization reaction.
It is completed under stirring for 3 hours at a temperature of 10°C. Excess nitrous acid is destroyed with a small amount of amidosulfonic acid. Subsequently for coupling N-ethyl-N-
(β-sulfoethyl)-aniline sodium salt
25.1 parts of cold aqueous solution are added and the pH value is brought to 5.5-6 by sparging with sodium bicarbonate. Ceremony after coupling The sodium salt of the compound is isolated by spray drying in a conventional manner. It has very good dye properties and gives dyeings and prints in blueish bordeaux tones with good fastness on cotton and wool by the usual application - and fixation method for textile materials reactive raw materials. . EXAMPLES 33 TO 49 In the following table examples, other disazo compounds according to the invention are shown in free acid form. This can be prepared, for example, analogously to the examples above, from those diazo and coupling components that are clear from the formula. It is preferably isolated from the reaction mixture in the form of its sodium salt. It is also a very good dye with fiber reactivity and has very good technical properties of use, which is customary for fiber-reactive dyes on the above textile materials, especially cellulosic fiber materials and wool. The application and fixing methods give dyeings and prints with good to very good fastness properties in the shades described.

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Table Examples 50 to 57 The method of Example 31 is carried out to prepare the disazo compounds according to the invention, with the exception that in this case N-(β-sulfoethyl)-N-ethyl-3-methyl is used as coupling component. - Replacement of aniline by an equivalent amount of one of the coupling components corresponding to general formula (3) described in the following table example. In addition to this, the disazo compounds according to the invention corresponding to the general formula (1) described are likewise obtained in good yields. These fiber-reactive disazo compounds according to the invention likewise exhibit very good dyestuff properties with very good technical properties of use, which make them suitable for fiber-reactive dyes in the aforementioned textile materials, in particular cellulosic fiber materials and wool. The customary application and fixing methods give dyeings and prints with good to very good fastness properties in the shades specified in the respective table examples. The formula member M present in the compounds described by the formula has the meaning given above and is preferably an alkali metal, especially sodium. The formula residue D ₃ for the compounds according to the invention is of the formula (wherein M has the above meaning).

Table Examples 58 to 71 In the following table examples, further disazo compounds according to the invention are shown in the form of free acids. This can be prepared, for example, analogously to the examples above, from those diazo and coupling components that are clear from the formula. It is preferably isolated from the reaction mixture in the form of its sodium salt. It is likewise a very good dye with fiber reactivity and has very good technical properties of use and is good in the shades described by the usual application and fixing methods for the fiber reactivity mentioned above. Gives dyeings and prints with to very good fastness properties.

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Claims (1)

[Claims] 1 General formula (1) [In the formula, Y is a vinyl group or the formula -CH ₂ -CH ₂ -Z (in the formula, Z
means an organic or inorganic alkaline removable residue or hydroxyl group), n represents a number of zero, 1 or 2, and D is a phenylene residue, which is a lower alkyl group. , lower alkoxy, hydroxy, lower alkanoylamino, benzoylamino, chlorine, bromine, fluorine, and carboxy and/or substituted with one or two substituents selected from the group consisting of carboxy and/or one sulfo group. Can you do it,
or D is a naphthylene residue selected from the group consisting of lower alkyl, lower alkoxy, lower alkanoylamino, benzoylamino, chlorine, bromine, fluorine, carboxy, and sulfo.
or can be substituted with two substituents, E being a 1,4-phenylene residue selected from the group consisting of lower alkyl, lower alkoxy, ureido, lower alkanoylamino, carboxy and sulfo. 1,4-naphthylene residue which can be substituted with one or two substituents or substituted by sulfo, A is an ethylene residue of the formula _-CH2 - _CH2- or Expression-
Ethyleneoxy residue of CH ₂ -CH ₂ -O- or formula -CH ₂ -CH ₂ -CH ₂ -, [formula], [formula] or [formula] (wherein X is a hydroxy group or a lower alkanoyloxy group or is a propylene residue represented by a halogen atom or a sulfato group or a phosphate group), or a residue of the formula [formula] or a residue of the formula [formula], and M is a hydrogen atom or a metal equivalent; , R ¹ is a hydrogen atom, a lower alkyl group, a lower alkenyl group, or a lower alkyl group substituted by phenyl and/or hydroxy, in which case the phenyl residue is substituted by methyl, methoxy and/or chlorine. or hydroxyalkyl groups esterified with acids having 2 to 4 carbon atoms in the alkyl residue, cyanalkyl groups having 2 to 4 C atoms in the alkyl residue, alkyl- or a carboxyalkylene, carbonamidoalkylene or carbalkoxyalkylene group each having 1 to 4 C-atoms in the alkylene residue, a halogenalkyl group or lower halogenalkenyl group having 2 or 3 C-atoms, or a group of formula -A- _SO3M as defined above, where ^R2 is a hydrogen atom, a lower alkyl group, a lower alkoxy group, which group may be substituted by hydroxy, acetoxy, cyan or halogen; or a halogen atom or a trifluoromethyl group, or an alkanoylamino group, such as an _acetylamino acid, a benzoylamino group or a ureido group; , the group is hydroxy, acetoxy,
It can be substituted by cyanogen or halogen or is a halogen atom. ] A water-soluble disazo compound represented by 2 The residue R ¹ is a hydrogen atom or an alkyl group having 2 to 4 C-atoms, which is substituted by a phenyl residue, a hydroxy group, an acetoxy group, a propionyloxy group, a cyan group, or a carbonamide group. or is a chloralkyl radical with 2 or 3 C-atoms or a radical of the formula -A-SO ₃ M as defined above, and in addition the residue R ² is a hydrogen atom - methyl - or ethyl, methoxy or ethoxy groups, which can be substituted by hydroxy, acetoxy or cyan groups or chlorine, or in particular chlorine or bromine atoms, likewise the residue R ³ is a hydrogen atom or a methyl or ethyl group, a methoxy or ethoxy group, which can be substituted by a hydroxy, acetoxy or cyan group or a chlorine atom, or is a chlorine or bromine atom; A compound according to claim 1, represented by general formula (1). 3 Residue E means a 1,4-phenylene residue,
This can be achieved by one or two lower alkyl groups, by one or two lower alkoxy groups, by one carboxy group or by one lower alkanoylamino group or by one ureido group or by one lower alkanoyl group. of the general formula (1), which can be substituted by an amino group and one sulfo group, or E means a 1,4-naphthylene residue, which is substituted by a sulfo group A compound according to claim 1 or 2. 4 D means a 1,4-phenylene residue or a 1,4-naphthylene residue, and both residues are one or two selected from the group consisting of methyl, methoxy, chlorine, bromine, carboxy, and sulfo. The compound according to claim 1, 2 or 3, which is represented by general formula (1) and may be substituted with a substituent. 5 General formula (1) [In the formula, Y is a vinyl group or a group represented by the formula -CH ₂ -CH ₂ -Z (wherein Z means an alkali-removable residue or a hydroxyl group, with or without a group), and n represents a number of zero, 1 or 2, and D is a phenylene residue, which is one or more selected from the group consisting of lower alkyl, lower alkoxy, lower alkanoylamino, benzoylamino, chlorine, bromine, fluorine, and carboxy. It can be substituted by two substituents and/or by one sulfo group, or D is a naphthylene residue, which is lower alkyl, lower alkanoyl, benzoylamino, chlorine, bromine, fluorine, can be substituted with one or two substituents selected from the group consisting of carboxy and sulfo, E is a 1,4-phenylene residue, which can be lower alkyl, lower alkoxy, ureido, lower alkanoyl A is a 1,4-naphthylene residue which can be substituted with one or two substituents selected from the group consisting of amino, carboxy and sulfo, or is substituted by sulfo, and A is of the formula - Ethylene residue of CH ₂ −CH ₂ or formula −CH ₂
-CH ₂ -O- ethyleneoxy residue or formula -
CH ₂ −CH ₂ −CH ₂ −, [formula], [formula] or [formula] (wherein X represents a hydroxy group, a lower alkanoyloxy group, a halogen atom, a sulfato group, or a phosphate group) or a residue of the formula [formula] or a residue of the formula [formula], M is a hydrogen atom or a metal equivalent, and R ¹ is a hydrogen atom, a lower alkyl group, a lower alkenyl group, or lower alkyl radicals substituted by phenyl and/or hydroxy, the phenyl residue can be substituted by methyl, methoxy and/or chlorine, or 2 to 4 carbon atoms in the alkyl residue. hydroxyalkyl groups esterified with acids, having 2 to 4 C atoms in the alkyl residue, cyanalkyl groups having 1 to 4 C atoms in the alkyl or alkylene residue, respectively a carboxyalkylene-carbonamidoalkylene- or carbalkoxyalkylene group, a halogenalkyl group or a lower halogenalkenyl group having 2 or 3 C-atoms or a group of the formula -A- _SO3M as defined above, R ² is a hydrogen atom, a lower alkyl group, a lower alkoxy group, and the group can be substituted with hydroxy, acetoxy, cyan, or a halogen, or is a halogen atom or a trifluoromethyl group, or an alkanoylamino group For example, it can be an acetylamino group, a benzoylamino group or a ureido group, and R ³ is a hydrogen atom, a lower alkyl group, a lower alkoxy group, which group can be substituted by hydroxy, acetoxy, cyan or halogen. or a halogen atom] A method of using a water-soluble disazo compound as a dye. 6. The method according to claim 5, which is used for dyeing or printing hydroxy group-containing or carbonamide group-containing fibers or leather.