CS231998B2 - Manufacturing process of water-soluble monoazocompounds - Google Patents

Abstract

Wasserlösliche Monoazoverbindungen der allgemeinen Formel (1) mit mindestens zwei wasserlöslich machenden Gruppen, in welcher bedeuten: R' ist Wasserstoff, Alkyl von 1 bis 4 C-Atomen, Alkoxy von 1 bis 4 C-Atomen oder Chlor, R2 ist Wasserstoff, Alkyl von 1 bis 4 C-Atomen oder Alkoxy von 1 bis 4 C-Atomen, D ist eine Gruppe der Formel (2a) oder (2b) in welchen die Gruppe -SO₃M jeweils in ortho-Stellung zur Azogruppe steht und M ein Wasserstoffatom oder das Äquivalent eines Metalls ist, R ist Methyl, Carboxy oder Carbalkoxy von 2 bis 5 C-Atomen, K ist Phenyl, das durch 1, 2 oder 3 Substituenten aus der Gruppe Sulfo, Carboxy, Sulfamoyl, Carbamoyl, Alkyl von 1 bis 4 C-Atomen, und Chlor und gegebenenfalls durch eine Gruppe der Formel -SO₂-Y' substituiert sein kann, in weicher Y' für die β-Hydroxyäthyl-Gruppe steht oder eine Gruppe Y der nachstehend angegebenen Bedeutung ist, oder K ist ein Mono-, Di- oder Trisulfonaphthyl-Rest; Y ist die Vinylgruppe oder eine Äthylgruppe, die in ß-Stellung einen als Anion alkalisch eliminierbaren Rest enthält, ausgenommen die Verbindung entsprechend der allgemeinen Formel (1), in welcher Y die ß-Sulfatoäthyl-Gruppe bedeutet und diese Gruppe -SO₂-Y in p-Stellung zur Aminogruppe gebunden ist, R' und R² beide Wasserstoff bedeuten, D einen Rest der Formel (2a) darstellt, R eine Carboxygruppe ist und K für den 2,5-Disulfophenyl-Rest steht.

Sie werden analog bekannten Verfahrensweisen aus den aus Formel (1) ersichtlichen Komponenten (der Anilinverbindung, Cyanurchlorid, der Diaminoverbindung H₂N-D-NH₂ und der Pyrazolon-Kupplungskomponente) hergestellt. Sie besitzen sehr gute faserreaktive Farbstoffeigenschaften und liefern beispielsweise auf Cellulosefasermaterialien farbtiefe und echte Färbungen und Drucke.

Description

The present invention relates to the technical field of fiber-reactive azo dyes. In particular, the invention relates to a process for the preparation of water-soluble monoazo compounds and their use as dyes.

The present invention relates to a process for the production of water-soluble monoazo compounds having fiber-reactive properties according to the general formula 1

Whose

1) and which contain at least two water-solubility-causing groups, such as carboxy, thiosulfato, phosphato and in particular sulfato and sulfo groups, the general symbols in formula 1 having the following meanings:

R 1 represents a hydrogen atom, a C 1 -C 4 alkyl group such as an ethyl group and in particular a methyl group, a C 1 -C 4 alkoxy group such as an ethoxy group and especially a methoxy group, or a chlorine atom;

Snamsná ^R2 is hydrogen, alkyl -s 1 -to 4 carbon atoms such -ethyl group, and in particular under a methyl -group, not bo alkoxy having 1 to 4 carbon atoms such as ethoxy group -A especially methoxy;

D represents a group of formula 2a or 2b

(2a) <2bJ in which the group —SO3M is always in the ortho position to the azo group a

M represents an atom, hydrogen or the equivalent of a monovalent, divalent or trivalent metal, such as ^1, in particular an alkali metal or an alkaline earth metal such as, for example, sodium, potassium and calcium,

R represents a methyl group or an alkoxycarbonyl group having 1 to 4 carbon atoms such as methoxykairbonylovou and ethoxycarbonyl or preferably kairboxyskupinu (formula -COOM wherein M is as defined above], with .symboly R 1, R ² and R may be mutually the same or different meanings;

K represents a phenyl group which is optionally substituted by 1, 2 or 3 substituents selected from the group consisting of sulfo, carboxy, sulfamoyl, carbamoyl, C1-C4alkyl, such as ethyl and especially methyl, C1-C4alkoxy carbon atoms such as ethoxy and especially methoxy, and chloro and optionally a group of the formula -SO2-Y ', in which * Y' is β-hydroxyethyl or · is Y as defined below, or

K represents a mono-, di- or trisulfonaphthyl radical;

Y represents a vinyl group or an ethyl group which, in its position, contains a residue which is eliminable by alkaline action as an anion, such as a β-thiosulfatoethyl group (corresponding to the formula - CH2 - CH2 - S - SO3M, where M has as defined above], a β-phosphatoethyl group (corresponding to the formula —CH2CH2 — OPO3M2, where M · is as defined above), a β-chloroethyl or β-acetyloxyethyl group, or preferably a β-sulfatoethyl group (corresponding to the formula —CH2 — CH2 — OSO3M wherein M is as defined above);

but excluding the compound represented by the general formula (1) in which Y is a β-sulfatoethyl group and the —SO2 — Y group is bonded in the p-position to the amino group, R1 and R2 are both hydrogen, D is a residue of formula 2a, R is and a K represents a 2,5-disulfophenyl radical (corresponding to the compound described first in columns 19/20 of German patent specification 1,265,698).

In a broader sense, those azo compounds corresponding to the general formula 1 in which K represents a 2,5-disulfophenyl radical may be excluded when D represents a group of formula 2a and R represents a carboxyl group.

K is preferably a monosulfophenyl group, a 2,4-disulfophenyl group. 2,5- (4'-isulfophenyl, 3,5-disulfophenyl, monochloronosulfophenyl, dichloronosulfophenyl, monomethylmonosulfophenyl, monochlormonomethylmonosulfophenyl or the radical of formula 2c or especially the radical of formula 2id

in which

R 1, R ² and Y 'have the above meanings and n is 0 or 1 (n = 0 is H) and

R3 and ^R4 which can be the same or; different are hydrogen or chlorine or methyl and

R 'represents a sulfo group or a -SO2-Y group in which Y is as defined above, or K is preferably a mono-, or trisulfonaphthyl radical.

The new azo compounds can exist both in their acid form and in their form. salts. They are preferably in the form of salts, in particular in the form of salts with alkali metals and metals. alkaline earth metals, and are also preferably used in the form of these salts for dyeing (to be understood here and in the general sense and including printing) of materials containing hydroxy and / or carboxamido groups, in particular fibrous materials.

Production method from above. of the above and defined novel azo compounds. of formula (1) according to the invention is characterized in that it is applied to a compound of formula (II)

in which

A represents a group of formula (a) or (b) Cl

AND

N, N-NH-D-NH 3

N

(b) or is hydrogen, and

R ^1, R ² and Y have the abovementioned meanings, in the case the amine of formula II wherein A represents a group of formula (a), after the diazotization of a diazonium salt with a compound of formula III

in which

R and К have the meanings given above and

В represents a hydrogen atom or represents a group of formula (b‘J or (c ‘)

wherein if A is a group of formula (а) then В is a hydrogen atom, if A is a group of formula (b) then В is a group of formula (b'and if A is a hydrogen atom, then В is a group of formula (c ^ť ) wherein the reactants are selected such that the resulting azo compound corresponding to formula 1 contains at least two groups which cause water solubility.

This procedure can be characterized in more detail in specific cases. The process is characterized in that the diazonium compound of the amine of formula (3) is used

Ct

-IL.J-NH-D-NH

N * (3} in which

R ¹ , R ² D and Y are as defined above, in the coupling reaction with an ipyrazole derivative of formula 4

in which

R and K have the meanings given above or that the aminoazo compound of formula 5

D, R and K have the meanings given above, in reaction with the dichlorotriazine derivative of general formula 6

Cl ·

in which

R ¹ , R ² and Y have the above meanings or that the dichlorotriazine derivative of the general formula 7

in which

D, R and K are as defined above, reacted with an amino compound of formula 8

R ⁱ (&) in which

R ^1, R ² and Y have the above meanings, wherein the reactants are chosen so that the resulting azo compound corresponding to the general formula 1 containing at least two groups that cause the solubility in water and which also eliminates the production of the above compounds are described in German Patent Specification 1,265,698.

In the starting compounds of formulas 3, 4, 5, 6, 7 and 8, the symbol Y (which may also be represented by the symbol Y ‘in the meaning of the symbol K) may also be a β-hydroxyethyl group. The compounds of the formula I thus obtainable in which Y or Y 'or both are a β-hydroxyethyl group can be converted into the corresponding compounds of the formula I according to the invention in which or Y 'represents an ethyl group which is substituted at the β-position with an ester residue. Advantageously, the esterification is sulfatization, i.e. the conversion of the β-hydroxyethyl group to the β-sulfatoethyl group analogously to a number of processes known from the literature, preferably using concentrated sulfuric acid or sulfuric acid containing sulfur trioxide as the sulfating agent.

This esterification, preferably sulfation, is necessary if Y in the starting compounds of formulas 3, 6 and 8 is β-hydroxyethyl.

The amines of the formula (3) which serve as starting materials can be prepared analogously to known processes, for example by reacting a diamine compound of the formula (N-D-NH2), where D is as defined above with a dichlorotriazine derivative as defined above. of formula (6) or by reaction of cyanuric chloride (2,4,6-trichloro-1,3,5-triazine) with a diamino compound of formula (II2N-D-NH2) as defined above to give a compound of formula (9)

Cl · (9i in which

D is as defined above, and this compound is then reacted with the ammonium of the above-defined general formula (8).

Aminoazo compounds of the formula (5) which serve as starting materials can also be prepared according to known methods, for example by the preparation of a compound of the formula (10).

R ³ —D — NH2 (10) wherein

D is as defined above and

R ³ is nitro or lower alkanoylamino, such as acetylamino, diazotized, the diazonium compound obtained is coupled with a pyrazolone derivative of the above-defined and defined general formula 4 and in the azo compound of general formula 11 thus produced

in which

D, R ³ , R and К are as defined above, when R ³ is nitro, it is reduced analogously to known methods, and when R ³ is lower alkanoylamino, it is hydrolyzed analogously to known methods to an amino group.

Likewise, the dichlorotriazine derivatives corresponding to the general formula (6) which serve as starting materials can be prepared analogously to known processes, for example by reaction of cyanuric chloride with an amine of the above-mentioned general formula (8).

The synthesis of the dichlorotriazine derivative of general formula (7) can be carried out analogously to known methods by condensation of cyanurchloiride with an amino compound of the above and defined general formula (5) or by reacting the diazonium amine compound of the above and defined general formula (9) with the pyrazolone derivative of the above and defined general formula (4).

both the reaction of the cyanuric chloride with the aminoazo compound of formula 5 leading to the compound of the formula 7 and the reaction of the cyanuric chloride with the amino compound of formula 8 leading to the compound of the formula 6 are. may be carried out in an organic or aqueous organic medium. Preferably, the reaction is carried out in an aqueous medium with the addition of acid binders such as alkali metal or alkaline earth metal carbonates, bicarbonates or hydroxides of alkali metals or alkaline earth metals or alkali metal acetates, the alkali and alkaline earth metals being preferably sodium, potassium and calcium. Tertiary amines such as pyridine or triethylamine or quinoline can also be used as acid binding agents. These condensation reactions are carried out at a temperature of between -10 ° C and + 40 ° C, preferably between -10 ° C and + 30 ° C, particularly preferred at a temperature between 0 ° C and + 10 ° C, as well as at a pH between 1.0 and 7.0.

The reaction of the dichlorotio + azmylamino compounds of formulas 6, 7 and 9 according to the invention with the corresponding amino compounds of formulas 5, 6 and the above defined general formula. of formula IhN-D-NH 2 to form compounds of formula 1, optionally to form intermediates of formula 3, can also be carried out in an organic or aqueous-organic medium. Preferably, however, the reaction is carried out in an aqueous medium, optionally adding an acid binding agent. as above agents. The real ε of the amino groups 3 by the chlorine triazine derivatives in the process according to the invention is preferably carried out at a temperature between 10 and 60 ° C, particularly preferably between 20 and 50 ° C and at a pH value between 2 and 9, in particular. 3 and 8.

The diazotization of the amino compounds of the general formula (3) or the general formula (9) is carried out analogously to known methods, for example in aqueous-organic and especially in aqueous, acidic medium by treatment with nitrous acid. The reaction of the diazonium compounds with the pyrazolone derivatives of the general formula (4) is likewise carried out analogously to known methods, for example in an aqueous-organic but mainly aqueous medium, in a slightly acidic to neutral or very weak alkaline pH range.

The ammos compounds of the formula (8) which serve as starting materials for the preparation of the compounds according to the invention are, for example:

1-Amino-3- (3-tert-butylethylsulfonyl) benzene, 1-aroino-2-methoxy-5-oxoethylsulfonyl) benzene, 1-amino-2-methoxy-4- (3-sulfoethylsulfonyl) benzene, 1- (2-methyl-5-methyl-5-methyl-5-methyl-5-methyl-5-methyl-5-methyl-5-methyl-4-methyl-5-methyl-4-methyl-4- (4-methyl-5-methyl-5-methyl) - (thioethoxyethylsulfanyl) benzene, 1-amino-4-methoxy-S- ( ₁ ((η ₁ ) (β-β-α) - (η 5 -phenyl) benzene), 1-amino-4-methyl- 5- (3-Sulfatoethylsulfonyl) benzene.

1-Amino-2-methoxy-5-methyl-4- (N, Z'-sulfoxoethylsulfonyl) benzene, lsamino +, + dimethoxy-4- (1,3-sulfoethylsulfonyl) benzene, 1-amino-2,4-dimethoxy- 5- (4-Sulfate-ethylsulfonyl) -benzene,

1-Amino-2-methyl-5-methoxy-4- (1S-trifluoromethylsulfonyl) benzene,

2-Chloro-1-amino-5- (N -phthaethylsulfonyl) benzene,

4-chloro-1-amino-2-methyl-3- (3-: sulfatoethylsulfonyl) benzene,

5- chloro-l-amino-2-lnethcι · xy-4- (3ssuifatoethylsulfonyl) benzene and the corresponding / S-hiasulf atoefhylsulf onylderiváty, 3-f ^QS "fatoethylsiulfonylderiváty, fonylderiváty, / + - ^ ^ read." Uy ( The hydroxy-vinyl-sulfonyl derivatives and the optional β-hydroxyethylsulphonyl derivatives of these n-sulfatoethylsulfonyl derivatives, further preferably 1-amino-4- (N-phenylphenylethylsulfones) benzene.

its corresponding thiosulfatoethyl derivatives, phosphatoethyl derivatives, chloroethyl derivatives, acetoxyethyl derivatives. and vinyl derivatives and optionally

The pyrazolone compounds which correspond to the general formula 4 and which serve as starting materials for the production of the azo compounds according to the invention are, for example, the following compounds:

1- (2'-sulfophenyl) -3-methylpyrazol-5-one,

1- (3‘-sulfophenyl) -3-methylpyrrazol-5-one,

1- (4'-sulfo-enyl) -3-methylpyrazol-5-ene, 1- (2 ', 4'-disullophenyl) -3-methylpyrazol-5-one, 1- (3', 5'-disulfide) enyl-3-methyl-3-methyl-1,3-aza-3-methyl-1,3-pyrazol-5-one, 1- [2 ', 5'-disulfophenyl) -3-methylpyazol-5-one, 1- (2') -chloro-4'-sulfophenyl) -3-methylpyrazol-5-one;

1- (2'-chloro-5 ^< -sull (oPrices · 1)

-5-one, l- (2 ', 5 ^{<dichloro-4 <-s} · ulfofenhl) -3-methylphrazol-5-one,

1- ^{(2R-methyl-4'-sulfofe:} · phenyl] -3-methy.lpyrazol-5-one, l- (4'-methyl-2'-snlfofenyl] -4-methylphr · azΌl-5-one; l- (2'-methyl-3-chloro-4 ^{s <-sulfofenyl)} -3-metihhlphrazcl-5-one,

1- (2'-chloro-6'-methyl-4'-enyl s'ulfof j -3-meethhlpyrazol-5-one, L - (- ^s -carboxylate xyfenhl · - · metihylpyr 3-triazol-5-oιn ,

1- (3'-phenyl] -3-methyiphraaol-5-one, l .- (4'sS'ulfamchlfe.nyl) -3- methylpyraaol-5-one, l- (6'-sulfonafl-2 ^<yl -3-Methylpyrazol-5-one

1- [4 ', 8'-disulfonaphth-2-yl) -3-methylpyrazol-5-one, 1- (5', 7'-disulfonaphth-2'-yl-3'-methylpyrazol-5-ol),

1- (3 ', 6', 8 ⁱ -trisulfonaft-2'-yl) -3-methylp'yraaol-5-one,

1- (4 ^<, 6 ', 8'-trisu.lf onaft-alkyl) -3-methylpyrazole-5-one;

1- (6'-51'-onan-1'-3-methylphrazol-5-one), 1- (7'-sulfonaphth-1'-yl) -3-methylpyrazol-5-one,

1- [3‘- (1H-Atoethylsulfonyl) phenyl] -3-methylpyrazol-5-one,

1- [4 '(/ 3-sulphate atoethylsulfonyl) phenyl] -3-methylpyrazole-5-one. L- [3' or 4 '- (/ - ₁ thio ^ullatoet: h.ylsulfonyl) phenyl] -3 methylpyrazo-5-one, 1- [3'- or 4 '- (R-isatoethylsulfonyl) phenyl] -3-methylpyrazol-5-one, 1- [3'- or 4' - [oS-] ace-oxyethylsulfonyl) phenyl ] -3-ιonethylpyrazol-5-one, l- [3 'or 4' - (/ ^ι ^ shiorethylsulfs ethenyl) phenyl] -3-methylpyrazole-5-one, l- [3'- or 4'-vinyl · sulfphenyl) -3-methylpyrazol-5-one;

1- [3'- or .4 '- ((^ - ^ 5 ^ <^ αΌsχett ^ i ^ ^ l ^ l ^ d LTO ₁ nylj phenyl] -3-methylpyrazole-5-one compounds further above. Mentioned of the type in which the carboxyl or methoxycarbonyl or ethoxycarbonyl group is present in place of the methyl group at the 3-position of the pyrazolone ring, further the pyrazol-5-one derivatives which in the 3-position of the pyrazolone ring are substituted by a methyl or carboxy or methoxycarbonyl or eth group and in each case they are substituted in the 1-position of the pyrazolone radical

2-methoxy-5-methyl-4- (β-sulfetylsulfsnyl) phenyl,

2,5-dimethoxy-4- [p-sulfonylsultonyl) phenyl,

2-methyl-5- (3S-sulfatoethylsulfanyl) -phenyl, .alpha.-methyl-5- (5-sulfanyl) -phenyl] -phenyl,

2-methoxy-5- (3S, 4-tert-ethylsulfsnyl) -phenyl,

4-methoxy-5- [(3-sulfatoethylsulfonyl) phenyl] phenyl,

2-i ^ ^{(^:} tho ^> ^ y - 41 _[[1- 3-sulfonic atsethylsultonyl jfenylovou group

2-methyl-4- (N-sulfattoethylsulfonyl) phenyl group,

2,4-Climethoxy-5- (3-sulfethoxyethylsulfonyl) phenyl,

2-methyl-5-methoxy-4- (3-sulfatoethylsulfonyl) phenyl or such phenyl; which is . sulfatoethylsulfonyl group replaced by ί. <.. ... Λ. - <

(1-Hiosulfato-ethylsulfonyl), (1-methylsulfonyl), (3-acetoxyethylsulfonyl), (3-acetoxyethylsulfonyl), (3-hydroxyethylsulfonyl) or vinylsulfonyl.

Diaminos Compounds corresponding from above. the above general formula. H2N — D — NH2, which serve as. The starting materials for the production of the azo compounds according to the invention are. such as 1,3-diaminobenzene-4-sulfonic acid and 1,4-diaminobenzene-2-sulfonic acid.

As nitro- and alkanoyl amino derivatives corresponding to the general formula. 10 that can. to produce · intermediates · in the synthesis of the compounds of the invention may be mentioned. for example 4-nitro-2-sulfoaniline, 4-acetylamino-2-sulfoaniline, 5-nitro-2-sulfonaniline and 5-acetyl amino-2-sulfoaniline.

The separation and isolation of the compounds of formula (1) produced by the process of the invention from the reaction mixture can be carried out by generally known methods, such as, for example. either by precipitation from the reaction mixture by means of electrolytes such as chloride; sodium or potassium chloride, by evaporating the reaction solution, for example by spray drying, and a buffering agent may be added to the reaction solution;

The compounds of the formula (1) produced by the process according to the invention are fiber-reactive and have very good dye properties. They can therefore be used for dyeing (including printing) materials containing hydroxyl groups and / or carboxamido groups. Solutions of the compounds of the invention may also be used. which arise during the synthesis, respectively. after addition of a buffer, optionally also after concentration, directly as liquid preparations for dyeing.

Subject of the present. of the invention is. thus also the use of compounds of the general formula. of formula 1. according to the invention for dyeing. (including .printing) materials containing. hydroxyl. and / or carboxamido groups and / or methods for their use on. of these substrates.

These materials are coming. in the form of fibrous materials, in particular in the form of fibrous materials. in the form of textile fibers such as yarns, coils and. of fabrics. This can be done. analogously to known procedures by:. The monoazo compound of formula 1 is applied in dissolved form. on the substrate or - eat. the substrate impregnates a. then. on this material or in this material. fixates, optionally under the effect of heat and / or optionally under the action of an alkaline active agent.

Materials. The hydroxyl-containing groups are materials of natural or synthetic origin, such as cellulose fiber materials or regenerated cellulose materials. at polyvinyl alcohols. Cellulose. fibrous. the materials are preferably cotton,. but. also . other plant fibers, such as. cannabis,. jute and ramie fibers. Regenerated. cellulosic fibers are, for example. viscose. staple and viscose rayon.

Materials. containing carboxamido groups are, for example, synthetic and. natural polyamides. a. polyurethanes,. especially in. in the form of fibers such as wool and others. animal fibers, silk, leather, polyamide-0.6, polyamide-6, polyamide- !! and polyamides.

The compounds of formula 1 prepared by the process according to the Invention This invention can be on the substrates mentioned, in particular the 'said fiber material, applied to and fixed ^one known application techniques for the dyes which are soluble in water, particularly for water-soluble dyes and fiber-reactive. Such dyeing and fixing procedures are described in the literature in numerous places.

Thus, these dyes provide very good dye yields, as well as excellent color compositions, to the cellulosic fibers by pulling out the long fiber using various acid-binding agents and optionally neutral salts, such as sodium chloride or sodium sulfate. The dyeing is preferably carried out in a water bath at temperatures between. 60-105 ° C, optionally at. temperatures up to 120 ° C per ° C. and optionally in the presence of conventional dyeing aids. In this case, the lacquer can be introduced into the hot bath and the bath is slowly heated to the desired dyeing temperature and the dyeing process is completed at this temperature. Neutral salts which accelerate the dye uptake can only be added to the bath, possibly even after reaching the temperature at which the dyeing itself is carried out.

Also, excellent dye yields and a very good dye composition are achieved on the cellulosic fibers by fixation, and the fixation can be carried out by dwelling at room temperature or at elevated temperature, for example up to about 60 ° C, by steaming or dry heat in the usual manner.

Also according to conventional printing processes for cellulose fibers, which can be carried out in a single phase, for example by printing with a printing paste containing sodium bicarbonate or other acid binding agent and subsequent steaming at temperatures of 100 to 108 ° C or biphasic, for example after printing neutral. or by weakly acid printing with ink and subsequent fixation by conducting the electrolyte material with a hot alkaline bath containing electrolyte, or by overprinting the printed material with an alkaline flotation bath containing electrolyte followed by delay or steaming or treatment. Intensive prints with a good state of contours and a clear white pool are obtained by dry heat on this over-flaked material, and the quality of these prints remains virtually unaffected by changing fixation conditions.

For dry heat fixing according to conventional thermofixation procedures, hot air at a temperature of 120 to 200 ° C is used. In addition to the usual water vapor at a temperature of 101 to 103 ° C, such superheated steam and pressure vapor at temperatures up to 160 ° C may be used.

Acid binding agents and agents for fixing the compound of formula 1 to cellulosic fibers are, for example, water-soluble alkali metal and optionally alkaline earth metal salts of inorganic or organic acids or compounds which release alkali in the heat. Particular mention should be made of alkali metal hydroxides and alkali metal salts derived from mild to moderate inorganic or organic acids, of which sodium and potassium are preferred. Such acid-binding agents are, for example, sodium bicarbonate, potassium carbonate, sodium formate, sodium phosphate, sodium phosphate, sodium trichloroacetate, water glass or sodium phosphate.

By treating the compounds of the invention with acid binding agents, optionally under the effect of heat, the compounds of the invention (dyes) chemically bind to cellulose fibers; on these fibrous materials, the compounds of the invention exhibit very high fixation yields using dyeing and printing processes. The dyeings on cellulose fibers exhibit excellent wet fastness after the usual rinsing action to remove unfixed dye fractions and, moreover, unfixed dye fractions are readily washable due to their good cold water properties.

The dyeing of polyurethane or natural or synthetic polyamide fibers is usually made of acidic. environment. Thus, for example, acetic acid and / or ammonium sulphate and / or acetic acid and ammonium ociian or. acetate. sodium to obtain the desired pH. In order to achieve a useful color uniformity, it is recommended to add conventional leveling aids such as triple cyanuric chloride reaction product. molar amounts of aminobenzenesulfonic acid and / or aminonaphthalenesulfonic acid or based on a reaction product such as stearylamine with ethylene oxide. As a rule, the dyeing material is introduced into the bath at a temperature of about 40 DEG C., where it is kept in motion for some time, the dyeing is then adjusted to the desired weakly acidic, preferably by adding a slightly acidic pH to the desired acid. between. 60 and 98 ° C. The dyeing may also be carried out at boiling temperatures of up to 120 ° C (under pressure).

Coloring and printing of which. is achieved using compounds. of the formula (1) according to the invention are generally characterized by bright greenish yellow to yellowish orange shades and a high color intensity. In particular, the dyeing and printing on cellulosic fibrous materials have good fastness to wind and good to very good wet fastness, such as · linen fastness, washboard fastness, water fastness, seawater fastness, color fastness and perspiration fastness, · they also have good pleating stability, ironing stability and abrasion stability.

Of particular importance is the use of the compounds of the formula I according to the invention for dyeing wool using fiber reactivity. In particular, it is also possible to dye wool with non-felt treatment or wool with little ¹ felt treatment (cf., for example, H. Rath, Lehrbuch der Textilchemie, Springen, Verlag 3rd edition (1972), pp. 295-299), in particular treated wool. by the so-called Hercosette procedure (page 298), J. Soc. Dyers and Colorist 19712, 93-99, and 1975, 33-44) with very good stability.

The method of dyeing wool is carried out by a conventional and known dyeing method, wherein the fiber-reactive compound of the formula I is preferably first applied from an acid dye bath having a pH of from about 3.5 to 5.5 under pH control by the extraction procedure and at the end of time dyeing, the pH is shifted to a neutral and possibly slightly alkaline range up to a pH of 8.5 in order to achieve a complete reactive bond between this dye of formula 1 and the fiber, particularly when the desired high color saturation is desired. At the same time, the non-reactively bound portion of the dye is released.

The method described herein also applies to dyeing fibrous materials from other natural polyamides or from synthetic polyamides and polynethanes. Dyeing is carried out at temperatures from 60 to 100 ° C, but may also be carried out in closed equipment, for dyeing at temperatures up to 106 · ^{C 1} C. Since the solubility of the compounds of the general formula · · 1 in water is very good, these compounds can also be used advantageously in conventional continuous dyeing processes. The color saturation achieved using the compounds of the formula I according to the invention is very high. Said compounds give bright, greenish-yellow to yellowish-orange shades on fibrous materials, particularly in reactive wool dyeing. A high degree of bath depletion can be found at temperatures of 100 to 106 ° C in dyeing.

In the case of the dyeing obtained by the compounds of the general formula (1) according to the invention, the otherwise customary additional action of ammonia on the dyeed goods can be dispensed with. Surprisingly, the dyes according to the invention exhibit a very good color composition in comparison with the structurally similar known dyes, while achieving brilliant shades even in deep tones. In addition, they exhibit a very good ability to combine with other fiber-reactive dye wool, which allows a surprisingly uniform coloring of the fibers. It is also possible to uniformly dye wool fibers of different provenance using the compounds according to the invention. Optionally, leveling aids such as N-methyltaurine can optionally be added to improve egality.

Using conventional dyeing aids which have a fiber affinity, the compounds of the present invention also provide uniform dyeing on wool with a non-shattering or a weak felting treatment. In light to medium color shades, even without additional ammonia treatment, a very good level of wet fastness can be achieved, but optionally, additional ammonia treatment can be advantageously used. In addition to the high light fastness of these wool dyes, very good wet fastnesses, in particular excellent sweat fastness under alkaline conditions and very good fastness in the wash at 60 ° C, even with high shades .

The following examples serve to illustrate the invention. Parts are by weight,% refers to percent by weight unless otherwise indicated. Parts by weight are relative to parts by volume as kilograms per liter.

The compounds described in the examples by formulas are given in the form of free acids; in general, these compounds are prepared and isolated in the form of their salts, such as, in particular, sodium or potassium salts, and in the form of salts, they are also used for dyeing. They can also be used in the synthesis of the starting materials mentioned in the following examples, in particular the examples summarized in the table, in the form of the free acid, as such or in the form of their salts, preferably alkali metal salts, such as sodium or potassium salts.

Example 1

and)

A solution of pH 6,148 parts of 4- (3-sulfatoethylsulfonyl) aniline in 500 parts of water is mixed into a suspension of 100 parts of cyanurchloiride and 3 parts of a conventional surfactant in 800 parts of ice and water. The reaction mixture is stirred for some time at a temperature between 0 and 5 ° C while maintaining the pH between 3.5 and 4.5 with sodium bicarbonate. The conversion of the acylation reaction is 99% or more. .

(b)

The reaction mixture produced according to (o) is mixed into a solution having a pH of between 6 and 7, consisting of 94 parts of 1,3-diaminobenzeline-4-sulfonic acid in about 350 parts of water. The reaction mixture is heated to a temperature of 40 ° C and then stirred at a temperature between 40 and 45 ° while maintaining the pH with sodium hydrogen sulphite between 5 and 6 until it is practically no longer possible to detect the presence diamino compounds.

O)

The reaction mixture obtained from the second acylation reaction according to paragraph b) is mixed with the addition of 10 g parts of ice and 150 parts by volume of a 31% aqueous hydrochloric acid solution. Diazotization is carried out by adding an aqueous solution of 35 parts sodium nitrite at a temperature between 0 ° C. and 10 ° C. The resulting diazotization mixture is then added to a solution having a pH of between 6 and 6.5, which consists of 142 parts of 1- (4'-sulfophenyl) -3-carboxypyrazol-5-one in about 1100 parts of water, with stirring, while maintaining the pH between 4.5 and 6 with sodium bicarbonate for the total time of the coupling reaction, stirring the reaction mixture for some time to complete the coupling.

The monoazo compound thus prepared is isolated in a conventional manner, for example by evaporating or drying the neutral solution obtained in the synthesis by spraying or salting out an electrolyte salt such as potassium chloride. An electrolyte-containing yellow powder is obtained which contains an alkali metal salt of the compound of the following formula such as. for example potassium salt:

CH.

| AND

2. 3

This azo compound according to the invention has very good dye properties, in particular it has very good reactive dye properties. to fibers, and proceeds on the materials described in the description, such as. especially on cellulosic fibrous materials, such as cotton, by application and fixation methods customary in the art, in particular using the methods described and used for fiber-reactive dyes, color-intensive, bright greenish-yellow dyes and prints with very good fastness to light and with good wet fastness, such as especially good fastness in underwear, washboard, sweat and discoloration.

Example 2

and)

A solution of 39 parts of cyanuric chloride in 150 parts by volume of acetone was added. leave stirring. pour on 300 parts of ice. About 1000 parts by volume of aqueous neutral are then mixed into this suspension. of a solution below 10 ° C containing 110 parts of the aminoazo compound of formula

The reaction mixture is stirred for a further 4 hours at 0 to 10 ° C until the presence of the amine can no longer be practically detected. The pH is maintained between 4 and 5 throughout the acylation reaction.

ь) '2

400 parts by volume of an aqueous neutral solution 59 parts of 4- (ε-sulfatoethylsulfonyl) aniline are mixed into the reaction mixture produced according to a). Thereafter, the reaction mixture is heated at 40-45 ° C for 2 hours and then stirred for another hour at a temperature between 40 ° C and 50 ° C, maintaining the pH with sodium bicarbonate between 4 ° C until completion of the acylation reaction. 5 and 6.5.

The monoazo compound of the invention produced according to this variant of the process is. The compound is isolated in the usual manner, for example according to the data given in Example 1. This compound is. The same monoazo compound according to the invention, which was produced according to example 1, and correspondingly has the same good barium forming properties and good stability as the compound according to the invention which was produced according to example 1.

Example 3

For the preparation of the monoazo compound of the invention, the processes described in Example 1 are followed, but replacing the 4- (4-sulfatoethylsulfonyl) aniline used in Example 1a therein with 156 parts of 4 - (.beta.-thiosulfatoethylsulfonyl) aniline.

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Example 4

In order to produce the monoazo after treating the reaction solution and isolating the monoazo, an electrolyte-containing powder is obtained which contains an alkali metal salt of a compound of the following formula such as sodium salt and / or potassium salt:

according to the invention, the methods described in Example 2 are followed, but the aqueous solution of 4- (β-sulfatoethylsulfonyl) aniline used therein is replaced in Example 2b with a solution of 39 parts of 4-vinylsulfonylaniline in 200 parts by volume of acetone.

After treatment of the reaction solution and isolation of the produced azo compound, an electrolyte containing a powder is obtained which contains an alkali metal salt of the compound of the above formula, such as the sodium salt of the compound of the formula

SO ₃ H

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This compound of the invention also exhibits very good dye properties and provides intensive, greenish-yellow dyeings and prints with good light fastness and dd imo by the application and fixation methods customary in the art for fiber-reactive dyes, for example on cotton. kir ý mistá 1 person t.

Example 5

In order to produce the monoazo compound of the present invention, the processes described in Example 2 are followed, but the aqueous solution of 4- (4-sulfatoethylsulfonyljaniline) used in 46 is replaced with 46 parts of pulverulent 4- (β-chloroethylsulfonyl) aniline.

After treatment of the reaction solution and isolation of the produced monoazo compound, an electrolyte-containing powder is obtained which consists of an alkali metal salt of a compound of the formula below, for example a sodium or potassium salt of the formula

Cl ·

This monoazo compound of the invention has very good properties as a colorant. This dye is obtained, for example, on cotton using the application and fixing methods customary in the art for fiber-reactive dyes, color-intensive, green-yellow dyes with very good light fastness and wet fastness.

Example 6

and)

A solution with a pH value of between 6 and 6.5 consisting of 59.2 parts of 4- (3/sulphonylthioletylphenyl) aniline in 200 parts of water is mixed into the suspension obtained by slow addition of the solution. 40 parts cyanuric chloride in 100 parts by volume of acetone to 320 parts of ice. During the acylation reaction, the pH is maintained between 3.5 and 4.5 with sodium bicarbonate and the temperature is maintained between 0 and 10 ° C. The reaction mixture was further stirred at this temperature until the presence of the amine was virtually no longer detectable.

(b)

1000 parts by volume of an aqueous, neutral solution containing 110 parts of the aminoazo given in the form of the formula in Example 2a) is allowed to flow to the reaction mixture prepared according to a) described above, and then the temperature of the reaction mixture is increased to Deň: 32 ° C. With the aid of sodium bicarbonate or sodium carbonate, the pH of the reaction mixture is maintained between 4.5 and 6 throughout the acylation reaction. The reaction mixture is further stirred at a temperature between 40 and 60 ° C until the acylation reaction is practically completed.

The monoazo compound thus prepared is isolated in a conventional manner, for example by precipitation with potassium chloride from the reaction solution. Filtration and drying and grinding of the precipitate yields a yellow, electrolyte-containing powder containing salt; as for example the potassium salt of the monoazo compound of the invention presented in the form of the formula in Example 1. The monoazo compound of the invention produced by the process variant described herein, which is identical to the compound described in Example 1, exhibits equally good dyeing properties and fastnesses dyeings and prints obtained with this compound.

Example 7

In order to produce the monoazo compound of the invention, the procedures of Example 1 are followed, but the 1,3-diaminobenzene-4-sulfonic acid used in Example 1a) is replaced with an equal amount of 1,4-diaminobenzene-2-sulfonic acid. The corresponding alkali metal salt of the compound of the following formula is obtained:

Cl ·

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N ~ N

OH

COOH which also has very good dye properties. This compound provides dyeing and printing processes customary for reactive dyes on cellulosic fibrous materials, such as cotton, color-intensive, bright, yellowish-orange coloring and prints with very good fastness to light and with very good wet fastness, such as good stability in underwear, washboard and sweat.

Examples 8 to 243

The following examples summarized in the table describe additional monoazo compounds of the invention which correspond to the general formula (1) by their use. components from which they are built together with the rest of the cyanuric chloride. These compounds can be prepared from these amino compounds and cyanuric chloride by the process of the invention, such as one of the process variants described in Examples 1-7 above. The compounds exhibit very good dyeing properties and provide on the materials described herein. as in particular on cellulosic fibrous materials such as cotton, color-intensive dyeing and prints with good fastness to the color shade shown for cotton in each example in the table.

In the examples given in the table, the symbols Z1 to Z have the following meanings:

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Z2: -SO2-CH2-CH2-S-SO3M

Zs: —SO2 —CH2 —CHa —Cl

Z4: -SOa-CI-I = CH2

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t-I CM (an example of a diaimine of the formula amine isomeric pyrazolone derivative of color number H2N-D-NH2 of formula 8 of formula 4 shade

CD 0 r-i CM what m T — 1 CM Cm CM CM CM CM CM CM cm CM CM CM CM

example of a diamine of the formula amino compound pyrazolomi derivative color number / H2N — D — NH2 of formula 8 of formula 4 shade

319'98 example of diaimines of general formula amino compound pyrazolone derivative color number H2N — D — NH2 of formula 8 of formula 4 shade

an example of a diamine of the formula amino compound pyrazolone derivative colored

The number <H2N — D — NH2 of formula 8 of formula 4 shade

к СП CM

СП

CM

СП 0 t — 1 СП Ml Μ см CM CM

an example of a diamine of the formula -amino amine pyrazolone derivative color number H2N — D — NH2 of formula 8 of formula 4 shade ^: —h ы ~ ^_ X

4- * d> N

XD X ode d ф ф

'X ^

WITH

X§ X code d φ ф

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CM c? xr CM

2β

Application Example 1:

parts of the compound of the invention (in the form of the sodium salt) of Examples 1, 2 or 6 are dissolved together with 50 parts of urea in 300 parts of water. The solution obtained is stirred at a temperature below 40 ° C in 400 parts of a neutral, aqueous 4% alginate sparger. 10 parts of sodium carbonate are then added and the mixture is supplemented with 4% v-oidine alginate dye to a total of 1000 parts. The mixture is mixed well and the cotton paste is printed with the printing paste which, after drying at 60 DEG C., is treated for 5 minutes with saturated steam at 100 DEG-103 DEG C. in a commercially available steaming unit. The printing is then completed by rinsing with cold and hot water, washing with neutral detergent and rinsing again in water. After drying the goods, a color-intensive greenish-yellow printing with very good fastness to light and very good wet fastness is obtained.

Application Example 2

The mercerized cotton fabric is padded with an aqueous dye bath at 20 ° C at a bath consumption of 80% by weight of the product, wherein the baling bath contains 20 grams per liter of sodium asasi compound of Examples 1, 2 or 6 as well as 18 g. g 33% sodium hydroxide. The weave cloth is wound on a pile, sealed in a foil and allowed to rest for 8 hours at room temperature. The dyeing is then completed by rinsing in cold water, followed by treatment with an aqueous bath containing a small amount of acetic acid and rinsing in cold and hot water. After drying, a color-intensive greenish-yellow coloring with very good light fastness and very good wet fastness is obtained.

Application Example 3

100 parts of mercerized cotton fabric are treated for 10 minutes at 60 ° C in 3000 parts by volume of an aqueous dye bath containing 5 parts of sodium salt of the compound of the invention of Example 1 as well as 150 parts of anhydrous sodium salt. After 10 minutes of treatment, 15 parts of anhydrous sodium carbonate and 4 parts of 33% sodium hydroxide are added. The dyeing is continued for 60 minutes at 60 ° C. Then, the dyeing process of the dyed fabric is completed in a conventional manner, for example as described in Application Example 2.

A color-intensive, greenish-yellow coloring with very good fastness to. light and with very good wet stability.

Application Example 4

100 parts of wool fabric is introduced into an aqueous dyebath at 40 ^Q C, consisting of 3000 parts of water, 2 parts of the sodium salt of the compound of the invention described octanoate ⁴ Example 1 to 0.15 parts adičiního product, 12 pmol of ethylene oxide with 1 mole of stearylamine, 2 parts of ammonium acetate and 2 parts of 60% aqueous acetic acid. The temperature of the dyeing bath was raised to boiling point for 30 minutes and dyeing was continued for 60 minutes at 100 degrees Celsius. After the usual rinsing and finishing of the obtained dyeing of the wool, this wool fabric exhibits a color-intensive, greenish-yellow hue with very good light fastness and very good wet fastness.

Application example 5

It is dyed as described in Application Example 4, but the wool fabric is replaced with 100 parts of ε-polycaprolactam fiber fabric. Color-intensive, greenish-yellow coloring with good use stability is also obtained.

According to the above application examples, other monoazo compounds of the present invention may also be used in the dyeing and printing processes described herein in the Examples illustrating the manufacturing process as well as in the Examples summarized in tabular form. In an analogous manner, for example, using these dyeing and printing methods as described in application examples 1 to 5, with some other dye according to the present invention, also very color-intensive results are obtained.

dyeing prints with good light fastness and good wet fastness in color shades, which are always given for the respective exemplary embodiments or for the examples summarized in the table.

Claims (13)

A process for the preparation of water-soluble monoazo compounds of the general formula 1 OH with at least two water solubility groups, wherein: R ¹ .zn <am ^: eaná. hydrogen atom; (4) carbon atoms, (C1-C4) alkoxyskuipin or chlorine; R ² is hydrogen, alkyl having 1 to 4 carbon atoms, or ·. (C 1 -C 4) alkoxy D represents a group of the formula 2a or 2b. except for compounds corresponding .obecnému formula 1, wherein Y is / -sulfatoethylovou group and the group -SO-Y is bonded at the p-position to amiinoskupině, ^R1 and R2 are both. hydrogen, D is a radical of formula (2a), R is a carboxy group and K is a 2,5-di-sulfophenyl radical, characterized in that the compound of the formula (II) in which the -SO-M group is always ortho-to the azo group and M is hydrogen, sodium or potassium, R is methyl, carboxy of the formula —COOM, wherein M has the above. meaning, or. is C1-C4alkoxycarbonyl wherein the R1, R2 and R3 symbols are the same or different from each other; K represents a phenyl group which is optionally substituted by 1, 2 or 3 substituents selected from the group consisting of sulfo, carboxy, sulfamoyl, carbamoyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy carbon atoms and chlorine and optionally a group of formula -SO2-Y ', wherein: Y ‘represents a hyd -hydroxyethyl group or a group Y as defined below, or K represents a mono-, di- or trisulfonaphthyl radical; Y represents a vinyl group or an ethyl group which contains, in the - position, a residue which is alkalinely eliminated as the anion, A is a group of formula (a) C 1-6 -nH-d-nh. N or (b) ηαόο or is hydrogen, and R 1, R ² and Y have the abovementioned meanings, in the case the amine of formula II wherein A represents a group. of formula (a) after its diazotization to diazonium. the salt is reacted with a compound of formula III wherein: R and K have the meanings given above and B represents a hydrogen atom or represents a group of formula (b‘j or [c‘J H ₂ N — D — N = N— (b ') or. CH Ct —t J J NHNH-D-N-N (c) wherein when A is a group of formula [a] then B is an atom. of hydrogen when A is a group of formula ('b) then B is a group of formula - (bj and if A is a hydrogen atom then B - is a group of formula - (c'), wherein the reaction components are selected such that - the resulting azo compound corresponding to the general formula 1 contained at least two groups which cause water solubility. 2. A process as claimed in claim 1, wherein the corresponding compounds of the formulas II and III are used as starting materials to give compounds of the formula I in which at least two water-solubility-causing groups are present, with the exception of a compound of formula 1, wherein K is a 2,5-disulfophenyl group when D is a group of formula 2a as defined in 1, and R is a carboxy group. 3. A process according to claim 1, wherein the corresponding compounds of the formulas II and III are used as starting materials to form a compound of the formula I having at least two water-solubility-causing groups in which: R 1 represents an alkyl group having from 1 to 4 carbon atoms, an alkoxy group having from 1 to 4 carbon atoms or a chlorine atom, R ² represents a hydrogen atom, an alkyl group -S 1 to 4 carbon atoms or alkoxy -s 1 to 4 carbon atoms, the -Symbol R 1, R ² and R may be mutually the same or different, and Y represents a vinyl group or an ethyl group which contains an alkali-eliminable residue in the form of an anion, or in which: R 1 and R 2 are both hydrogen and the group -SO 2 -Y, where Y is as defined above, is bonded in meta-position to the amino group, -a D, - R, Κ, M and Y ‘have the meanings given in point 1. 4. Process according to claim 1 or 3, characterized in that the corresponding compounds of the formulas II and III are used as starting materials to give the compounds of the formula I with at least two water-solubility groups in which R1, R2 , Y, D and R have the meanings given in item 1, and K represents a monosulfophenyl group, a 2,4-disulfophenyl group, a 2,5-disulfophenyl group, a 3,5-disulfophenyl group, a monochlormonosulfophenyl group, a dihormonosulfophenyl group, a monomethylmonosulfophenyl group, an imonochlormonomethylmonosulfophenyl group or a residue of formula 2c wherein: R 1, R 2 and Y ‘have the meanings given in -1 and n is -n 0 or 1. 5. The method of item 1 or 3-. -se characterized in that -with starting from -compound corresponding to formulas II and III to give a Compound of Formula I, -s least -dvěma solubilising groups of water in -Which R 1, R ² and Y 'have the the meanings given in (1) and (K) are those of formula (2d) wherein: R3 and ^R4, which are mutually -stejné or different, represent a hydrogen or chlorine atom or- -methyl -group and R &lt; 1 &gt; -sulfosulfone or a group -SO2-Y in which Y is as defined above. 6. A process according to claim 1 or 3, wherein the corresponding compounds of formulas II and III are used as starting materials to form compounds of formula 1 with at least two water-solubility groups in which R1, R2, Y D and R have the meanings given in -1 and K represents a monosulfo-, disulfo- or trisulfonaphthyl radical. 7. A process according to any one of claims 1 to 6, characterized in that the corresponding compounds of the formulas II and III are used as starting materials to produce the compounds of the general formula: The compound of formula 1 wherein R is carboxy. Process according to one of Claims 1 to 6, characterized in that: the corresponding compounds (II) and (III) are used as starting materials to give a compound of the formula (1) in which R represents a methyl group. Process according to one of Claims 1 to 6, characterized in that the corresponding compounds of the formulas II and II are used as starting materials. III to form compounds of formula 1 wherein R is methoxycarbonyl or ethoxycarbonyl. 10. Method according to one of the points. 1- to 9, characterized in that the corresponding compounds of the formulas II and III are used as starting materials to give compounds of the general formula 1 in which Y represents a vinyl group or preferably a bisulfatoethyl group. 11. A process according to claim 1, wherein the corresponding compounds of the formulas II and III are used as starting materials to form the compounds of the formula: - £ SO. i * C CH ^^ SO ^ M where ...... M is as defined in point 1. 12. A process according to claim 1, wherein the corresponding compounds of formulas II and III are used as starting materials to form compounds of formula Cl N li ^CH Í CH ^ OSO ^ COOH in which M is as defined in point 1. 13. A process according to claim 1, for the preparation of compounds of the formula I in which Y represents an ethyl group which is substituted in the β-position by an ester residue, preferably a sulfato group, characterized in that in the starting materials mentioned in point 1 of the symbols Y or both represent a β-hydroxyethyl group and the obtained azo compound corresponding to the general formula 1, in which Y represents a group, is reacted with an esterifying or acylating agent, preferably a sulphating agent.