DE4241924A1 - - Google Patents

Abstract

Fibre-reactive disazo compounds of the formula <IMAGE> in which the symbols are as defined in the specification, which compounds are in free acid or salt farm, and mixtures thereof, are useful for dyeing or printing hydroxy group- or nitrogen-containing organic substrates, for example leather and fibre material comprising natural or synthetic polyamides or natural or regenerated cellulose: the most preferred substrate is a textile material comprising cotton. The dyeings and printings obtained show good general fastness properties such as good light fastness, wet fastnesses and resistance towards oxidative influenced.

Description

The invention relates to fiber-reactive disazo compounds, processes for their manufacture and use as reactive dyes in dyeing and Printing process.

The invention relates to compounds of the formula I.

and their salts, in which
D represents a radical (a) or (b),

each R₁ and R₃, independently of one another, is hydrogen, -COOH or -SO₃H, each R₂ and R₄, independently of one another, is hydrogen, C _1-4 -alkyl or C _2-4 -hydroxyalkyl, and
Q is a heterocyclic reactive radical or one of the following radicals -COCHY₂-CH₂Y₁, -COCY₂ = CH₂ or -COCH₂Y₁, wherein
Y₁ for chlorine, bromine, -OSO₃H or -SSO₃H, and
Y₂ represents hydrogen, chlorine or bromine,
m for 1 or 2,
n for 0, 1 or 2, and
Z for the rest

stand,
with the proviso that the azo groups are each in the ortho position to the amino and hydroxyl group of the disulfonaphthyl radical, and mixtures of the compounds of the formula I and their salts.

Unless otherwise stated, a compound of the formula I be any alkyl or alkoxy group linear or branched. In a hydroxy substituted alkyl group attached to nitrogen be the hydroxy group is preferably found on a carbon atom that is not is directly bound to nitrogen.

The unfixed sulfo group in 1-amino-8-hydroxynaphthalene disulfone The acid residue is preferably in the 3 position.

R₁ preferably represents R _1a as -SO₃H or -COOH, in particular for -SO₃H.

R₂ is preferably R _2a as hydrogen, methyl, ethyl or 2-Hy droxyäthyl; more preferred for R _2b as hydrogen, methyl or ethyl; particularly preferred for hydrogen.

R₃ is preferably R _3a as hydrogen or -SO₃H, in particular -SO₃H.

R₄ is preferably R _4a as hydrogen, methyl, ethyl or 2-Hy droxyäthyl; more preferred for R _4b as hydrogen, methyl or ethyl; particularly preferred for hydrogen.

Q as a heterocyclic reactive radical is preferably a pyrimidine or Triazine residue, which is a labile halogen substituent, especially fluorine or carries chlorine.

Q is more preferably a radical as a heterocyclic reactive group  of the formula (c)

wherein
T for

Y _c for H, F, Cl, -CN, -CHO, -SR₅, -SOR₅, -SO₂R₅ or -SO₂F, Z₁ for H, F, Cl, Br, -NR₆R₇ or -OR₅,
Z₂ for F, Cl, Br or

A⊖ for a non-chromophoric anion,
R₅ is hydrogen, C _1-4 -alkyl, C _1-4 -hydroxyalkyl, phenyl or phenyl monosubstituted by carboxy or sulfo,
each R₆ and R₇, independently, is hydrogen; C _1-4 alkyl, C _2-4 hydroxyalkyl, phenyl or phenyl monosubstituted by C _1-4 alkyl, C _1-4 alkoxy, sulfo or carboxy; Phenyl (C _1-3 alkyl) or phenyl (C _1-3 alkyl), the phenyl ring of which is monosubstituted by C _1-4 alkyl, C _1-4 alkoxy, sulfo or carboxy; - (CH₂) _t -SO₂-X,
-CH₂CH₂-O- (CH₂) _t -SO₂-X or

wherein
t for 2 or 3,
X for -CH = CH₂ or -CH₂CH₂-Y, and
Y for hydroxy or a group which can be split off under alkaline conditions, such as, for example, -OSO₃H, Cl, Br, -OPO₃H₂, -SSO₃H, -OCOCH₃; -OCOC₆H₅ or -OSO₂CH₃ stand,
or
-NR₆R₇ for a piperidine, piperazine, N-methylpiperazine or morpholine ring and
R₈ represent hydroxy, -NH₂, methoxy or ethoxy.

A⊖ is preferably a chloride, acetate or methyl sulfate ion.  

Y is preferred as a group which can be split off under alkaline conditions for -OSO₃H, Cl or -SSO₃H; particularly preferred for -OSO₃H.

X preferably denotes X _a as -CH = CH₂, -CH₂CH₂OH or -CH₂CH₂OSO₃H; more preferably X _b as -CH = CH₂ or -CH₂CH₂OSO₃H; in particular X _c as -CH₂CH₂OSO₃H.

The radical (c) preferably represents a radical (c₁) or (c₂),

wherein
Z₁ ′ for Cl, -OC _1-2 alkyl or -NR _6a R _7a ,
each R _6a and R _7a , independently of one another, for hydrogen, methyl, ethyl, 2-hydroxyethyl, phenyl or phenyl monosubstituted by methyl, methoxy, sulfo or carboxy, - (CH₂) _t -SO₂-X _a or CH₂CH₂-O (CH₂ ) _t -SO₂-X _a , or
-NR _6a R _7a for a piperidine or morpholine ring,
Z₂ ′ for F or Cl,
Y _c ′ for hydrogen, Cl, -CN, -CHO or -SO₂CH₃,
Z₁ '' for hydrogen, F or Cl and
Z₂ '' stand for F or Cl.

The following radicals should be mentioned specifically as radical (c₁) or (c₂):

wherein Z₂ ', t and X _{c are} as defined above, or

where Y _c 'is as defined above.

More preferably stand (c₁) for the remainder (c₁ ′) as remainder (c₁), wherein Z₁ ′ is Cl or -NR _6a R _7a ; and (c₂) for the remainder (c₂ ′) as the remainder (c₂), in which Y _c ′ is hydrogen, Cl or -CN and Z₁ ′ ′ F or Cl.

Q is preferably Q _a as radical (c), -COCHY₂-CH₂Y₁ or -COCY₂ = CH₂; more preferred for Q _b as the residue (c₁) or (c₂); even more preferred for Q _c as the residue (c₁ ′) or (c₂ ′); particularly preferred for Q _d as the residue (c₂ ').

The radical (a) preferably denotes the radical (a₁),

wherein -NR _4b -Q _b is in position 4 or 5;
more preferably the rest (a₂),

wherein -NH-Q _c is in position 4 or 5;
in particular the radical (a₃) as the radical (a₂), in which Q _{c is} Q _d .

The rest (b) preferably represents (b₁),

wherein n 'is 0 or 1;
more preferably for (b₂) as the residue (b₁), where Q _{b is} Q _c and the positions are as follows:

• (i) n ′ = 1, -CH₂-NH-Q _c in position 5; m = 1 and the sulfo group in position 1;
• (ii) n ′ = 1, -CH₂-NH-Q _c in position 5, m = 2 with the sulfo groups in positions 1 and 7;
• (iii) n ′ = 0, -NH-Q _c in position 6, m = 2 with the sulfo groups in positions 4 and 8;

particularly preferably for (b₃) as the radical (b₂), where Q _{c is} Q _d .

D is preferably D₁ as the radical (a₁) or (b₁); more preferably D₂ than Balance (a₂) or (b₃); even more preferably D₃ as residue (a₂); in particular D₄ as the rest (a₃).  

Preferred compounds of the formula I correspond to the formula Ia

and their salts, in which the azo groups are each in the ortho positions to the amino and hydroxyl group of the disulfonaphthyl radical and D₂, R _1a , R _2b and z are as defined above.

Compounds of the formula Ib are more preferred

and their salts, in which D₃, R _2b and Z are as defined above, and in which -NR _2b -Z is in position 4 or 5.

Compounds of the formula Ib, in which

• (1) R _{2b represents} hydrogen;
• (2) those of (1), wherein the -NH-Z radical is in the 5-position;
• (3) those of (1) or (2), wherein D₃ is D₄.

The nature of the cation of the sulfo groups and possibly to additionally present carboxy groups in compounds of formula I, if these are in salt form is not a critical factor, but rather it can be any one in the chemistry of reactive dyes act as a non-chromophoric cation. The prerequisite is that the corresponding salts meet the condition of water solubility.

Examples of suitable cations are alkali metal ions or unsubstituted or substituted ammonium ions, such as, for example, lithium, sodium, potassium, ammonium, mono-, di-, tri- and tetramethylammonium, triethylammonium and mono-, di- and triethanolammonium. Preferred cations are the alkali metal ions and ammonium, of which sodium is particularly preferred.
In general, the cations of the sulfo groups and optionally carboxy groups in a compound of the formula I can be identical or different and represent a mixture of the above-mentioned cations, ie the compound can also be present in mixed salt form.

The invention further comprises a method for producing the ver Compounds of the formula I, characterized in that 1-amino-8- hydroxynaphthalene-3,6- or -4,6-disulfonic acid couples on both sides and though

• on the one hand with the diazonium salt of the amine of the formula II, D-NH₂ (II) where D is as defined above,
• - and on the other hand with the diazonium salt of the amine of formula III, wherein R₁, R₂ and Z are as defined above.

Both coupling reactions can be carried out according to a known method leads. Preferably, the clutch on the NH₂ side first carried out using an acidic reaction medium, preferably at pH 2-3, to which the coupling on the OH side is in neutral to weakly alkaline environment, preferably at pH 7.5-9.

The isolation of the compounds of the formula I can be known per se Done wisely; e.g. B. can the compounds by usual salting out with Alkali metal salts separated from the reaction mixture, filtered off and (in a vacuum) are dried at a slightly elevated temperature.

Depending on the reaction and isolation conditions, a Compound of formula I as free acid or preferably in salt form or  obtained as a mixed salt and then contains, for example, one or several of the above cations. Salts or mixed salts can but also starting from the free acid in a conventional manner and vice versa or it can also be a conventional one Salting can be made.

The rest Z of the formula

can exist in two isomeric forms with the unfixed fluorine substituted either in position 2 or in position 6 of the pyrimidine ring. Other pyrimidine residues as stated as the meaning of Q. and which bear unfixed substituents can in analog isomes their forms.

In general, it is preferred to obtain the isomeric compound mixture obtained to use as such; is a separation into the individual isomers not required, but could, if desired, be carried out according to the usual methods Methods are done.

The starting compounds of the formulas II and III are either known or can be obtained analogously to methods known per se from known starting materials.
Amines of the formula III are obtained, for example, by condensation of compounds of the formula IV,

wherein R₁ and R₂ are as defined above, with 2,4,6-trifluoropyrimidine receive; this condensation occurs at temperatures between 0 ° -40 ° C, preferably 0 ° -20 ° C, and pH 6-9 performed.  

Amines of the formula II are obtained analogously to the above procedure, by using a benzene or naphthalene diamine with a Group Q introducing compound condensed accordingly.

The compounds of formula I and mixtures thereof are reactive dyes fabrics; they are suitable for dyeing or printing hydroxy group or nitrogenous organic substrates. As preferred substrates These include leather and fiber materials made from natural or syn synthetic polyamides and especially from natural or regenerated ones Cellulose, such as cotton, viscose or cellulose exist or ent hold. The most preferred substrate is textile material made of cotton exists or contains them.

The compounds of the formula I can be used in dyeing liquors or in printing pastes after all dyeing or printing processes customary for reactive dyes be used. It is preferred to dye according to the exhaust process, a temperature range of 30-80 ° C and in particular of 50-60 ° C is applied.

The compounds according to the invention can be used as a single dye or because of their good combinability also as a combination element with other reactive dyes of the same class that dye comparable properties z. B. regarding general fastness properties, extract value etc., are used. The combination stains obtained show just as good fastness properties as the dyeings with single dye.

With the compounds of the formula I, good extraction and fixing values are obtained. The unfixed dye can be easily washed out. The dyeings and prints obtained show good lightfastness. They also have good wet fastness properties such. B. with regard to washing, water, seawater and perspiration fastness and have good resistance to oxidative influences such as chlorine-containing water, hypochlorite bleaching, peroxide bleaching and perborate-containing detergents.
Particularly noteworthy is the surprising resistance of the dyeings to acid hydrolysis for this class of dyes. For example, when exposed to dilute acetic acid, the dyeings show only slight soiling of unstained accompanying tissue.

The following examples serve to illustrate the invention. In the Examples mean parts by weight or volume and percentages Ge percentages by weight or volume; the temperatures are in degrees Celsius give.

Example 1

188 parts of 2,4-diaminobenzenesulfonic acid are suspended in 1700 parts of water and dissolved by adding 30% sodium hydroxide solution at pH 7. 140 parts of 2,4,6-trilfuoropyrimidine are added dropwise at this pH. After three hours of reaction at 0 °, the reaction product is diazotized in the usual manner with sodium nitrite.
152 parts of finely ground 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are sprinkled into the diazonium salt solution obtained above. The pH of the reaction mixture is first gradually increased to 2.5 within two hours by adding sodium acetate solution and then to pH 7.5 by adding sodium carbonate solution. The reaction mixture is salted out with sodium chloride and filtered off. The dye is dried at 60 ° in a vacuum; he has the formula (cited as free acid)

and dyes cotton in deep blue tones. These colorations have recorded fastness properties such as light and wet fastness properties, and are also resistant to oxidative influences.  

Examples 2-42

Analogous to the method described in Example 1, can be used corresponding starting materials other compounds of formula I. can be produced, which are listed in the following table. The dyes correspond to the formula (A),

for which the variables are listed in the table.
In the event that different residues of diazo components are present, ie if, for example, Q and Z have different meanings, the coupling reactions must be carried out in successive separate steps, an equimolar amount of each individual diazo component being used at the specific pH as described in Example 1 reached.

In the table, Z represents the rest of the formula

and Q for the radicals Q₁-Q₁₇ in the following meaning:
Q₁ as Z;

The compounds of Examples 2-42 can on substrates, which from Cel Lulose fibers exist or contain them, and in particular on textiles material made of cotton are used, the usual pull-out drive or use known printing processes. It who the colors and prints in deep navy blue tones. The Far Exercises and prints on cotton show good light and wet fastness Properties and are also resistant to oxidative influences.  

table

Compounds of Formula (A) - Examples 2-42

According to the method described in Example 1, the dyes are Examples 1 to 42 obtained as sodium salts. You can be dependent from the chosen implementation and isolation conditions or by subsequent measures in a known manner in the form of free Acid or in another salt form or mixed salt form be put and then, for example, one or more of those in the Be contain further cations.

As already mentioned in the introduction to the description, the colors substances of Examples 1-42 with respect to the reactive radical Z of the formula

Mixtures of isomers; they contain the compound in which the unfixed fluorine substituent in the pyrimidine ring is in the 2-position, in addition to the corresponding compound in which the fluorine substituent is in the 6-position, the latter compound normally predominating in terms of quantity. The same applies to the rest Q in the meaning of Q₁, Q₂ or Q₄.
These isomer mixtures obtained from production can be used as such in customary dyeing and printing processes. Isolation of a single isomeric compound is normally not necessary.

Below are uses of the dyes described illustrated.

Instructions for use A

In a dyebath containing 0.3 parts in 300 parts of demineralized water of the dye from Example 1 and 15 parts of Glauber's salt (calcined) contains, 10 parts of cotton fabric (bleached) are entered at 40 °. After 30 minutes at 40 °, the addition is carried out at intervals of 10 minutes of a total of 6 parts of soda (calcined) in 0.2 portions; 0.6; 1,2 and finally 4 parts, keeping the temperature at 40 ° becomes. The dyeing is then continued at 40 ° for one hour. On finally the dyed material is running in flowing cold for 3 minutes Water, then rinsed in running hot water for 3 minutes. The coloring is countered in 500 parts of demineralized water for 15 minutes were washed to the boil with 0.25 parts of Marseille soap. After rinsing centrifuged in running water (hot for 3 minutes) and the dye Exercise dried in a drying cabinet at approx. 70 °. You get a deep blue Cotton dyeing of very good fastness properties, particularly high wetness shows authenticity and is stable against oxidative influences.

Application regulation B

A dye bath containing 10 parts of Glauber's salt (calcined) in 300 parts of demineralized water is added to 10 parts of cotton material (bleached). The bath is heated to 40 ° within 10 minutes, then 0.5 part of the dye from Example 1 is added. After a further 30 minutes at 40 °, 3 parts of soda (calcined) are added, then the dyeing is continued for 45 minutes at 40 °.
The dyed material is rinsed with running cold water, then with hot water and washed boiling analogously to that given in regulation A. After rinsing and drying, a deep blue cotton dyeing is obtained which has the properties listed for regulation A.

In an analogous manner as described in regulations A and B can also the dyes of Examples 2-42 or dye mixtures of the Examples 1-42 can be used for dyeing. The deep blue colorations obtained have good fastness properties.

Instructions for use C

A printing paste with the ingredients

40 parts of the dye from Example 1
100 parts of urea
350 parts of water
500 parts of a 4% sodium alginate thickener
10 parts of sodium bicarbonate
1000 pieces in total

is applied to cotton material using the usual printing processes. The printed material is steamed at 102-104 ° for 4-8 minutes and then rinsed cold and hot. Then the fixed cotton material washed at the boil (analogous to regulation A) and dried. The received one navy blue print shows good general fastness properties.

Analogously to regulation C, the dyes of Examples 2-42 can also be used or dye mixtures of Examples 1-42 for tree printing wool can be used. In all cases, deep blue prints are included maintain good fastness properties.

Claims (14)

1. Compounds of formula I. and their salts, in which
D represents a radical (a) or (b), each R₁ and R₃, independently of one another, is hydrogen, -COOH or -SO₃H,
each R₂ and R₄, independently of one another, is hydrogen, C _1-4 alkyl or C _2-4 hydroxyalkyl, and
Q is a heterocyclic reactive radical or one of the following radicals -COCHY₂-CH₂Y₁, -COCY₂ = CH₂ or -COCH₂Y₁, wherein
Y₁ for chlorine, bromine, -OSO₃H or -SSO₃H, and
Y₂ represents hydrogen, chlorine or bromine,
m for 1 or 2,
n for 0, 1 or 2, and
Z for the rest stand,
with the proviso that the azo groups are each in the ortho position to the amino and hydroxyl group of the disulfonaphthyl radical, and mixtures of the compounds of the formula I and their salts. 2. Compounds according to claim 1, wherein Q is a heterocyclic Reactive residue for a pyrimidine or triazine residue, the labi len halogen substituents. 3. Compounds according to claim 1 or 2, wherein D represents a radical of Formula (a) stands. 4. Compounds according to any one of claims 1-3, wherein R₁ is R _1a as -COOH or -SO₃H, and R₃ is R _3a as hydrogen or -SO₃H. 5. Compounds according to any one of claims 1-4, wherein R₂ is R _2a and R₄ are R _4a , each R _2a and R _4a , independently of one another, what is hydrogen, methyl, ethyl or 2-hydroxyethyl. 6. Compounds according to any one of claims 1-5, wherein Q is Q _a as a radical (c), as -COCHY₂-CH₂Y₁ or -COCY₂ = CH₂, wherein
Y₁ chlorine, bromine, -OSO₃H or -SSO₃H, and
Y₂ is hydrogen, chlorine or bromine, Y _c for H, F, Cl, -CN, -CHO, -SR₅, -SOR₅, -SO₂R₅ or -SO₂F,
Z₁ for H, F, Cl, Br, -NR₆R₇ or -OR₅,
Z₂ for F, Cl, Br or and A⊖ represent a non-chromophoric anion,
R₅ is hydrogen, C _1-4 -alkyl, C _1-4 -hydroxyalkyl, phenyl or phenyl monosubstituted by carboxy or sulfo,
each R₆ and R₇, independently, is hydrogen; C _1-4 alkyl, C _2-4 hydroxyalkyl, phenyl or phenyl monosubstituted by C _1-4 alkyl, C _1-4 alkoxy, sulfo or carboxy; Phenyl (C _1-3 alkyl) or phenyl (C _1-3 alkyl), the phenyl ring of which is monosubstituted by C _1-4 alkyl, C _1-4 alkoxy, sulfo or carboxy; - (CH₂) _t -SO₂-X,
-CH₂CH₂-O- (CH₂) _t -SO₂-X or wherein
t for 2 or 3,
X for -CH = CH₂ or -CH₂CH₂-Y, and
Y represents hydroxy or a group which can be split off under alkaline conditions,
or
-NR₆R₇ a piperidine, piperazine, N-methylpiperazine or morpholine ring and
R₈ is hydrogen, -NH₂, methoxy or ethoxy. 7. Compounds according to claim 1, which correspond to the formula Ia and their salts, in which the azo groups are each in the ortho positions to the amino and hydroxyl groups of the disulfonaphthyl radical,
Z is as defined in claim 1,
R _{1a is} as defined in claim 1,
R _1a for -COOH or -SO₃H,
R _{2b represents} hydrogen, methyl or ethyl; and
D₂ represents a radical (a₂) or (b₃), wherein -NH-Q _c is in the 4- or 5-position; wherein
m for 1 or 2, and
n ′ stands for 0 or 1,
and the substituents occupy the following positions:

• (i) n ′ = 1, -CH₂-NH-Q _d in position 5; m = 1 and the sulfo group in position 1;
• (ii) n ′ = 1, -CH₂-NH-Q _d in position 5, m = 2 with the sulfo groups in positions 1 and 7;
• (iii) n ′ = 0, -NH-Q _d in position 6, m = 2 with the sulfo groups in positions 4 and 8;

Q _{c is} a radical (c₁ ′) or (c₂ ′), and
Q _{d is} a radical (c₂ ′), where (c₁ ′) stands for (c₁) and (c₂ ′) stands for (c₂), wherein
Z₁ ′ for chlorine or -NR _6a R _7a ,
each R _6a and R _7a independently of one another, for hydrogen, methyl, ethyl, 2-hydroxyethyl, phenyl, phenyl monosubstituted by methyl, methoxy, sulfo or carboxy, - (CH₂) _t -SO₂-X _a or -CH₂CH₂-O (CH₂ ) _t -SO₂X _a , wherein
t for 2 or 3, and
X _{a represents} -CH = CH₂, -CH₂CH₂OH or -CH₂CH₂OSO₃H,
or
-NR _6a R _7a for a piperidine or morpholine ring,
Z₂ ′ for F or Cl,
Y _c 'for hydrogen, Cl or -CN, and
each Z₁ '' and Z₂ '' stand for F or Cl. 8. Compounds according to claim 7, which correspond to the formula Ib, and their salts, in which
R _2b and Z are as defined in claim 7, and
-NR _2b -Z is in 4- or 5-position, and
D₃ is a radical (a₂) as defined in claim 7. 9. Compounds according to claim 8, wherein R _{2b is} hydrogen and -NH-Z is in the 5-position. 10. A process for the preparation of compounds of formula I, defined in claim 1, characterized in that coupling on both sides to 1-amino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid

• - On the one hand with the diazonium salt of the amine of formula II, D-NH₂ (II) wherein D is as defined in claim 1, and
• on the other hand with the diazonium salt of the amine of formula III, wherein R₁, R₂ and Z are as defined in claim 1.

11. Process for dyeing or printing hydroxy groups or nitrogenous organic substrates, characterized in that one with a compound of formula I, defined in claim 1, or with Mixtures of these colors or prints.   12. The method according to claim 11, for dyeing or printing leather or of fiber materials made from natural or synthetic poly amides or natural or regenerated cellulose or these contain. 13. The method according to claim 12, for dyeing or printing text til material that consists of or contains cotton.