HK1075268A - Water-soluble reactive mono- and di-azo dyes - Google Patents

Description

water-soluble monoazo and disazo reactive dyes

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The present invention relates to the field of fibre-reactive dyes.

EP-A785237 discloses reactive dyes comprising the following structural elements:

the present invention now provides dyes of the general formula (I):

wherein:

m is 1 or 2, and m is,

n is a number of 0 or 1,

q is 0, 1, 2 or 3, and

p is 0, 1 or 2,

r is 0, 1 or 2, and

p + r is 1 or 2, and

X₁is a group-CH₂CH₂Z or-CH ═ CH₂Z is a base-eliminable group,

m is hydrogen, ammonium, an alkali metal or an equivalent of an alkaline earth metal,

X₂is alkyl, alkoxy, halogen, COOM or SO₃M，

L is a direct bond or an alkylene group,

l' is a direct bond or a group of the formula:

X₃is a heterocyclic reactive group of the general formula (IIa) or (IIb):

or an active group of formula (IIc), (IId) or (IIe):

wherein:

X₄to X₆Independently hydrogen or halogen, with the proviso that at least one X₄To X₆The radical (b) is a halogen,

X₇is halogen or X₈And are and

X₈is a substituent of the general formula (III):

wherein:

R₁is hydrogen, an alkyl group or an aryl group,

b is alkylene, alkylene interrupted by oxygen, arylene or aralkylene, and

R₂is a group SO₃M、SO₂-CH₂CH₂Z or SO₂-CH＝CH₂Wherein Z is as defined above,

and the absence or presence of the ring labeled a.

In the compounds of the formula (I), the alkali metal M may in particular be lithium, sodium or potassium, while calcium is a particularly suitable alkaline earth metal. Preferably, M is hydrogen or sodium.

Halogen X₂、X₄To X₆And X₇In particular fluorine or chlorine.

Alkyl radical R₁Or X₂Is preferably C₁-C₈Alkyl, more preferably C₁-C₄An alkyl group. Examples of such alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl. Particularly preferred alkyl groups are methyl and ethyl. Similar remarks apply to alkoxy radicals R₁Or X₂. Thus, particularly preferred alkoxy groups are methoxy and ethoxy.

Aryl radical R₁In particular phenyl, which may also be substituted by, for example, C₁-C₄Alkyl radical, C₁-C₄Alkoxy, chlorine, fluorine or SO₃The H group is substituted one or more times.

Alkylene B or L is preferably C₁-C₈Alkylene, more preferably C₁-C₄An alkylene group. Examples of such alkylene groups are methylene, ethylene, n-propylene, isopropylene and butylene groups. Alkylene interrupted by oxygen, especially- (CH)₂)_u-O-(CH₂)_v-, wherein u and v are independently 1 to 3. Arylene B is in particular phenylene and naphthylene, preferably meta-and para-phenylene.

The aralkylene radical B is preferably a radical of the general formula (IVa) or (IVb):

wherein s is 1 to 4, and the free bond on the aromatic nucleus may be linked to N or to R₂The above.

The base may eliminate the group Z and,that is, groups Z which can be eliminated under the dyeing conditions include, for example, chlorine, bromine, sulfato, thiosulfato, phosphato, C₂-C₅Alkanoyloxy such as acetoxy, for example benzoyloxy, sulphobenzoyloxy or p-toluenesulphonyloxy, preferably sulphato.

The groups "sulfato", "thiosulfato" and "phosphato" all include the acid form and the salt form. Thus, the thiosulfato group has the formula-S-SO₃The general formula of M and phosphate radical is-OPO₃M₂And sulfato groups of the formula-OSO₃M, wherein M is as defined above.

Preferred compounds of formula (I) satisfy the condition p + r ═ 1, while particularly preferred compounds of formula (I) satisfy the condition p + r ═ 2. If m is 1, p + r is preferably 1.

X₂Preferably C₁-C₄Alkyl radical, C₁-C₄Alkoxy or SO₃M, more preferably methyl, ethyl, methoxy, ethoxy or SO₃M, wherein M is hydrogen or sodium.

L and L' are each preferably a direct bond.

X₃Preferred are groups of the formula:

or

Wherein:

hal' is chlorine or bromine,

R₁' is hydrogen, methyl, ethyl or phenyl,

b' is ethylene, propylene or-CH₂CH₂-O-CH₂CH₂-, and

R₂' is-SO₂CH₂CH₂OSO₃M or-SO₂CH＝CH₂。

If r is 2, the radical X₃May have the same or different meanings. Similarly, if q is 2 or 3, the group X₂Can have identical or different meanings, if p is 2, the radical X₁May have the same or different meanings.

Particularly preferred dyes of the formula (I) correspond to the formula (Ia):

wherein X₁To X₃A, L, L', M, M, r, p and q are as defined above.

In addition, particularly preferred dyes of the general formula (I) correspond to the general formula (Ib):

wherein X₁To X₃A, L, L', M, M, r, p and q are as defined above.

In addition, particularly preferred dyes of the formula (I) correspond to the formula (Ic):

m, X therein₂And q is as defined above, V is X₃-NH-L-or X₁-O₂S-L' -, wherein X₁、X₃A, L and L' are as defined above.

Particularly preferred dyes of the formula (I) correspond to the following formulae (Id) to (Iq):

wherein in each case:

m is hydrogen or sodium, and

X₂' is hydrogen, methyl, ethyl, methoxy, ethoxy, COOM or SO₃M, and

u is-SO₂CH₂CH₂OSO₃M、-SO₂CH＝CH₂or-NH-U ', wherein M is hydrogen or sodium and U' is one of the following formulae:

wherein:

hal' is chlorine or fluorine,

R₁' is hydrogen, methyl, ethyl or phenyl,

b' is ethylene, propylene or-CH₂CH₂-O-CH₂CH₂-, and

R₂' is-SO₂CH₂CH₂OSO₃M or-SO₂CH＝CH₂。

The dyes of the general formula (I) according to the invention are generally in the form of solid or liquid (dissolved) preparations. For example, in solid form, they generally include those electrolyte salts which are commonly used in water-soluble dyes and in particular in fibre-reactive dyes, such as sodium chloride, potassium chloride and sodium sulphate, and may additionally include those auxiliaries which are commonly used in commercially available dyes, such as buffer substances which are capable of adjusting the pH of aqueous solutions to 3 to 7, such as sodium acetate, sodium borate, sodium bicarbonate, sodium dihydrogen phosphate, sodium tricitrate and disodium hydrogen phosphate, small amounts of siccatives, or, if they are liquid, aqueous solutions (including thickeners commonly used in printing pastes), those which ensure the durability of the formulation, such as mildewcides.

The dyes of the general formula (I) according to the invention are preferably in the form of dye powders or dye granules which comprise from 10 to 80% by weight, based on the powder or granule, of electrolyte salts, also known as standardizers. The particles have a particle size of in particular 50 to 500 μm. These solid preparations may additionally comprise the abovementioned buffer substances in a total amount of up to 10% by weight, based on the preparation. When the dye is an aqueous solution, the total dye content of such aqueous solutions is up to about 50% by weight, such as from 5 to 50% by weight, for example, the electrolyte salt content of such aqueous solutions is preferably less than 10% by weight, based on the aqueous solution. In general, the aqueous solutions (liquid preparations) may comprise up to 10% by weight, preferably up to 2% by weight, of the abovementioned buffer substances.

Although having the same chromophore group, wherein p ≠ 0 and/or those comprising X therein₈The dyes of the general formula (I) which are radicals of the formula (III) can be present in the fibre-reactive radical SO₂X₁And/or R₂The aspects have different structures. In particular, for the same chromophore, SO₂X₁And R₂On the one hand may be-SO₂CH＝CH₂And on the other hand may be-SO₂CH₂CH₂Z, particularly preferably is β -sulfatoethylsulfonyl. The dye moiety in the form of vinylsulfonyl can be up to about 30 mole percent, based on the individual dye chromophore. The molar ratio between the vinylsulfonyl dye moiety and the β -ethyl-substituted dye moiety is preferably from 5: 95 to 30: 70.

The dyes of the general formula I according to the invention can be prepared, for example, by diazotizing aromatic amines of the general formula (V) and coupling the diazo compounds with compounds of the general formula (VI),

wherein p, q, r, A, L, X₁、X₂And X₃The definition of (A) is the same as that of (B),

in this preparation process, one equivalent of a compound of the formula (V) is used per equivalent of a compound of the formula (VI) to give the dyes of the formula (I) according to the invention in which m is 1. Alternatively, the use of two equivalents of the compound of the formula (V) per equivalent of the compound of the formula (VI) leads to dyes of the formula (I) according to the invention in which m is 2.

When attempting to prepare a compound of the general formula (I) of the present invention in which m is 2, the condition p + r ═ 1 or 2 cannot be satisfied in the aromatic compound of the general formula (V). Instead, p and r are chosen such that the resulting compound of general formula (I) of the invention satisfies the condition p + r ═ 1 or 2.

In a preferred embodiment of the preparation process according to the invention, one equivalent of the aromatic amine of the formula (V) is first diazotized and the diazo compound is coupled with one equivalent of the compound of the formula (VIa) at a pH value in the range from 0 to 6, preferably from 1 to 4,

wherein M is as defined above.

The monoazo dyes obtained correspond to the general formula (Ir):

wherein p, q, r, A, L, X₁、X₂、X₃And M is as defined above.

The dye with the general formula (Ir) dyes cotton into golden yellow to reddish yellow color and has good overall fastness.

The dye of the formula (Ir) can then, if desired, be reacted with a further equivalent of an aromatic amine of the formula (V) and diazotized beforehand by known methods to give the disazo dye of the formula (Ia) or (Ib).

In the preparation of the compounds of the general formula (I) according to the invention in which m is 2, two equivalents of the aromatic amine are dependent on the variables p, q, r, L', X₁、X₂、X₃The same or different and the same or different.

If two equivalents of aromatic amine are in the variables p, q, r, L', X₁、X₂And X₃When the same applies, the reaction is particularly preferably carried out in a one-pot process ("one-pot coupling process"). In this case, two equivalents of the aromatic amine of the formula (V) are diazotized and the diazo compound is coupled with one equivalent of the compound of the formula (VI).

The compounds of the general formula (I) according to the invention obtained by the one-pot coupling process correspond to the compounds obtained by the "continuous coupling process", i.e. by coupling in double succession one equivalent in each case of an aromatic amine of the general formula (V) having the same structure.

Dyes of the general formula (I) of the present invention, wherein m is 2 and p + r ═ 1, can be prepared by diazotizing an aromatic amine of the general formula (V) wherein p + r ═ 0 and reacting the diazo compound with a compound of the general formula (VI) to give a compound of the general formula (VII):

wherein q, n, A, X₂And M is as defined above. Then, in a second step, a compound in which p + r is 1The aromatic amine of the general formula (V) is diazotized and the diazo compound is further coupled with the compound of the general formula (VII) to give the disazo dye of the present invention.

Conversely, it Is of course also possible first to diazotize the aromatic amines of the formula (V) in which p + r ═ 1 and to couple the diazo compounds with the compounds of the formula (VI) to give the dyes of the formula (Is) according to the invention:

wherein n, p, q, r, A, L, X₁、X₂、X₃And M is as defined above, and wherein p + r ═ 1. Then in a second step, the aromatic amine of formula (V) wherein p + r ═ 0 is diazotized and the diazo compound is further coupled to give the disazo dye of the present invention.

In both cases, the first and second diazonium components are suitably selected so that the resulting monofunctional disazo reactive dyes are isomeric with each other.

Preferred aromatic amines of the general formula (V) wherein p + r ═ 0 are aniline derivatives or naphthylamine derivatives, but their sulfonic acid forms are preferred.

Examples thereof may include aniline-2-sulfonic acid, aniline-3-sulfonic acid, aniline-4-sulfonic acid, 4-methylaniline-2-sulfonic acid, 4-methylaniline-3-sulfonic acid, 4-methylaniline-2, 5-disulfonic acid, 4-methoxyaniline-2-sulfonic acid, 4-methoxyaniline-2, 5-disulfonic acid, 2-chloroaniline-5-sulfonic acid, 2-chloroaniline-4-sulfonic acid, 2-methoxy-5-methylaniline-4-sulfonic acid, 2, 5-dimethoxyaniline-4-sulfonic acid, aniline-2, 4-disulfonic acid, aniline-2, 5-disulfonic acid, 2-methoxyaniline-5-sulfonic acid, aniline-2, 5-disulfonic acid, 1-aminonaphthalene-2-sulfonic acid, 1-aminonaphthalene-3-sulfonic acid, 1-aminonaphthalene-4-sulfonic acid, 1-aminonaphthalene-5-sulfonic acid, 1-aminonaphthalene-6-sulfonic acid, 1-aminonaphthalene-7-sulfonic acid, 1-aminonaphthalene-8-sulfonic acid, 1-aminonaphthalene-3, 6-disulfonic acid, 1-aminonaphthalene-3, 7-disulfonic acid, 1-aminonaphthalene-4, 8-disulfonic acid, 2-aminonaphthalene-1-sulfonic acid, 2-aminonaphthalene-5-sulfonic acid, 2-aminonaphthalene-6-sulfonic acid, 2-aminonaphthalene-7-sulfonic acid, 2-aminonaphthalene-8-sulfonic acid, 1-aminonaphthalene-5-sulfonic acid, 1-aminonaphthalene-sulfonic acid, 2-aminonaphthalene-1, 5-disulfonic acid, 2-aminonaphthalene-4, 8-disulfonic acid, 2-aminonaphthalene-5, 7-disulfonic acid, 2-aminonaphthalene-6, 8-disulfonic acid, 2-aminonaphthalene-3, 6-disulfonic acid, 2-aminonaphthalene-1, 5, 7-trisulfonic acid and 2-aminonaphthalene-3, 6, 8-trisulfonic acid.

Preferred aromatic amines of the formula (V) in which p + r.noteq.0 correspond to the compounds described above, but additionally bear the corresponding number of substituents-L' -SO₂X₁and/or-L-NH-X₃。

The diazotisation and coupling reactions required for the preparation of the dyes of the general formula (I) are known per se to the person skilled in the art and can be carried out in the customary manner as is fully described in the relevant literature. In the case of the preparation processes shown, the dyes of the general formula (I) according to the invention are obtained in the form of solutions and suspensions and can be isolated, for example, by salting out. The dye may also be dried by spraying, although it is further possible to carry out evaporative concentration of the solution or suspension.

The aromatic amines of the formula (V) are known per se and can be prepared by methods which are well known to those skilled in the art.

In some cases, compounds of the general formula (VI) (e.g.3-sulfomethylaminoaniline-6-sulfonic acid in JP 60243157 and JP 6157650) are likewise described. They can be prepared, for example, by reacting a compound of the general formula (VIII) with formaldehyde bisulfite of the formula (IX),

wherein n is 0 or 1, and the compound is,

wherein M is as defined above. For this reaction, formaldehyde bisulfite is generally added to a solution of the compound of the formula (VIII) at a pH of from 3 to 9 and the condensation is carried out at a reaction temperature of from 30 to 80 ℃.

The reactive dyes of the general formula (I) according to the invention have useful application properties. They are useful for dyeing and printing hydroxyl-and/or carboxamido-containing materials, for example in the form of sheet-like structures such as paper and leather, or in the form of films such as polyamide films, or in bulk such as polyamide and polyurethane, but are used in particular in the dyeing and printing of the fibrous form of these materials. They are preferably used for dyeing and printing all kinds of cellulosic fibre materials. They are furthermore suitable for dyeing or printing hydroxyl-containing fibers present in blend fabrics, for example blends of cotton with polyester fibers or polyamide fibers. It can also be used for printing textiles or paper by the inkjet method.

The present invention therefore also provides the use of the reactive dyes according to the invention for dyeing or printing the materials mentioned or, respectively, a process for dyeing or printing such materials in a conventional manner using one or more reactive dyes of the general formula (I) according to the invention as colorants.

The solutions obtained by the synthesis of the reactive dyes of the general formula (I) according to the invention, where appropriate after addition of buffer substances and likewise after concentration or dilution, can advantageously be used directly as dyeing liquor.

The material is preferably in the form of a fibrous material, particularly preferably in the form of a fabric, such as a woven fabric or yarn in a bundled or wound form.

Hydroxyl-containing materials are those from natural or synthetic sources, such as cellulosic fiber materials or their remnants and polyvinyl alcohol. The cellulosic fibrous material is preferably cotton, but also includes other plant fibers such as flax, hemp, jute and ramie fibers; regenerated cellulose fibers are, for example, short viscose and long viscose.

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

The dye mixtures of the general formula (I) according to the invention can be applied to and fixed on the substrates, in particular on the fibre materials, by known application techniques for water-soluble dyes, in particular fibre-reactive dyes.

For example, any of a number of different acid-binding agents, with or without neutral salts such as sodium chloride or sodium sulfate, can produce dyeings having excellent color yields when applied to cellulosic fibers by the exhaust process at large bath ratios. Preference is given to dyeing in an aqueous dyebath at a temperature of from 45 to 105 ℃ under pressure at a temperature of up to 130 ℃ and, where appropriate, in the presence of customary dyeing auxiliaries. One possible method in this case is to introduce the material into a warm bath and gradually heat the bath to the desired dyeing temperature and complete the dyeing operation at this temperature. The neutral salt which promotes exhaustion of the dye may suitably be added to the dye bath only after the actual dyeing temperature has been reached.

The pad dyeing process likewise provides excellent colour yield and good dye build-up on cellulose fibres, in which case the dye can be fixed batchwise by fixing in a conventional manner, for example by steaming or dry heating, at room temperature and at elevated temperatures, for example at temperatures up to about 60 ℃.

Similarly, conventional printing processes for cellulose fibers can be carried out in a single stage, such as by printing with a printing paste comprising sodium bicarbonate or other acid-binding agent, and subsequently steaming at a temperature of 100 to 103 ℃; or in two stages, such as printing with neutral or weakly acidic printing dyes, followed by overdiaying the printed material through a hot alkaline bath containing an electrolyte or with a padding liquor containing a basic electrolyte, and then fixing the package of material overdiayed with alkali or by subsequent steaming or subsequent dry heat treatment. Changes in the fixing conditions have only a minor effect on the printing result.

When fixing by dry heat according to the conventional hot fixing method, hot air of 120 to 200 ℃ is used. In addition to the conventional steaming treatment at 101 to 103 c, it is also possible to use superheated steam and high-pressure steam, the temperature of which is up to 160 c.

Acid-binding agents for fixing dyes to cellulose fibers include water-soluble basic salts of alkali metals and alkaline earth metals, such as inorganic or organic acids, or compounds that release alkali upon heating. Alkali metal hydroxides and alkali metal salts of weak to moderately acidic organic or inorganic acids are particularly mentioned, the preferred alkali metal compounds being sodium and potassium compounds. Examples of such acid-binding agents include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium trichloroacetate, water glass or sodium phosphate. The reactive dyes of the general formula (I) according to the invention are distinguished by high reactivity, good fixing power, very good dye build-up and high light and perspiration fastnesses. Therefore, they can be used in the exhaust dyeing process with low dyeing temperature and require only a short steaming time in the pad-steam process. The degree of fixation is high, unfixed parts are easy to clean, and the difference between the degree of exhaust and the degree of fixation is very small, i.e. the soaping loss is very small. They are also particularly suitable for printing, in particular on cotton, but also for printing nitrogen-containing fibres, such as wool or silk or blend fabrics comprising wool or silk.

The reactive dyes of the general formula (I) according to the invention have the additional feature that after the dyeing operation the unfixed dye parts on the fibre material are very easy to wash off without the dyes removed at the same time as the washing off contaminating the white. This results in an advantage of the dyeing operation in that the washing cycle is saved, thereby saving the operation cost.

The dyeings and prints produced with the reactive dyes of the general formula (I) according to the invention, in particular on cellulosic fibre materials, have high tinctorial strength and high fibre-dye binding stability in both the acidic and the alkaline range, as well as good light fastness and very good wet fastnesses, such as fastness to washing, water, sea water, cross-dyeing and perspiration, and also fastness to dry heat setting, pleating and rubbing.

The following examples serve to illustrate the invention. Parts and percentages are by weight unless otherwise indicated. Parts by weight versus volume refer to kilograms versus liters.

The compounds described in the examples with the formula are in the form of the free acid. However, they are usually prepared and isolated in the form of their alkali metal salts, preferably lithium, sodium or potassium salts, and used for dyeing in the form of their salts, and similarly, in the following examples, in particular in the tables, the starting compounds and the components expressed as free acids or in the form of their salts, preferably alkali metal salts, are used in the synthesis.

The dyes according to the invention were measured for their maximum absorbance in the visible range (. lamda.) in aqueous solution of alkali metals_max)。

Example 1:

synthesis (precursor) of the Compound of formula (VI)

18.8 parts of 2, 4-diaminobenzenesulphonic acid are suspended in 150 parts of water and neutralized by dropwise addition of a 20% strength sodium hydroxide solution. At 20 ℃ 14.7g of formaldehyde bisulfite (Na salt) were added and the mixture was heated to 50 ℃. Followed by stirring at a pH of 5.0 to 5.5 for 4 hours. The resulting solution was concentrated by evaporation or used directly in the next reaction.

The yellowish residue obtained after concentration by evaporation corresponds to the compound of formula (VIa):

¹H-NMR(400MHz，d₆-DMSO)：δ(ppm)＝3.77(d，2H，³J＝6.6Hz，CH₂)，5.28(s，2H，NH₂)，5.54(t，1H，³J＝6.6Hz，NH)，5.82(dd，1H，³J＝8.1Hz，⁴J＝2.2Hz，Har)，5.86(d，1H，⁴J＝2.2Hz，H₈，)，7.08(d，1H，³J＝8.1Hz，H_ar)。

example 2:

a suspension of 28.1g of 4- (2' -sulfatoethylsulfonyl) aniline in 200 parts of water is mixed at 15 ℃ in succession with 0.5g of the commercial dispersant and 21 parts of 31% strength hydrochloric acid, and the mixture is stirred for 15 minutes. 13.2 parts of 40% strength aqueous sodium nitrite solution are added dropwise and the mixture is stirred with excess nitrite for a further 60 minutes. Excess nitrite is then destroyed by adding 10% strength sulfamic acid. The suspension of the diazonium salt is then mixed with the solution of the compound of formula (VIa) prepared in example 1. The pH was then adjusted to 5-6 by addition of 15 strength% sodium carbonate solution and coupling was completed at 20 ℃.

Concentrating the solution by evaporation to give a dye of formula (Ie):

which dyes and prints cotton to a reddish yellow shade (lambda) with good fastness properties_max＝445nm)。

By reacting amines R-NH₂Diazotization and coupling of the diazo compound with compound (VIa) in a manner analogous to that described in example 2 gives the dyes of examples (3) to (17).

Example 18

18.8 parts of 2, 4-diaminobenzenesulphonic acid are suspended in 150 parts of water and made neutral by dropwise addition of lithium hydroxide solution. The solution is cooled to 10 ℃ and mixed dropwise with 17.4 parts of 2, 4, 6-trifluoropyrimidine over 1 hour, the pH being kept at 5.5 using 15% strength sodium carbonate solution. When the dropwise addition is complete, the mixture is warmed to 20-25 ℃ and stirring is continued for 1 hour, then filtered and 6.9 parts of sodium nitrite are added.

The filtrate was cooled to 10 ℃ by adding ice, and then it was added dropwise over 30 minutes to 100 parts of ice and 60 parts of concentrated hydrochloric acid (31%). The mixture was stirred for 1 hour, then excess nitrite was destroyed by adding sulfamic acid.

To this acid diazotisate is then added a solution of the compound (VIa) from example 1, and the pH is adjusted to 5.0 to 5.5 by adding a 15% strength sodium carbonate solution.

Concentrating the resulting solution by evaporation to give a dye of the formula:

which dyes or prints cotton to a yellow shade (lambda) with good fastness properties_max＝406nm)。

By reacting the amine compounds R-NH shown in the following table₂Diazotization and subsequent coupling in analogy to the procedure described in example 18 gave the dyes of examples (19) to (32).

Example 33

28.1 parts of 4- (2' -sulfatoethylsulfonyl) aniline are dissolved in 250 parts of water and neutralized by addition of solid sodium bicarbonate. To the solution was added 4.2 parts of sodium fluoride, followed by cooling to 0-5 ℃ by adding ice. Then after 5 minutes 13.5 parts of trifluorotriazine are added dropwise, the pH initially dropping off sharply and subsequently stabilizing in the range from 4.5 to 5.0.

When the addition was complete, stirring was continued for 15 minutes. Subsequently, 18.8 parts of a neutralized aqueous solution of 2, 4-diaminobenzenesulfonic acid was added dropwise, and the pH was adjusted to 6.0 to 6.5. The reaction was terminated by heating in the range of 30 to 35 ℃ and then stirring for 60 minutes. The resulting solution is filtered and 6.9 parts of sodium nitrite are added.

The resulting solution was cooled to 10 ℃ by adding ice and added dropwise over 30 minutes to 100 parts of ice and 60 parts of concentrated hydrochloric acid (31%). The mixture was stirred for 1 hour, then excess nitrite was destroyed by adding sulfamic acid.

To this acidic diazotized material is then added a solution of the compound (VIa) of example 1.

The pH was stabilized at 2.0 to 2.5. After subsequent stirring of the mixture for 1 hour, the pH is adjusted to 5.5 using sodium carbonate solution and then with NaH₂PO₄/Na₂HPO₄And (6) buffering. The resulting solution was concentrated by evaporation.

To obtain a dye of the formula:

which dyes or prints cotton to a yellow shade (lambda) with good fastness properties_max＝408nm)。

By reacting the amine compounds R-NH shown in the following table₂Diazotization and subsequent coupling in the manner of example 33 gives the dyes of examples (35) to (47).

Example 48

33.7 parts of 4- (2' -sulfatoethylsulfonyl) aniline are dissolved in 250 water, and 0.5g of a commercial dispersant and 25 parts of 31% strength hydrochloric acid are successively added at 15 ℃ and the mixture is stirred for 15 minutes. 16 parts of a 40% strength aqueous sodium nitrite solution are then added dropwise and the mixture is subsequently stirred with excess nitrite for 60 minutes.

Excess nitrite was destroyed by adding 10% strength sulfamic acid. The dye solution of example 2 was then added to the diazonium salt suspension, followed by stirring for 15 minutes. The pH was then adjusted to 5.0-5.5 by the addition of 15% strength sodium carbonate solution to complete the coupling.

The resulting solution was concentrated by evaporation. To obtain a dye of the formula:

which dyes or prints cotton to a dark orange color (lambda)_max＝428nm)。

By first contacting the compound prepared in example 1 with A as described in example 2₁-NH₂Reacted with A as described in example 48₂-NH₂Reaction to give the dyes of the general formula set out in the table below:

example 92

17.3 parts of aniline-4-sulfonic acid are dissolved in 200 parts of water and acidified by addition of 21 parts of 31% strength hydrochloric acid. It was ice-cooled to 10-15 ℃ and then 13.2 parts of a 40% strength sodium nitrite solution was added dropwise. Stirring for 60 minutes in the presence of excess nitrite. Excess nitrite was reduced by addition of 10% strength sulfamic acid solution.

The solution obtained in example 1 is then added to the diazonium salt suspension, the pH is adjusted to 4 to 5 by adding a 15% strength sodium carbonate solution and the coupling is then completed.

To obtain a dye of the formula:

a suspension of 33.7g of 4- (2' -sulfatoethylsulfonyl) aniline in 250 parts of water is admixed at 15 ℃ in succession with 0.5g of commercial dispersant and 25 parts of 31% strength hydrochloric acid and subsequently stirred for 15 minutes. 16 parts of a 40% strength aqueous sodium nitrite solution are then added dropwise, and the mixture is subsequently stirred for 60 minutes in the presence of excess nitrite.

Excess nitrite was destroyed by adding 10% strength sulfamic acid. The dye solution described above was then added to the diazonium salt suspension and stirred for 15 minutes. The pH was then adjusted to 5.0-5.5 by addition of 15% strength sodium carbonate solution and the coupling was completed.

Concentrating the resulting solution by evaporation to give a dye of the formula:

which dyes or prints cotton to a yellowish brown shade (lambda)_max＝431nm)。

Examples 93 to 135

In analogy to the procedure described in example 92, using the reactive amines A of examples 49 to 91₁-NH₂Instead of 4- (2' -sulfatoethylsulfonyl) aniline diazotization and coupling in the second stage gives a dark orange dye of the formula:

example 136

19.1 parts of aniline-4-sulfonic acid are dissolved in 220 parts of water and acidified by adding 23 parts of 31% strength hydrochloric acid. It is cooled to 10-15 ℃ with ice and then 14.5 parts of a 40% strength sodium nitrite solution are added dropwise. Stirring for 60 minutes in the presence of excess nitrite. Excess nitrite was reduced by addition of 10% strength sulfamic acid solution.

The dye solution of example 2 is then added to the diazonium salt suspension, the pH is adjusted to 4-5 by addition of a 15% strength sodium carbonate solution, and the coupling is then completed.

The resulting solution was concentrated by evaporation to give the dye of the formula:

which dyes or prints cotton to an orange-brown shade (lambda)_max＝435nm)。

Examples 137 to 181

The dye solutions of examples 3 to 47 were used in place of the dye solution of example 2 to give a dark orange dye of the formula:

example 182

30.3 parts of 2-naphthylamine-4, 8-disulfonic acid are dissolved in 300 parts of water and acidified by addition of 21 parts of 31% strength hydrochloric acid. It was cooled to 10-15 ℃ with ice, and then 13.2 parts of a 40% strength sodium nitrite solution was added dropwise. Stirring for 60 minutes in the presence of excess nitrite. Excess nitrite is reduced by adding a few drops of 10% strength sulfamic acid solution.

The solution obtained in example 1 is then added to the diazonium salt suspension, the pH is adjusted to 4 to 5 by adding a 15% strength sodium carbonate solution and the coupling is then completed. Obtaining a solution of a dye of formula:

a suspension of 33.7g of 4- (2' -sulfatoethylsulfonyl) aniline in 250 parts of water is mixed at 15 ℃ in succession with 0.5g of the commercial dispersant and 25 parts of 31% strength hydrochloric acid and subsequently stirred for 15 minutes. 16 parts of a 40% strength aqueous sodium nitrite solution are then added dropwise and the mixture is stirred for 60 minutes in the presence of excess nitrite.

Excess nitrite is then destroyed by adding a 10% strength sulfamic acid solution. The above dye solution was then added to the diazonium salt suspension and the mixture was stirred for 15 minutes. The pH is then adjusted to 5.0-5.5 by adding a 15% strength sodium carbonate solution and the coupling is then completed.

Concentrating the resulting solution by evaporation to give a dye of the formula:

which dyes or prints cotton to a yellowish brown shade (lambda)_max＝439nm)。

Examples 183 to 225

In analogy to the procedure described in example 182, using the reactive amines A from examples 49 to 91₁-NH₂Instead of 4- (2' -sulfatoethylsulfonyl) aniline diazotization and coupling in the second stage gives a dark orange dye of the formula:

example 226

33.3 parts of 2-naphthylamine-4, 8-disulfonic acid are dissolved in 350 parts of water and acidified by adding 25 parts of 30% strength hydrochloric acid. It is cooled to 10-15 ℃ with ice and then 14.5 parts of a 40% strength sodium nitrite solution are added dropwise. Stirring for 60 minutes in the presence of excess nitrite. Excess nitrite is then reduced by adding a few drops of 10% strength sulfamic acid.

The dye solution obtained in example 2 is then added to the diazonium salt suspension, the pH is adjusted to 4 to 5 by adding a 15% strength sodium carbonate solution and the coupling is then completed.

Drying and concentrating the obtained solution to obtain the dye with the following formula:

which dyes or prints cotton to an orange brown shade (lambda)_max＝429nm)。

Examples 227 to 271

The dye solution of example 2 was replaced with the solutions of examples 3 to 47 to give a dark orange dye of the formula in analogy to the procedure described in example 226:

example 272

A suspension of 61.8g of 4- (2' -sulfatoethylsulfonyl) aniline in 500 parts of water is mixed at 15 ℃ in succession with 0.5g of the commercial dispersant and 50 parts of 31% strength hydrochloric acid and subsequently stirred for 15 minutes. 32 parts of a 40% strength aqueous sodium nitrite solution are then added dropwise and the mixture is stirred for 60 minutes in the presence of excess nitrite.

Excess nitrite is then destroyed by adding a 10% strength sulfamic acid solution. The solution from example 1 was then added to the diazonium salt suspension and the mixture was stirred for 15 minutes. The pH is then adjusted to 5.0-5.5 by adding a 15% strength sodium carbonate solution and the coupling is then completed.

Concentrating the resulting solution by evaporation to give a dye of the formula:

which dyes or prints cotton to dark orange to orange shades (lambda)_max＝428nm)。

Examples 273 to 317

In analogy to the procedure described in example 272, 2.2 equivalents of the reactive amine A from examples 49 to 91 are used₁-NH₂Replacing the 4- (2' -sulfatoethylsulfonyl) aniline diazotized and reacting the diazo compound with 1 equivalent of the coupling agent of example 1 gave a dark orange dye of the formula:

Claims (11)

1. A dye of the general formula (I):

wherein:

m is 1 or 2, and m is,

n is a number of 0 or 1,

q is 0, 1, 2 or 3, and

p is 0, 1 or 2,

r is 0, 1 or 2, and

p + r is 1 or 2, and

X₁is a group-CH₂CH₂Z or-CH ═ CH₂Z is a base-eliminable group,

m is hydrogen, ammonium, an alkali metal or an equivalent of an alkaline earth metal,

X₂is alkyl, alkoxy, halogen, COOM or SO₃M，

L is a direct bond or an alkylene group,

l' is a direct bond or a group of the formula:

X₃is a heterocyclic reactive group of the general formula (IIa) or (IIb):

or a reactive group of formula (IIc), (IId) or (IIe):

wherein:

X₄to X₆Independently hydrogen or halogen, with the proviso that at least one X₄To X₆The radical (b) is a halogen,

X₇is halogen or X₈And are and

X₈is a substituent of the general formula (III):

wherein:

R₁is hydrogen, an alkyl group or an aryl group,

b is alkylene, alkylene interrupted by oxygen, arylene or aralkylene, and

R₂is a group SO₃M、SO₂-CH₂CH₂Z or SO₂-CH＝CH₂Wherein Z is as defined above,

and the absence or presence of the ring labeled a.

2. The dye of claim 1, wherein X₂Is C₁-C₄Alkyl radical, C₁-C₄Alkoxy or SO₃M, M is as defined in claim 1.

3. The dye according to claim 1 and/or 2, wherein X₃Is a group of the formula:

or

Wherein:

hal' is chlorine or bromine,

R₁' is hydrogen, methyl, ethyl or phenyl,

b' is ethylene, propylene, or-CH₂CH₂-O-CH₂CH₂-, and

R₂' is-SO₂CH₂CH₂OSO₃M and-SO₂CH＝CH₂。

4. A dye according to one or more of claims 1 to 3, wherein m is 1.

5. A dye according to one or more of claims 1 to 3, wherein m is 2.

6. The dye according to one or more of claims 1 to 5, which corresponds to the general formula (Ia):

wherein X₁To X₃A, L, L', M, M, r, p and q are as defined in claim 1.

7. The dye according to one or more of claims 1 to 3 and 4 to 6, which corresponds to the general formula (Ib):

wherein X₁To X₃A, L, L', M, r, p and q are as defined in claim 1.

8. The dye according to one or more of claims 1 to 4 and 6, which corresponds to the general formula (Ic):

m, A, X therein₂And q is as defined in claim 1, V is X₃-NH-L-or X₁-O₂S-L' -, wherein X₁、X₃L and L' are as defined in claim 1.

9. The dye according to one or more of claims 1 to 8, which corresponds to one of the general formulae (Id) to (Iq):

wherein in each case:

m is hydrogen or sodium, and

X₂' is hydrogen, methyl, ethyl, methoxy, ethoxy, COOM or SO₃M, and

u is-SO₂CH₂CH₂OSO₃M、-SO₂CH＝CH₂or-NH-U ', wherein M is hydrogen or sodium, and U' is one of the following formulae:

wherein:

hal' is chlorine or fluorine,

R₁' is hydrogen, methyl, ethyl or phenyl,

b' is ethylene, propylene or-CH₂CH₂-O-CH₂CH₂-, and

R₂' is-SO₂CH₂CH₂OSO₃M or-SO₂CH＝CH₂。

10. A process for the preparation of dyes of the general formula (I) according to one or more of claims 1 to 9, which comprises diazotizing an aromatic amine of the general formula (V) below and coupling the diazo compound with a compound of the general formula (VI) below,

wherein p, q, r, L, X₁、X₂And X₃Is as defined in claim 1, wherein,

11. use of a dye of the general formula (I) according to one or more of claims 1 to 9 for dyeing and printing hydroxyl-and/or carboxamido-containing material, in particular fiber material.