HK1072065B - Reactive azo dyes, preparation thereof and use thereof - Google Patents
Reactive azo dyes, preparation thereof and use thereof Download PDFInfo
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- HK1072065B HK1072065B HK05104868.6A HK05104868A HK1072065B HK 1072065 B HK1072065 B HK 1072065B HK 05104868 A HK05104868 A HK 05104868A HK 1072065 B HK1072065 B HK 1072065B
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Description
The technical field of the invention is fiber reactive dyes. Dyes having a structure similar to the dyes of the invention described below but differing in their reactivity by means of (reaktiverker) are already known from the documents DE-A-4434989, DE19600765, DE 19810906 and EP-A922735. These known dyes have a series of industrial drawbacks which require improvement in the dyeing of textile materials.
It has now surprisingly been found that dyes of the general formula (1) below are distinctly superior to the known dyes.
The invention relates to reactive dyes of the general formula (1)
Wherein
R represents hydrogen, alkyl or substituted alkyl,
X1represents halogen, amino, substituted or unsubstituted amino or X2,
X2a substituent represented by the general formula (2)
Wherein
R represents a substituted or unsubstituted aryl group,
b represents an alkylene group which may be interrupted by an oxygen atom; and
r represents a group-SO2CH＝CH2or-SO2CH2CH2Z, wherein Z represents a group which can be eliminated by the action of a base;
n and m represent 0 or 1, and
m represents hydrogen, ammonium, an alkali metal or an alkaline earth metal equivalent (Aquivalent).
In the general formula (1), the alkali metal represented by M is particularly lithium, sodium and potassium, and the alkali metal is particularly calcium. Preferably, M represents hydrogen or sodium.
X1Halogen represented is in particular fluorine or chlorine, substituted amino is in particular amino substituted by aryl which may carry one or more fibre-reactive groups-SO2CH＝CH2or-SO2CH2CH2Z ', wherein Z' is a group which can be eliminated by the action of a base. Preferably the amino group is substituted by sulphatoethylsulphonylphenyl or p-sulphatoethylsulphonylphenyl. The alkyl group represented by R is preferably (C)1-C8) Alkyl, particularly preferably (C)1-C4) -an alkyl group. Examples of such alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl. The alkyl group represented by R may be represented by SO, for example3H-group substitution. RIAryl radicals which may in particular also be represented by (C)1-C4) Alkyl radicals, (C)1-C4) Alkoxy, chlorine, fluorine or SO3The H-group is substituted one or more times. Preferably R1Represents a phenyl or aryl group bearing a sulfo group.
The alkylene group represented by B is preferably (C)1-C8) Alkylene, particularly preferably (C)1-C4) -an alkylene group. Examples of such alkylene groups are methylene, ethylene, n-propylene, isopropylene and butylene groups. Alkylene interrupted by an oxygen atom is preferably a radical- (CH)2)2-O-(CH2)2-。
The groups which Z represents can be eliminated by the action of a base, i.e. under dyeing conditions, are, for example, chlorine, bromine, sulfate (sulfoto), thiosulfate, phosphate (Phosphoto), (C)2-C5) Alkanoyloxy, such as, for example, acetoxy, benzoyloxy, sulfobenzoyloxy or p-tolylsulfonyloxy, with sulfuric acid radicals being preferred.
The radicals "sulfate", "thiosulfate" and "phosphate" include not only their acid forms but also their salt forms. Thus corresponding to a thiosulphate group of formula-S-SO 3M, formula-OPO3M2Phosphoric acid group and the general formula-OSO3A sulfate group of M, wherein M has the above-mentioned meaning.
Preferred reactive dyes according to the invention are those of the formula (1) in which the radicals of the formula (2) correspond to the radicals (2-1) to (2-4),
wherein M has the above-mentioned meaning.
Particular preference is given according to the invention to dyes of the formulae (1a) to (1c)
Wherein M, n and X have the above-mentioned meanings.
The reactive dyes of the general formula (1) according to the invention are generally present as preparations in solid or liquid (dissolved) form. In solid form, they generally comprise the electrolytic salts customary in water-soluble and especially fibre-reactive dyes, such as sodium chloride, potassium chloride and sodium sulphate, and may also comprise the customary formulations in commercially available dyes, such as buffer substances which adjust the pH in aqueous solution between 3 and 7, such as sodium acetate, sodium borate, sodium bicarbonate, sodium dihydrogen phosphate, sodium tricitrate and disodium hydrogen phosphate, drying accelerators in small amounts, or, if they are present in liquid aqueous solutions (including thickeners), substances which ensure the durability of the formulation, such as, for example, mildewcides.
The reactive dyes of the general formula (1) according to the invention are preferably present as pulverulent or granulated dyes, comprising from 10 to 80% by weight, based on the total amount of the powder or granule, of an electrolytic salt (which is also referred to as a diluent). The particle size of the particulate dye is in particular from 50 to 500 μm. These solid formulations may also contain selected buffer substances in an amount of up to 10% by weight of the formulation. If the dye is present in the form of an aqueous solution, the total content of dye in the aqueous solution is up to about 50% by weight, for example 5 to 50% by weight, wherein the content of electrolytic salts in the aqueous solution is preferably less than 10% by weight, calculated as aqueous solution. The aqueous solutions (liquid formulations) generally contain up to 10% by weight, preferably up to 2% by weight, of selected buffer substances.
The reactive dyes of the general formula (1) according to the invention can have fibre-reactive radicals R of different structures with the same chromophore2. In particular, R is under the same chromophore2In one aspect, represents-SO2CH＝CH2And on the other hand represents-SO2CH2CH2Z, particularly preferably represents a β -sulfatoethylsulfonyl group. In this case, up to about 30 mole% of the dye, based on the respective dye chromophore, is present as vinylsulfonyl. Preferably, the molar ratio of vinylsulfonyl dye to β -ethyl-substituted dye is from 5: 95 to 30: 70.
The invention also relates to a method for producing the reactive dyes of the general formula (1).
The reactive dyes can be obtained, for example, by reacting compounds of the general formula (3)
Wherein X1、X2M and n have the abovementioned meanings,
is diazotized and reacted with a compound of formula (4).
Alternatively, the compound of formula (5)
Wherein R, M, m and n have the above-mentioned meanings,
condensed with a halogenotriazine of the general formula (6),
wherein X1And X2Having the above meanings, and X3Represents fluorine or chlorine.
The compounds of the general formula (6) can again be obtained from trifluorotriazine or trichlorotriazine and one or two compounds of the general formula (2').
Wherein X2The compounds of formula (1) representing a group of formula (2) may alternatively be obtained by reaction of a compound of formula (5) with a trihalotriazine, followed by condensation with an amine of formula (2').
Wherein X1And X2Dyes of the general formula (1) having the same meaning but not representing halogen can be obtained even where X is1The dyes of the general formula (1) representing halogen are fused and reacted with the reactive amines of the general formula (2') in aqueous solution.
The compounds of the general formula (3) can be obtained in different ways.
If X is2Is a radical of the formula (2), by reacting the halogenotriazines (6) with diaminobenzenesulphonic acids or diaminobenzenedisulphonic acids, preferably 1, 3-diaminobenzene-4-sulphonic acid, 1, 4-diaminobenzene-2-sulphonic acid and also 1, 4-diaminobenzene-2, 5-disulphonic acid and 2, 4-diaminobenzene-1, 5-disulphonic acid, or by fusing trichloro-or trifluorotriazines with diaminobenzenesulphonic acid or diaminobenzenedisulphonic acid and subsequently with amines of the general formula (2').
The diazotisation, coupling and fusion reactions described above are known per se to the skilled worker and are generally carried out in the manner and method described in detail in the relevant literature.
The dyes of the general formula (1) according to the invention are obtained as a solution or suspension in the preparation process described above and can be isolated by salting out. It is likewise possible to spray dry it, evaporation of the solution or suspension also being possible.
The reactive dyes of the general formula (1) according to the invention have interesting application properties. The dyes are used for dyeing and printing hydroxyl-and/or carboxamido-containing materials in the form of flat surfaces, such as paper and leather, or in the form of foils, such as foils made of polyamides, or in the form of dough, such as dough of polyamides and polyurethanes, but in particular in the form of fibers of the above-mentioned materials. Preferably, the dyes are used for dyeing and printing all kinds of cellulose-containing fibre materials. Furthermore, the dyes are also suitable for dyeing or printing hydroxyl group-containing fibers contained in blend fabrics, for example mixtures of cotton with polyester fibers or polyamide fibers. The dyes can also be used for printing on textiles or paper by means of jet printing.
The present invention therefore also relates to the use of the reactive dyes of the general formula (1) according to the invention for dyeing and printing the abovementioned materials, and to a process for dyeing or printing these materials in a process which is conventional per se, in which one or more reactive dyes of the general formula (1) according to the invention are used as dyeing agents.
Advantageously, the reactive dyes of the general formula (1) according to the invention formed during the synthesis can, if desired after addition of buffer substances, if desired also be used directly as liquid preparations for dyeing after concentration or dilution.
Preferably the above materials are used in the form of fibrous materials, in particular textile fibers such as fabrics or threads, for example in the form of bundles or clews.
Hydroxyl-containing materials are those of natural or synthetic origin, such as, for example, cellulosic fibrous materials or recyclates thereof and polyvinyl alcohol. The cellulosic fibrous material is preferably cotton, but may also be vegetable fibres, such as flax, hemp, jute and ramie fibres. Regenerated cellulose fibers are, for example, artificial wool and viscose rayon.
Materials containing carboxamide groups are, for example, synthetic and natural polyamides and polyurethanes, especially in the form of fibers, for example wool and other animal hair, silk, leather, polyamide-6, polyamide-11 and polyamide-4.
The reactive dyes of the general formula (1) according to the invention are applied to the abovementioned materials, in particular to the abovementioned fibre materials, and fixed, according to the coating techniques known for water-soluble, in particular fibre-reactive dyes. With this dye it is possible to obtain dyeings having very good dyeing results on cellulose fibres after removal of the faded out dye liquor using different acid-bound preparations and, if desired, neutralizing salts such as sodium chloride or sodium sulphate. The dyeing is preferably carried out in a water bath under pressure at from 40 to 105 ℃ and, if desired, up to 130 ℃ and, if desired, in the presence of customary dyeing auxiliaries. The material is therefore placed in a hot bath and slowly heated to the desired dyeing temperature, and the dyeing process is carried out at this temperature until the end. The neutral salt which promotes the dye fading can, if desired, also be added immediately after the actual dyeing temperature has been reached.
After the pad dyeing process, outstanding dyeing results and very good color profiles are likewise obtained on the cellulose fibers, where the fixation takes place in the customary manner by retention at room temperature or elevated temperature, for example up to 69 ℃, by evaporation or by heating with drying.
A bright-colored print with a good profile and a clear white background is also obtained after the conventional cellulose fiber printing process, which can be carried out in one step by printing with a printing paste containing sodium bicarbonate or other acid-binding agents and subsequent evaporation at from 100 to 103 ℃, or in two steps, i.e. printing with neutral or weakly acidic printing dyes and subsequent over-padding with hot electrolyte-containing alkaline baths or with alkaline padding liquors with electrolyte (Uberklotzen), for example, and finally staying or evaporating or treating the alkaline over-padded material with dry heat. The detachment of the print depends only to a small extent on the fixing conditions associated with the change.
According to the conventional thermosetting method, hot air of 120 to 200 ℃ is used in fixing by heating with drying. In addition to conventional water vapor at 101 to 103 ℃, superheated steam and pressurized steam at temperatures up to 160 ℃ may be used.
The auxiliaries which are acid-binding and which act to fix the dye on the cellulose fibers are, for example, water-soluble alkaline salts of alkali metals or alkaline earth metals of inorganic or organic acids or compounds thereof which release alkali on heating. In particular alkali metal hydroxides and alkali metal salts of weak to medium-strength inorganic or organic acids, the preferred basic compounds being potassium and sodium compounds. Examples of acid-binding auxiliaries are sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium hydrogen phosphate, disodium hydrogen phosphate, sodium trichloroacetate, water glass or trisodium phosphate.
The reactive dyes of the general formula (1) according to the invention are distinguished by high reactivity, good fixing power, very good combining power (Aufbauvermogen) and high fastness to light and perspiration. The dyes can therefore be used at low temperatures according to the fading dyeing process (Ausziehfarbeverfahren) and only short evaporation times are required in the Pad-Steam process (Pad-Steam-Verfahren). The fixation rating is high and the unfixed portions are easy to wash off, wherein the difference between the fading rating and the fixation rating is not very pronounced, i.e. the soap loss (seifverlux) is very low. They are likewise particularly suitable for printing predominantly on cotton, but also on nitrogen-containing fibres, for example wool or silk or wool-or silk-containing blend fabrics.
The reactive dyes of the general formula (1) according to the invention are furthermore distinguished in that after dyeing on the fibre material the unfixed dye is very easy to wash off without soiling white clothes which are present simultaneously in the washing process by the dye which has fallen off. The advantage thus obtained for this dyeing method is the saving of the washing cycle and therefore of the costs.
The dyeings and prints obtained with the reactive dyes of the general formula (1) according to the invention have, in particular, high dyeing strength on cellulose fibres and high fibre-dye binding stability in both the acid and alkaline range, and furthermore have good fastness to light and very good fastness to moisture, for example to washing, to water, to sea water, to topping and to perspiration, and also good wrinkle, to iron and to rub.
The following examples serve to further illustrate the invention. Parts are parts by weight and percent units are% by weight unless otherwise indicated. Parts by weight relate to parts by volume, for example between kilograms and litres.
The compounds in the structural film form are illustrated in the examples in the form of the free acids. Generally, these compounds are prepared and isolated in the form of their alkali metal salts, for example lithium, sodium or potassium salts, and are used for dyeing in the form of their salts. Also in the following examples, in particular in the tables, the starting compounds and components mentioned as free acids are used in the synthesis reaction as such or in the form of their salts, preferably in the form of alkali metal salts. ,
for illustrating the absorption maximum (. lamda.) in the visible range of the dyes of the inventionMaximum of) By means of the base thereofThe metals are measured in aqueous solution.
Example 1
18.4 parts of 2, 4, 6-trichloro-1, 3, 5-triazine are suspended in 200 parts of ice-water at 0 to 5 ℃ for 30 minutes. 30.9 parts of (2- (anilino) -ethyl) - (2-sulfatoethyl) -sulfone are then added within 30 minutes, and the reaction mixture is maintained at pH2.5 during the addition by simultaneous metered addition of a 15% soda solution. After stirring at 0 to 5 ℃ for 1 hour, 26.8 parts of 1, 4-diaminobenzene-2, 5-disulfonic acid are added and the pH is adjusted to 5.5 with 15% soda solution. The reaction mixture was then heated to 35 ℃ and stirred for 30 minutes. Cooled to 10 ℃, reacted with 6.9 parts of sodium nitrite and the solution was added dropwise to a mixture consisting of 100 parts of ice and 40 parts of concentrated hydrochloric acid (31%). Stir for 1 hour and remove excess nitrite by addition of sulfamic acid.
23.9 parts of 7-amino-1-hydroxy-naphthalene-3-sulfonic acid are dissolved in 300 parts of water while maintaining neutrality by adding a caustic soda solution. The solution was added dropwise over 30 minutes in a diazotization bath cooled to 10 ℃. The pH value is adjusted to 1.5-2.0. Adjusted to 2.5 with 15% soda solution over 30 minutes and stirred at elevated temperature for 3 hours. Subsequently adjusted to pH6 with soda solution and NaH2PO4/Na2HPO4And (6) buffering. The obtained solution was evaporated.
Obtaining a dye of the formula
The dyes are used to dye and print cotton in the light blue-red shade, which has good fastness, especially high light fastness.
In a similar manner, the dyes of examples (2) to (32) were obtained. To this end, the corresponding reactive amines and trichlorotriazines are introduced for the reaction and subsequently displaced by the fused component, diazotized and coupled onto the coupling component.
| Examples | Reactive amines | Fused Components | Coupling component | Color tone | λ |
| 2) | (2- (anilino) -ethyl) - (2 sulfatoethyl) -sulfone | 1, 4-diaminobenzene-2, 5-disulfonic acid | 7-amino-1-hydroxynaphthalene-3, 6-disulfonic acid | Red wine | 528 |
| 3) | Same as above | Same as above | 7-sulfomethylamino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 536 |
| 4) | Same as above | 2, 4-diaminobenzene-1, 5-disulfonic acid | 7-amino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 519 |
| 5) | Same as above | Same as above | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 521 |
| 6) | Same as above | Same as above | 7-sulfomethylamino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 532 |
| 7) | Same as above | 1, 4-diaminobenzene-2-sulfonic acid | 7-amino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 517 |
| 8) | Same as above | Same as above | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 524 |
| 9) | Same as above | 1, 3-diaminobenzene-4-sulfonic acid | 7-amino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 510 |
| 10) | Same as above | Same as above | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 514 |
| 11) | (3- (anilino) -propyl) (2-sulfatoethyl) -sulfone | 1, 4-diaminobenzene-2, 5-disulfonic acid | 7-amino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 524 |
| 12) | Same as above | Same as above | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 527 |
| 13) | Same as above | Same as above | 7-sulfomethylamino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 537 |
| 14) | Same as above | 2, 4-diaminobenzene-1, 5-disulfonic acid | 7-amino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 519 |
| 15) | Same as above | Same as above | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 521 |
| 16) | Same as above | Same as above | 7-sulfomethylamino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 532 |
| 17) | Same as above | 1, 4-diaminobenzene-2-sulfonic acid | 7-amino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 518 |
| 18) | Same as above | Same as above | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 524 |
| 19) | Same as above | 1, 3-diaminobenzene-4-sulfonic acid | 7-amino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 510 |
| 20) | Same as above | Same as above | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 514 |
| 21) | (2- (4-sulfophenyl-amino) ethyl) - (2-sulfatoethyl) -sulfone | 1, 4-diaminobenzene-2, 5-disulfonic acid | 7-amino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 523 |
| 22) | Same as above | Same as above | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 528 |
| 23) | Same as above | Same as above | 7-sulfomethylamino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 537 |
| 24) | Same as above | 2, 4-diaminobenzene-1, 5-disulfonic acid | 7-amino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 518 |
| 25) | Same as above | Same as above | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 522 |
| 26) | Same as above | Same as above | 7-sulfomethylamino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 531 |
| 27) | Same as above | 1, 4-diaminobenzene-2-sulfonic acid | 7-amino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 517 |
| 28) | Same as above | 1, 4-diaminobenzene-2-sulfonic acid | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 525 |
| 29) | Same as above | 1, 3-diaminobenzene-4-sulfonic acid | 7-amino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 511 |
| 30) | Same as above | Same as above | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 515 |
| 31) | (3- (4-sulfophenyl-amino) propyl) - (2-sulfatoethyl) -sulfone | 1, 4-diaminobenzene-2, 5-disulfonic acid | 7-amino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 524 |
| 32) | Same as above | Same as above | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 528 |
| 33) | Same as above | Same as above | 7-sulfomethylamino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 537 |
| 34) | Same as above | 2, 4-diaminobenzene-1, 5-disulfonic acid | 7-amino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 519 |
| 35) | Same as above | Same as above | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 522 |
| 36) | Same as above | Same as above | 7-sulfomethylamino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 532 |
| 37) | Same as above | 1, 4-diaminobenzene-2-sulfonic acid | 7-amino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 518 |
| 38) | Same as above | Same as above | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 523 |
| 39) | Same as above | 1, 3-diaminobenzene-4-sulfonic acid | 7-amino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 510 |
| 40) | Same as above | Same as above | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 515 |
EXAMPLE 41
21.8 parts of 4-nitroaniline-2-sulfonic acid are stirred in 400 parts of water and neutralized with a caustic solution. 6.9 parts of sodium nitrite are added and stirred until completely dissolved.
The solution was added dropwise to prepared 100 parts of ice and 30 parts of concentrated hydrochloric acid (31%) at 0 to 5 ℃ and stirred for 60 minutes. The remaining nitrite was removed by addition of sulfamic acid.
31.9 parts of 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid are dissolved in 300 parts of water while maintaining neutrality by adding a caustic soda solution, and this solution is added dropwise over 30 minutes to a suspension of the diazonium salt. The pH was slowly adjusted to 2 with soda solution and stirred for 1 hour. A dye solution is obtained which comprises the compound of the formula (7) in the form of the free acid
The solution of compound (7) is adjusted to pH8.5 with a caustic solution and heated to 70 ℃. A solution of 5.6 parts NaHS in 50 parts water was added dropwise and stirred for 30 minutes. The resulting compound is precipitated by heating 150 parts of sodium chloride, filtered and washed with an aqueous solution of sodium chloride. The compound obtained is the free acid of formula (8).
51.9 parts of compound (8) are dissolved in 500 parts of water. 18.4 parts of 2, 4, 6-trichloro-1, 3, 5-triazine are suspended in 200 parts of ice-water at 0 to 5 ℃ for 30 minutes. 30.9 parts of (2- (anilino) ethyl) - (2-sulfatoethyl) -sulfone are then added within 30 minutes, and the reaction mixture is maintained at pH2.5 during the addition by simultaneous metered addition of a 15% soda solution. The mixture was stirred at 0 to 5 ℃ for 1 hour, and the obtained suspension was added to a solution of compound (8). The reaction mixture was adjusted to pH6 with soda solution and heated to 35 ℃. Stirred for 1 hour. The end of the reaction was determined by membrane chromatography. The dye of example (6) is precipitated by heating potassium chloride, filtered off and dried.
The cotton is dyed with the dye to a light blue-red shade.
The compounds of examples 5), 13) and 14) were prepared in a similar manner by the fusion of compound (8) with the corresponding triazine derivative.
The compound of the general formula (5) is prepared by changing the coupling component in the compound (8) according to the above-mentioned method. These compounds can be converted into dyes of the general formula (1) by reaction with the corresponding triazine derivatives.
Example 42
51.9 parts of compound (12) is dissolved in 500 parts of water, 4.2 parts of sodium fluoride is added, and cooled to 5 ℃. 13.5 parts of 2, 4, 6-trifluorotriazine are then added. The pH is first lowered and then maintained at about 4-4.5. Stirred for 15 minutes.
Subsequently, 40.3 parts of a neutral aqueous solution of (3- (4-sulfophenylamino) -propyl) - (2-sulfatoethyl) -sulfone are added dropwise to the reaction mixture, heated to 25 ℃ and the pH is kept constant at 6 to 6.5 by adding a soda solution.
The end point of the reaction was determined by membrane chromatography. The dye of formula (9) in the free acid form is kept constant after evaporation of the solution.
The cotton is dyed with the dye to a light blue-red shade.
The compounds of examples 43) to 48) were prepared in an analogous manner according to the methods described.
| Examples | Reactive amines | Coupling component in Compound of formula (12) | Color tone | λ max |
| 43) | (3- (4-sulfophenylamino-) -propyl) - (2-sulfatoethyl) -sulfone | 7-amino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 518 |
| 44) | (2- (4-sulfophenylamino-) -ethyl) - (2-sulfatoethyl) -sulfone | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 525 |
| 45) | Same as above | 7-amino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 518 |
| 46) | (2- (anilino) -ethyl) - (2-sulfatoethyl) -sulfone | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 524 |
| 47) | Same as above | 7-amino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 519 |
| 47) | (3- (anilino) -propyl) - (2-sulfatoethyl) -sulfone | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 524 |
| 48) | Same as above | 7-amino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 518 |
Example 49
32.3 parts of (3- (anilino) -propyl) - (2-sulfatoethyl) -sulfone are dissolved in 200 parts of water at pH5 by addition of 15% soda solution and 4.6 parts of sodium fluoride are added. Cooled to 0 ℃ and 13.5 parts of 2, 4, 6-trifluorotriazine are added to the solution. The pH value is first lowered and then maintained at 3.5 to 4.0. The reaction mixture was stirred for 15 minutes. 18.8 parts of 2, 4-diamino-benzene-1, 5-disulfonic acid are then added, adjusted to 5.5 with soda solution and heated to 20 to 25 ℃. After stirring for 1 hour, 6.9 parts of sodium nitrite were added. This solution was then added over 30 minutes to a mixture consisting of 100 parts ice and 50 parts concentrated hydrochloric acid (315). The solution was stirred for 1 hour, then the remaining nitrite was removed by adding sulfamic acid.
23.9 parts of 7-amino-1-hydroxy-naphthalene-3-sulfonic acid are dissolved in 300 parts of water while being kept neutral by adding a caustic solution. Heated to 50 ℃ and 13.4 parts of formaldehyde-disulphite (sodium salt) are added. After stirring for 30 minutes, it is cooled to 20 ℃ and the solution is added dropwise to the diazotised solution cooled to 10 ℃. The pH value is adjusted to 1.5-2. The pH was adjusted to 2-2.5 with soda solution and stirred at elevated temperature for 3 hours. The solution was adjusted to pH6 with soda solution and NaH2PO4/Na2HPO4Buffered and evaporated.
Obtaining a dye of the formula
The cotton is dyed with the dye to a light blue-red shade.
In a similar manner, the dyes of examples 50) to 80) and of examples 42) to 48) described in the table below were prepared by fusing the reactive amine as starting material with trifluorotriazine, with the corresponding fused component, diazotized and coupled on the corresponding coupling component.
| Examples | Reactive amines | Fused Components | Coupling component | Color tone | λ max |
| 50) | (3- (anilino) -propyl) - (2-sulfatoethyl) -sulfone | 2, 4-diaminobenzene-1, 5-disulfonic acid | 7-amino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 518 |
| 51) | Same as above | Same as above | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 522 |
| 52) | Same as above | Same as above | 7-sulfomethylamino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 535 |
| 53) | Same as above | 1, 4-diaminobenzene-2, 5-disulfonic acid | 7-amino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 525 |
| 54) | Same as above | Same as above | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 528 |
| 55) | Same as above | 1, 3-diaminobenzene-4-sulfonic acid | 7-amino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 510 |
| 56) | Same as above | Same as above | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 514 |
| 57) | (2- (anilino) -ethyl) - (2-sulfatoethyl) -sulfone | 2, 4-diaminobenzene-1, 5-disulfonic acid | 7-sulfomethylamino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 532 |
| 58) | Same as above | Same as above | 7-amino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 519 |
| 59) | Same as above | Same as above | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 523 |
| 60) | Same as above | 1, 4-diaminobenzene-2, 5-disulfonic acid | 7-sulfomethylamino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 536 |
| 61) | Same as above | Same as above | 7-amino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 525 |
| 62) | Same as above | Same as above | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 528 |
| 63) | Same as above | 1, 3-diaminobenzene-4-sulfonic acid | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 510 |
| 64) | Same as above | Same as above | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 514 |
| 65) | (2- (4-sulfophenylamino) ethyl) - (2-sulfatoethyl) -sulfone | 2, 4-diaminobenzene-1, 5-disulfonic acid | 7-amino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 518 |
| 66) | Same as above | Same as above | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 521 |
| 67) | Same as above | Same as above | 7-sulfomethylamino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 532 |
| 68) | Same as above | 1, 4-diaminobenzene-2, 5-disulfonic acid | 7-amino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 524 |
| 69) | Same as above | Same as above | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 528 |
| 70) | Same as above | Same as above | 7-sulfomethylamino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 536 |
| 71) | (2- (4-sulfophenylamino) ethyl) - (2-sulfatoethyl) -sulfone | 1, 3-diaminobenzene-4-sulfonic acid | 7-amino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 510 |
| 72) | Same as above | Same as above | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 515 |
| 73) | (3- (4-sulfophenylamino) propyl) - (2-sulfatoethyl) -sulfone | 1, 4-diaminobenzene-2, 5-disulfonic acid | 7-amino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 524 |
| 74) | Same as above | Same as above | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 527 |
| 75) | Same as above | Same as above | 7-sulfomethylamino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 536 |
| 76) | Same as above | 2, 4-diaminobenzene-1, 5-disulfonic acid | 7-amino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 519 |
| 77) | Same as above | Same as above | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 522 |
| 78) | Same as above | Same as above | 7-sulfomethylamino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 531 |
| 79) | Same as above | 1, 3-diaminobenzene-4-sulfonic acid | 7-amino-1-hydroxy-naphthalene-3-sulfonic acid | Red wine | 511 |
| 80) | Same as above | Same as above | 7-amino-1-hydroxy-naphthalene-3, 6-disulfonic acid | Red wine | 515 |
Example 81
28.1 parts of 4- (2' -sulphatoethylsulphonyl) -aniline are dissolved in 250 parts of water, while being neutral by the addition of a 15% soda solution. The dye of example (8) was added to this solution and adjusted to pH 5.5-6. Heating to 80 ℃ maintains the pH in an adjustable range by heating the soda solution. The course of the reaction was followed by membrane chromatography. At the end of the reaction the dye solution is cooled, buffered and dried. A powder having the following structure was obtained.
The dyes are used to dye cotton in the light blue-red shade, which has good fastnesses, in particular high lightfastness.
In a similar manner, examples 82) to 88) listed in the following table were obtained by fusing the dyes of the listed examples as starting materials to a reactive amine.
| Examples | Starting dye examples | Reactive amines | Color tone | λ max |
| 82) | 8) | 4- (2' -sulphatoethylsulphonyl) -N-ethyl-aniline | Red wine | 527 |
| 83) | 3) | 3- (2' -sulphatoethylsulphonyl) -aniline | Red wine | 536 |
| 84) | 40) | 4- (2' -sulphatoethylsulphonyl) -aniline | Red wine | 516 |
| 85) | 26) | 3- (2' -sulphatoethylsulphonyl) -aniline | Red wine | 533 |
| 86) | 17) | (2- (anilino) ethyl) - (2-sulfatoethyl) -sulfone | Red wine | 520 |
| 87) | 8) | (2- (anilino) ethyl) - (2-sulfatoethyl) -sulfone | Red wine | 528 |
| 88) | 26) | 4-(2’-Sulphatoethyl sulphonyl) -aniline | Red wine | 533 |
Claims (7)
1. Reactive dyes of the general formula (1)
Wherein
R is hydrogen or SO3H substituted C1-C4An alkyl group, a carboxyl group,
X1is a fluorine compound, and is characterized in that,
X2a substituent of the general formula (2)
Wherein
R1Is phenyl or SO3H is a monosubstituted phenyl group,
b is C1-C4An alkylene group; and
R2is a group-SO2CH＝CH2or-SO2CH2CH2Z, wherein Z is sulfato;
n and m are each 0 or 1, and
m is hydrogen, ammonium, lithium, sodium or potassium.
2. A reactive dye according to claim 1, wherein n is 1.
3. A reactive dye according to claim 1 having the structure of one of formulae (1a) to (1 c):
wherein M, n and X1Each having the meaning as claimed in claim 1.
4. A reactive dye according to any one of claims 1 to 3, wherein M is hydrogen or sodium.
5. A process for preparing a reactive dye according to any one of claims 1 to 4, which comprises reacting a reactive amine component of the general formula (3)
Wherein X1、X2M and n each have the meanings given in any one of claims 1 to 4The meaning of (a) is given,
diazotized and reacted with a compound of formula (4).
6. A process for preparing a reactive dye according to any one of claims 1 to 4, which comprises reacting a compound of the general formula (5)
With a trihalotriazine, followed by condensation with an amine of the general formula (2),
r, R therein1、R2B, M, n and m each have the definitions given in any one of claims 1 to 4.
7. Use of a reactive dye according to any one of claims 1 to 4 for dyeing and printing hydroxyl-and/or carboxamido-containing material.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10159001.6 | 2001-11-30 | ||
| DE10159001A DE10159001A1 (en) | 2001-11-30 | 2001-11-30 | Azo reactive dyes, process for their preparation and their use |
| PCT/EP2002/013410 WO2003046087A1 (en) | 2001-11-30 | 2002-11-28 | Reactive azo dyes, method for the production and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| HK1072065A1 HK1072065A1 (en) | 2005-08-12 |
| HK1072065B true HK1072065B (en) | 2008-07-11 |
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