DE2805199A1 - Diazo dyes contg. 2-amino 8-hydroxy naphthalene-sulphonic acid gp. - give fast red to blue shades on natural and synthetic polyamide(s), etc. - Google Patents

Abstract

Disazo cpds. of formula (I) are claimed in which D is the residue of a diazocomponent (II), (III), or (IV): R1 is CF3, -COOM1, -COOR2 or a gp. -NHR3, -NR3R4 or -NR5COR6 which is meta- or para- to the azo gp. and ring A may be further substd. by 1 or 2 halogen, 1-4C alkyl, 1-4C alkoxy or 1 CF3 gp.; R2 is 1-12C alkyl; R3 and R4 (same or different) are 1-6C alkyl; R5 is H or 1-4C alkyl; R6 is 1-6C alkyl, 1-6C alkoxy or 1-6C alkyl substd. by a Cl or OMe gp.; B is a divalent phenylene-1,4, naphthylene-1,4 or 1,2,3,4-tetrahydronaphthylene-5,8 gp.; and M and M1 (same or different) are H or one equiv. of a colourless cation. The SO3M gp. is the only sulpho gp. in the mol., and is situated in the 5- or 6-position of the naphthyl gp. (I) give good red to blue shades and prints on substrates such as natural and synthetic polyamides, basic modified polyolefins, polyurethanes, leather, etc. The colours are fast to light, moisure, sweat and rubbing.

Description

Anionic disazo compounds, method of preparation

and use The invention relates to a Sulfo group-containing disazo compounds and mixtures thereof, processes for their Manufacture and use.

The disazo compounds according to the invention correspond to the formula wherein D is the residue of a diazo component of the formula (a), (b) or (c) R1 is trifluoromethyl, -COOM1, -COOR2 or a radical -NHR3, -NR3R4 or -NR5COR6 meta or para to the azo group and the ring A can be further substituted by one or two substituents from the series halogen, (1-4C) alkyl ( preferably methyl), (1-4C) alkoxy (preferably methoxy) and trifluoromethyl (only one trifluoromethyl radical), R2 (l-12C) alkyl, R3 and R4 independently of one another (1-6C) alkyl, R5 hydrogen or (1-4C) Alkyl, R6 (1-6C) alkyl, (1-6C) alkoxy or (1-6C) alkyl monosubstituted by chlorine or methoxy, B is a divalent radical from the series phenylene-1,4, naphthylene-1,4 or 1, 2,3,4-Tetrahydronaphthylene-5,8 and M and M1 are independently hydrogen or an equivalent of a colorless cation and the SO3M group is the only sulfo group present in the molecule in position 5 or 6 of the naphthyl radical.

The compounds of the formula (I) and their mixtures are anionic Dyes.

The alkyl radicals listed for R2, R3, R4, R5 and R6 can be straight-chain or be branched.

R2 preferably denotes a (1-8C) alkyl radical and stands in particular preferred for R'2 meaning (1-4C) alkyl.

The alkyl radicals defined for R3 and R4 preferably contain independently from one another 1-4C atoms; they are more preferably R3 and R4 in the meaning of in each case methyl or ethyl and in particular for methyl.

R5 in the meaning of (1-4C) alkyl preferably represents methyl.

R5 preferably represents R51 in the meaning of hydrogen or methyl, especially for hydrogen.

R6 as (1-6C) alkyl preferably represents a (1-4C) -alkyl radical, more preferably for methyl or ethyl and in particular for methyl; R6 as substituted Alkyl radical preferably represents one which is terminally substituted by chlorine or methoxy (1-3C) alkyl radical. R6 in the meaning of a (1-6C) alkoxy radical preferably represents a (l-4C) alkoxy radical and particularly preferred for metnoxy.

R6 preferably represents R6 in the meaning of (1-4C) -alkyl, through Chlorine or methoxy terminated (1-3C) alkyl or of (1-4C) alkoxy; further preferred for R611 meaning methyl or ethyl, methoxy, 2-methoxyethyl or 3-methoxypropyl; particularly preferred for R6 'meaning methyl or methoxy 6 and very particularly preferably methyl.

R1 preferably represents R1 in the meaning of trifluoromethyl, -COOR2 ,, -NHR31, -NR3R4 or -NR5COR6; further preferred for R1 in the meaning of -COOR2 or -NR5COR6; even more preferred for R1 "in the meaning of -NR5COR6 'and especially for -NHCOCH3.

Halogen as a substituent of ring A is preferably chlorine or Bromine and especially chlorine.

The ring A is preferably not further substituted or it carries one or two further substituents from the group consisting of chlorine, methyl and methoxy.

If there is a further substituent in addition to R1 in ring A, then are for the two substituents the positions 2,4; 2,5 and 3,4 preferred; in particular the two substituents are preferably in position 3,4.

If there are two further substituents in addition to R1 in ring A, take this prefers the positions 2,3,5; 2,4,5 or 2,4,6, of which particularly preferred the positions 2,4,5 and 2,4,6.

D as radical (a) preferably represents a radical (a1) wherein ring A bears no further substituents or one or two further substituents from the series halogen, (1-4C) -alkyl, (1-4C) alkoxy and trifluoromethyl (only one trifluoromethyl radical), chlorine, methyl and methoxy being particularly preferred as substituents are. More preferably, (a1) contains the radical R1.

(A) is particularly preferably a radical (a,) wherein R7 is hydrogen, chlorine, methyl or methoxy, in particular hydrogen, and very particularly preferably for (a3) D preferably represents a radical (a1) or (b); more preferably for a radical (a2) and particularly preferably for a radical (a3).

The divalent radical B is preferably 1,4-naphthylene; 1,2,3,4-tetrahydronaphthylene-5,8 or a radical of the formula (d) wherein R8 and Rg independently of one another are hydrogen, (1-4C) alkyl or (1-4C) alkoxy.

The alkyl radical given for R8 or Rg preferably contains 1 or 2 carbon atoms and means in particular methyl.

The alkoxy radical given for R8 or Rg preferably contains 1 or 2 carbon atoms and means in particular methoxy.

R8 preferably represents R8 in the meaning of methyl, methoxy or Ethoxy, particularly preferred for methoxy.

Rg preferably represents R 'in the meaning of hydrogen, methyl, Methoxy or ethoxy and especially preferred for Rg in the meaning of methyl or methoxy.

The radical (d) preferably denotes the radical (dl) in which R8 stands for R8 and Rg stand for R '; more preferably the 8 9 9 radical (d2), in which R8 is methoxy and Rg for Rg, of which in particular for methoxy '.

B preferably denotes 1,4-naphthylene or a radical of the formula (d), of which particularly preferably the radical of the formula (d), even more preferably a radical of formula (dl) and in particular (d2).

Compounds preferred in the context of the present invention correspond of the formula (I), in which D is a radical of the formula (a) or (b) and B is a radical of formula (d) or represent 1,4-naphthylene; compounds are further preferred of the formula (I), in which D is a radical of the formula (a1) (preferably with the radical R1 in the meaning of R1) and B for a radical of the formula (dl) or for 1,4-naphthylene stand; Of these, those compounds are particularly preferred in which -D stands for one Remainder of the formula (a2) and the sulfo group in the naphthalenic end component is in position 6; Compounds of the formula (I) are very particularly preferred, wherein D is a radical of the formula (a3), B is a radical of the formula (d2) and the sulfo group in the naphthalene end component is in position 6.

M and M1, meaning a colorless cation, can be one in the Chemistry of anionic dyes represent common cation. Preferably mean M and M1 independently of one another are an alkali metal ion or an unsubstituted, low molecular weight alkyl-substituted or hydroxyalkyl-substituted ammonium ion corresponding to orme N (R10) 4, in which each R10 independently of one another is hydrogen, (1-3C) alkyl or Denotes hydroxy- (2-4C) alkyl.

For those present side by side in substituted ammonium ions Remnants are to be excluded from such arrangements which are from a steric point of view and for reasons of stability known to bring problems such as a tetraalkanolammonium ion.

Examples of such cations are lithium, sodium or potassium, Ammonium, triethylammonium, mono-, di- or triethanolammonium or mono-, di- or Mention triisopropanolammonium.

Preferably M and M1 are identical. Alkali metal ions are called cations preferred.

The disazo compounds of the formula (I) according to the invention or mixtures thereof are obtained by converting the diazo compound of an amine of the formula D - N = N - B - NH2 (11) or mixtures thereof to a compound of the formula wherein the SO3M group is in position 5 or 6, or couples on a mixture thereof.

The coupling reaction takes place in an acidic medium in the usual way In this way, a pH range from 3.0 to 4.5 is preferably chosen.

The diazotization of the monoazoamino compound of the formula (II) is after per se known methods carried out.

The compounds of the formula (II) are either known compounds or can be prepared in a manner known per se by acidic coupling of the diazo compound of an amine D-NH2 to a compound B-NH2.

The compounds of the formula (III) are known.

The disazo compounds of the Formula (I) in the form of the salts, usually the sodium or potassium salts, and can be isolated as such from the reaction mixture by methods known per se will. However, they can also be isolated in the form of the free acids by adding acid If desired, this can be done by subsequent reaction with customary bases such as hydroxides, carbonates, bicarbonates or acetates the transfer into the corresponding salts.

The compounds of formula (I) and their mixtures in the form of the free Acids or in salt form can be used for dyeing, padding and printing of any substrates which can be dyed with anionic dyes can be used. Suitable substrates are for example natural and synthetic polyamides, basic modified Polyolefins or polyurethanes as well as leather.

With particular advantage, however, the dyes are used for dyeing, Padding and printing of fiber material made from natural and synthetic polyamides such as wool, silk and especially nylon are used, with red to green tinges dark blue tones can be achieved.

The fiber material can be colored by any suitable method especially after the padding process or the exhaustion process, of which the latter it is preferred that the compounds of the formula (I) are in particular neutral dyes are.

The compounds of the formula (I) or mixtures thereof can be used as such or can also be used in the form of liquid or solid preparations. the Processing to stable liquid-aqueous or solid coloring preparations can be based on generally known manner, e.g.

by dissolving in suitable solvents, optionally with additives an auxiliary, for example a stabilizer or solubilizer such as urea or then by grinding or granulating. Such preparations can, for example, according to the information in French patents 1,572,030 or 1,581,900.

There is also the possibility of the compounds in the form of cold-dispersible compounds To use preparations. For this purpose, the dyes in the presence of one or more Customary anionic dispersants and optionally other auxiliaries on the A mechanical way of dry or wet grinding with the dispersion medium water Subjected to comminution down to a particle size below 20 p and optionally then dried by atomization. Distribute the preparations made in this way when placed in cold water again in finely dispersed form and are therefore easy to use.

The dyes of the formula (I) have good solubility and good solubility Building capacity. With the dyes of the formula (I) according to the invention or mixtures very intense and even, in particular streaky, coloring can be obtained from it Achieve opaque dyeings of nylon that have good general fastness properties, especially wet fastness properties show how fastness to washing or perspiration, fastness to rubbing and good fastness to light show.

The dyes of the formula (I) according to the invention can be combined easily with other neutral dyes, whereby the good properties of the dyeings remain.

In the following examples, parts mean parts by weight and Percent weight percent; the temperatures are given in degrees Celsius.

Example 1 15.0 parts of 4-aminoacetanilide are concentrated with 24 parts.

Hydrochloric acid and 7.0 parts of sodium nitrite are diazotized in the usual way at 0 °. The excess nitrite is destroyed with sulfamic acid.

15.3 parts of l-amino-2,5-dimethoxybenzene are dissolved in 80 parts of water 600 registered, by adding 10 parts of conc. Dissolve hydrochloric acid and add ice 0-4 ". The above solution is left to this solution within half an hour Run in solution of the diazotized 4-aminoacetanilide. By adding sodium acetate the pH is kept at 3.0 to 3.5. Leave at 0-40 for 2 hours, then more Stir for 16 hours at room temperature. The precipitated dye is filtered and washed with a 5% hydrochloric acid solution.

The paste of the aminomonoazo dye is mixed with 70 parts of water and dissolved at 800 with 120 parts of glacial acetic acid.

The temperature is then adjusted to 0-4 "by adding ice. It is left an aqueous solution of 8.0 parts of sodium nitrite is run in and stirring is continued for 2 hours; then the excess nitrite is destroyed with sulfamic acid.

23.9 parts of 2-amino-8-hydroxynaphthalene-6-sulfonic acid are stirred with 100 parts of water and dissolved by adding about 12 parts of 30% sodium hydroxide solution. This solution is added to the above diazomonoazo solution within one hour, the pH being kept at 3.5-4.0 by adding sodium acetate. The reaction mixture is stirred for a further 16 hours at 0 °, then adjusted to pH 8.5 with sodium hydroxide solution and stirred at room temperature for 2 hours. The precipitated dye is filtered, washed neutral with a 5% sodium chloride solution and dried. He corresponds to the formula and dyes natural and synthetic polyamide fibers in dark blue tones; the dyeings show good light fastness and good wet fastness.

Further compounds of the formula (I) can be prepared analogously to Example 1; for these dyes that of the formula correspond, the following table 1 lists the variables R1, R7, R8 and Rg. With the dyes of Examples 2 to 5, 7, 8 and 10 to 34, dyeings with a dark blue shade are achieved on polyamide, with the dyes of Examples 6 and 9 with a violet shade. The dyeings obtained show properties comparable to those obtained with the dye from Example 1.

Table 1 E.g. R1 (position) R7 (position) R8 R9 No. 2 NHCOOCH3 (4) H OCH3 CH3 3 NHCOOCH3 (3) H do. do. 4 do. H do. OCH3 5 NHCOCH3 (4) H do. CH3 6 do. H CH3 do. 7 NHCOCH3 (3) H OCH3 OCH3 8 do. H do. CH3 9 do. H CH3 do. 10 do. H OCH3 H 11 th. CH3 (4) do. OCH3 12 do. Cl (4) do. do. 13 N (CH3) COCH3 (4) H do. do. 14 N (CH3) COCH3 (3) H do. do. 15 NHCOCH2Cl (4) H do. CH3 16 do. H do. OCH3 17 NHCOCH2C1 (3) H do. do. 18 ° C C2H5 (2) H do. do. 19 COOC2H5 (4) H do. do. 20 COO (n) C4Hg (4) H do. H 21 0F3 (3) H do OCH3 22 CF3 (2) Cl (5) do. CH3 E.g. No. R1 (position) R7 (position) R8 R9 23 NHCOOC2H5 (3) H OCH3 H 24 NHCOOC2H5 (4) H do. OCH3 25 NHCOC2H5 (4) H do. CH3 26 NHCOC2H5 (3) H do. * do. 27 NHCOO (n) C4H9 (4) H do. OCH3 28 NHCOOCH2CH20CH3 (4) H do. CH3 29 NHCOOCH2CH20CH3 (3) H do. H 30 NHCOO (CH2) 3OCH3 (4) HHH 31 NHCH3 (4) H OCH3 OCH3 32 N (C2H5) 2 (4) H do. do. 33 N (CH3) COCH3 (4) H do. H 34 NHCOCH3 (3) CH3 (4) do. CH3 Further compounds of the formula (I), which can be prepared analogously to Example 1, correspond to the formula the variables D and B are given in Table 2 below for these dyes. With the dyes from Examples 35 to 42 and 44 to 46, dyeings with dark blue shades are achieved on polyamide, with the dye from Example 43 with violet shades. The colorations obtained show properties comparable to the coloration obtained with the dye from Example 1.

Table 2 Ex. D 35 CH3CONH + t 36 t do. NHCOCH3 37 CH3CONH ¼ 38 t do. NHCOCH3 39 CH3 \ - / - i / NHCOCH3 OCH3 40 t + 0 CH3 OCH 41 do. CH, OCH 42 do. 43 do. 44 0 COOC 2H5 NrP DB N-COCH, 3 CH3 46 CH3CON do. CH3 Analogously to Example 1, the 5-sulfonic acid derivatives corresponding to the above Examples 1-46 can also be prepared by replacing the coupling component 2-amino-8-hydroxynaphthalene-6-sulfonic acid with 2-amino-8-hydroxynaphthalene-5-sulfonic acid.

Dyeing instructions In one of 4000 parts of water, 10 parts of anhydrous Bring sodium sulfate and 2 parts of the dye from Example 1 existing dyebath 100 parts of pre-wetted nylon cloth (nylon 66) are used for 400.

The dye liquor is heated to boiling temperature in the course of 30 minutes, hold it at this temperature for 1 hour, add 4 parts of glacial acetic acid and finish dyeing by taking another 30 minutes Heating to boiling temperature. During the dyeing process, the evaporated water is continually replaced. Then takes you take the dark blue colored nylon cloth from the liquor, rinse it with water and dry it. -Wool can be dyed using the same procedure.

In an analogous manner, with the dyes from Examples 2-46 or mixtures thereof.

The dyeings have good lightfastness and good wetfastness.

Printing specification Polyamide is mixed with a printing paste of the following composition printed: 30 parts of dye according to Example 7 50 parts of urea 50 parts of a Solubilizer (e.g. thiodiethylene glycol) 290 parts of water 500 parts of a suitable Thickener (e.g.

based on locust bean gum) 20 parts of an acid donor (e.g. Ammontartrat) 60 parts thiourea The printed textile material is during Steamed for 40 minutes at 1020 (saturated steam), then rinsed with cold water, followed by 5 minutes Washed at 600 with a dilute solution of a commercially available detergent and again rinsed cold. A dark blue print is obtained of very good wet and light fastness properties.

In an analogous manner, printing pastes can be produced that are used as a component a dye of Examples 1 to 6 or 8 to 46 or several dyes of Examples 1 to 46 contain; these pastes can be analogous to those given above Regulation to be used for printing.

Claims (22)

Claims 1. Disazo compounds of the formula wherein D is the residue of a diazo component of the formula (a), (b) or (c) R1 is trifluoromethyl, -COOM1, -COOR2 or a radical -NHR31 -NR3R4 or -NR5COR6 meta or para to the azo group and the ring A can be further substituted by one or two substituents from the series halogen, (l-4C) alkyl, ( 1-4C) alkoxy and trifluoromethyl (only one trifluoromethyl radical), R2 (1-12C) alkyl, R3 and R4 independently of one another (1-6C) alkyl, R5 hydrogen or (1-4C) alkyl, R6 (1-6C) alkyl , (1-6C) alkoxy or (1-6C) alkyl monosubstituted by chlorine or methoxy, B is a divalent radical from the series phenylene-1,4, naphthylene-1,4 or 1,2,3,4-tetrahydronaphthylene-5 , 8 and M and M1 are independently hydrogen or an equivalent of a colorless cation and the SO3M group is the only sulfo group present in the molecule in position 5 or 6 of the naphthyl radical, or mixtures thereof. 2. Compounds according to claim 1, in which R2 represents R2 in the meaning of (1-4C) alkyl. 3. Compounds according to claim 1, wherein R3 and R4 are independent of one another for R3 and R4 are methyl or ethyl. 4. Compounds according to claim 1, wherein R5 represents R: in the meaning is hydrogen or methyl. 5. Compounds according to claim 1, wherein R6 represents R6 in the meaning of (1-4C) alkyl, (1-4C) alkoxy or # -chloro- or -methoxy-substituted (1-4C) alkyl stands. 6. Compounds according to any one of claims 1-5, wherein R1 is R1 in the meaning of trifluoromethyl, -COOR2, -NHR3, -NR3R4 or -NR5COR6. 7. Compounds according to claim 6, wherein R1 for R1 has the meaning of -COOR2 or -NR'COR "with R6 meaning methyl, ethyl, methoxy, 2-methoxyethyl or 3-methoxypropyl. 8. Compounds according to claim 7, wherein R1 for R1 means of -NR51COR6 "with R6" in the meaning of methyl or methoxy, in particular with Methyl stands. 9. Compounds according to claim 6, wherein (a) represents a radical (a1) stands in which Ri is defined according to claim 6 and the ring A has no further or one or two further substituents from the series halogen, preferably chlorine, (1-4C) alkyl, preferably methyl, (1-4C) alkoxy, preferably methoxy, and trifluoromethyl (only one trifluoromethyl radical) carries. 10. Compounds according to claim 9, wherein (a) represents a radical (a2) in which R1 is as defined in claim 8 and R7 is hydrogen, chlorine, methyl or methoxy. 11. Compounds according to any one of the preceding claims 1-10, wherein B is naphthylene-1,4; 1,2,3,4-tetrahydronaphthylene-5,8 or a radical of the formula (d) and R8 and Rg, independently of one another, denote hydrogen '(1-4C) alkyl or (1-4C) alkoxy. 12. Compounds according to claim 11, wherein (d) represents a radical (dl) R8 stands for R8 in the meaning of methyl, methoxy or ethoxy and Rg stands for R9 'means hydrogen, methyl, methoxy or ethoxy. 13. Compounds according to claim 11, wherein B is 1,4-naphthylene or a Remainder (d) means. 14. Compounds according to claim 1, wherein D is a radical of the formula (a) or (b) and a radical of the formula (d) as defined in claim 11, or 1,4-naphthylene. 15. Compounds according to claim 14, wherein D is a radical of the formula (al) as defined in claim 9 and B a radical of formula (dl) as in claim 12 defined, mean. 16. Compounds according to claim 15, wherein D is a radical of the formula (a2) as defined in claim 10, and the sulfo group in the naphthalene End component is in position 6. 17. Compounds according to claim 16, wherein D is a radical of the formula (a2), in which R1 'stands for -NHCOCH3 and R7 for Was-1 3 7 hydrogen, B one A radical of the formula (dl) in which R8 stands for methoxy and R 'for methyl or methoxy ste-9 hen, mean and the sulfo group is in position 6. 18. A process for the preparation of compounds of the formula (I) according to claim 1 or mixtures thereof, characterized in that the diazo compound of an amine of the formula D - N = N - B - NU2 (11) or mixtures thereof is converted to a compound of the formula or a mixture of these. 19. Process for dyeing or printing with anionic dyes Dyeable substrates, characterized in that a compound of the formula (I) or mixtures thereof according to one of the preceding claims 1-17 are used. 20. The method according to claim 19, characterized in that one as a substrate, natural or synthetic polyamides, polyurethanes, basic modified ones Polyolefins or unfortunately uses. 21. The method according to claim 20, characterized in that one uses wool, silk or, in particular, nylon as substrate. 22. The substrates dyed or printed according to claims 19-21.