Claims
- 1. Disazo dyestuff which in the form of the free acid corresponds to the formula ##SPC25##
- wherein
- A is alkylene of 2-5 carbon atoms;
- B is 1,4-phenylene or 1,4-naphthylene;
- R.sub.1, r.sub.2, and R.sub.3 independently are hydrogen, chloro, bromo, alkyl of 1-4 carbon atoms, cyanoalkyl of 1-4 carbon atoms, alkoxy of 1-6 carbon atoms, or alkoxy of 1-6 carbon atoms substituted by hydroxy or phenyl;
- R.sub.4 is alkyl of 1-4 carbon atoms, phenyl., or phenyl substituted by halo, alkyl of 1-4 carbon atoms, or alkoxy of 1-4 carbon atoms;
- R.sub.5 is hydrogen, alkyl of 1-4 carbon atoms, or alkyl of 1-4 carbon atoms substituted by cyano, CONH.sub.2 of carboxy;
- R.sub.6 is alkyl of 1-4 carbon atoms alkoxy of 1-6 carbon atoms, chloro, bromo, or fluoro, nitro, sulfo, or cyano;
- m is a number from 1 to 4; and
- n is a number from 0 to 2.
- 2. The dyestuff of claim 1 wherein B is 1,4-phenylene.
- 3. Disazo dyestuff which in the form of the free acid corresponds to the formula ##SPC26##
- wherein
- A is alkylene of 2-5 carbon atoms;
- R.sub.1 ' is hydrogen, chloro, or methyl;
- R.sub.2 ' is hydrogen, chloro, methyl, ethyl, methoxy, or ethoxy;
- R.sub.3 ' is hydrogen, methoxy, or ethoxy;
- R.sub.4 ' is methyl or phenyl;
- R.sub.5 ' is hydrogen, alkyl of 1-4 carbon atoms or alkyl of 1-4 carbon atoms substituted by cyano, carbonamido, CONH.sub.2 or carboxyl; and
- m' is the number 1 or 2.
- 4. The dyestuff of claim 3 wherein A is --CH.sub.2 CH.sub.2 --.
- 5. Disazo dyestuff which in the form of the free acid corresponds to the formula ##SPC27##
- wherein
- A is alkylene of 2-5 carbon atoms;
- R.sub.1 is hydrogen, chloro, bromo, alkoxy of 1-6 carbon atoms, or alkyl of 1-4 carbon atoms;
- R.sub.4 is alkyl of 1-4 carbon atoms or phenyl;
- R.sub.5 is hydrogen, alkyl of 1-4 carbon atoms, or alkyl of 1-4 carbon atoms substituted by cyano, carbonamido, CONH.sub.2 or carboxyl; and
- m is a number from 1 to 4.
- 6. Disazo dyestuff which in the form of the free acid corresponds to the formula ##SPC28##
- wherein
- R.sub.1 ' is hydrogen, chloro, or methyl;
- R.sub.4 ' is methyl or phenyl;
- R.sub.5 ' is alkyl of 1-4 carbon atoms or alkyl of 1-4 carbon atoms substituted by cyano, carbonamido, CONH.sub.2 or carboxyl; and
- m' is the number 1 or 2.
- 7. Disazo dyestuff of claim 1 of the formula ##SPC29##
- 8. Disazo dyestuff of claim 1 of the formula ##SPC30##
- 9. Disazo dyestuff of claim 1 of the formula ##SPC31##
- 10. Disazo dyestuff of claim 1 of the formula ##SPC32##
- 11. Disazo dyestuff of claim 1 of the formula ##SPC33##
Priority Claims (1)
| Number |
Date |
Country |
Kind |
| 2110230 |
Mar 1971 |
DT |
|
Parent Case Info
This is a continuation of application Ser. No. 231,729, filed Mar. 3, 1972, and now abandoned.
The subject of the present invention are new, valuable disazo dyestuffs which in the form of the free acid correspond to the general formula ##SPC2##
In the general formula (I),
If n or m >1, the radicals R.sub.1 and R.sub.6, respectively, can be identical or different.
Suitable radicals A are, for example --CH.sub.2 --CH.sub.2 --, --CH.sub.2 --CH.sub.2 --CH.sub.2 --, ##EQU1##
Suitable radicals B are, for example, the radicals of the formulae ##SPC3##
R.sub.2 and R.sub.3 have the abovementioned meaning.
Preferred alkyl groups are those with 1-4 C atoms. Except R.sub.4, the alkyl groups can possess further substituents. Suitable alkyl groups are, for example, --CH.sub.3, --C.sub.2 H.sub.5, --C.sub.3 H.sub.7, --C.sub.4 H.sub.9 and C.sub.2 H.sub.4 CH. Suitable phenylgroups R.sub.4 are phenyl and phenyl substituted by halogen, especially C1, Br, alkyl, especially C.sub.1 - C.sub.4 - alkyl and alkoxy, especially C.sub.1 -- C.sub.4 -- alkoxy.
Preferred alkoxy groups are those with 1-6 C atoms. The alkoxy groups can possess further substituents, for example OH groups. Suitable alkoxy groups are, for example, --OCH.sub.3, --OC.sub.2 H.sub.5, --OC.sub.3 H.sub.7, --OC.sub.4 H.sub.9, --OCH.sub.2 CH.sub.2 OH, and --OCH.sub.2 C.sub.6 H.sub.5.
Preferred dyestuffs are those of the formula ##SPC4##
Particularly valuable dyestuffs are those of the formula ##SPC6##
The dyestuffs of the formula (I) are manufactured if amines of the formula ##SPC8##
A further process for the manufacture of the dyestuffs (I) is that amines of the formula ##SPC11##
A further variant of the process according to the invention for the manufacture of the disazo dyestuffs (I) is that the monoazo dyestufs of the formula (X) are converted into the dyestuffs of the formula (VII) by means of sulphonating agents, such as concentrated sulphuric acid, sulphuric acid monohydrate or oleum, diazotised and coupled with indoles of the formula (VIII).
Examples of suitable amines of the formula (IX) are: ethylene glycol-(4-aminophenyl)-ether, trimethylene glycol-(4-aminophenyl)-ether, propylene glycol-(4-aminophenyl)-ether, ethylene glycol-(2-methyl-4-aminophenyl)-ether, trimethylene glycol-(2-methyl-4-aminophenyl)-ether, propylene glycol-(2-methyl-4-aminophenyl)-ether, ethylene glycol-(3-methyl-4-aminophenyl)-ether, trimethylene glycol-(3-methyl-4-aminophenyl)-ether, ethylene glycol-(2-ethyl-4-aminophenyl)-ether, ethylene glycol-(3-ethyl-4-aminophenyl)-ether, trimethylene glycol-(3-ethyl-4-aminophenyl)-ether, ethylene glycol-(2-methoxy-4-amino-phenyl)-ether, trimethylene glycol-(2-methoxy-4-aminophenyl)-ether, ethylene glycol-(3-methoxy-4-aminophenyl)-ether, trimethylene glycol-(3-methoxy-4-aminophenyl)-ether, ethylene glycol-(2-ethoxy-4-aminophenyl)-ether, ethylene glycol-(3-ethoxy-4-aminophenyl)-ether, ethylene glycol-(2-chloro-4-aminophenyl)-ether, trimethylene glycol-(2-chloro-4-aminophenyl)-ether, propylene glycol-(2-chloro-4-aminophenyl)-ether, ethylene glycol-(3-chloro-4-aminophenyl)-ether, trimethylene glycol-(3-chloro-4-aminophenyl)-ether, ethylene glycol-(2-bromo-4-aminophenyl)-ether, ethylene glycol-(3-bromo-4-aminophenyl)-ether, ethylene glycol-(2,5-dimethyl-4-amino-phenyl)-ether, trimethylene glycol-(2,5-dimethyl-4-amino-phenyl)-ether, ethylene glycol-(2,6-dimethyl-4-aminophenyl)-ether, trimethylene glycol-(2,6-dimethyl-4-aminophenyl)-ether, ethylene glycol-(2,3-dimethyl-4-aminophenyl)-ether, ethylene glycol-(3,5-dimethyl-4-aminophenyl)-ether, ethylene glycol-(2,3,5-trimethyl-4-aminophenyl)-ether, trimethylene glycol-(2,3,5-trimethyl-4-aminophenyl)-ether, ethylene glycol-(2,3,5,6-tetramethyl-4-aminophenyl)-ether, ethylene glycol-(2,5-dichloro-4-aminophenyl)-ether, ethylene glycol-(2,6-dichloro-4-aminophenyl)-ether, trimethylene glycol-(2,6-dichloro-4-aminophenyl)-ether, ethylene glycol-(2-chloro-4-amino-5-methylphenyl)-ether or their acid sulphuric acid esters.
Examples of suitable middle components of the formula (VI) are: aniline, 2-aminotoluene, 3-aminotoluene, 2-aminoethylbenzene, 3-amino-ethylbenzene, 3-chloroaniline, 2-bromoaniline, 2-ami anisole, 3-aminoanisole, 2-amino-ethoxybenzene, 3-amino-ethoxybenzene, 1-amino-2,3-dimethylbenzene, 1-amino-2,5-dimethylbenzene, 1-amino-3,5-dimethylbenzene, 3-amino-4-methoxy-toluene, 2-amino-4-methoxy-toluene, 2-amino-1,4-dimethoxybenzene, 2-amino-4-ethoxy-toluene, 2-amino-1,4-diethoxybenzene, .alpha.-naphthylamine or their N-sulphonic acid or their N-.omega.-methanesulphonic acids.
Examples of suitable coupling components (VIII) are: 2-methylindole, 2-phenylindole, 1-methyl-2-phenylindole, 1,2-dimethylindole, 1-.beta.-cyanoethyl- 2-methylindole, 1-.beta.-cyanoethyl-2-phenylindole, .beta.-(2-phenylindolyl-1)-propionic acid amide, .beta.-(2-methylindolyl-1)-propionic acid amide, .beta.-(2-methylindolyl-1)-propionic acid, 2-.beta.-naphthyl-indole, 2-p-biphenylylindole, 2,5-dimethylindole, 2,4-dimethyl-7-methoxyindole, 2-phenyl-5-ethoxyindole, 2-methyl-5-ethoxyindole, 2-methyl-5-chloroindole, 2-methyl-6-chloroindole, 2-methyl-5-nitroindole, 2-methyl-5-cyanoindole, 2-methyl-7-chloroindole, 2-methyl-5-fluoroindole, 2-methyl-5-bromoindole, 2-methyl-5,7-dichloroindole, 1-.beta.-cyanoethyl-2,6-dimethylindole and 2-phenylindole-5-sulphonic acid and 1-methyl-2-phenyl-indole-5-sulphonic acid. The indole-sulphonic acids are obtained by the process described in German Patent Specification 137,117. Thereby, at least from the in 5-position unsubstituted indoles, the corresponding indole-5-sulphonic acids are formed.
The diazo components of the formula (V) as well as of the formula (IX) are diazotised in a manner which is in itself known, for example in an acid aqueous solution by means of sodium nitrite solution at 0.degree.-20.degree.C, and are combined with the coupling components of the formula (VI). The coupling can be carried out in a neutral to strongly acid pH range, but preferably in a weakly acid pH range, in an aqueous or organic-aqueous medium.
The monoazo dyestuff formed can be isolated either directly by virtue of their insolubility in water, if diazo components of the formula (IX) and coupling components of the formula (VI) with Z = H are employed, or by salting out if diazo components of the formula (V) or (IX) and coupling components of the formula (VI) with Z = SO.sub.3 H or --CH.sub.2 SO.sub.3 H are employed. In general, in the latter case, isolation of the monoazo dyestuff is only necessary after the amino group of the coupling component has been liberated by alkaline or acid saponification. If diazo components of the formula (V) and coupling components of the formula (VI) with Z = SO.sub.3 H or --CH.sub.2 SO.sub.3 H have been employed, an alkaline treatment for liberating the amino group of the coupling component is preferred, since under these conditions the acid sulphuric acid ester is stable. An intermediate isolation of the monoazo dyestuffs is, however, not always necessary -- they can also be further diazotised without isolation.
The further diazotisation of the aminoazo dyestuffs (VII) and (X) with Z = H can be carried out, for example, in an acid aqueous dispersion by means of sodium nitrite solution, for which the diazotisation temperatures can be between 0.degree. and 30.degree.C. Aminoazo dyestuffs of the formula (VII) with Z = H can furthermore also be diazotised indirectly by dissolving them in an alkaline solution, adding sodium nitrite solution and pouring the mixture into aqueous hydrochloric acid, or treating it with hydrochloric acid. The conversion of the aminoazo dyestuff (X) with Z = H into the acid sulphuric acid ester can be effected by introducing (X) into concentrated sulphuric acid, sulphuric acid monohydrate or oleum at room temperature and stirring for several hours longer. The acid sulphuric acid ester of the dyestuff can then be precipitated by pouring into ice water and can be isolated, or can be further used by direct further diazotisation.
The coupling of the diazotised aminoazo dyestuffs (VII) with the terminal components (VIII) to give the disazo dyestuffs (I) is also effected in a manner which is in itself known, for example in a neutral, weakly acid or strongly acid aqueous medium or in an aqueous-organic medium. The disazo dyestuffs of the formula (I) are in general rather sparingly soluble in an acid medium and can be isolated by simply filtering them off, if necessary after addition of sodium chloride. If the dyestuffs are impure, they can be redissolved in hot water and reprecipitated, in a known manner, if necessary with addition of alkali. The more sparingly soluble dyestuffs (I) which have been isolated under acid conditions can be made readily water-soluble by mixing them with salts of strong bases and weak acids, for example trisodium phosphate, disodium hydrogen phosphate, sodium tetraborate, sodium metaphosphate, sodium metasilicate or sodium carbonate.
The coupling of the diazotised aminoazo dyestuffs (X) with the terminal components (VIII) to give the disazo dyestuffs (XI) is also carried out in a manner which is in itself known, for example in a neutral, weakly acid or strongly acid aqueous medium or in an aqueous-organic medium. The water-insoluble disazo dyestuffs can be easily isolated by filtration. After drying, they are converted into the disazo dyestuffs (I) by introducing them into concentrated sulphuric acid, sulphuric acid monohydrate or oleum and stirring for several hours longer, and these dyestuffs are isolated by precipitation in ice water and filtration and freed of adhering sulphuric acid by subsequent washing with water or dilute alkalis.
The new dyestuffs are particularly suitable for dyeing and printing natural and synthetic fibre materials containing amide groups, for example materials of wool, silk and polyamide such as poly-.epsilon.-caprolactam or the reaction products of hexamethylenediamine and adipic acid. The dyeings obtained, especially those on polyamide materials, are distinguished by good fastness properties, especially by good fastness to wet processing and good fastness to light. The neutral affinity, and the behaviour on combination with other suitable dyestuffs for this material, are also good.
US Referenced Citations (3)
Continuations (1)
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Number |
Date |
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| Parent |
231729 |
Mar 1972 |
|
Patent Grant
3956267
