Claims
- 1. An azo dyestuff compound of the formula
- wherein
- D is phenyl or phenyl substituted by chloro, nitro, cyano, methylsulfonyl, aminosulfonyl, phenoxy, methoxy, trifluoromethyl, carbomethoxy, bromo, methyl or N-chloro, N,N,N-trimethylaminoacetyl;
- A is para-phenylene which is unsubstituted or substituted by C.sub.1 -C.sub.2 -alkoxy, C.sub.1 -C.sub.2 -alkyl, phenoxy, phenylthio, benzyl, phenyl, cyclohexyloxy, chloro, bromo, C.sub.1 -C.sub.12 -hydrocarbylcarbonylamino, C.sub.1 -C.sub.14 --hydrocarbyloxycarbonylamino, C.sub.1 -C.sub.15 -hydrocarbylaminocarbonylamino, formylamino, trifluoromethyl, C.sub.1 -C.sub.12 -hydrocarbylcarbonyl (methyl) amino, C.sub.1 -C.sub.6 -alkylsulfonylamino or halogenated C.sub.1 -C.sub.3 -hydrocarbylcarbonylamino;
- X and X' independently represent --O--, --S-- or --NH--;
- R.sub.1 is C.sub.1 -C.sub.4 -alkyl that is unsubstituted or substituted by cyano, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.10 -hydrocarbylcarbonyloxy, C.sub.1 -C.sub.10 -hydrocarbyloxycarbonyl, C.sub.1 -C.sub.10 -hydrocarbylaminocarbonyloxy, phenyl, methoxyphenylcarbonyloxy, hydroxy, or a group of the formula --X--CO--Y--CO--X'--R'.sub.3 ;
- R.sub.2 is C.sub.1 -C.sub.4 -alkylene, or ethyleneoxyethylene;
- R'.sub.3 is alkyl of 1 to 8 carbon atoms; and the group --CO--Y--CO-- represent endomethylenetetrahydrophthalyl, hexahydrophthalyl or tetrahydrophthalyl.
- 2. An azo compound as claimed in claim 1, of the formula ##STR39##
- 3. An azo compound as claimed in claim 1, of the formula ##STR40##
- 4. An azo compound as claimed in claim 2 of the formula ##STR41##
- 5. An azo compund as claimed in claim 3 of the formula ##STR42##
- 6. An azo dyestuff compound according to claim 1, of the formula ##STR43##
- 7. an azo dyestuff compound according to claim 1 of the formula ##STR44##
Priority Claims (1)
| Number |
Date |
Country |
Kind |
| 16350/69 |
Nov 1969 |
CH |
|
Parent Case Info
This is a continuation of application Ser. No. 341,669 filed Mar. 15, 1973 (now abandoned) which application was a continuation of application Ser. No. 84,467, filed Oct. 27, 1970 and now abandoned.
This invention provides new valuable azo compounds free from sulphonic acid groups of the formula ##STR2## wherein D is the radical of a diazo component, A is an optionally substituted 1,4-phenylene radical, R.sub.2 is an optionally substituted alkylene radical, X is an -NH-group, a sulphur atom or preferably an oxygen atom, Y is a cycloaliphatic radical, X' is an -NH-group, a sulphur atom or preferably an oxygen atom, R.sub.1 is an optionally substituted alkyl radical and R.sub.3 is an organic radical, preferably an alkyl radical.
According to the invention, the compounds may be obtained when (a) a diazonium compound of a diazo component is coupled with a coupling component of the formula
Compounds of interest are those of the following formulae free from acid groups: ##STR3## wherein D, A, X, X', R.sub.1 and Y have the meanings given above and R.sub.3 ' is an alkyl group.
Compounds of the formulae ##STR4## wherein D, A, R.sub.1, R.sub.3 ' and Y have the same meanings as above, are particularly preferred.
The group A advantageously has the formula ##STR5## wherein c is in the ortho-position to the azo group and d is in the ortho-position to the amino group.
The radicals c and d each represents a hydrogen or chlorine atom, a lower alkyl or alkoxy radical, for example methyl, ethyl, methoxy or ethoxy, and also a phenylthio or phenoxy radical.
The radical c can also represent a bromine atom, a trifluoromethyl group and an acylamino group which may be alkylated, preferably methylated, at the nitrogen atom, and in which the acyl radical is the radical of a carboxylic acid, for example a formyl, acetyl, propionyl, butyryl or benzoyl radical, the radical of an organic monosulphonic acid, for example a methane sulphonic, ethane sulphonic or p-toluene monosulphonic acid radical, or the radical of a carbonic acid monoester or carbonic acid monoamide, for example, a methoxycarbonyl, phenoxycarbonyl, aminocarbonyl or butylaminocarbonyl radical.
The group R.sub.1 can represent a hydrogen atom, an alkyl group or a substituted alkyl group. As examples of a substituted alkyl group there may be mentioned: .beta.-chloroethyl, .beta.,.beta.,.beta.-trifluorethyl, .beta.,.gamma.-dichloropropyl, benzyl, .beta.-phenylethyl, .beta.-cyanoethyl, alkoxyalkyl, for example .beta.-ethoxyethyl or .delta.-methoxybutyl, hydroxyalkyl, for example .beta.-hydroxyethyl or .beta.-.gamma.-dihydroxypropyl, carbalkoxy, for example .beta.-carbo-(methoxy-, ethoxy- or propoxy)-ethyl (wherein the terminal alkyl group can carry a cyano, carbalkoxy, acyloxy or alkoxy group in the .omega.'-position), .beta.- or .gamma.-carbo(methoxy or ethoxy)-propyl, acylaminoalkyl, for example .beta.-(acetyl- or formyl)-aminoethyl, acyloxyalkyl, for example .beta.-acetoxyethyl or .beta.,.gamma.-diacetoxypropyl, .beta.-alkylsulphonylalkyl, for example .beta.-methanesulphonylethyl or .beta.-ethanesulphonylethyl, alkylcarboamoyloxyalkyl or arylcarbamoyloxyalkyl, for example .beta.-methylcarbamyloxyethyl, alkyloxy-carbonyloxyalkyl, for example .beta.-(methoxy-, ethoxy- or isopropoxy)-carbonylethyl, .gamma.-acetamidopropyl, .beta.-(.beta.'-acetylethoxycarbonyl)-ethyl, .beta.-[.beta.'-(cyano-, hydroxy-, methoxy- or acetoxy)-ethoxy-carbonyl]-ethyl, cyanoalkoxyalkyl, .beta.-carboxyethyl, .beta.-acetyl-ethyl, .beta.-diethylaminoethyl, .beta.-cyanoacetoxyethyl, .beta.-benzoyloxyethyl or .beta.-(p-alkoxy- or phenoxy-benzoyloxy)-ethyl. The group R.sub.1 in general contains up to eight carbon atoms. The term "lower alkyl group" represents optionally substituted alkyl radicals having up to 8 carbon atoms.
As examples of alkylene radicals R.sub.2, the following may be mentioned (in which the terminal amino group of the azo dyestuff is also included so as to characterise the position):
The diazo radical D is mainly derived from monocyclic or bicyclic amines of the formula
As examples there may be mentioned: 2-aminothiazole, 2-amino-5-nitrothiazole, 2-amino-5-methylsulphonyl-thiazole, 2-amino-5-cyanothiazole, 2-amino-4-methyl-5-nitrothiazole, 3-amino-5-nitro-benzisothiazole, 3-amino-5-nitro-7-bromobenzisothiazole, 3-amino-benzlsothiazole, 3-amino-5-chlorobenzisothiazole, 3-amino-7-chloro-benzisothiazole, 3-amino-4-chlorobenzisothiazole, 3-amino-5,7-dichloro-benzisothiazole, 3-amino-5-chloro-7-bromo-benzisothiazole, 3-amino-6-methyl-benzisothiazole, 3-amino-5,7-dibromo-benzisothiazole, 2-amino-4-methylthiazole, 2-amino-4-phenylthiazole, 2-amino-4-(4'-chloro)-phenylthiazole, 2-amino-4-(4'-nitro)-phenylthiazole, 3-aminopyridine, 3-aminoquinoline, 3-aminopyrazole, 3-amino-1-phenylpyrazole, 3-aminoindazole, 3-amino-1,2,4-triazole, 5-(methyl-, ethyl-, phenyl- or benzyl)-1,2,4-triazole, 3-amino-1-(4'-methoxyphenyl)-pyrazole, 2-aminobenzthiazole, 2-amino-6-methoxybenzthiazole, 2-amino-6-chlorobenzthiazole, 2-amino-6-cyanobenthiazole, 2-amino-6-thiocyanobenzthiazole, 2-amino-6-nitrobenzthiazole, 2-amino-6-carboethoxybenzthiazole, 2-amino-(4- or 6)-methylsulphonylbenzthiazole, 2-amino-1,3,4-thiadiazole, 2-amino-1,3,5 -thiadiazole, 2-amino-4-phenyl- or -4-methyl-1,3,5-thiadiazole, 2-amino-5-phenyl-1,3,4-thiadiazole, 2-amino-3-nitro-5-methylsulphonyl-thiophene, 2-amino-3,5-bis-(methylsulphonyl)-thiophene, 5-amino-3-methyl-isothiazole, 2-amino-4-cyanopyrazole, 2-(4'-nitrophenyl)-3-amino-4-cyanopyrazole, 3- or 4-aminophthalimide, aminobenzene, 1-amino-2-trifluoromethyl-4-chlorobenzene, 1-amino-2-cyano-4-chlorobenzene, 1-amino-2-carbomethoxy-4-chlorobenzene, 1-amino-2-carbomethoxy-4-nitrobenzene, 1-amino-2-chloro-4-cyanobenzene, 1-amino-2-chloro-4-nitrobenzene, 1-amino-2-bromo-4-nitrobenzene, 1-amino-2-chloro-4-carbethoxybenzene, 1-amino-2-chloro-4-methylsulphonylbenzene, 1-amino-2-methylsulphonyl-4-chlorobenzene, 1-amino-2,4-dinitro-6-methylsulphonylbenzene, 1-amino-2,4-dinitro-6-(2'-hydroxy-ethylsulphonyl)-benzene, 1-amino-2,4-dinitro-6-(2'-chloroethylsulphonyl)-benzene, 1-amino-2-methylsulphonyl-4-nitrobenzeno, 1-amino-2-methylsulphonyl-4-nitrobenzene, 1-amino-2,4-dinitrobenzene, 1-amino-2,4-dicyanobenzene, 1-amino-2-cyano-4-methylsulphonylbenzene, 1-amino-2,6-dichloro-4-cyanobenzene, 2-cyano-4-chloroaniline, 2-cyano-4-chloro-6-bromoaniline, 2-cyano-4,6-dibromoaniline, 1-amino-2,6-dichloro-4-nitrobenzene, 1-amino-2,4-dicyano-6-chlorobenzene, 4-aminobenzoic acid cyclohexyl ester, 1-amino-2,4-dinitro-6-chlorobenzene and especially 1-amino-2-cyano-4-nitrobenzene, also 1-aminobenzene-2-, -3- or -4-sulphonic acid amides, for example N-methylamide or N,N-diamethylamide or N,N-diethylamide, N,.gamma.-isopropoxypropyl-2-aminonaphthalene-6-sulphonic acid amide, N,.gamma.-isopropoxypropyl-1-aminobenzene-2-, -3- or -4-sulphonic acid amide, N-isopropyl-1-aminobenzene-2-, -3- or -4-sulphonic acid amide, N,.gamma.-methoxypropyl-1-aminobenzene-2-, -3- or -4-sulphonic acid amide, N,N-bis-(.beta.-hydroxyethyl)-1-aminobenzene-2-, -3- or -4-sulphonic acid amide, 1-amino-4-chlorobenzene-2-sulphonic acid amide and the N-substituted derivatives thereof, 2-, 3- or 4-aminophenylsulphamate, 2-amino-4-, -5- or -6-methylphenylsulphamate, 2-amino-5-methoxy-phenylsulphamate, 3-amino-6-chlorophenylsulphamate, 3-amino-2,6-dichlorophenylsulphamate, 4-amino-2- or -3-methoxyphenylsulphamate, N,N-dimethyl-2-aminophenylsulphamate, N,N-di-n-butyl-2-aminophenylsulphamate, N,N-dimethyl-2-amino-4-chlorophenylsulphamate, N,n-propyl-3-aminophenylsulphamate, N,N-di-n-butyl-3-aminophenylsulphamate, O(3-aminophenyl)N-morpholine-N-sulphonate, O(3-aminophenyl)-N-piperidine-sulphonate, N-cyclohexyl-O-(3-aminophenyl)sulphamate, N(N-methylaniline)-O-(3-aminophenyl)-sulphonate, N,N-diethyl-3-amino-6-methylphenyl-sulphamate, N-ethyleneimine-O-(4-aminophenyl)-sulphonate, N,N-dimethyl-4-aminophenylsulphamate, O-(n-propyl)-O-(3-aminophenyl)-sulphonate, O,.beta.-chloroethyl-O-(2-aminophenyl)-sulphonate, O-benzyl-O-(3-aminophenyl)-sulphonate and O-ethyl-O-(4-amino-2,6-dimethylphenyl)-sulphonate, 4-aminoazobenzene, 3,2'-dimethyl-4-aminoazobenzene, 2-methyl-5-methoxy-4-aminoazobenzene, 4-amino-2-nitroazobenzene, 2,5-dimethoxy-4-aminoazobenzene, 4'-methoxy-4-aminoazobenzene, 2-methyl-4'-methoxy-4-aminoazobenzene, 3,6,4'-trimethoxy-4-aminoazobenzene, 4'-chloro-4-aminoazobenzene, 2'- or 3'-chloro-4-aminoazobenzene, 3-nitro-4-amino-2', 2'-dichloroazobenzene and 4-aminoazobenzene-4'-sulphonic acid amide.
Instead of the above-mentioned diazo components that are free from ionic groups which impart solubility in water, those that contain fibre-reactive groups may also be used, for example s-triazinyl radicals, which carry 1 or 2 halogen atoms, for example fluorine, chlorine or bromine atoms on the triazine ring, pyrimidyl radicals which carry one or two chlorine atoms or fluorine atoms or one or two arylsulphonyl or alkanesulphonyl groups on the pyrimidine ring, mono- or bis-(.gamma.-halogen-.beta.-hydroxypropyl)-amino groups, .beta.-halogenoethylsulphamyl radicals, .beta.-halogenoethoxy groups, .beta.-halogenoethylmercapto groups, 2-chlorobenzthiazolyl-6-azo groups, 2-chlorobenzthiazolyl-6-amino groups, .gamma.-halogeno-.beta.-hydroxy-propylsulphamyl radicals, chloroacetylamino groups, .alpha.,.beta.-dibromopropionyl groups, vinylsulphonyl groups and 2,3-epoxypropyl groups.
Suitable fibre-reactive diazo components are, for example, N,.beta.-chloroethyl-3-chloro-4-aminobenzenesulphamide (hydrochloride), N,.beta.-chloroethyl-4-aminobenzenesulphamide (hydrochloride), 3-bromo-4-amino-.omega.-chloroacetophenone, N,.gamma.-chloro-.beta.-hydroxypropyl-4-aminobenzenesulphamide, N..beta.-chloroethyl-1-amino-4-naphthylsulphonamide, N,.beta.-chloroethyl-1-amino-3,5-dichloro-benzenesulphamide and 4-(.gamma.-chloro-.beta.-hydroxypropoxy)-aniline.
The diazotisation of the diazo components mentioned can be carried out according to the position of the particular amino group, for example with a mineral acid and sodium nitrite or, for example, with a solution of nitrosylsulphuric acid in concentrated sulphuric acid.
The coupling can also be effected in known manner, for example in a neutral to acid medium, if desired in the presence of sodium acetate or similar buffer substances that influence the rate of coupling, or of catalysts, for example dimethylformamide, pyridine or its salts.
The coupling components can be obtained by acylating an amine of the formula ##STR8## wherein A, R.sub.1, R.sub.2 and X have the meanings given above, with a monoester or monoamide of a cycloaliphatic carboxylic acid of the formula HOOC--Y--CO--X'--R.sub.3 or reactive derivatives thereof, for example a halide or anhydride.
Suitable cycloaliphatic carboxylic acid monoesters, monothioesters and monoamides are for example derived from the following cycloaliphatic dicarboxylic acids: tetrahydrophthalic acid, methyl-tetrahydrophathalic acid, isomerised 4-methyl-tetrahydrophthalic acid, endomethylenetetahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, endomethylene-hexahydrophthalic acid, hexahydroterephthalic acid and hydrogenated benzenetricarboxylic and benzenetetracarboxylic acids.
Suitable amines of the formula ##STR9## are for example: N,n-butyl-N-.beta.'-hydroxyethylaniline, N-methyl-N-.beta.'-hydroxyethylaniline, N-.beta.-cyanoethyl-N-.beta.'-hydroxyethylaniline, N,.beta.-cyanoethyl-N,.beta.'-hydroxyethyl-3-chloroaniline, N-ethyl-N,.beta.'-hydroxyethyl-2-methoxyaniline, N-ethyl-N,.beta.'-hydroxyethyl-2-methylaniline, N.beta.-cyanoethyl-N,.beta.'-hydroxyethyl-2-acetylaminoaniline, N,.beta.-(.beta.'-cyanoethyoxyethyl)-N,.beta."-hydroxyethylaniline, N,.beta.-cyanoethyl-N,.beta.'-hydroxyethyl-3-methylaniline and N,.gamma.-methylaminopropyl-N-ethylaniline.
Suitable monoesters, monoamides and monothioesters are for example the monomethyl and monobutyl esters, the N-butylmonoamides and N-ethylmonoamides, and the ethyl thioesters of the above-mentioned cycloaliphatic dicarboxylic acids.
In order to increase the absorption capacity, the dyestuffs can be manufactured from mixtures of several components. This may be carried out for example by coupling mixtures of coupling components with a single diazo component. Such mixtures of coupling components may for example be obtained by using, as monoester halide (a) mixtures of different alkyl monoester chlorides which are derived from different alkyl groups, and reacting the mixture with a bis-(.beta.-hydroxyethyl)-aniline.
A single monoester chloride may also be used as starting material and reacted (b) together with an equal molar amount of a fatty acid chloride with a bis-(.beta.-hydroxyethyl)-aniline. The variants (a) and (b) may also be combined. Mixtures of the dyestuffs of the formulae:
Those of the above-mentioned heterocyclic diazo components which contain a quaternatable nitrogen atom can also be combined oxidatively in the N-alkylated form as hydrazones or as azosulphones (compare Angewandte Chemie, Volume 70, 215 (1958); Volume 74, 818 (1962); Volume 80, 343 (1968).
Those of the new compounds that contain a quaternated amino group can also be obtained by quaternating the corresponding dyestuffs which contain a non-quaternated amino group by treatment with alkylating agents.
Such alkylating agents or quaternating agents are for example: esters of strong mineral acids or organic sulphonic acids, for example dimethyl sulphate or diethyl sulphate, alkyl halides for example methyl chloride, bromide or iodide, aralkyl halides, for example benzyl chloride, esters of low molecular alkane-sulphonic acids, for example methyl esters of methane sulphonic acid, ethane sulphonic acid or butane sulphonic acid, and esters of benzene sulphonic acids which may carry additional substituents, for example methyl, ethyl, propyl or butyl esters of benzene sulphonic acid; .alpha.,.beta.-unsaturated compounds in the presence of strong acids, for example acrylamide in the presence of hydrogen chloride or galcial acetic acid may also be used as alkylating agents.
The alkylation is advantageously carried out by heating in an inert organic solvent, for example hydrocarbons, for example benzene, toluene or xylene, halogenated hydrocarbons, for example carbon tetrachloride, tetrachloroethane, chlorobenzene, o-dichlorobenzene or nitrohydrocarbons, for example nitromethane, nitrobenzene or a nitronaphthalene. acid anhydrides, acid amides or nitriles, for example acetic anhydride, dimethylformamide or acetonitrile, and also dimethylsulphoxoide, can be used as solvents during the alkylation. Instead of a solvent, a large excess of alkylating agent may also be used. In this case it is necessary, however, to take care that the mixture does not become over-heated, since the reaction is strongly exothermic. Nevertheless it is necessary in most cases, especially in the presence of organic solvent, to heat the reaction mixture externally in order to start the reaction. In special cases the alkylation can also be carried out in an aqueous medium or using an alcohol, if desired in the presence of a small amount of potassium iodide.
Where purification of the dyestuff salts is necessary, it is advantageously effected by dissolving these in water, with any unreacted starting dyestuff being filtered off as an insoluble residue. The dyestuff can again be separated from the aqueous solution by adding water-soluble salts, for example sodium chloride.
The non-quaternated dyestuffs are as a rule insoluble in water.
The new compounds, their mixtures with one another and their mixtures with other azo dyestuffs are excellently suitable for dyeing and printing leather, wool, silk and particularly synthetic fibres, for example acrylic or acrylonitrile fibres, polyacrylonitrile fibres and copolymers of acrylonitrile and other vinyl compounds, for example acrylic esters, acrylamides, vinylpyridine, vinyl chloride or vinylidene chloride, copolymers of dicyanoethylene and vinyl acetate, as well as fibres of acrylonitrile block copolymers, fibres of polyurethanes, polyolefines, for example basically-modified, nickel-modified or unmodified polypropylene, cellulose triacetate and cellulose 21/2-acetate, and especially fibres of polyamides, for example nylon 6, nylon 6,6 or nylon 12 and aromatic polyesters, for example those from terephthalic acid and ethylene glycol or 1,4-dimethylcyclohexane, and copolymers from terephthalic acid and isophthalic acid and ethylene glycol.
For dyeing in aqueous liquors, the water-insoluble dyestuffs are advantageously used in a finely divided form and dyeing is carried out with the addition of dispersing agents, for example sulphite cellulose waste lye or synthetic detergents, or a combination of different wetting agents and dispersing agents. As a rule it is advisable to convert the dyestuffs to be used, before dyeing, into a dyeing preparation that contains a dispersing agent and finely divided dyestuff in such a form that on dilution of the dyestuff preparations with water a fine dispersion is produced. Such dyestuff preparations can be obtained in known manner, for example by grinding the dyestuff in a dry or wet state with or without addition of dispersing agents during the grinding process.
To obtain intense dyeings on polyethylene terephthalate fibres it is desirable to add a swelling agent to the dye bath or to carry out the dyeing process under pressure at temperatures above 100.degree., for example at 120.degree. C. Suitable swelling agents are aromatic carboxylic acids, for example salicylic acids, phenols, for example o- or p-hydroxydiphenyl, aromatic halogen compounds, for example o-dichlorobenzene or diphenyl.
For thermofixing the dyestuff, the padded polyester fabric is heated to temperatures of above 100.degree. C., for example between 180.degree. and 210.degree. C., advantageously after prior drying, for example in a stream of warm air.
The dyeings obtained according to the above processes can be subjected to an after-treatment, for example by heating with an aqueous solution of a non-ionic detergent.
Instead of being applied by impregnation, the compounds indicated can also be applied by printing according to the present process. For this purpose, a printing colour is for example used that contains the finely dispersed dyestuff in addition to the auxiliary agents generally used in printing, for example wetting agents and thickeners.
Furthermore, dyeing can for example be carried out in organic solvent liquors, for example a mixture of perchloroethylene and dimethylformamide or methanol.
Using the present process, strong dyeings and prints are obtained that have good fastness properties, especially good fastness to thermofixing, sublimation, pleating, exhaust gas, cross-dyeing, dry-cleaning and chlorine, and good wet fastness properties, for example fastness to water, washing and perspiration. The very high melting points of the new compounds, which permit easier conditioning as dyestuffs, should also be emphasised.
The new water-insoluble compounds can also be used for the spin dyeing of polyamides, polyesters and polyolefines. The polymers to be coloured, advantageously in the form of powder, granules or chips, a ready made-up spinning solution or in the fused state, is mixed with the dyestuff, which is introduced in the dry state or in the form of a dispersion or solution into a solvent, which may be volatile. After homogeneous distribution of the dyestuff in the solution or melt of the polymer, the mixture is processed in known manner by casting, pressing or extrusion to give fibres, yarns, monofilaments, films and the like.
In the examples that follow, the parts denote parts by weight and the percentages denote percentages by weight unless otherwise stated.
US Referenced Citations (1)
| Number |
Name |
Date |
Kind |
|
2354187 |
Felix et al. |
Jul 1944 |
|
Foreign Referenced Citations (1)
| Number |
Date |
Country |
| 1,218,091 |
Jun 1966 |
DT |
Continuations (2)
|
Number |
Date |
Country |
| Parent |
341669 |
Mar 1973 |
|
| Parent |
84467 |
Oct 1970 |
|
Patent Grant
4039529
