GB2024235A

GB2024235A - Water-insoluble azo dyestuffs, process for their manufacture and their use

Info

Publication number: GB2024235A
Application number: GB7920036A
Authority: GB
Original assignee: Hoechst AG
Current assignee: Hoechst AG
Priority date: 1978-06-08
Filing date: 1979-06-08
Publication date: 1980-01-09
Also published as: FR2428062A1; IT7923330A0; FR2428062B1; IT1120787B; DE2825189A1; JPS54161636A; BE876875A; CH643579A5; MX148996A; IN150557B; GB2024235B

Abstract

The present invention provides water-insoluble azo dyestuffs of the general formula (I> <IMAGE> wherein D represents the radical of a diazo component of the benzene, azobenzene, naphthalene, thiazole, benzothiazole, thiadiazole, benzisothiazole or indazole series, which is free from sulfonic acid groups and in which the ring or each ring independently is unsubstituted or substituted by one or more substituents selected from halogen atoms, for example fluorine, chlorine and bromine atoms, and nitro, cyano, alkyl, alkoxy, alkylsulfonyl, sulfonamido, trifluoromethyl, alkycarbonyl, chloralkylcarbonyl, alkylcarbonylamino, chloroalkylcarbonylamino, benzoyl, chlorobenzoyl, benzoylamino, chlorobenzoylamino, phenoxy, oxime, carboxylic acid alkyl ester and carboxylic acid amide groups, the alkyl and alkoxy groups and moieties each having from 1 to 4 carbon atoms, R1 and R2, which may be the same or different, each represents an alkyl group having from 1 to 4 carbon atoms, and R3 represents a hydrogen atom or an alkyl or alkoxy group having from 1 to 4 carbon atoms.

Description

SPECIFICATION Water-insoluble azo dyestuffs, process for their manufacture and their use.

The present invention provides water-insoluble azo dyestuffs of the general formula (I)

wherein D represents the radical of a diazo component of the benzene, azobenzene, napthalene, thiazole, benzothiazole, thiadiazole, benzisothiazole or indazole series, which is free from sulfonic acid groups and in which the ring or each ring independently is unsubstituted or substituted by one or more substituents selected from halogen atoms, for example fluorine, chlorine and bromine atoms, and nitro, cyano, alkyl, alkoxy, alkylsulfonyl, sulfonamido, trifluoromethyl, alkylcarbonyl, chloroalkylcarbonyl, alkylcarbonylamino, chloroalkylcarbonylamino, benzoyl, chlorobenzoyl, benzoylamino, chlorobenzoylamino, phenoxy, oxime, carboxylic acid alkly ester and carboxylic acid amide groups, the alkyl and alkoxy groups and moieties each having from 1 to 4 carbon atoms, R1 and R2, which may be the same or different, each represents an alkyl group having from 1 to 4 carbon atoms, and R3 represents a hydrogen atom or an alkyl or alkoxy group having from 1 to 4 carbon atoms.

The present invention also provides a process for the manufacture of the above dyestuffs, which comprises diazotizing in known manner a diazo component of the general formula (II) D- NH2 (II) wherein D is defined as above, and coupling the resulting product with a coupling component of the general formula (III)

wherein R1, R2 and R3 are defined as above, in an acidic or neutral, aqueous, aqueous-organic or organic medium, preferably an aqueous medium, and optionally in the presence of an acid-binding agent.

As organic solvents which may be used there may be mentioned hydrophilic organic solvents, for example methanol, ethanol, propanol, butanol, acetone or dimethylformamide.

As acid-binding agents which may be present during coupling there may be mentioned organic bases such as pyridine, picoline ortriethylamine, and inorganic bases such as alkali metal and alkaline earth metal carbonates, for example sodium or potassium carbonate, or magnesium oxide, or particular sodium acetate.

The coupling components of the formula (III) may be prepared in simple manner by reacting an alkylerylamine of the formula (IV)

wherein R2 and R3 are defined as above, with an itaconic acidester of the formula (V)

wherein R1 is defined as above, in the presence of a catalyst for accelerating the reaction, such as acetic acid or hydrochloric acid, at an elevated temperature and optionally under elevated pressure.

As examples of diazo components of the general formula D-NH2. for preparation of the dyestuffs of the formula (I), there may be mentioned: aniline, p-toluidine, o-anisidine, m-anisidine, p-anisidine, p-phenetidine, p-phenoxyaniline, 2-fluoro, 3 fluoro- and 4-fluoroaniline, 2-chloro, 3-chloro- and 4-chloroaniline, 2-bromo-, 3-bromo- and 4-bromoaniline, 2-trifluoro-methyl-, 3-trifluoromethyl- and 4-trifluoromethylaniline, anthranilic acid methyl ester, anthranilic acid ethyl ester, 3-aminobenzoic acid methyl ester, 3-aminobenzoic acid ethyl ester, 4-aminobenzoic acid methyl ester, 4-aminobenzoic acid ethyl ester, 4-aminobenzoic acid phenyl ester, 4-aminobenzoic acid amide, 2-amino-, 3-amino- and 4-aminophenyl- methylsulfone, 4-aminophenylethlsulfone, 2-amino-, 3-amino- and 4-aminophenylsulfonamide, 4-aminophenylsulfonic acid dimethylamide, 2-amino-, 3-aminoand 4-aminobenzonitrile, 2-amino-, 3-amino- and 4-aminoacetophenone, 2-amino-, 3-amino- and 4aminobenzophenone, 2-nitro-, 3-nitro- and 4-nitroaniline, 2-acetamino-, 3-acetamino- and 4acetaminoaniline, 2-methyl-4-nitroaniline, 2-methoxy-4-nitroaniline, 2-chloro-4-nitroaniline, 2-bromo-4nitroaniline, 2-amino-5-nitrobenzoic acid methyl ester and 2-amino-5-nitrobenzoic acid ethyl ester, 2-amino-5-nitrophenylmethylsulfone, 2-amino-5-n itrophenylsulfonic acid amide, 2-cyano-4-nitroaniline, 4-aminobenzaldoxime, 2-acetamino-4-nitroaniline, 2-trifluoromethyl-4-nitroaniline, 2,6-dichloro-4nitroaniline, 2-chloro-4-nitro-6-methoxyaniline, 2-amino-3-chloro-5-nitribenzoic acid methyl ester, 2-amino 3-chloro-5-nitro-phenylmethylsulfone, 2-chloro-4-nitro-6-cyanoaniline, 2-chloro-4,6-dinitroaniline, 2-chloro 4-nitro-6-trifluoro-methylaniline, 2-ch loro-4-nitro-6-bromoa niline, 2-amino-3-methoxy-5-nitrobenzoic acid methyl ester, 2-methoxy-4-nitro-6-cyanoaniline, 2-methoxy-4,6-di-nitroaniline, 2-amino-3-cyano-5 nitrobenzoicacid methyl ester, 2-amino-3,5-di-nitrobenzoic acid methyl ester, 2-amino-3-bromo-4-nitrobenzoic acid methyl ester, 2-amino-3-cyano-5-nitrophenylmethyl-sulfone, 2-amino-3,5-dinitrophenylmethylsulfone, 2-amino-3-bromo-5-nitrophenylmethylsulfone, 2,6-di-cyano-nitroaniline, 2cyano-4, 6-dinitroaniline, 2-cyano-4-nitro-6-trifluoro-methylaniline, 2-cyane-4-nitro-6-bromaniline, 2,4,6-trinitroaniline, 2,4-di-nitro-6-trifluoromethylaniline, 2-bromo-4,6-di-nitroaniline, 2,6-di-bromo-4-nitroaniline, 2,4-di-chloroaniline, 2,4-di-bromoaniline, 2,4-dicyanoaniline, 2,4-di-nitroaniline, 2,5-di-chloroaniline, 2,5-dibromoaniline, 2,5-di-cyanoaniline, 2-aminotherephthalic acid methyl ester, 3,4-di-chloroaniline, 2,6-di chloroaniline, 4-methyl-2-nitroaniline, 4-methoxy-2-nitroaniline, 4-chloro-2-nitro-aniline, 4-bromo-2nitroaniline, 4-cyano-2-nitroaniline, 4-trifluoromethyl-2-nitroaniline, 4-amino-3-nitrophenyl-methylsulfone, 2,4,6-trichloroaniline, 2,4,5-trichloroaniline, 2,4-dichloro-6-nitroaniline, 2,4,6-tribromoaniline, 4phenylazoaniline, 2-aminothiazole, 5-nitro-2-aminothiazole, 5-ethoxycarbonyl-2-aminothiazole, 5-cyano-2aminothiazole, 2-aminobenzothiazole, 6-methyl-2-aminobenzothiazole, 6-methoxy-2-aminobenzothiazole, 6-cyano-2-aminobenzothiazole, 6-nitro-2-aminobenzothiazole, 6-methylsulfonyl-2-amino-benzothiazole, 6chloro-2-aminobenzothiazole, 2-amino-1 ,3,4-thiadiazole, 3-amino-5-nitro-2,1 -benzoisothiazole and 3aminoindazole.

The dyestuffs according to the invention are insoluble in water. They may be separated, for example, by filtration and they may be freed from adherent electrolyte by washing with water.

In the process of the invention either a single diazo component or a mixture of two or more diazo components of the formula (it), and either a single coupling component or a mixture of two or more coupling components of the formula (III), may be used.

The dyestuffs according to the invention may be used alone or in admixture with one another or with other dyestuffs. They are preferably used in the form of a dyeing or printing preparation, for example an aqueous dispersion, a solution in an organic solvent, or an emulsion or dispersion which may contain water in addition to a solvent or a mixture of solvents. The dyestuffs according to the invention may be used for dyeing or printing synthetic fibrous materials, for example fibers of cellulose-diacetate, cellulose-21/2 acetate or cellulose triacetate, polyamides such as poly-s-caprolactam or polyhexamethylenediamineadipate, polyurethanes, polycarbonates, or especially linear polyesters such as polythlene terephthalate.

The above-mentioned synthetic fibrous materials may be present in the form of blends of fibers of two or more of the above materials or blends with natural fibers such as cellulose fibers or wool. They may further be present in various processing states, for example as tops, flocks, filaments, woven fabrics or knitted fabrics.

The dyestuffs according to the invention may be applied in known manner, generally in an aqueous dispersion or alternatively in an organic solvent. Dispersion of the dyestuff may be carried out by grinding it in the presence of a dispersion agent, for example a condensation product of formaldehyde with a naphthalenesulfonic acid. The actual dyeing conditions may vary widely and depend on the nature of the synthetic fibrous material and on its process state.

For example, the dyeing of shaped articles of cellulose acetate is generally carried out at a temperature in the range of from about 75" to 85 , and that of cellulose triacetate articles at a temperature in the range of from about 90" to 1 250C. The dyestuffs are applied to polyamide fiber materials at a temperature in the range of from about 900 to 1200C.Polyester fiber materials are dyed according to usual methods, in the presence of a carrier such as o- or p-phenylphenol, methylnaphthalene or methylsalicylate, at a temperature from about 10000 up to about 130"C, or without the use of a carrier at a correspondingly higher temperature, for example in the range of from 1200 to 140"C. Alternatively, the dyestuffs may be applied by padding with or without the use of thickeners, such as a tragacanth thickener, followed by fixation under the action of heat, for example steam or dry heat, for a period from about half a minute to 30 minutes, at a temperature from about 1000 to 230"C. For improving the fastness to rubbing, the dyed material is advantageously freed from superficially adherent dyestuff, for example by flushing or by a reductive aftertreatment. The aftertreatment is carried out generally at 60 to 1 200C in a liquor containing aqueous sodium hydroxide solution, sodium dithionite and a non-ionogenic detergent such as an ethylene oxide-phenol addition product.

For dyeing synthetic fiber materials from organic solvents, the dyestuff is left in the solution for absorption on the fiber at room temperature or preferably at a temperature of from about 700 to 1300C, optionally under pressure, or fabrics or knitted fabrics are successively impregnated with a dyestuff solution, dried and submitted to a brief heat treatment, for example at a temperature of from 1800 to 210'C, in continuous manner.Suitable solvents for the exhaust process are, for example, solvents which are not miscible with water and have a boiling point in the range of from 400 to 170 C, such as aliphatic halogenohydrocarbons, for example methylene chloride, trichioroethane, trichloroethylene, perchloroethylene or trifluorotrichlor- oethane. In particular for a continuous dyeing process solvents which are miscible with water, such as alcohols or dimethylformamide, may be used. The solvents may be present as mixtures and contain further auxiliaries which are soluble in solvents, such as oxalkylation products of fatty alcohols, alkylphenols or fatty acids.

For producing prints on synthetic fiber materials, for example those made from polyesters, polyamides or cellulose triacetate, the dyestuffs may be used in the form of aqueous compositions which may contain, in addition to the finely dispersed dyestuff, suitable thickeners and fixation accelerators. Fixation is generally carried out upon printing and drying by steaming at atmospheric pressure or under elevated pressure upto 2.5 atmosphere gauge for a period of from 10 to 60 minutes or by the action of hot air having a temperature of from 1600 to 210"C for a period of from 30 seconds to 10 minutes.

The dyestuffs according to the invention make it possible to produce on the above-specified fiber materials, with a very good color yield, colorations of high tinctorial strength and good structure. They may have a range of shades from yellow to blue and they have a high fastness to light, to water, to alkalies, to washing, to perspiration and to thermofixation.

The following Examples illustrate the invention. Parts are by weight.

Example 1: 10.9 Parts of 2-bromo-4-nitroaniline were dissolved in a sufficient quantity of glacial acetic acid. The resulting solution was introduced into a mixture of 200 parts of water and 20 parts of 33% hydrochloric acid.

The temperature was reduced to 0 to 5 C by the addition of ice. Next, the mixture was diazotized by the addition of 10ml of 5N sodium nitrite solution. The mixture was stirred for 1 hour, supplemented with 2 parts of amidosulfonic acid and clarified with kieselguhr. The resulting solution of 14 parts of N-methylsuccinic acid dimethyl ester-N-ethylaniline in acetic acid, while stirring.Coupling was completed in an acidic medium at 0 to 5"C. After about 12 hours the resulting dyestuff of the formula

was filtered off, washed until electrolyte-free and dried, 16 Parts of a red dyestuff powder were obtained, suitable for dyeing polyester fibers in aqueous dispersion in clear, red shades having high fastness to light and to sublimation.

Example 2: 7.3 Parts of 2-amino-5-nitrothiazole were dissolved in 30 ml 85% phosphoric acid. Diazotization was carried out at 0 to 5 C by slowly introducing 16 parts of 40% nitrosysulfuric acid. The diazotized mixture was stirred at the specified temperature for 30 minutes. The the excess nitrite was destroyed with 2 parts of amidosulfonic acid.

The resulting diazonium salt solution was allowed to flow slowly into a cooled solution of 13.3 parts N-methylenesuccinic acid dimethyl ester-N-methylaniline in 50 ml acetone while stirring and cooling. Solid sodium acetate were thereafter added as a buffer.

After stirring for 2 hours the coupling liquor was introduced into 1000 parts of water, the precipitated dyestuff of the formula

was washed until free from electrolyte and dried.

The resulting dyestuff had a very good absorptive power on fiber materials and polyesters, cellulose acetates and polyamides in aqueous dispersion and gave brilliant violet shades of high tinctorial strength and good fastness to light and to sublimation.

Example 3: By a process analogous to that of Example 1 or Example 2, further dyestuffs according to the invention, having the shade indicated, may be prepared using the components indicated in the following Table: Example D-NH2 R1 R2 R3 Shade on No. polyester (Formula Ill) fibers 3. 4-nitroaniline CH3 CH3 H orange 4. 2-cyano-4-nitroaniline CH3 CH3 H red 5. 2-cyano-4-nitro-6- CH3 CH3 H blueish red bromoaniline 6. 4-aminobenzoic acid ethyl CH3 CH3 H gold yellow ester 7. 4-aminoazobenzene CH3 CH3 H orange 8. 4-amino-3-chloro-azobenzene CH3 CH3 H blueish red 9. 2,4,5-trichloroaniline CH3 CH3 H gold-yellow 10. 4-aminoacetanilide CH2 CH3 H gold-yellow 11. 4-cyanoaniline CH3 C2H5 H gold-yellow 12. 2-bromo-4-cyanoaniline CH3 CH3 H orange 13. 2-chloro-4-nitroaniline CH3 CH3 H scarlet 14 4-aminobenzaldoxime CH3 CH3 H reddish yellow 15. 2-cyano-4-nitroaniline CH3 CH3 H blueish red 16. 2,4-dinitroaniline CH3 CH3 H red 17. 2,4-dinitro-6-chloroaniline CH3 CH3 H blueish red 18. 2,6-dichloror-4-nitroaniline CH3 CH3 H ginger 19. 4-aminobenzoic acid ethyl CH3 CH3 H gold-yellow ester 20. 2-methoxy-4-nitroaniline CH3 CH3 H red 21. 2-amino-5-nitrothiazole CH3 C2H5 H violet 22. 2-amino-6-nitrobenzothiazole CH3 C2H5 H red 23. 2-methyl-4-nitroaniline CH3 C2H5 H red 24. 2,4-dinitro-6-bromoaniline CH3 C2H5 H blueish red 25. 3-amino-5-nitrobenzothiazole CH3 C2H5 H blue 26. 4-nitroaniline CH3 C2H5 CH3 scarlet 27. 2-chloro-4-nitroaniline CH3 C2H5 CH3 red 28. 2-cyano-4-nitroaniline CH3 C2H5 CH3 blueish red 29. 2,4-dinitroaniline CH3 C2H5 CH3 blueish red 30. 2,4-dinitro-5-chloroaniline CH3 C2H5 CH3 violet 31. naphthylamine CH3 C2H5 OCH3 ginger 32. 4-chloro-2-triflurormethyl CH3 C2H5 OCH3 orange aniline 33. 4-nitro-2-methylsulfonyl CH3 C2H5 OCH3 violet aniline 34. 2-nitroaniline CH3 C2H5 OCH3 red 35. 3-phenyl-5-amino-1,2,4- CH3 C2H5 OCH3 red thiadiazole

Claims

1. Awater-insoluble azo dyestuff of the general formula (I)

wherein D represents the radical of a diazo component of the benzene, azobenzene, naphthalene, thiazole, benzothiazole, thiadiazole, benzisothiazole or indazole series, which is free from sulfonic acid groups and in which the ring or each ring independently is unsubstituted or substituted by one or more substituents selected from halogen atoms and nitro, cyano, alkyl, alkoxy, alklsulfonyl, sulfonamido, trifluoromethyl, alkylcarbonyl, chloroalkylcarbonyl, alkylcarbonylamino, chloroalkylcarbonylamino, benzoyl, chlorobenzoyl, benzoylamino, chlorobenzoylamino, phenoxy, ozime, carboxylic acid alkyl ester and carboxylic acid amide groups, the alkyl and alkoxy groups and moieties each having from 1 to 4 carbon atoms, R1 and R2, which may be the same or different, each represents an alkyl group having from 1 to 4 carbon atoms, and R3 represents a hydrogen atom or an alkyl or alkoxy group having from 1 to 4 carbon atoms.

2. A dyestuff as claimed in claim 1, wherein a halogen atom ring substituent is a fluorine, chlorine or bromine atom.

3. The dyestuff of the formula

4. The dyestuff of the formula

5. The dyestuff of the formula

6. The dyestuff of the formula

7. A process for preparing a dyestuff of the general formula (I) given in claim 1, which comprises diazotizing a diazo component of the general formula (II) D-NH2 (II) wherein D is defined as in claim land coupling the resulting product with a coupling component of the general formula (III)

wherein R1, R2 and R3 are defined as in claim 1, in an acidic or neutral aqueous, aqueous-organic or organic medium.

8. A process as claimed in claim 7, wherein the coupling medium comprises water and/or an organic solvent selected from methanol, ethanol, propanol, butanol, acetone and dimethylformamide.

9. A process as claimed in claim 7 or claim 8, wherein coupling is carried out in the presence of an acid-binding agent.

10. A process as claimed in claim 9, wherein the acid binding agent is pyridine, picoline, triethylamine, sodium, carbonate, potassium carbonate, magnesium oxide or sodium acetate.

11. A process as claimed in claim 7, conducted substantially as described herein.

12. A process as claimed in claim 7, conducted substantially as described in Example 1 or Example 2.

13. A dyestuff as claimed in claim 1, whenever prepared by a process as claimed in any one of claims 7 to 12.

14. A dyeing or printing process wherein a dyestuff as claimed in any one of claims 1 to 6 and 13 is used.

15. A process as claimed in claim 14, wherein a fibrous material of cellulose diacetate, cellulose 21/2 acetate, cellulose triacetate, a polyamide, a polyurethane, a polycarbonate or a linear polyester is dyed or printed.

16. A process as claimed in claim 14, conducted substantially as described herein.

17. A fibrous material of cellulose diacetate, cellulose 21/2 acetate, cellulose triacetate, a polyamide, a polyurethane, a polycarbonate or a linear polyester, wherever dyed or printed with a dyestuff as claimed in any one of claims 1 to 6 and 13.

18. Adyeing or printing preparation which contains a dyestuffas claimed in any one of claims 1 to 6 and 13.