FIBER-REACTIVE YELLOW AZO DYESTUFFS

Abstract: Water-soluble fiber-reactive yellow dyestuffs of the formula wherein M is hydrogen or an alkali metal, such as sodium, potassium or lithium, or the equivalent of an alkaline earth metal, such as of calcium, and X is the vinyl group or a group of the formula (2) -CH₂ - CH₂ - Z (2) in which Z is hydroxy, chlorine, bromine, sulfato, thiosulfato, phosphato, acetyloxy, propionyloxy or di-(lower alkyl)-­ amino. Process for their preparation. Liquid compositions of said dyestuffs are also disclosed. Use of these dyestuffs in coloring a material made of cellulose, wool, silk and/or polyamide fibers.

Description: FIBER-REACTIVE YELLOW AZO DYESTUFFS The present invention provides new water-soluble, fiberreactive monoazo dyestuffs, and liquid compositions thereof. In US-PS 3,519,616, there is disclosed, in Example 3, a reactive dyestuff of the formula EMI1.1 which is said to provide greenish yellow dyeings having good fastness to wetting and to light. Applicants have now found new, water-soluble fibe-reactie dyestuffs of the general formula (1) EMI1.2 wherein M is hydrcgen or an alkali metal, such as sodium, potassium or lithium, or the equivalent of an alkaline earth metal, such as of calcium, and X is the vinyl group or a group of the general formula (2) CH2 - CH2 - Z (2) in which Z is hydroxy, chlorine, bc31ine, sulfato (of the formula -OSO3'; ; with M being defined as above), thiosul fato (of the formula -S-SO3M with M being defined as above), phosphato (of the formula -OPO3M2 with M being defined as above), acetyloxy, propionyloxy or di-(lower alkyl)-amino. Liquid compositions containing 5 to LIS % of said dyestuff in water are also provided. The term "lower" means that the group indicated so, contains 1 to LI C-atoms. The dyestuff of the present invention can be prepared according to the invention by coupling the N-acetoacetyl derivative of 2-methoxy-5-methyl-4-sulfo-aniline of the formula (3) EMI2.1 in which M is defined as above, with a diazotized amino compound of the general formula (4) EMI2.2 in which X is defined as above, while employing the conventional coupling conditions for preparing acetoacetylanilide-azo dyestuffs, such as a temperature of from OOC to 250C and a pH of from 4 to 7. After preparation, the dyestuff may be isolated as a powder, either by salting it out of solution or by spray drying, and brought to standard strength by the addition of inorganic salt, generally sodium sulfate. Advantageously, the prepared dyestuff may be used directly as a liquid composition after standardizing with water. Such liquid compositions will contain from 5 to 45 % (by weight) of the water soluble dyestuff of the present invention, preferably 10 to 20 %, and water. Said liquid composition may also optionally contain from 0 to 10 %, preferably 0 to 6 %, of inert inorganic salt, typically the alkali metal (lithium, sodium, potassium) and ammonium chlorides and sulfates and mixtures thereof. While said liquid composition may also optionally contain up to 5 % of buffer substances, it is preferred that the composition remain substantially free of a buffer. It is also preferred that liquid compositions of the dyestuff having the B-sulfatoethylsulfonyl group be maintained at a pH of from about 2.5 to about 4.5 for maximum stability. The dyestuff of the present invention is suitable for the dyeing of cellulosic materials such as eotton, linen, viscose rayon or staple fibers. It can be applied by any one of the usual dyeing and printing methods for reactive dyestuffs and yields on cellulosic materials, in the presence of alkaline agents, brilliant yellow shades having excellent fastness properties, and particularly superior color yield and build up (ratio of dyestuff concentration to color intensity) in both exhaust and continuous dyeings. The present dyestuffs may also be used on wool, silk or polyamide fibers. The invention may be further illustrated by the following Examples in which the parts and percentages are by weight. EXAMPLE 1 68.2 Parts of 2,5-dimethoxyaniline-4-ss-sulfatoethylsulfone were dissolved in 320 parts of water at pH 6.0-6.5 by the addition of 14 parts of sodium carbonate. 28 parts of celite and 8 parts of Fuller's Earth were added and the solution clarified. The residue was washed with 100 parts of water. 28 parts of 93 % sulfuric acid was added, the solution iced to 0-50C and diazotized with 33.8 parts of an aqueous 40.l % sodium nitrite solution. The excess nitrite was decomposed by the addition of one part of sulfamic acid. The diazo solution was then added to a slurry consisting of 135 parts of water and 56 parts of 2-methoxy5-methyl-4-sulfo-acetoacetanilide while maintaining the pH at 4-5 with 16 parts of sodium carbonate. The resulting solution was spray dried to yield 188.3 parts of a dyestuff powder containing 15.0 % inorganic sulfate salts and 0.09 Z inorganic chloride salts, and the alkali metal salt of the formula EMI4.1 This powder may then be blended with 125.5 parts of anhydrous sodium sulfate to yield 313.8 parts of standard strength powder. Alternatively, the dyestuff solution of Example 1 before spray-drying can be standardized as a liquid dyestuff solution by the addition of water and adjusting the pH to 2.5-4.5 to yield, for example, 1255 parts of standardized liquid dyestuff. Example 2 Liquid compositions of this ss-sulfatoethylsulfonyl dyestuff were tested for stability in the following manner: A liquid composition of said dyestuff, obtainable by making the aqueous dyestuff solutions up to containing about 14-18 % dyestuff and 0 to 6 % inorganic salt was placed in a covered glass container, adjusted to an initial pH as indicated in the following Table and stored in an oven at 400C. Each aqueous dyestuff sample was analyzed for vinylsulfone content prior to the storage test and from time to time thereafter. The net increase in vinylsulfone content for various storage periods is shown in the Table. As can be seen from the Table, the liquid dyestuff composition maintained at pH 4.5 (or lower) and containing no buffer showed dramatically less vinylsulfone formation during storage than the corresponding composition maintained at higher pH. Vinylsulfone formation (final % minus initial %) Initial Buffer pH Content 7 days 14 days 28 days 105 days 5.5 % 3.7 % 4.5 % 5.3 % 7.8 % 4.5 o % 0.8 % 0.7 % 1.4 % 2.4 % Example 3 48.6 Parts of 2,5-dimethoxy-aniline-4-vinylsulfone, dissolved in a mixture of 300 parts of water and 28 parts of an aqueous 93 % sulfuric acid, were diazotised at a temperature of O - 50C by means of 33.8 parts of an aqueous 40.1 % sodium nitrite solution in the conventional manner. The excess nitrite was decomposed by the addition of one part of sulfamic acid. The diazo solution was then added to a slurry consisting of 135 parts of water and 56 parts of 2-methoxy-5-methyl-4-sulfo-acetoacetanilide while maintaining the pH at 4-5 with 16 parts of sodium carbonate. The dyestuff according to the invention, obtained, is separated by saling out with sodium chloride and isolated by filtration. After drying, a dyestuff powder is obtained containing, besides electrolytes (such as sodium chloride), the alkali metal salt (sodium salt) of the compound of the formula EMI6.1 This azo compound according to the invention has very good dyestuff properties, as mentioned in the description part. Examples 4 and 5 In the Table Example which follow, further monoazo dyestuffs according to the invention are described in the free acid form. They are preferably in form of their alkali metal salts, such as sodium, potassium or lithium salts. They can be prepared, according to the invention, analogously to Example 1, employing the equivalent amount of 2, 5-dimethoxy-aniline-LI-F-thiosulfatoethylsulfone or 2,5-dimethoxy-aniline-4-S-phosphatoethylsuleone in place of 2,5-dimethoxy-aniline-4-S-sulfaeoethylsulrone as the diazo component. These azo dyestuffs according to the invention have also good fibre reactive dyestuff properties, and they yield, by application and fixation methods conventionel in the dyeing and printing technique for fibre reactive dyestuffs, on the materials mentioned in the description part, brilliant yellow dyeings and prints having good fastness properties. EMI7.1 <tb> Exam <SEP> le <SEP> D <SEP> estuff <SEP> accordin <SEP> to <SEP> the <SEP> Invent <SEP> ion <tb> <SEP> OCH3 <SEP> 0CH3 <tb> <SEP> NH-CO-CH <SEP> - <SEP> N <SEP> = <tb> <SEP> I <SEP> N1 <tb> <SEP> / <SEP> OCH3 <SEP> OCH3 <tb> <SEP> < <SEP> NH-CO-CH <SEP> - <SEP> N <SEP> = <SEP> N <SEP> < <SEP> CH <tb> <SEP> HO <SEP> Co <SEP> SO2 <SEP> -C1 <SEP> H2 <tb> <SEP> 3CH <SEP> I <tb> <SEP> 4 <SEP> CH3 <SEP> CH3 <SEP> OCH3 <SEP> 5--SO3H <tb> <SEP> SSO3H <tb> <SEP> OCH <SEP> OCH3 <tb> <SEP> 4 <SEP> NH-CO-CH <SEP> - <SEP> N <SEP> = <tb> <SEP> I <SEP> I <SEP> ' <tb> <SEP> 3 <SEP> S <SEP> l <SEP> t <SEP> S02-lCH2 <tb> <SEP> CH <SEP> I <tb> <SEP> 5 <SEP> CH3 <SEP> CH3 <SEP> OCH3 <SEP> C1H2 <tb> <SEP> OPO <SEP> 3H2 <tb> Examples 6 to 8 In the Table Examples which follow, further monoazo dyestuffs according to the invention are described in the free acid form. They are preferably in form of their alkali metal salts, such as sodium, potassium or lithium salts. They can be prepared, according to the invention, analogously to Example 3, employing the equivalent amount of 2,5-dimethoxy-aniline-4-ss-acetyloxyethylsulfone or 2,5-di methoxy-aniline-4-B-propionyloxyethylsulfone or 2,5-dimeth oxy-aniline-4-B-diethylaminoethylsulfone in place of 2,5-dimethoxy-aniline-4-vinylsulfone as the diazo component. These azo dyestuffs according to the invention have also good fibre reactive dyestuff properties, and they yield by application and fixation methods conventional in the dyeing and printing technique for fibre reactive dyestuffs, on the materials mentioned in the description part, brilliant yellow dyeings and prints having good fastness properties. EMI8.1 <tb> Example <SEP> Dyestuff <SEP> according <SEP> to <SEP> the <SEP> invention <tb> <SEP> OCR <SEP> OCR <tb> <SEP> 4 <SEP> NH-CO-CH <SEP> - <SEP> N <SEP> = <SEP> N <tb> <SEP> 6 <SEP> HO3S <SEP> 1 <SEP> S02-CH, <tb> <SEP> CH3 <SEP> CH3 <tb> <SEP> 3 <SEP> 3 <SEP> OCR3 <SEP> 2 <tb> <SEP> O-CO-CK3 <tb> <SEP> SOCH3 <SEP> OCR <tb> <SEP> S <SEP> NH-CO-CH <SEP> - <SEP> N <SEP> = <SEP> N <tb> <SEP> HO <SEP> 3S <SEP> C10 <SEP> 0 <SEP> 2-C1R2 <tb> <SEP> 7 <SEP> CH3 <SEP> CH3 <SEP> OCH <tb> <SEP> 3 <SEP> OCR3 <SEP> j <SEP> 2 <tb> <SEP> 3 <SEP> O-CO-C <SEP> H <tb> <SEP> OCR <SEP> OCH <tb> <SEP> H-CO-CH <SEP> - <SEP> N <SEP> = <tb> <SEP> 3 <SEP> X <SEP> CO <SEP> Ns0 <SEP> 2-C1R2 <tb> <SEP> 8 <SEP> CH3 <SEP> CH3 <SEP> SOCH3 <SEP> CH2-N(C2H5)2 <tb> Example 9 100 Parts of a woolen yarn are prewashed in usual manner and introduced into 3,000 parts of an aqueous dyebath having a temperature of 400C, which contains 2 parts of amnonium acetate and the pH of which has been adjusted at 5.5 by acetic acid. The material is treated for 5 minutes in said bath. 3 Parts of the dyestuff according to the invention as specified in Example 3, which have been dissolved in a small quantity of water, are added, the dyebath is heated within 30 minutes to boiling temperature and the material is treated at said temperature for 45 minutes The yarn is removed from the bath, rinsed with water, then in an aqueous bath containing a small quantity of acetic acid and with water again, and dried. There is obtained a dyeing having a clear, brilliant yellow shade and having very good fastness properties to wetting.

Claims: Patent Claims: 1. A water-soluble fiber-reactive dyestuff of the general formula (1) EMI10.1 wherein M is hydrogen or an alkali metal, or the equIva- ent of an alkaline earth metal, and X is the vinyl group or a group of the general formula (2) - CH2 - CH2 - Z (2) in which Z is hydroxy, chlorIne, bromine, sulfato, t?iO sulfato, phosphato, acetyloxy, propionyloxy or di-(lower alkyl)-amino. 2. h dyestuff according to claim 1 of the formula EMI10.2 in which M is defined as f clalin 1. 3. k dyestuff according to claim 1 of the formula EMI11.1 in which M is defined as in claim 1. 4. A process for the preparation of a dyestuff of the general formula (1) mentioned and defined in claim 1, which comprises coupling a compound of the formula (3) EMI11.2 in which M is defined as in claim 1, with a diazotized amino compound of the general formula (4) EMI11.3 in which X is defined as in claim 1. 5. A liquid dyestuff composition comprising 5 to 45 % of a water-soluble dyestuff according to claim 1, and water. 6. A liquid dyestuff composition comprising 5 to 145 % of a water-soluble dyestuff according to claim 2, and water. 7. A liquid dyestuff conposition according to claim 5 or 6, which dditionaly comprises from 0 to 6 % inert inorganic salt. 8. A liquid dyestuff composition according to claim 5, 6 or 7, wherein said inert inorganic salt is selected from the alkali metal and ammonium chlorides and sul fates and mixtures thereof. - 9. A liquid dyestuff composition according to claim 5, 6, 7 or 8, which comprises from. 10 to 20 % of said water soluble dyestuff. 10. A liquid dyestuff composition according to clai 5, 6, 7, 8 or 9, which is maintained at a pH of from. about 2.5 to about it.5. 11. Use of a dyestuff of claim I for coloring a material made of cellulose, wool, silk and/or polyamide fibers. 12. A process for coloring 2 material nae of cellulose, wool, silk and/or polyamide fibers, which co.-. > rises bringing in contact an aqueous solution of the dye stuff of formula (1) of claim 1, with said material and subjecting the material treated thus to the action of heat and/or of an agent having an alkaline reac tion.

Inventors: CORSO, ANTHONY J., PHILLIPS, THOMAS S.
Applicants: AMERICAN HOECHST CORPORATION
Application year: 1984
Main classification: C09B62
IPC codes: D06P1, C09B62