GB1564288A

GB1564288A - Reactive dyestuffs

Info

Publication number: GB1564288A
Application number: GB982578A
Authority: GB
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1977-03-17
Filing date: 1978-03-13
Publication date: 1980-04-02
Also published as: FR2384002A1; DE2711614A1; FR2384002B1; JPS53115743A

Description

(54) REACTIVE DYESTUFFS We, BAYER AKTIENGESELLSCHAFT, a body corporate organised under the laws of Federal Republic of Germany, of Leverkusen, Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The invention relates to anthraquinone reactive dyestuffs of the general formula

wherein R denotes hydrogen or optionally substitu ter C--C-alkyl B denotes a direct bond,

and X denotes a trihalogenopyrimidinyl radical, preferably 2,4 - difluoro - 5 - chloro pyrirnidinyl radical, or denotes a fluoro triazinyl or 2,3 - dichioroquinoxaline 6 - carbonyl radical.

Particularly suitable fluorotriazinyl radicals are those which contain, as the second substituent in the triazine ring, amino, monoalkylamino or dialkylamino, phenylamino, monosulphophenylamino or disulphophenylamino or toluidino radicals wherein alkyl represents, in particular, C1-C-alkyl.

The present invention also relates to processes for the preparation of anthraquinone reactive dyestuffs of the formula (I).

The following processes may be mentioned specifically: 1. Dyestuffs of the formula

wherein R, B and X have the meanings indicated above, are converted into compound of the formula (I) by sulphonation, for ex ample with oleum.

2. Dyestuffs of the formula

wherein R and B have the meaning indicated above, are reacted with 1 mol of a reactive component Y-X, wherein Y represents a substituent which can be split off under the reaction conditions and X has the meaning indicated in formula (I), by conventional processes, with the elimination of 1 mol of H-Y to give (I).

The starting materials used for the preparation of (II) are compounds of the formula

which, in turn, are readily accessible by subjecting 1 - amino - 2 - sulpho - 4 - bromoanthraquinone to a condensation reaction with gamines of the formula

in an aqueous medium in the presence of copper or copper salts and acid acceptors.

The following are examples of amines of the formula (IV): 1 - amino - 3 - aminomethyl - benzene, 1 - amino - 3 - N - methyl- amino - methyl - benzene, l - amino - 3 - N - ethylaminomethyl- benzene, 1 - amino - 3 - N - - hydroxyethyl - aminomethylbenzene and l - amino - 3 - N - isopropyl aminomethyl - benzene.

The sulphonation of the compounds (11) and/or (IIa) is carried out by means of oleum which advantageously contains 5 to 25% of sulphur trioxide, and at temperatures between 10 and 700C, preferably between 20 and 45 , whilst stirring well. The reaction takes 1 to 20 hours. In order to isolate the product, the sulphonation melt is discharged onto ice and, depending on its solubility, the product is isolated with or without adding a salt, such as sodium chloride or potassium chloride.

The acylation of the compounds (IIa) and/ or (III) with fibre-reactive components Y-X can be effected in a manner which is in itself known, for example in an aqueous medium, with the addition of acid-binding agents, such as sodium hydroxide, sodium carbonate, calcium carbonate, magnesium carbonate or sodium bicarbonate. The reaction temperature to be selected here depends on the reactivity of the fibre-reactive component.

Examples of suitable reactive components Y-X are tetrachloropyrimidine, 2,4,6 - trifluoro - 5 - chloropyrimidine, difluoro amino-uiazine, difluoro - methylamino - triazine, difluoro - o - sulphophenylamino - tri- azine, difluoro - m - sulphophenylamino - triazine or difluoro - p - sulphophenylaminotriazine, difluorophenylaminotriazine, dF fluoro - o - toluidino - triazine, difluoro - m - toluidino - triazine or difluoro - ptoluidino - triazine, difluoro - methoxytriazine and 2,3 - dichloro - quinoxaline - 6carboxylic acid chloride.

The new dyestuffs are suitable for dyeing and printing materials containing hydroxyl or amide groups, such as textile fibres, filaments and fabrics composed of wool, silly, synthetic polyamide and polyurethane fibres, and for dyeing and printing, in a manner fast to washing, natural or regenerated cellulose, the treatment of cellulose materials being effected by the processes which have been disclosed for reactive dyestuffs, appropriately in the presence of acid-binding agents and, if appropriate, by the application of beat.

The invention also relates to anthraquinone compounds of the formula

wherein R hydrogen or optionally substituted C1C±alkyl and B a direct bond,

and preferably to those of the formula (V) having R=H or CH3 and B=a direct bond.

The formulae indicated are those of the free acids. The dyestuffs are generally isolated and employed for dying, in the form of their alkali metal salts, in particular their sodium salts.

Example 1 43.7 of 1 - amino - 4 - (3' - N - methylaminomethyl - phenylamino) - anthraquinone2 - sulphonic acid are introduced in portions into 70 ml of 20% strength oleum. The mixture is stirred for 2 hours at 300 and sub sequently for 2 hours at 400. The completion of the reaction is confirmed by means of a thin layer chromatogram. If starting material or mono-sulphonic acid is still present, the warming must be continued. The melt is discharged onto 400 g of ice and the precipitation of the trisulphonic acid is completed by adding 20 g of sodium chloride. After being filtered off, the product is dissolved in water and neutralised with sodium hydroxide solution and 5% strength by volume sodium chloride solution is added.The paste obtained by the isolation process, which is moist with water, can be used direct for the further reactions. The product is readily soluble in water to give a blue colour. An analysis of the sulphonation product gives a ratio of nitrogen to sulphur of nearly 3:3.

The position of the two newly attached sulpho groups was determined by 'H--NMR spectroscopy (60 MHz; for example: D,--DMSO).

In addition to the characteristic AA'BB' spectrum of the anthraquinone protons C.CRN 3 singlet signals are evident in the aromatic range at =7.40, 8.05 and 8.25 ppm, which are assigned to the protons at C2', C, and C,'.

Example 2 59.7 g of 1- amino - 4 - (3' - N - methylaminomethylphenylamino) - anthraquinone 2,4',6' - trisulphonic acid (prepared in accordance with the instructions of Example 1) are dissolved in 1 1 of water. After cooling to 10 C, 16.9 g of 2,4,6 - trifluoro - 5 - chloro pyrimidine are added dropwise, a pH of 8 8.5 being maintained by simultaneously adding 100 ml of 2 N NaOH. After the completion of the acylation, the product is salted out with 25% /O strength by volume sodium chloride. After being filtered off, dried and ground, a blue dyestuff powder is obtained, which dissolves readily in water to give a blue colour.In the form of the free acid, the dyestuff corresponds to the formula

Printing Instruction A clear, reddish-tinged blue print with good fastness to wet processing and light is obtained if cotton nettle is printed with a print paste containing, per kilogram, 20 g of the dyestuff prepared in accordance with Example 2, 100 g of urea, 300 ml of water, 500 g of alginate thickener (60 g of sodium alginate/kg of thickener) and 10 g of sodium carbonate, and made up to 1 kg with water, and is dried, steamed for 1 minute at 1030C, rinsed with hot water and soaped at the boil.

Padding Instruction 30 parts of the dyestuff prepared in accordance with Example 2 are dissolved in 1,000 parts of water. A cotton fabric is padded with this solution and is squeezed out to give a loss in weight of 90%. Whilst it is still moist, the cotton is treated for 30 minutes at 700 in a bath which contains 200 parts of calcined sodium sulphate and 10 parts of calcined sodium carbonate dissolved in 1,000 parts of water. The dyeing is then finished in the usual manner. A brilliant reddish-tinged blue with excellent fastness to wet processing and light is obtained.

If the procedure according to the instructions of Example 2 is followed, but an equivalent quantity of one of the reactants listed below is used instead of 2,4,6 - trifluoro - 5 chloro - pyrimidine, valuble dyestuffs which dye cotton, by one of the dyeing processes listed above, in a clear, reddish-tinged blue shade, are also obtained.

Examples Reactive component 3 2,3 - Dichloroquinoxaline - 6 carboxylic acid chloride 4 2,4,5,6 - Tetrachloropyrimidine.

Example 5 17.3 g of m - sulphanilic acid are dissolved in 0.5 1 of ice water. 13.5 g of 2,4,6 trifluoro - 1,3,5 - triazine are then run in dropwise, dilute sodium hydroxide solution being added simultaneously in order to maintain a pH of 3w. After the cyanuric fluoride has been added, stirring is continued for a few minutes more and a neutral solution of 59.7 g of a 1 - amino - 4 - (3' - N - methyl aminomethyl - phenylamino) - anthraquinone2,4',6' - trisulphonic acid in 1 l of water is then added dropwise. At the same time, dilute sodium hydroxide solution is again added at such a rate that the pH is 7-8.

A temperature of 0-50C is maintained during the condensation reaction by the addition of ice. The dyestuff is precipitated by adding 25% strength by volume sodium chloride.

After being filtered off, dried and ground, a blue powder which is readily soluble in water is obtained. In the form of the free acid, the dyestuff corresponds to the formula

If the procedure according to the instruc tions of this example is followed, but a quan tity of amine equivalent to the m - sulphani lic acid is used, valuble dyestuffs are again produced, which dye cotton, in accordance with one of the dyeing examples listed sub sequently to Example 2, in a brilliant, redi dish-tinged blue shade.

Example Amine 6 o- sulphanilic acid 7 p - sulphanilic acid 8 1 - amino - 2 - methoxy - 5 sulpho- benzene 9 1-amino-2-supho-4- chloro - benzene 10 aniline - 2,4 - disulphonic acid 11 aniline - 2,5 - disulphonic acid Example 12 55.6 g of the aminoanthraquinone dyestuff of the formula

'it is obtained by acylating, with p - nitrobenzoyl chloride, the dyestuff obtained in accordance with the instructions of Example 1 and subsequently reducing the nitro group with sodium sulphide to give the amino group) are dissolved in 11 of water. 16.4 g of 2,4,6trifluoro - 5 - chloro - pyrimidine are added dropwise at 1520 , a pH of 67 being maintained by adding a 10% strength sodium carbonate solution simultaneously. The acylated dyestuff is precipitated with 10% strength by volume potassium chloride. After being filtered off, dried and ground, a blue dyestuff powder is obtained, which dissolves readily in water to give a blue colour.In the form of the free acid, the dyestuff corresponds to the formula

Dyeing Example 168 ml of water at 2025 are initially introduced into a dye beaker of 300 ml capacity, which is placed in a waterbath which can be heated. 0.3 g of the dyestuff obtained in accordance with Example 12 are thoroughly stirred with 2 ml of cold water, to give a paste and 30 ml of hot (700) water are added; the dyestuff thereupon dissolves. The dyestuff solution is added to the water introduced initially and 10 g of cotton yarn are kept in continuous agitation in this dye liquor. The temperature of the dye liquor was increased to 40 50 in the course of 10 minutes, 10 g of anhydrous sodium sulphate are added and dyeing is continued for a further 30 minutes.

4 g of anhydrous sodium carbonate are then added to the dye liquor and dyeing is carried out for 60 minutes at 4050o. The dyed material is then taken out of the dye liquor, the liquor adhering is removed by wringing or squeezing out and the material is rinsed, first with cold water and then with hot water, until the rinsing liquor is no longer stained.

The dyed material is then soaped for 20 minutes at the boil in 200 ml of a liquor which contains 0.2 g of sodium alkylsulphate, is rinsed again and is dried at 60--700 in a drying cabinet. A brilliant, reddish-tinged blue with excellent fastness to washing and light is obtained.

Example 13 58.3 g of 1 - amino - 4 - (3' - amino methylphenylamino) anthraquinone - 2,4',6' trisulphonic acid (the dyestuff is prepared in accordance with the instructions of Example 1) are dissolved in 1 1 of water. After cooling to 100C, 16.9 g of 2,4,6 - trifluoro - 5 chloro - pyrimidine are added dropwise, a pH of & .5 being maintained by adding 100 ml of 2 N sodium hydroxide solution simultaneously. After the acylation is complete, the product is salted out with 25 ó strength by volume potassium chloride. After being filtered off, dried and ground, a blue dyestuff powder is obtained, which dissolves readily in water to give a blue colour. In the form of the free acid, the dyestuff corresponds to the formula

WHAT WE CLAIM IS: - 1.A dyestuff which, in the form of its free acid, corresponds to the general formula

in which R denotes a hydrogen atom, or an option ally substituted C1 to C4 alkyl group, B denotes a direct bond,

and X denotes a trihalogenopyrimidinyl, fluorotriazinyl or 2,3 - dichloroquinoxaline - 6 carbonyl radical.

2. A dyestuff according to claim 1, in which X denotes a 2,4 - difluoro - 5 - chloro pyrimidinyl radical.

3. A dyestuff according to claim 2, in which X denotes a fluorotriazinyl radical which contains, as the second substituent in the triazine ring, an amino, monoalkylamino, dialkylamino, phenylamino, monosulphophenylamino, disulphophenylamino, or toluidino radical.

4. A dyestuff according to claim I, as hereinbefore specifically identified.

5. A process for the production of a dyestuff as claimed in claim 1, in which a dyestuff of the general formula

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **. 'it is obtained by acylating, with p - nitrobenzoyl chloride, the dyestuff obtained in accordance with the instructions of Example

1 and subsequently reducing the nitro group with sodium sulphide to give the amino group) are dissolved in 11 of water. 16.4 g of 2,4,6trifluoro - 5 - chloro - pyrimidine are added dropwise at 1520 , a pH of 67 being maintained by adding a 10% strength sodium carbonate solution simultaneously. The acylated dyestuff is precipitated with 10% strength by volume potassium chloride. After being filtered off, dried and ground, a blue dyestuff powder is obtained, which dissolves readily in water to give a blue colour.In the form of the free acid, the dyestuff corresponds to the formula

Dyeing Example

168 ml of water at 2025 are initially introduced into a dye beaker of 300 ml capacity, which is placed in a waterbath which can be heated. 0.3 g of the dyestuff obtained in accordance with Example 12 are thoroughly stirred with 2 ml of cold water, to give a paste and 30 ml of hot (700) water are added; the dyestuff thereupon dissolves. The dyestuff solution is added to the water introduced initially and 10 g of cotton yarn are kept in continuous agitation in this dye liquor. The temperature of the dye liquor was increased to 40 50 in the course of 10 minutes, 10 g of anhydrous sodium sulphate are added and dyeing is continued for a further 30 minutes.

4. A dyestuff according to claim I, as hereinbefore specifically identified.

in which R, B and X have the same meanings as in claim 1 is sulphonated.

6. A process according to claim 5, in which 5 to 25% strength oleum is used as the as the sulphonating agent.

7. A process according to claims 5 or 6, in which the sulphonation is carried out between 10 and 700C.

8. A process according to claim 7, in which the sulphonation is carried out between 20 and 45"C.

9. A process for the production of a dyestuff as claimed in claim 1, in which a dyestuff of the general formula

in which R and B have the same meaning as in claim 1, is reacted with a reactive compound of the general formula Y-X in which Y denotes a substituent which can be split off under the reaction conditions and X has the same meaning as in claim 1, with the elimination of HY.

10. A process according to claim 9 in which the reactive compound XY is any of those hereinbefore specifically mentioned.

11. A process for the production of a dyestuff as claimed in claim 1, when carried out substantially as described in any of Examples 2 to 13.

12. A dyestuff as claimed in claim 1, when produced by the process of any of claims 6 to 12.

13. A process for dyeing or printing a fibre material which contains hydroxyl groups or amide groups, comprising treating the fibre material with a dyestuff as claimed in any of claims 1 to 4 and 12.

14. A process according to claim 13 when carried out substantially as described in the "Printing Instruction" or "Padding Instruction" following Example 2 or the "Dyeing Example" following Example 12.

15. A fibre material which contains hydroxyl groups or amide groups when dyed or printed by the process of claims 13 or 14.

16. An anthraquinone compound, which, in the form of the free acid, corresponds to the general formula

in which R and B have the same meanings as in claim 1.

17. An anthraquinone compound according to claim 16, in which R denotes a hydrogen atom, or a methyl group and B denotes a direct bond.

18. An anthraquinone compound according to claim 16, substantially as hereinbefore specifically identified.