IL25615A - Fibre-reactive dyestuffs and processes for their manufacture and use - Google Patents

Description

Case 5690/E Israel Patents Form No PATENTS AND DESIGNS ORDINANCE Specification FIBRE-REACTIVE DYESTUFFS AND PROCESSES FOR THEIR MANUFACTURE AND USE Q-n s"'? -p nm C II O1? o ' τοτπ We, CIBA LIMITED, of l l, Klybeckstrasse, Basle, Switzerland, a body corporated according to the laws of Switzerland, do hereby declare the nature of this invention and in what manner the same is to be performed, to be particularly described and ascertained in and by the following statement:- The present invention provides new dyestuffs of the formula H in which one X represents a grouping of the formula the other X represents a hydrogen atom or an -SO^H group, Y represents a hydrogen atom, a methyl group or an -SO^H group* Z represents a fibre-reactive substituent that is preferably heterocyclic, n is an integer not less than 2 and at least one of the symbols X and T represents an -SO^H group.

The dyestuffs of the invention can be made by coupling and/or by condensation* For example, diazo compounds prepared from amines of the formula in which one X represents an -NHL group and the other X and the symbols T and Z have the meanings given above, or tetrazo compounds of diamines in cases when a diazotlzable amino group is present in the substituent Z, can be coupled with 1-[-di- or tri-sulphonaphthyl]-5-pyrazolone-3-carboxylic acid.

As examples of such pyrazolones the following may be mentioned: l-ITaphthyl-( 21 )-3-carboxy-5-pyrazolone- ' ,8r or -6' , 8 or 51 »7,-disulphonic acid, 1-naphthyl-(2* )-3-carboxy-5-pyrazolone-41 ,61 ,8*-trisulphonic acid, 1-naphthyl-(2» )-3-carboxy-5-pyrazolone-31 » 61 ,8*-trisulphonic acid, 1-naphthyl-(2* J^-carboxy-i-pyrazolone^1 »5* ,7*-trisulphonic acid* 1-naphthyl-( 11 )-3-carboxy-5-pyrazolone-3' » 6'-disulphonic acid and 1-naphthyl-(l 1 )-3-carboxy-5-pyrazolone-3* ,6*,8*-trisulphonic acid.

These pyrazolone-3-carboxylic acids can be prepared by condensing the appropriate hydrazinonaphthalene sulphonic acids (obtained by reduction of the corresponding diazonaphthalene sulphonic acid with zinc subchloride) with the sodium salt of oxaloacetic acid monoethylester (obtained by partial hydrolysis of the corresponding oxaloacetic acid diethylester with an equivalent proportion of sodium hydroxide) in a slightly acid to neutral medium with subsequent ring closure of the hydrazone formed in an alkaline medium.

The amines, whose diazo or tetrazo compounds are to be coupled with these coupling components in accordance with the invention, are obtainable from the corresponding meta- or para-diaminobenzene-mono- or di-sulphonic acids by condensation with acid halides which contain a fibre-reactive, preferably heterocyclic, acyl residueo Acid halides of the kind defined which may be mentioned are, for example, acrylic acid chloride, β-chloro- or β-bromo-propionic acid chloride, a-chloro- or a-bromacrylic acid chloride or bromide, α,β-dichloropropionic acid chloride, chlorocrotonlc acid chloride and, advantageously, 2-chlorobenzoxazole carboxylic acid chlorides, 4,5-dichloro-1-phenylpyridazone-carboxylic or sulphonic acid chloride, 4,5-dichloropyridazone-propionic acid chloride, 3»6-dichloropyridazine-5-carbox lic acid chloride, 1 ,4-dichlorophthalazine-carboxylic or sulphonic acid chloride* 2.3-dichloroquinoxaline-carboxylic or sulphonic acid chloride* 2.4-dichloroquinazoline-carboxylic or sulphonic acid chloride, 2-chlorobenzthiazole-5-» 6- or 7-carboxyllc acid chloride, 2-chlorobenzthiazole-6- or 7-sulphonic acid chloride, tetrachloro-pyridazine, 2,4,6-tri- or 2, 4,5» 6-tetrachloropyrimidine, 2,4-dichloropyrimidine-5-sulphonic acid, 5-nitro- or 5-cyano-2,4>6-trichloropyrimidine, 5-nitro-6-methyl-2, 4-dichloropyrimidine, 2,6-diehloropyrimidine-4-carboxylic acid chloride, 2,4-dichloro-pyrimidine-5-sulphonic acid chloride, 2,4,6-trichloro-1 ,3»5-triazine, and also 4» 6-dichloro-1 ,3,5-triazines substituted in 2-position by an aryl or alkyl residue, for example, a phenyl, methyl or ethyl residue, or by the residue of an aliphatic or aromatic mercapto compound bound through the sulphur atom or of an hydroxyl compound bound through the oxygen atom, or especially by an HO-MH or -NH2 group or by the residue of a hydrazino or ureido compound or the residue of an aliphatic, heterocyclic or aromatic amino compound bound through its nitrogen atom. As compounds of the kind defined whose residues can be bound in 2-position to a triazine nucleus by reaction with trihalogenated triazines there may be mentioned, for example, aliphatic or aromatic mercapto or hydroxyl compounds, for example, thioalcohols, thioglycollic acid, thiourea, thio-phenols, methyl alcohol, ethyl alcohol, isopropyl alcohol, glycollic acid, phenol, chlorophenols, nitrophenols, phenol carboxylic acids, phenol sulphonic acids, naphthols, naphthol-sulphonic acids and so forth, but especially ammonia and compounds containing acylatable amino groups, for example, hydroxylamine, alkoxylamine, hydrazine, phenylhydrazine, phenyl- hydrazine sulphonic acids, carbamic acid and the derivatives thereof, semi- and thiosemi-carbazides and carbazones, methyl-amine, ethylamine, isopropylamine, methoxyethylamine, methoxy-propylamine, dimethylamine, diethylamine, methylphenylamine, ethylenephenylamine, chlorethylamine, ethanolamines, propanol-amines, benzylamine, cyclohexylamine, morpholine, piperidine, piperazine, aminocarbonic acid esters, aminoacetic acid ethyl esters, ami noethane sulphonic acid, N-methylaminoethane sulphonic acid, but especially aromatic amines, for example, aniline, N-methylaniline, toluidines, xylidines, chloranilines, para- or meta-aminoacetanilide, nitranilines, aminophenols, nitrotoluidines, phenyldiamines, toluylenediaminesf anisidine, phenetidine, diphenylamine, naphthylamines, aminonaphthols, diaminonaphthalenes and especially aniline derivatives containing acidic groups, for example, sulphanilic acid, metanilic acid, orthanilic acid, anilinedisulphonic acid, aniline-to-methane sulphonic acid, aminodibenzoic acids, naphthylamino-mono-, di- and trisulphonic acids, aminobenzoic acids, for example, 2-hydroxy-5-aminobenzoic acid, aminonaphthol-mono-, di- and trisulphonic acids and the like, as well as coloured compounds or compounds having dyestuff characteristics, for example, ^-nitro- '-aminostilbene disulphonic acid, 2-nitro-4'-aminodiphenylamine-4, 3*-disulphonic acid and especially amino-azo dyestuffs or aminoanthraquinones or phthalocyanines which still contain at least one reactive amino group, for example, compounds of the formula in. which X represents a hydrogen or halogen atom or a sulphonic acid group, R represents an ethylene, phenylene or diphenylene residue that may be substituted, Z represents a hydrogen atom or an alkyl residue, Pc represents a phthalocyanine residue, ¥ represents HO- or -HH2 and n and m represent 1, 2 or 3· The introduction of the substituent at the 2-position of the triazine residue may also be effected after the condensation with the starting diamine or after the manufacture of the dyestuff· The acyl derivatives of the meta- or para-diaminobenzene-mono- and disulphonic acids to be used in accordance with the invention can be diazotized in the usual manner or tetrazotized when they contain two diazotizable -NH2 groups. Coupling also takes place very easily in an aqueous medium.

The dyestuffs of the invention can also be obtained when the 1,3- or 1 , -diaminobenzene-mono- or disulphonic acid or a monoacetyl derivative thereof is diazotized, coupled with one of the coupling components indicated above and the monoazo dyestuff obtained, which contains a free amino group in the diazo residue (in some cases, after elimination of the acetyl group), is condensed with one of the above indicated acylating agents which contains a fibre-reactive substituent.

The exchangeable halogen atoms of the fibre-reactive substituents in the dyestuffs obtainable by the process of the invention can easily be replaced, for example, by reaction with ternary amines or with hydrazines (for example, dimethyl-hydrazine), in which process fibre-reactive dyestuffs are formed in which the eliminable substituent is a quaternary ammonium or hydrazinium group bound to a carbon atom, especially a carbon atom of a heterocyclic residue, that is to say, for example, a group of the formula ' in which represents a hydrogen atom, an amino group that may be substituted or an etherified hydroxy or mercapto groupo The dyestuffs obtainable by the process of the invention are new. They are valuable dyestuffs suitable for dyeing and printing a very wide variety of materials, especially poly-hydroxylated materials of fibrous structure, for example, materials containing cellulose These include both man-made fibres, for example, fibres made from regenerated cellulose and natural cellulosic materials, for example, pulp, linen and especially cotton. They are suitable for application by the so-called direct dyeing method using a long liquor-to-goods ratio in which dyeing is carried out in an aqueous alkaline bath that may contain a high concentration of salt. They can also be applied by printing and pad-dyeing techniques in which the dyestuffs are applied to the material to be coloured by printing or padding and fixed thereon by means of an agent capable of binding acid, if necessary, with the application of heat.

In order to improve the properties of wet fastness it is generally advantageous to submit the dyeings and prints so obtained to a thorough rinse with cold and hot water, if necessary, in the presence of a substance having a dispersing action and that as ists diffu on n d tu t m have been fixed.

The dyestuffs of the invention are distinguished mainly by their high degree of fixation and by the ease with which unfixed dyestuff can be washed out* The dyeings produced therewith have a very good fastness to washing.

The most valuable dyestuffs of the present invention are those containing the residue of a β-naphthyl-di- or tri-sulphonic acid at 1-position of the pyrazolone ring and, because they are more easily obtainable, particularly those containing the residue of a β-naphthyl-di- or tri-sulphonic acid which is unsubstituted in a position vicinal to the pyrazolone bond.

The products obtainable by the process of the invention have advantages over the nearest comparable known dyestuffs from the corresponding pyrazolones having a methyl group in 3-position; for example, the printing pastes show greater stability and the prints produced therewith are more level.

They are also tinctorially stronger and thus yield dyeings and prints of greater intensity* The following Examples illustrate the invention. Unless otherwise stated, the parts and percentages are by weight* Example 1 33·7 Parts of the primary condensation product obtained from 1 mol of cyanuric chloride and 1 mol of 1 ,3-diaminobenzene-6-sulphonic acid are diazotized and coupled with 41.4 parts of 1-naphthyl-(2t )-3-carboxy-5-pyrazolone-4f ^-disulphonic acid in the presence of sodium bicarbonate. The dichlorotriazine dyestuff so formed is salted out,'"''filtered, the paste is mixed with an aqueous solution comprising 5 parts of disodium phosphate and 5 parts of monosodium phosphate, and the mixture is dried at 4o°C. The dyestuff obtained dyes cotton very fast yellow tints.

A dyestuff having similar properties is obtained by using as coupling component 1-naphthyl- (2 ' ) -;5-carboxy- -pyrazolone- 1 , 6 ' , 81 -trisulphonic acid and also by using cyanuric bromide instead of cyanuric chloride.

Example 2 50 Parts of a 10$ ammonia solution are added to the solution of the dichlorotriazine derivative obtained by the method described in Example 1 (after coupling), and the mixture is stirred for 3 hours at 3 °C. The monochlorotriazine dye-stuff so formed is salted out, filtered and dried. It dyes cotton pure yellow tints fast to light.

Example 3 46.7 Parts of the secondary condensation product obtained from 1 mol of cyanuric chloride, 1 mol of aminobenzene-3-sulphonic acid and 1 mol of l,3-diaminobenzene-6-sulphonic acid are diazotized in aqueous solution with 25 parts of 30 hydrochloric acid and a solution of 6.9 parts of sodium nitrite and then introduced into a solution of 41.4 parts of 1-naphthyl- (2' )-5-carboxy-5-pyrazolone-4',8'-disulphonic acid made slightly alkaline with sodium carbonate. The reaction is kept slightly alkaline by the addition of sodium carbonate. After coupling, the monoazo dyestuff is salted out, isolated by filtration and dried. It dyes cotton very fast yellow tints.

A dyestuff having similar properties is obtained by using 1-naphthyl- (2 ' )-3-carboxy-5-pyrazolone-4 ' , 6 ' , 8 ' -trisulphonic acid as coupling component.

Example 4 3-Acetylamino-l-aminobenzene-6-sulphonic acid is 4* ,8'-disulphonic acid and the acetyl group in the product so obtained is split off by heating with a sodium hydroxide solution. 61.4 Parts of the aminoazo dyestuff so obtained are dissolved in 800 parts of water and the solution is added to an ice-cold ruspension of 19 parts of cyanuric chloride. The mixture is stirred for several hours at a temperature between 5 suad 10°C and the pH is kept at between 4 and 5 by the addition of a dilute sodium hydroxide solution. After condensation, a solution of 53.3 parts of disodium salt of 1-amino-4~(3'-amino-phenylamino)-anthraquinone-2,4'-disulphonic acid is added. The reaction mixture is heated to 60°C and held at that temperature for 4 to 6 hours, the pH being kept at between 5 and 7. The green dyestuff that forms is salted out, filtered and dried. It dyes cotton strong, fast yellowish green tints.

A dyestuff having similar properties is obtained by using 1-amino-4-( 4*-aminophenylamino)-anthraquinone-2,31-disuiphonic acid as blue component.

A dyestuff having similar properties is obtained by using 1-naphthyl-(2t )-3-carboxy-4' ,6* ,8'-trisulphonic acid as coupling component in the preparation of the monoazo dyestuff.

Dyeing prescription: 2 Parts of dyestuff are dissolved in 100 parts of water. A cotton fabric is padded with this solution, the pressure at the nip being adjusted in a manner such that the fabric retains 7 $ of its dry weight of dyestuff solution.

The fabric so treated is dried, impregnated at room temperature with a solution containing 10 parts of sodium hydroxide and 300 parts of sodium chloride per litre, squeezed to a li uor ick-u of 7 and then steamed for 60 seconds at 100 to 101°C. The material is then rinsed, treated in a 0.5 sodium bicarbonate solution, rinsed, soaped at the boil for 15 minutes in a 0.3$ solution of a non-ionic detergent, rinsed again and then dried.

Printing prescription: 2 Parts of dyestuff are mixed with 20 parts of urea, the mixture is dissolved in 28 parts of water and the solution is stirred into 40 parts of a 5$ sodium alginate thickener. 10 Parts of a 10$ sodium carbonate solution are then added.

A cotton fabric is pri ited with this printin paste on a roller printing machine, dried, and then steamed for 8 minutes at 100°C i£ saturated steam. The printed fabric is then thoroughly rinsed in cold and hot water and dried.

Example 5 3-Acetylamino-1-aminobenzene-6-sulphonic acid is diazotized, coupled with 1-naphthyl-( 2* )-3-carboxy-5-pyrazolone-4* ,6' ,8'-trisulphonic acid and the acetyl group in the product so obtained is split off by heatin with a sodium hydroxide solution. 69· 4 Parts of the aminoazo dyestuff so obtained are dissolved in 800 parts of water and the solution is added to an ice-cold suspension of 19 parts of cyanuric chloride. The mixture is stirred for several hours at a temperature between 5 and 10°G and the pH is kept at between 4 and 5 by the addition of a dilute sodium hydroxide solution. After condensation, 20 parts of ammonia (25$) are added and the batch is heated for 3 to. 4 hours at 35 to 40°C, The yellow dyestuff that forms is salted out, filtered and dried. It dyes cotton strong yellow tints. obtained by replacing the 3-acetylamino-l-aminobenzene-6-sulphonic acid by 4-acetylamino-1-aminobenzene-3-sulphonic acid.

Example 6 6 Parts of asymmetric dimethylhydrazine are added drop-wise to a solution of the dyestuff obtained in the manner described in Example 5 in 800 parts of water and the mixture is stirred for one hour at room temperature. The solution so obtained is evaporated to dryness at low temperature in vacuo* The dyestuff so obtained, which no longer contains organic chlorine, dyes cotton pure yellow tints.

Example 7 A solution of 19 parts of cyanuric chloride in 60 parts of acetone is added to a neutral solution of 37·6 parts of 1,3-phenylenediamine-6-sulphonic acid in 600 parts of water. The mixture is stirred for one hour at a temperature between 5 and 10°C and then for two hours at 20°C, the reaction being kept slightly acid to neutral by the addition of dilute sodium hydroxide solution. After condensation, the batch is tetra-zotized with hydrochloric acid and 14 parts of sodium nitrite and the tetrazo compound is introduced into an aqueous solution comprising 100 parts of 1-naphthyl-(2* )-3-carboxy-5-pyrazolone-41 »6' ,8*-trisulphonic acid which has been neutralized with sodium hydroxide, and 40 parts of sodium bicarbonate. After coupling, the dyestuff is precipitated by the addition of potassium chloride, filtered and dried. It dyes cotton pure yellow tints.

The following Table contains further Examples of components from which dyestuffs can be obtained by the process described in Example 3· The amines obtained from the compounds listed in Columns I and II are diazotized and coupled with the pyrazolones listed in Column III.

I II III IV 2,4,5,6-tetra- 1 ,3-diamino- 1-naphthyl-(2' )- yellow chlorop rimi- benzene-6- 3-carboxy-5-pyra- dine sulphonic zolone-4* jS'- acid disulphonic acid 2,4» 6-trichlaro- II 1-naphthyl-(2' )- It pyrimidine 3-carboxy~5-pyra- zolone-4*,6,,8*- tris lphonic acid 2, 4» 6-tribromo- II II II pyrimidine 2,6-dichloro- tl II It pyrimidine-4- carboxylic acid 2,4-cichloro- 11 II N pyrimidine-5- sulphonic acid -nitro-6- w II M methyl-2,4- dichloro- pyrimidine 2, 4-diehloro- M II II pyrimidine-5- carboxylic acid chloride acrylic acid M II II chloride β-chloro- 1 , 4-phenylene- 1-naphthyl-(2t )- reddish propionic acid diamine-6- 3-carboxy-5- yellow chloride sulphonic pyrazolone-41 ,8'- acid disulphonic acid α,β-dichloro- tl •1 II propionic acid chloride 2,4-dichloro-6- II II yellowish phenylamino- orange triazine-4!- sulphonic acid • • Example 8 Parts of copper phthalocyanine are stirred into 260 parts of chlorosulphonic acid in a manner such that the temperature does not exceed 30°C. The batch is stirred for 30 minutes at room temperature. The temperature of reaction mixture is brought up to 130 to 133°C during 1-jr hours and ¾pt at That temperature for another 4 hours. The reaction mixture is allowed to cool and is then discharged on to a mixture comprising 250 parts of water, 140 parts of sodium chloride and 1,500 parts of comminuted ice while stirring. The batch is stirred for a short time, filtered, and the filter residue is washed with a mixture of 300 parts by volume of saturated sodium chloride solution and 150 parts of ice. A sulphochloride is obtained which, in the form of a moist paste, is condensed wit the aminochlorotriazine intermediate product, which is prepared follows:- 37 Parts of the compound of the formula are dissolved in 500 parts of water in the form of the sodium salt and the solution is neutralized. The copper phthalo-cyanine sulphochloride paste obtained in the manner described in the preceding paragraph is suspended therein at 0 to 5°C in the presence of comminuted ice and the batch is neutralized with . dilute sodium hydroxide solution. The mixture is stirred well for 6 hours at 5 to 0°C and the pH is kept at 7.5 to 8 by strewing in about 15 parts of sodium carbonate in portions.

The temperature is allowed to rise slowly to 20°0 and stirring is continued for a further 12 hours. The solution that forms is adjusted to pH 7 with dilute hydrochloric acid, 15 to 20$ of sodium chloride is added, the batch is filtered and the condensation product so obtained is washed well with 200 parts by volume of a 1 $ sodium chloride solution.

The moist filter cake is stirred into 400 parts of ice-water and diazotized at 0 to 5°C with a 2 sodium nitrite solution in the presence of 60 parts by volume of a 30# (approximately) aqueous solution of e-naphthalene sulphonio acid containing sulphuric acid. The equivalent amoun (calculated on the consumption of nitrite) of 1^naphtnyl-(2* )-3-carboxy-5-pyrazolone-4r,6 ,8*-trisulphonic acid is dissolved in 500 parts of water in the presence of 50 parts of sodium ¾ carbonate; the diazo suspension is added thereto. The temperature is kept at 5 to 10°C for 6 hours by the addition of ground ice, the batch is heated slowly to 20°G and stirring is continued for a further 15 hours.

The dyestuff is precipitated at 30 to 35°0 by the addition of 5% sodium chloride to the reaction mixture, isolated by filtration and then dried in vacuo at 40 to 60°C.

It dyes cotton, wool and polyamide fibres brilliant, yellowish green tints fast to washing*

Claims (1)

1. HAVING NOW particularly described and ascertained t nature of our said invention and in what manner the same is we declare that what we claim is A process for the manufacture of a reactive dyeetuff of the formula in which one represents a grouping of the formula and the other X represents a hydrogen atom or an T represents a hydrogen a methyl group or an Z represents a represents an integer not less than 2 and in whioh at least one of the symbols and represents an wherein such an azo dyeetuff prepared by coupling a corresponding or tetrazo compound with a or aoid or by condensing a corresponding dyeetuff with an aoylating A process as claimed in Claim wherein the substituent Z is a heterocyclic A process as claimed in Claim 1 or wherein a dyeetuff of the formula indicated containing a pyrasolone residue in whioh Z represents a heterocyclic substituent is A process as claimed in any one of Claims 1 to wherein an azo dyestuff containing a residue of the formul is at group with an aold halide containing a process as claimed Claim wherein the aold contains a heterocyclic A process as in any one of Claims 1 to wherein a of the formula used in which R represents a residue having a sulphonic group in or or in A as claimed in Claim wherein a compound obtained rom an amine of the formula which Y represents a chlorinated quinasoline or oxaline residue A process as claimed in any one of Claims 1 to wherein the acid halide used is a quinasoline or quinoxaline compound oontaining at least two chlorine A process as claimed in Claim tha condensation effected with ehloride and a ehlorina atom in tha dyeetuff obtainad which contains a residue ia replaced by condensation with or an A process aa claimed in any one of Claims 1 to vherain the reactive obtained la converted into a reactive dyeetu by with a tertiary amine or A process aa claimed in Claim wherein the hydraaine used A proceas for the manufacture of aa claimed Claim 1 from an of the components specified herein as A process for manufacture of dyeetuffs conducted substantially aa ths or with reference to the Table The dyeetuffs obtainable by a prooees claimed in any one of Claims 1 to dysetuffs of the formula whioh one X represents a grouping of the formula and the other repreaente a hydrogen atom or an T represents a hydrogen a methyl group or an Z re resents a substltuent and represents an not less than 2 and in vhioh at least of the symbols X and T represents an A prooesa ae claimed in Claim wherein Z is a heterocyclic Azo as in Claim 15 or 16 in which the azo and the group are in to each dyestuf s of the formula in which Z represents a a or a or residue or a residue and represents a residue containing a acid group in or or in An dyestuff as claimed in Claim 15 obtained from any of the specified herein substantially as Any one of the dyestuffs obtainable as described in the Examples or with reference to the Table A dyeing or printing process which a dyestuff claimed in any one of Claims to 20 dyeing or printing process as claimed in Claim 21 substantially as described and exemplified Dyeing or printing preparations which contain at least one of the dyestuffs claimed in any one of the 14 to A dyeing or printing preparation obtainable substantially as described in any one of the Examples Material dyed or printed by a process claimed in Claim 21 or Dated this 19th day of 1966 For the Applicants GO insufficientOCRQuality