GB2039289A - Reactive dyestuffs - Google Patents

Abstract

Dyestuffs of the formula <IMAGE> wherein U is Z, N(R)-T, V is Z2-N(R)-P, W is Z1-N(R)-T1-N(R)-Z3-N(R)-P n,m,P = 0,1N2, and if P=O n and m >/= 1, A is the radical of a chromophore, T is a 1,3,5-triazinyl radical substituted in the 4 and 6 positions, T1 is a 1,3,5-triazinyl radical, Z1 and Z2 are direct bonds or bridge members linked to a C atom of an aromatic-carbocyclic or aromatic heterocyclic ring in A, Z3 is a bridge member, R is HN a substituent and P is a 2-fluoro-5-chloro-6-methyl pyrimidyl radical and their use for the dyeing and printing of materials containing hydroxyl groups and nitrogen groups, in particular fibre materials of cellulose or wool.

Description

SPECIFICATION Reactive dyestuffs The present invention relates to reactive dyestuffs which contain at least one 1,3,5-triazinyl radical and at least one 2-fluoro-5-chloro-6-methylpyrimidyl radical.

Preferred dyestuffs correspond to the formula

wherein

n,mandp=0,1or2,andifp=0,nandm1and,preferably,ifp=1or2,nandm=0, A = the radical of a chromophore, T = a 1,3,5-triazinyl radical substituted in the 4-position and 6-position, T1 = a 1,3,5-triazinyl radical, preferably with a fibre-reactive su bstitutent which can be split off as an anion, Z1 and Z2 = a direct bond or a bridge member linked to a C atom or an aromatic-carbocyclic or aromatic-heterocyclic ring in A, Z3 = a bridge member, R = H or a substituent and P = 2-fluoro-5-chloro-6-methylpyrimidyl.

Preferred dyestuffs are those in which p = 1 and m and n = 0, those in which p = 0 and n and m = 1, and also those in which T = a fibre-reactive 1,3,5-triazinyl radical, and, quite generally, water-soluble dyestuffs.

Particularly suitable radicals A are those of monoazo or polyazo dyestuffs, optionally containing metals, anthraquinone dyestuffs, phthalocyanine dyestuffs, oxazine dyestuffs, nitrodiphenylamine dyestuffs and formazan dyestuffs.

Examples of suitable bridge members Z1 and Z2 are alkylene, CO and SOp. Z1 and Z2 preferably represent a direct bond.

Suitable bridge members Z3 are, in particular, optionally substituted phenylene, naphthylene and alkylene.

Substitutents which may be mentioned are: sulpho, C1-C4-alkyl, C1-C4-alkoxy and halogen. The following bridge members may be mentioned as examples:

R preferably represents H or CH3.

Preferred dyestuffs are those of the formulae (Il)-(VIII) and metal complexes thereof:

K1-N=N-D1-NH-T3-NH-Z3-NH-P (Ill A) D1-N=N-K1-NH-T3-NH-Z3-NH-P (Ill B)

R' = H, optionally substituted alkyl or aryl

wherein D = the radical of an aromatic-carbocyclic diazo component, preferably sulphophenyl, which is optionally substituted by methyl, ethyl, methoxy, ethoxy, chlorine, carboxyl or nitro, or optionally substituted sulphonaphthyl.

K = the radical of a coupling component which is phenolic or enolic or contains amino groups, in particular a coupling component of the hydroxybenzene, aminobenzene, hydroxynaphthalene, aminonaphthalene, amino-hydroxy-naphthalene, pyrazolone, pyridone, aminopyrazole or acetoacetic acid arylide series, T2 = a 1 ,3,5-triazinyl radical with at least one fibre-reactive substituent which can be split off as an anion, T3 = a 1 3,5-triazinyl radical with a fibre-reactive substituent which can be split off as an anion, Z3 = C2-C4-alkylene, 1,3-or 1 ,4-phenylene, optionally substituted by sulpho, carboxyl or methyl, or 1,8-, 2,5- or 2,6-diaminonaphthylene, optionally substituted by sulphonic acid.groups, B = SO3H, CH3 or Cl, B' = SO3H, CH3, OCH3 or NHacyl (acyl = -COCH3 or -CO-N H2), Q = CH3, COOH, CN or CONH2, Z4 = a direct bond or -CH2-, D1 = phenyl, optionally substituted by SO3H, CH3, C2H5, OCH3, OC2H5, Cl, COOH or NO2, or sulphonaphthyl, optionally substituted by Cl, NO2, OH or acylamino, and K1 = hydroxyphenyl, aminophenyl, hydroxynaphthyl, aminonaphthyl or aminohydroxynaphthyl, optional ly substituted by SO3H, COOH, C1-C4-alkyl, C1-C4-alkoxy, halogen (Cl or Br), acylamino, in particular C1-C4-alkylcarbonylamino, optionally substituted phenylcarbonylamino, ureido, nitro, OH or pyrazolon-5 yl.

Suitable metal complex dyestuffs are 1:1 and 1:2 metal complex reactive dyestuffs based on at least one metallisable dyestuff of the formula

wherein D2 = the radical of a metallisable diazo component with an OH or COOH group in the o-position relative to the azo bridge and K2 = the radical of a coupling component which couples in the o-position relative to a phenolic or enolic OH group.

Possible metals are, in particular, Cu, Cr and Co. In the case of the Cu complexes, the 1:1 complexes are of particular importance. In the case of the 1:2 complexes, the second dyestuff radical can likewise be derived from the formula (IX), it being possible for both radicals to be identical or different, or the second dyestuff radical can be a radical of any desired metallisable dyestuff.

Radicals derived from the formula (IX) are, of course, particularly suitable as the second dyestuff radical, it being possible for the dyestuffs to be symmetric or unsymmetric. Such dyestuffs contain two radicals W or U and V in the molecule.

Particularly valuable dyestuffs are 1:2 Cr complex dyestuffs and 1:2 Co complex dyestuffs based on identical dyestuffs (II and Ill), and in particular mixtures of the 1:2 Cr and 1:2 Co complexes of identical dyestuffs.

Symmetric or unsymmetric 1:2 Cr complexes and 1:2 Co complexes based on dyestuffs of the formula (IX), and mixtures thereof, are also preferred.

Preferred dyestuffs are, quite generally, the 1:2 Cr complexes and 1:2 Co complexes of dyestuffs of the formula D3-N=N-K3-Z1-N-W' (X) R wherein D3 = an optionally substituted o-hydroxy-phenyl, o-carboxy-phenyl or o-hydroxynaphthyl radical,

= the radical of an aminohydroxynaphthalene or aminophenol or a pyrazolone which contains amino groups, which radical couples in the o-position relative to the phenolic or enolic OH group, and

Examples of suitable radicals D2 and D3, in the case where the reactive group W is bonded to K2 or K3, are o-hydroxyphenyl, o-carboxyphenyl and o-hydroxynapthyl, which can contain substitutents such as sulpho, halogen, in particular Cl and Br, nitro, alkyl, in particular C1-C4-alkyl, and alkoxy, in particular C1-C4-alkoxy.

Examples of preferred radicals D2 and D3 are 2-hydroxyphenyl, 2-hydroxy-5-nitro-phenyl, 2-hydroxy-3sulpho-5-nitro-phenyl, 2-hydroxy-3-nitro-5-sulphophenyl, 2-hydroxy-5-sulphophenyl, 2-hydroxy-4sulphophenyl, 2-hydroxy-3-chloro-5-sulpho-phenyl, 2-hydroxy-5-chloro-phenyl, 2-hydroxy-3-sulpho-5chlorophenyl, 2-hydroxy-3-nitro-5-chlorophenyl, 2-hydroxy-3-chloro-5-nitrophenyl, 2-hydroxy-3,5dinitrophenyl, 2-hydroxy-3,5-dichlorophenyl, 2-hydroxy-4-nitro-phenyl, 2-hydroxy-5-methyl-phenyl, 2hydroxy-4-methyl-phenyl, 2-carboxy-phenyl, 2-hydroxy-4-sulpho-naphthyl and 2-hydroxy-4-sulpho-6-nitronaphthyl.

Examples of suitable radicals

Examples of suitable radicals -K2-Z1-N- and -K3-Z1.N- R R are o-hydroxy-amino-sulpho-naphthyl radicals and aminophenyl- and aminonaphthyl-pyrazolonyl radicals.

Examples of such radicals are in particular

wherein R1 = C1-C4-alkyl, COOH, CONH2 or CN and the ring A can contain further substitutents, in particular Cl, Br, C1-C4-alkyl, C1-C4-alkoxy orsulpho.

Particularly suitable radicals of this type are

Examples of radicals K2 and K3 which are free from reactive groups are o-hydroxyphenyl radicals, o-hydroxy-naphthyl radicals, o-hydroxy-sulphonaphthyl radicals, phenylpyrazolyl radicals and radicals of acetoacetanilides.

Examples of such radicals are in particular

wherein R1 = C1-C4-alkyl, CN, COOH or CONH2 and the ring A can contain further substitutents, in particular Cl, Br, C1-C4-alkyl, C1-C4-alkoxy or sulpho.

Particularly suitable radicals of this type are

wherein the ring B can contain further substituents, such as Cl, Br, C1-C4-alkyl, C1-C4-alkoxy or sulpho.

Preferred dyestuffs are the 1:2 Cr complexes and 1:2 Cr complexes and 1:2 Co complexes of dyestuffs of the formulae wherein

wherein R2 = NO2, SO3H or Cl, R3 = SO3H, halogen, in particular Cl, or C1-C4-alkyl and R1 = C1-C4-alkyl, CN, COOH or CON H2.

(The dyestuffs (Xl) - (XV) which contain NH2, acetylamino or benzoylamino instead of -NH-W1 are particularly suitable as the 2nd component for metal complex dyestuffs with only one reactive group, in particular for those with the particular dyestuffs Xl to XV).

Preferred dyestuffs are furthermore those of the abovementioned formulae in which

Amongst the dyestuffs (Xl) - (XV), those symmetric or asymmetric 1:2 Cr complexes or 1:2 Co complexes in which the 2nd dyestuff is likewise a dyestuff of the general formula (Xl) - (XV), or mixtures of these Cr and Co complexes, are preferred.

The following dyestuffs are preferred as the second component in 1:2 Cr mixed complexes and 1:2 Co mixed complexes with only one reactive radical:

Other suitable dyestuffs are described, for example, in Belgian Patent Specification 664,682.

The dyestuffs are prepared in a manner which is known per se, by reacting the corresponding dyestuffs or dyestuff products, for example diazo components or coupling components, containing amino groups with compoundsT-Y1 (XVII), P-Y1 (XVIII) or

wherein Y1 represents a group which can be split off as an anion, in particular halogen, and then converting the products into the end products.

Suitable starting dyestuffs are, in particular, the dyestuffs on which the dyestuffs Il-VIII are based and which contain a group -NHR, -NH2 or

The reaction is carried out in a known manner in an aqueous, organic-aqueous or organic medium at about 0-7o'C in the presence of acid-binding agents, such as sodium carbonate, sodium bicarbonate or dilute sodium hydroxide solution.

The metal complexes are prepared in a manner which is known per se: A) 1:1 or 1:2 metal complexes based on at least one metallisable dyestuff of the formula

are reacted with a compound of the formula

preferablv with 1 mol of \XXtx per -NH-R group. wheletll Y1 is a radical which can be split off, in particular halogen, such as Cl, Y = a substitutent and Z3 has the abovementioned meaning.

The 1:2 complexes are prepared in a known manner, by metallising the corresponding azo dyestuffs.

B) 1:1 or 1:2 metal complexes of dyestuffs of the formula (XX) are first reacted with 1 mol, per group -NH-R, of a compound (XXII)

wherein Y1 and Y2 = a radical which can be split off, in particular halogen, such as Cl, and Y = a substituent, and the product is then reacted with the equivalent amount of a compound of the formula

wherein R and Z3 have the abovementioned meaning.

The calculated amount of a solution of cyanuric chloride in an organic solvent, such as acetone, or of an aqueous suspension of cyanuric chloride is introduced, for example, into a solution or suspension of the metal complex dyestuff, adjusted to O > C, the pH being kept at 4-7 with an alkali, for example dilute sodium carbonate solution. The mixture is stirred at 0- until the starting dyestuff has disappeared and the calculated amount of an aqueous solution or aqueous

paste of HNZN < 9 R R Cl C113 R ' is then introduced. The pH of the reaction solution is kept 4-6.5 by adding an alkali, such as dilute sodium carbonate solution, and the reaction solution is warmed to 40-50ç. The reaction has ended after 2-5 hours.

C) Dyestuffs of the formula [D-N=N-K4NH (XXIII) R are first reacted according to one of the processes described in A and B to give reactive dyestuffs of the formula

and the reactive dyestuff is then optionally converted into the 1:1 or 1:2 metal complex dyestuff in a known manner.

D) Alternatively, a suitable coupling component is first reacted with the reactive component according to one of the processes described in A or B, the product is then coupled to a diazo component and the coupling product is metallised.

E) Chromium mixed complex reactive dyestuffs of the formula

are prepared by a process in which the 1:1 Cr complex, which is free from reactive groups, of one of the two monoazo dyestuffs is first prepared by customary processes, this complex is reacted with 2nd monoazo dyestuff, which is free from reactive groups, to give the chromium mixed complex and, finally, the mixed complex is converted into the reactive dyestuff by one of the processes described in A and B.

Preferred anthraquinone dyestuffs correspond to the formula

o / / sO3 wherein (xxI) o NH-W2 O NHW2 W2 = Z4-N-T1-N-Z3-N-P (XXVII) R R R Z4 = an arylene radical, preferably an optionally substituted phenylene, diphenylene or stilbene radical, and the ring I can be substituted, for example by halogen (chlorine or bromine), sulpho or nitro.

Preferred phthalocyanine dyestuffs correspond to the formula

wherein R5 and R6 = H or optionally substituted C1-C4-alkyl, or together C4-C5-alkylene, optionally interrupted by N or 0, and Pc = the radical of a Cu phthalocyanine or Ni phthalocyanine, the total number of substitutents on the Pc skeleton being S 4.

The new dyestuffs are particularly suitable for dyeing and printing materials containing hydroxyl groups and materials containing nitrogen groups, in particularfibre materials of cellulose or wool.

The present invention also relates to intermediate products of the formula

in particular those in which halogen = Cl and R = H.

Example 1 1. 1 Preparation of the reactive component A suspension of 48.3 parts of the condensation product of 2,5-diaminobenzenesulphonic acid and 2,4-difluoro-5-chloro-6-methylpyrimidine is introduced into a suspension of 26.7 parts of cyanuric chloride in 200 parts of ice-water at 0". During this addition, the pH value is kept at 6 by adding 20 % strength sodium carbonate solution dropwise. The reaction mixture is stirred at 0-5" until the pH value no longer changes.

1.2 A solution of 46.2 parts of 1 -amino-8-hydroxynaphthalene-3,6-disulphonic acid in 200 parts of water is introduced into the suspension of the reactive component prepared according to 1.1. During this addition, the pH value of the reaction mixture is kept at 6 by adding 20 % strength sodium carbonate solution dropwise, and the mixture is warmed slowly to 40". The mixture is stirred at this temperature until the pH value no longer changes. The intermediate product is precipitated with sodium chloride and filtered off at room temperature. 55.3 parts of the intermediate product obtained are suspended in 700 parts of water. The suspension obtained by diazotising 22 parts of 2-aminonaphthalene-1,5-disulphonic acid is then allowed to run in and the pH value is kept at 7-8 during the coupling by adding 20 % strength sodium carbonate solution dropwise. When the coupling has ended, the dyestuff which has precipitated is filtered off and dried at 50"C.

The reactive dyestuff corresponds to the formula

A brilliant bluish-tinged red reactive dyeing or a reactive print is obtained on cotton.

If equivalent amounts of 1-amino-8-hydroxynaphthalene-4,6-disulphonic acid (K-acid), 2-amino-S- hydroxynaphthalene-7-sulphonic acid (I-acid), 2-amino-5-hydroxynaphthalene-1 ,7-disulphonic acid or 2amino-8-hydroxynaphthalene-6-sulphonic acid (Gamma-acid) are used to prepare the coupling component instead of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid (H-acid), and equivalent amounts of 2-aminobenzenesulphonic acid, aniline, 5-methyl-,methoxy- or -ethoxy-2-aminobenzenesulphonic acid or 2-methyl- or -methoxy-5-aminobenzenesulphonic acid are used instead of the diazo component 2 aminonaphthalene-l ,5-disulphonic acid, valuable reactive dyestuffs for cotton which give orange-coloured to red shades are obtained.When 2,5-diaminobenzene-1,4-disulphonic acid, 2,5-diamino-4-carboxybenzenesulphonic acid, 2,4-diaminobenzenesulphonic acid, 2,4-diaminobenzene-1 5-disulphonic acid, 2,4diaminotoluene-5-sulphonic acid or 2,6-diaminotoluene-4-sulphonic acid are used instead of 2,5diaminobenzene-sulphonic acid, reactive components which are used for the preparation of the coupling components and which, with the diazo components indicated, give dyestuffs which are likewise valuable reactive dyestuffs, are built up.

1.3 0.1 mol of the monoazo dyestuff 1-(2,4-dichloro-1,3,5-triazin-6-ylamino)-3,6-disulpho-8-hydroxy-7-[(2- sulphophenyl)azo]-naphthalene is prepared in a known manner.

A paste of 0.1 of 4-(2'-fluoro-5'-chloro-6'-methyl-pyrimidylamino)-2-aminobenzenesulphonic acid is added to a solution of this monoazo dyestuff. The pH value is kept at 5.5 by adding a 10% strength sodium carbonate solution dropwise. The mixture is warmed to 30"C and stirred until the reaction has ended. The dyestuff of the formula

is then salted out with sodium chloride in the customary manner and isolated. After drying, a dark powder is obtained, which dissolves in water giving a red-coloured solution and dyes cotton with reactive dyeings in red shades or gives a red reactive print which is distinguished by a high fixing yield.

Example 2 2. 1, A solution of 27.2 parts of 2,4-diaminobenzene-sulphonic acid in 200 parts of water is introduced into the suspension of the reactive component prepared according to Example 1. During this addition, the pH value of the reaction mixture is kept between 5 and 6 by adding 20% strength sodium carbonate solution dropwise, and the mixture is warmed slowly to 40 . The mixture is stirred at this temperature until the pH value no longer changes. The intermediate product is salted out with NaCI and filtered off at room temperature.

2.2 46 parts of the intermediate product obtained are suspended in 1,000 parts of water and diazotised in the customary manner. The viscous suspension obtained is introduced into a solution of 21.6 parts of 1-(4'-sulpho-2'-methylphenyl)-5-pyrazolone-3-carboxylic acid in 250 parts of water at +5 . The pH is kept at 5-6 during the coupling by adding 20 % strength carbonate solution dropwise. When the coupling has ended, the reaction mixture is adjusted to pH 7 and the dyestuff is salted out with NaCI. The dyestuff of the formula

which has precipitated is filtered off and dried at 50". A brilliant greenish-tinged yellow reactive dyeing or a yellow reactive print is obtained on cotton.

If the pyrazole compounds listed in the following table are used instead of the above coupling component, dyeings or prints, the colour shade of which is indicated, are obtained.

Colour shade 1-(3'-Sulphophenyl)-3-methyi- greenish-tinged yellow pyrazolone 1-(4'-Sulphophenyl)-3-methyl- somewhat reddishpyrazolone tinged yellow 1-(2',5',4'-Dichlorosulphophenyl)- yellow 3-methyl-pyrazolone 1-(2'-Methyl-4'-sulphophenyl)-3- yellow methyl-pyrazolone 1-(4'-Sulphophenyl)-3-pyrazolone- somewhat reddish3-carboxylic acid tinged yellow 1-(3'-Sulphophenyl)-3-methyl-5- greenish-tinged yellow amino-pyrazole 1-(2'-Naphthyl-8'-sulpho)-3-methyl- greenish-tinged yellow 5-amino-pyrazole Example 3 55.3 parts of the coupling component obtained according to Example 1 are suspended in 700 parts of water.The suspension obtained by diazotising 46 parts of the intermediate product prepared according to 2.1 is then allowed to run in at 5" and the pH value is kept at 7.5-8.5 during the coupling by adding 20 % strength sodium carbonate solution dropwise. When the coupling has ended, the dyestuff of the formula

is precipitated with about 10 % of the volume of KCl,filtered off and dried at 50 . A brilliant bluish-tinged red reactive dyeing or a reactive print is obtained on cotton.

Example 4 0.1 mol of 4-(2'-fluoro-5'-chloro-6'-methylpyrimidylamino)-2-aminobenzenesulphonic acid are stirred in 350 parts of water and the mixture is combined with a suspension, prepared in the customary manner, of 0.1 mol of cyanuric chloride in 300 parts of water and ice. The mixture is stirred at 0" until the condensation reaction has ended (about 5 hours), the pH being kept at 5 to 6 by adding 10% strength sodium carbonate solution dropwise. This suspension of the reactive component is combined with a suspension of 42.1 parts of 4,8-disulpho-2-[(2-methyl-4-amino-phenyl)-azo]-naphthalene (aminoazo compound) in 250 parts of water, the mixture is warmed slowly to 40" and a pH of 5.5 - 6 is maintained by adding 20 % strength sodium carbonate solution dropwise, until the condensation reaction has ended.The reactive dyestuff obtained is isolated with sodium chloride and dried. A dark powder which gives a reddish-tinged yellow reactive print on cotton is obtained.

If 4,8-disulpho-2-[(2-methyl-4-amino-5-methoxy-phenyl)-azoj-naphthalene, 4-amino-2-methyl-5methoxyphenylazobenzene-4'-sulphonic acid or -3'-sulphonic acid or 4-amino-3-methoxyazobenzene-3'- or -4'-sulphonic acid are used as the aminoazo compound instead of the aminoazo compound used above, reddish-tinged to greenish-tinged yellow reactive prints are obtained.

If 4-(2'-fluoro-5'-chloro-6'-methylpyrimidyl-amino)-2-aminobenzene-1 ,5-disulphonic acid or 4-(2'-fluoro5'-chloro-6'-methylpyrimidyl-amino)-1 aminobenzene-2-sulphonic acid or -2,5-disulphonic acid are used instead of the abovefluoro-amino compound, yellow reactive dyestuffs are likewise obtained.

Example 5 0.1 mol of the diazo component prepared by subjecting 0.1 mol of cyanuric chloride to a condensation reaction with 0.1 mol of 2,4-diaminobenzenesulphonic acid and subjecting the product to a second condensation reaction with 0.1 mol of 3-aminobenzenesulphonic acid is stirred in 400 parts of water with 30 parts of 28 % strength hydrochloric acid and is diazotised directly at 0-5" in the customary manner. The diazotised directly at 0-5" in the customary manner.The diazonium salt suspension obtained is combined after destroying excess nitrous acid with amidosulphonic acid, with 0.1 mol of a solution of the coupling component 1 -(2-fluorn-5-ch Ioro-6-methyl-pyrimid-4-yI-amino )-8-hydrnxy-naphtha lene-3,6-disu Iphonic acid, which was prepared in a known manner, and coupling is carried out at 0-5" and at pH 6-8 by adding 20 % strength sodium carbonate solution.

After isolating and drying the product, a dark powder which dissolves in water giving a red-coloured solution is obtained. Cotton is dyed in red shades by the dyeing procedure for reactive dyestuffs. The reactive print obtained on cotton is red. The fixing yield of the dyestuff is very good. If the equivalent amount of the pyrimidyl-naphthalene-4,6-disu Iphonic acid is used as the coupling component instead of the pyrimidyl-naphthalene-3,6-disulphonic acid, red reactive dyestuffs are likewise obtained; using 2-(2-fluoro 5-chloro-6-methylpyrimid-4-ylamino)-5-hydroxy-naphthalene-7-sulphonic acid as the coupling component, orange to red reactive dyestuffs are obtained.

If the equivalent amounts of 2-or 4-aminobenzenesulphonic acid, 3-amino-4- or -6-methylbenzenesulphonic acid, 5-amino-2-methoxy- or -ethoxy-benzenesulphonic acid, aniline, o-toluidine, ammonia or diethylamine are used for the preparation of the diazo component instead of 3-aminobenzenesulphonic acid, red or orange-coloured reactive dyestuffs which have a good fixing yield are likewise obtained.

If the equivalent amounts of 2,5-diaminobenzenesulphonic acid or ,4-disulphonic acid are used for the preparation of the diazo component instead of 2,4-diaminobenzenesulphonic acid and the abovementioned amino compounds are used for the second condensation reaction, red-violet to blue-violet reactive dyestuffs are obtained.

Example 6 0.1 mol of the condensation product of 2,4-difluoro-5-chloro-6-methyl-pyrimidine and 2,5diaminobenzenesulphonic acid (diazo component) are stirred in 300 parts of water with 30 parts of 28 % strength hydrochloric acid, and are diazotised with 70 parts of 10 % strength sodium nitrite solution at 0 to 10" in the course of one hour.

When the diazotisation has ended, excess nitrous acid is destroyed with amidosulphonic acid.

The diazonium salt solution is combined with a solution of 0.1 mol of the coupling component 1 -[2-chloro-4-(3-sulphophenylamino)-1 ,3,5-triazin-6-yl-amino)-8-hydroxy-naphthalene-3,6-disulphonic acid, which was prepared in the customary manner, and coupling is effected at 0-5" and at pH 6 to 8 by adding 20 % strength sodium carbonate solution dropwise.

The dyestuff obtained is isolated with sodium chloride. After drying, a dark powder which dissolves in water giving a violet-coloured solution and gives a violet-coloured reactive print on cotton is obtained.

If triazinyl-naphthalene-4,6-disulphonic acid is used as the coupling component instead of the 3,6disulphonic acid, violet reactive prints are obtained. Using 2-[2-chloro-4-(3-sulphophenylamino)-1,3,5- triazin-6-yl-amino]-5-hydroxy-naphthalene-7-sulphonic acid, red shades are produced.

If the condensation products obtained using 2,4-diaminobenzenesulphonic acid or 2,4-diaminobenzene1,5-disulphonic acid are used instead of the above diazo component, after diazotisation and coupling of the diazotisation product with the coupling components indicated, bifunctional reactive dyestuffs which dye cotton in orange-coloured or red shades or give orange-coloured or red prints on cotton are obtained; using 2,5-diaminobenzene-1 ,4-disulphonic acid, red to violet colour shades are obtained.

If 2-or 4-sulphophenylamino-, 2,4-, 2,5-or 3,5- disulphophenylamino-, 2-methyl- or -methoxy-4- or -5-sulphophenylamino-, 4-methyl-, -methoxy- or -ethoxy-2- or -5-sulphophenylamino-, 2-or on 4-hydroxy-3,5- disulphophenylamino- or N-methyl--a minomethanesulphonic acid-triazinylnaphthalenesulphonic acid is used as coupling components instead of the 3-sulphophenylamino-triazinyl-naphthalene compounds, valuable reactive dyestuffs which give shades similar to those indicated above are obtained.

Example 7 0.1 mol of the copper complex of an aminoazo dyestuff, of the formula

prepared in a known manner, by coupling diazotised 2-amino-naphthalene-4,8-disulphonic acid with 1 -acetylamino-8-hydroxynaphthalene-3,6-disulphonic acid, subjecting the coupling product to oxidative coppering and then saponifying the N-acetyl group under alkaline conditions, is dissolved in 750 ml of water at a neutral pH value. A solution of 0.1 mol of 4-(2-fluoro-5-chloro-6-methyl-pyrimidyl)-amino-2aminobenzenesulphonic acid in about 1,200 ml of water is added to a suspension of 0.1 of cyanuric chloride in ice-water at 0" and the pH is kept at 5.5 by adding 20 % strength sodium carbonate solution dropwise, until the reaction has ended. This mixture is then combined with the dyestuff solution described above.A pH value of 5-6 is maintained, at 40"C, by adding 20 % strength sodium carbonate solution dropwise, until the condensation reaction has ended. The product is isolated in the customary manner, for example by salting out with sodium chloride. The dried dyestuff is a dark powder which dissolves in water giving a blue-coloured solution and dyes cotton in dark blue shades with a good fixing yield by dyeing and printing processes known for reactive dyestuffs.

If an equivalent amount of 5-(2-fluoro-5-chloro-6-methyl-pyrimidyl)-amino-2-aminobenzenesulphonic acid is used for the preparation of the reactive component instead of 4-(2-fluoro-5-chloropyrimidyl)-amino-2aminobenzenesulphonic acid, a similar dark blue reactive dyestuff is obtained.

If the copper complex compounds of the formulae

prepared in the customary manner are used as the dyestuff component, after reaction with the reactive components described, reactive dyestuffs which dye cotton in violet shades are obtained.

If the copper complex of a disazo dyestuff, of the formula

is used as the dyestuff component and the reaction is carried out with the reactive components described above, dark blue reactive dyestuffs are obtained.

If the copper complex dyestuffs of the formulae

(colour shade: blue) (colour shade: blue) (colour shade: red-violet) (colour shade: red-violet) are used, after reaction with the above reactive components, reactive dyestuffs giving the shades indicated are obtained.

The dyestuffs can also be prepared as follows: The abovementioned solution of 0.1 mol of the above copper complex of an aminoazo dyestuff is first reacted with a suspension of 0.1 mol of cyanuric chloride at 0-5". A suspension of 0.1 mol of 4- or 5-(2-fluoro-5-chloro-6-methyl-pyrimidyl)-amino-2-aminobenzenesulphonic acid is then added and the condensation reaction is effected at 30-45"C and at pH 5-7, 20% strength sodium carbonate solution being added dropwise. The dyestuffs obtained are salted out in the customary maner, for example with NaCI, and isolated. They are identical to the dyestuffs prepared by the above process.

Example 8 Cellulose fabric is printed with a printing paste consisting of 80 g of dyestuff of Example 1, 150 g of urea, 20 g of sodium bicarbonate, 10 g of sodium m-nitrobenzenesulphonate, 240 g of water and 500 g of 4 % strength alginate thickener, dried, steamed at 1 00"C for 2 minutes and rinsed with hot water. A red print with good fastness to wet processing and a high fixing yield is obtained.

Example 9 Asolution of 18.5 parts by weight of cyanuric chloride in 140 parts by volume of acetone is added dropwise to a solution of the 1:2 Co complex obtained from 0.1 mol of the monoazo dyestuff of the formula

in 600 parts by volume of water at 0"C in the course of 30 minutes.The pH is kept at 4-5.5 with about 28 parts by volume of 20 % strength by volume sodium carbonate solution and the mixture is stirred at 0"C for 2 hours. 0.1 mol of the reactive component of the formula

(prepared by reacting 2,4-difluoro-5-chloro-6-methyl-pyrimidine with 2,4-diamino-benzene-1-sulphonic acid) is then introduced and the mixture is stirred, warmed to 40-50"C and stirred at 40-50"C for 6 hours, the pH being kept at 5-6 with 20 % strength by volume sodium carbonate solution. The mixture is then clarified and the filtrate is evaporated at 70-80"C in a rotary evaporator.

Example 10 1,000 parts by volume of an aqueous suspension of 0.1 mol of the reactive component

are added dropwise to a solution of the 1:2 Cr complex obtained from 0.1 mol of the monoazo dyestuff of the formula

in 600 parts by volume of water at 40-50"C and at pH 6.5. The pH is kept at 5.5-6.5 with 20 % strength by volume sodium carbonate solution and the mixture is stirred at 40-50" for 5 hours. After clarifying, the filtrate is evaporated to dryness at 70"C In a rotary evaporator. When powdered, the dyestuff is a black powder which gives a greenish-tinged grey print with good fastness properties when printed on cotton and viscose staple by the printing process for reactive dyestuffs.

The reactive component is prepared by stirring 0.1 mol of the compound

in 520 parts by volume of water and cooling the mixture to 0"C with 140 parts by weight of ice. A solution of 18.5 parts by weight of cyanuric chloride in 140 parts by volume of acetone is added dropwise in the course of 45 minutes, the pH being kept at 5.5-6.5 with 20 % strength by volume sodium carbonate solution. The mixture is subsequentiy stirred at 0-2"C and at pH 5.5-6.5 and is clarified.

Example 17 A solution of the 1:2 Cr complex obtained from 0.2 mol of the monoazo dyestuff of the formula

and of the 1:2 Co complex obtained from 0.1 mol of the same monoazo dyestuff in 1,150 parts by volume of water is cooled to 0 by external cooling. The pH of the solution is 6. A suspension of 55.6 parts by weight of cyanuric chloride in 100 parts by volume of water, 200 parts by weight of ice and 4.15 parts by weight of a commercially available non-ionic emulsifier based on a fatty alcohol polyglycol ether is then introduced.The mixture is stirred at 0"C for 2 hours and the pH is kept at 5-6 with 20 % strength by volume sodium carbonate solution. 0.3 mol of the reactive comDonent

is then added as an aqueous paste and the batch is warmed to 40-50"C and stirred at 40-50"C for 4 hours, the reaction solution being kept at a pH of 5-6 with 20 % strength by volume sodium carbonate solution. The mixture is clarified with a little active charcoal and the solution is evaporated at 70"C in a rotary evaporator.

After powdering the residue, a black powder which gives, on cotton and viscose staple, neutral black reactive prints with good fastness properties is obtained.

In an analogous manner to that described in Examples 1 - 3 and using the correspondng starting compounds, the dyestuffs described in the following table, which dye cellulose materials in the colour shades indicated, are obtained.

Dyestuff Metal Colour complex

greenish 1:2 Cr tinged black 1:2 Cr brown 1:2 Co brown 1:2 Co brown 1:2 Co brown brownish1:2 Co tinged yellow brownish1:2 Co tinged orange reddish1:2 Co tinged brown reddish1:2 Co tinged brown 1:2 Co black 1:2Cr black Dyestuff Metal Colour complex

1:2 Co corinth Mixture of 1:2 Cr and 1:2 Co in the molar black ratio 2:1 Mixture of 1:2 Cr and 1:2 Co in black the molar ratio 2:1 1:2 Cr blue reddish tinged 1:2 Co navy blue 1:2 Cr navy blue 1:2 Co corinth greenish1:2 Cr tinged grey 1:2 Co corinth 1:2 Cr grey 1:2 Cr grey 1:2 Cr grey Dyestuff Metal Colour complex

1:2 Cr grey Mixed cobalting in the molar Metal Colour ratio 1:1 complex

1:2 Co brown Mixture of the 1: :2 Co complexes in the molar Colour ratio 1:1

brown brown brown brown Dyestuff Metal Colour complex

1:2 Cr black 1:2 Co corinth 1:2 Co brown Mixture of 1:2 Cr and 1:2 Co in black the molar ratio 2:1 Mixture of 1:2 Cr and 1:2 Co in black the molar ratio 2:1 Mixture of 1:2 Cr and 1:2 Co in black the molar ratio 2:1 Example 12 0.1 mol of the 1:1 Cr complex of the monoazo dyestuff of the formula

and 0.1 mol of the monoazo dyestuff of the formula

are stirred in 700 parts by volume of water, the mixture is warmed to 70" and the dyestuffs are converted into the mixed chromium complex at a pH of 6-7 in the course of 2 hours.The mixture is clarified with a little active charcoal, and 1,000 parts by volume of an aqueous suspension of 0.1 mol of

(the preparation is described in Example 10) are added to the filtrate and the mixture is stirred at 40-50"C for 5 hours, the pH being kept at 5-6 with 20 % strength by volume sodium carbonate solution.

To isolate the reactive dyestuff, the mixture is evaporated at a water bath temperature of 70" in a rotary evaporator. A black dyestuff powder which gives a black print with good fastness properties when printed onto cotton by the printing process for reactive dyestuffs is obtained.

In an analogous manner and using the corresponding starting compounds, the dyestuffs described in the following table, which dye cellulose materials in the colour shades indicated, are obtained.

Mixed chromium complex Colour

brown olive olive green brown brown Mixed Chromium Complex Colour

brown brown brown brown brown brown black black Example 13 150 ml of an hydrous HF are initially introduced into a stirred V4A steel autoclave with a reflux condenser, manometer and relief valve, and 197.5 g of 2,4,5-trichloro-6-methyl-pyrimidine are added dropwise at 0-5"C.

The autoclave is closed, N2 is forced in to a pressure of 5 bars and the autoclave is then heated. From 80", a rise in pressure due to the HCI formed can be observed, and is very rapid at about 1 00"C. The pressure is adjusted to 18 bars via the relief valve. The autoclave is heated to 165"C under this pressure, according to the rate at which the HCI is evolved. The mixture is subsequently allowed to react at this temperature for 11/2 hours and is cooled and distilled. After first runnings of HF, 150 g of a coarse distillate and 11 g of a distillation residue are obtained. According to gas chromatography, the distillate has the composition: 76.5 % of 2,4-difluoro-5-chloro-6-methyl-pyrimidine,19.4 of 2,5-dichloro-4-fiuoro-6-methyl-pyrimidine and 1.4 % of 2,4,5-trichloro-6-methylpyrimidine.

Redistillation gives: 100 g of 2,4-difluoro-5-chloro-6-methylpyrirnidine as a liquid of boiling point 158 159"C and nD 1.4778 and 25 g of 4-fluoro-2,5-dichloro-6-methylpyrimidine with a boiling point of 86"/20 mars and nD 1.5178.

Claims (25)

1. A reactive dyestuff which contains at least one 1 3,5-triazinyl radical and at least one 2-fluoro-5-chloro6-methylpyrimidyl radical.

2. A reactive dyestuff according to claim 1 of the general formula (U)m~A~(V)n (W)p in which U denotes a radical of the general formula -Z1-N-T, R V denotes a radical of the general formula Z2-N-P, R W denotes a radical of the general formula -Z1-N-T1-N-Z3-N-P, R R R n,mandpare0, 1 or2,andifpisO,nandm1 andifpisl or2,nandmare0, A denotes a radical of a chromophore, T denotes a 1 ,3,5-trianzinyl radical substituted in the 4-position and 6-position, T1 denotes a 1,3,5-triazinyl radical, Z1 and Z2 denote a direct bond or a bridge member linked to a C atom of an aromatic-carbocyclic or aromatic-heterocyclic ring in A, Z3 denotes a bridge member R denotes a hydrogen atom or a substitutent and P denotes 2-fluoro-5-chloro-6-methylpyrimidyl.

3. A reactive dyestuff according to claim 2 in which p is 1 and m and n are 0, orp and m and n are 1.

4. A reactive dyestuff according to claim 2 or 3 in which TorT1 denotes a fibre-reactive triazinyl radical.

5. A reactive dyestuff according to any of the foregoing claims containing one or more groups which confer solubility in water.

6. A reactive dyestuff according to claim 4 in which T1 denotes a 1,3,5-trianzinyl radical with a fibre-reactive substitutent which can be split off as an anion under the dyeing conditions.

7. A reactive dyestuff according to claim 1 of the general formula in which

D denotes a radical of an aromatic-carbocyclic diazo component.

K denotes a radical of a coupling component which is phenolic or enolic or contains amino groups, T2 denotes a 1,3,5-triazinyl radical with at least one fibre-reactive substitutent which can be split off as an anion under the dyeing conditions, and P and R have the same meanings as in claim 1.

8. A reactive dyestuff according to claim 7 of the general formula

in which D, K and T2 have the same meanings as in claim 7 and P and R have the same meaning as in claim 1.

9. A reactive dyestuff according to claim 1 of the general formula

in which D and K have the same meanings as in claim 7, P and R have the same meanings as in claim 1, T3 denotes a 1,3,5-triazinyl radical with only one fibre-reactive substitutent which can be split off as an anion under the dyeing conditions, Z3 denotes a C2 to C4 alkylene, 1,3- or ,4-phenylene radical optionally substituted by sulpho, carboxyl or methyl, or a 1,8-, 2,5- or 2,6- diaminonaphthylene radical optionally substituted by one or more sulphonic acid groups.

10. A reactive dyestuff according to claim 9 of the general formula K1-N=N-D1-NH-T3-NH-Z3-NH-P (IIIA) or D1-N=N-K1-NH-T3-NH-Z3-NH-P (IIIB) in which Z3 and T3 have the same meaning as in claim 9, P has the same meaning as in claim 1, and D1 denotes a phenyl radical optionally substituted by SO3H, CH3, C2H5, OCH3, OC2H5, Cl, COOH or NO2, or a sulphonaphthyl radical optionally substituted by Cl, NO2, OH or acylamino, and K1 denotes a hydroxyphenyl, aminophenyl, hydroxynaphthyl, aminonaphthyl or aminohydroxynaphthyl radical, optionally substituted by SO3H, COOH, C1 to C4 alkyl, C1 to C4 alkoxy, chlorine, bromine, acylamino optionally substituted phenylcarbonylamino, ureido, nitro, hydroxyl or pyrazolon-5-yl.

11. A reactive dyestuff according to claim 10 in which K1 denotes a hydroxyphenyl, aminophenyl, hydroxynaphthyl. aminonaphthyl or aminohydroxynaphthyl radical optionally substituted by (C1 to C4 alkyl)-carbonylamino.

12. A reactive dyestuff according to claim 1 of the general formula

in which D and K have the same meanings as in claim 7, T3 has the same meaning as in claim 9, P has the same meaning as in claim 1, and B denotes a SO3H or methyl group or a chlorine atom.

13. A reactive dyestuff according to claim 1 of the general formula

in which D and T2 have the same meanings as in claim 7, P has the same meaning as in claim 1, and Z3 has the same meaning as in claim 9.

14. A reactive dyestuff according to claim 1 of the general formula

in which D has the same meaning as in claim 7, P has the same meaning as in claim 1, Z3 and T3 have the same meaning as in claim 9, R' denotes a hydrogen atom or an optionally substituted alkyl or aryl group, and O denotes a methyl, cyano, COOH or CONH2 group.

15. A reactive dyestuff according to claim 1 of the general formula in which P has the same meaning

(Fto355 1 -3 N:N,%,,NT3z3Nc;iiP) as in claim 1, (5l) Z3 and T3 have the same meanings as in claim 9, and B' denotes a SO3H, methyl, methoxy or NH acyl group in which "acyl" denotes - COCH3 - CO-NH2.

16. A reactive dyestuff according to claim 15 of the general formula

in which P has the same meaning as in claim 1, T2 has the same meaning as in claim 7, Z3 and T3 have the same meanings as in claim 9, D1 has the same meaning as in claim 10, and Z4 denotes a direct bond or -CH2-,

17. A dyestuff according to any of claims 7 to 9 and 12 in which K denotes a coupling component of the hydroxybenzene, aminobenzene, hydroxynaphthalene, aminonaphthalene, amino-hydroxy-naphthalene, purazolone, pyridone, aminopyrazole or acetoacetic acid arylide series.

18. A dyestuff according to any of claims 7 to 9, 12 to 14 and 17 in which D denotes a sulphophenyl radical which is optionally substituted by methyl, ethyl, methoxy, ethoxy, chlorine, carboxyl or nitro, or an optionally substituted sulphonahpthyl radical.

19. A 1:1 or 1:2 methyl complex reactive dyestuff according to claim 1, based on at least one metallisable dyestuff of the general formula

in which D2 denotes a radical of a metallisable diazo component with an OH or COOH group in the o-position relative to the azo bridge and K2 denotes a radical of a coupling component which couples in the o-position relative to a phenolic or enolic OH group, and in which W, U and V have the meaning indicated in claim 2.

20. A 1:2 Cr or 1:2 Co complex of a dyestuff according to claim 1 of the general formula D3-N=N-K3-Z1-N-W' R in which D3 denotes an optionally substituted o-hydroxyphenyl, o-carboxy-phenyl or o-hydroxynaphthyl radical,

denotes a radical of an aminohydroxynaphthalene or aminophenol or a pyrazolone which contains one or more amino groups, which radical couples in the o-position relative to the phenolic or enolic OH group, and W' denotes

in which R, T1, Z3 and P have the same meanings as in claim 2.

21. A reactive dyestuff as claimed in claim 1 as hereinbefore specifically identified.

22. A process for the production of a dyestuff as claimed in claim 1 when carried out substantially as described in any one of Examples 1 to 12.

23. A dyestuff as claimed in claim 1 when produced by the process of claim 22.

24. A process for dyeing or printing a material containing hydroxyl groups or a material containing nitrogen comprising treating the material with a dyestuff as claimed in any of claims 1 to 21 and 23.

25. A material containing hydroxyl groups or a material containing nitrogen when dyed or printed by the process of claim 24.