GB2034731A - Anthraquinone reactive dyestuffs - Google Patents

Abstract

Reactive dyestuffs of the formula <IMAGE> wherein S is a substituent, n is 0, 1 or 2, A is an aliphatic bridge member, X is F, Cl, Br, R1 and R2 independently denote hydrogen or an optionally substituted alkyl group, and R3 is a radical of the benzene or naphthalene series or optionally substituted alkyl, with the proviso that at least one of the radicals R2 and R3 contains at least one group conferring solubility in water and their use for the dyeing and printing of textile materials containing hydroxyl groups and nitrogen groups, in particular textile materials of natural and regenerated cellulose, and furthermore of wool, silk and synthetic polyamide and polyurethane fibres. Dyeings obtained are distinguished by good fastness properties to light and wet processing.

Description

SPECIFICATION Anthraquinone reactive dyestuffs The present invention relates to anthraquinone reactive dyestuffs of the formula

wherein A = an aliphatic bridge member, X=F,ClorBr, R1 and R2 = H or optionally substituted alkyl, R3 = a radical of the benzene or naphthaiene series or optionally substituted alkyl, at least one of the radicals R2 or R3 containing at least one group which confers solubility in water, preferably a SO3H or COOH group, S = a substituent, such as Cl, Br, hydroxyl and, in particular, SO311, and n=O-2.

Suitable alkyl radicals are, in particular, C 1-C4-alkyl radicals, which can contain substituents, such as hydroxyl, halogen, cyano, alkoxy, acyloxy and sulpho, carboxyl or XSO3H.

Examples of suitable radicals R3 are phenyl, 2-, 3- or 4-sulphophenyl, 2,4-, 2,5- or 3,5disuiphophenyl, 2-, 3- or 4-carboxyphenyl, 2-carboxy-4- or -5-sulphophenyl, 3-carboxy-5-sulphophenyl, 2-methyl-4,5-disulphophenyl, 4-methyl-2- or -3-sulphophenyl, 2-methyl-4- or -5-sulphophenyl, 2,6dimethyl-3- or -4-sulphophenyl, 2,4-dimethyl-6-sulphophenyl, 2-chloro-4- or -5-sulphophenyl, 3 chioro-2-methyl-6-sulphophenyl, 4-methoxy-2- or -3-sulphophenyl, 2-methoxy-5-sulphophenyl, 2-(p- hydroxyethoxy)-5-sulphophenyl, 4-(p-hydroxyethoxy)-2-sulpho- or -3-sulpho-phenyl, 4sulphomethylphenyl, 1,5-, 3,6-, 4,8-, 5,7- or 6,8-disulpho-2-naphthyl, 2,4-, 3,7-, 3,8-, 4,8-, 5,7- or 6,8disulpho-1 -naphthyl, 1,5,7- or 3,6,8-trisulpho-2-naphthyl and 3,5,7- or 3,6,8-trisulpho-1 -naphthyl, 2sulphoethyl, 2-sulphatoethyl, 3-sulpho-1-propyl and sulphomethyl.

Preferred groupings

are those of the formula

wherein R2' = H or CH3 and Ra' = sulphophenyl, disulphophenyl, sulphocarboxyphenyl, disulphonaphthyl or trisulphonaphthyl.

Suitable aliphatic bridge members are, for example, straight-chain or branched alkylene which has 2-1 5 C atoms in the chain and optionally can be interrupted by hetero-atoms, in particular 0 or N, and can contain optionally substituted C4-C6-cycloalkylene rings.

Examples of bridge members of this type are the following:

Preferred dyestuffs within the scope of the dyestuffs (I) are those of the formula

and in particular those of the formula

wherein X=ForCland A'= straight-chain or branched C2-C8-alkylene or

The new dyestuffs are obtained by subjecting anthraquinone compounds of the formula

A, S, n and R1 have the meaning indicated, to condensation reactions with dihalogenotriazinylamino compounds of the formula

wherein R2, R3 and X have the meaning indicated.

Examples of compounds of the formula (IV) which are suitable ffor the condensation reaction are 1 -amino-4-(2-amino-ethylamino)-anthraquinone-2-sulphonic acid, 1 -amino-4-(2-methylamino- ethylamino)-anthraquinone-2-sulphonic acid, 1 -amino-4-(3-amino-1 -propylamino)-anthraquinone-2sulphonic acid, 1-amino-4-(3-amino-2-methyl-1-propylamino)-anthraquinone-2-sulphonic acid, 1 amino-4-(4-a mi no-I -butylamino)-anthraquinone-2-sulphonic acid, 1 -amino-4-( 5-amino-1 - pentylamino)-anthraquinone-2-sulphonic acid, 1 -amino-4-(6-amino-1 -hexylamino)-anthraquinone-2 sulphonic acid, 1 mino-4-(2-amino-1 ,2-dimethyl-ethylamino)-anthraquinone-2-sulphonic acid, 1- amino-4-(3-amino-1,3-dimethyl-1-propylamino)-anthraquinone-2-sulphonic acid, 1-amino-4-(4amino-2-pentylamino)-anthraquinone-2-sulphonic acid, 1 -amino-4-(3-amino-2,2-dimethyl-1 - propylamino)-anthraquinone-2-su Iphonic acid, 1 -amino-4-(4-amino-2,3-dimethyl-1 -butylamino)anthraquinone-2-sulphonic acid, 1 -amino-4-(3-methylamino-1 -propylamino)-anthraquinone-2 sulphonic acid, 1 -amino-4-(4-methylamino-1 -butylamino)-anthraquinone-2-sulphonic acid, 1 mino-4- [2-(2-hydroxyethylamino)-ethylamino]-anthraquinone-2-sulphonic acid, 1 -amino-4-[2-(2 sulphatoethyla mino)-ethylamino]-anthraquinone-2-sulphonic acid, and 1-amino-4-[2-(2- sulphoethylamino)-ethylamino]-anthraquinone-2-sulphonic acid, and the condensation products of 1 mol of 1 -amino-4-bromoanthraquinone-2-sulphonic acid with in each case 1 mol of the following a liphatic-alicyclic amines: 1 -amino-3-aminomethylcyclohexane, 1 -amino-4-a minoethylcyclohexane, 1 ,4-bis-aminomethylcyclohexane, 1 ,3-bis-aminomethyl-cyclohexane, 1 -amino-4-(2-aminoethyl)cyclohexane, 1 -amino-3-(2-aminoethyl)-cyclohexane, 1-am ino-2-(2-aminoethyl)-cyclohexane, 1a m ino-4-(3-a mino-1 -propyl)-cyclohexane, 1 -amino-3-(3-amino- 1 -propyl)-cyclohexane, 1 -amino-2-(3- aminopropyl)-cyclohexane, 1 -amino-4-(4-amino- 1 -butyl)-cyclohexane, 1 -a minomethyl-4-(2- aminoethyl)-cyclohexane, 1-aminomethyl-2-(2-aminoethyl)-cyclohexane, 1 ,4-bis(2-aminoethyl)- cyclohexane, 1 ,3-bis-(2-aminoethyl)-cyclohexane, 1 1 -bis-(aminomethyl)-cyclohexane, 1 -amino-3 aminomethyl-3,5,5-trimethylcyclohexane, 1-a mino-methyl-2-(3-amino- 1 -prnpyl)-cyclohexane, 1 - aminomethyl-3-(3-amino-1 -propyl)-cyclohexane, 1 -aminomethyl-4-(3-amino- 1 -propyl)-cyclohexane and 1 ,2-bis-aminomethyl-cyclobutane.

Examples of compounds of the formula (V) which are suitable for the condensation reaction are 2,4-difluoro-6-(2'-, 3'- Qr 4'-sulphophenylamino)-triazine, 2,4-difluoro-6-(2',4'-, 2',5'-, 3',4'- or 3',5' disulphophenyiamino)-triazine, 2,4-difluoro-6-( 1 ',5'-, 3',6'-, 4',8'-, 5' ,7'- or 6',8'-disulpho-2' naphythylamino)-triazine, 2,4-difluoro-6-(2',4'-, 3',7'-, 3',8'-, 4',8'-, 5',7'- or 6',8'-disulpho-1 '- naphthylamino)-triazine, 2,4-difiuoro-6-(1',5',7'- or 3',6',8'-trisulpho-2'-naphthylamino)-triazine, 2,4 difluoro-6-(3' ,5' ,7'-trisulpho-1 '-naphthylamino)-triazine, 2,4-difluoro-6-(2'-, 3'- or 4' carboxyphenylamino)-triazine, 2,4-difluoro-6-(2'-carboxy-4'- or -5'-sulphophenylamino)-triazine, 2,4 difluoro-6-(3'-carboxy-5'-sulphophenylamino)-triazine, 2,4-difluoro-6-(2'-methyl-4'- or -5' sulphophenylamino)-triazine, 2,4-difluoro-6-(4'-methyl-2'- or -3'-sulphophenylamino)-triazine, 2,4 difluoro-6-(2'-methyl-4',5'-disulphophenylamino)-triazine, 2,4-difluoro-6-(2',6'-dimethyl-3'-sulpho- or 2',4'-dimethyl-6'-sulphophenyla mino)-triazine, 2,4-difluoro-6-(4'-methoxy-2'-sulpho- or -4'-methoxy 3'-sulpho- or -2'-methoxy-5'-su lphophenylamino)-triazine, 2,4-difluoro-6-(2'-ss-hydroxyethoxy-5'- su Ipho- or 4'-p-hydroxyethoxy-2'-su Ipho- or -4' -p-hydroxyethoxy-3 '-su Ipho-phenylam ino)-triazine, 2,4 difluoro-6-(2'-, 3'- or 4'-sulphophenylmethylamino)-triazine, 2,4-difluoro-6-(2'-carboxy-5' sulphophenyl-metylamino)-triazine, 2,4-difluoro-6-(3'- or 4'-sulphomethyl-phenylamino)-triazine, 2,4 difluoro-6-[N-(sulphomethyl)-phenylaminojtriazine and 2,4-difluoro-6-[3'-sulpho-N-(carboxymethyl) phenylamino]-triazine, and the analogous 2,4-dichloro- or2,4-dibromo-6-arylaminotriazines, 2,4 difluoro-6-(N-methyl-N-sulphomethylamino)-triazine, 2,4-difluoro-6-[N-methyl-N-(2-sulphoethyl) amino]-triazine and 2,4-difluoro-6-(2-sulphoethylamino)-triazine, and the corresponding 2,4-dichloro and 2,4-dibromo compounds.

The reaction of the aminoalkylaminoanthraquinone compounds (IV) with the dihalogenotriazinylaryl compounds (V) is carried out in an aqueous or organic-aqueous medium at temperatures from 100 to 800, preferably at 0--500, and at pH values of 5-10, preferably 6.0-9.0, in the presence of alkaline condensing agents, such as aqueous alkali metal hydroxide solutions, alkali metal carbonate solutions or alkali metal phosphate solutions.

The preparation of the 2,4-dihalogeno-6-aminotriazines (V) can be carried out, for example, by condensation of 2,4,6-trihalogeno-triazines with amines of the formula

wherein R2 and R3 have the meaning indicated above, in an aqueous, aqueous-organic or organic medium in the presence of basic condensing agents, such as, for example, aqueous alkali metal hydroxide solutions, alkali metal carbonate solutions, alkali metal bicarbonate solutions or alkali metal phosphate solutions or N,N-dialkylanilines or trialkylamines.

The difluorotriazinyl compounds (V) can also be prepared bythemethods indicated in German Offenlegungsschrift (German Published Specification) 1,644,616.

A particularly preferred and appropriate method is a procedure in which the solutions of the reactive components (V) obtained by condensation of 2,4,6-trihalogenotriazines with amines are reacted directly, without intermediate isolation, with the aminoalkylaminoanthraquinone compounds (lav).

According to another preparation procedure, the new reactive dyestuffs (I) are also obtained by reacting the aminoalkylaminoanthraquinone compounds (IV) with 2,4,6-trihalogenotriazines in an aqueous, aqueous'organic or organic medium to give intermediate products of the formula

wherein P1, A, X, S and n have the meaning indicated above, and subjecting these reactive dyestuff intermediate products to a condensation reaction with the amines (Vl) in a second reaction step.

The new dyestuffs are extremely valuable products which are suitable for very diverse application purposes. As water-soluble compounds, they are preferably of interest for dyeing textile materials containing hydroxyl groups and textile materials containing nitrogen groups, in particular textile materials of natural and regenerated cellulose, and furthermore of wool, silk and synthetic polyamide and polyurethane fibres.

The materials mentioned are dyed or printed by the processes customary for reactive dyestuffs.

Brilliant blue dyeings and prints which are fast to light and wet processing are obtained.

The temperatures given in the examples are in 00. The formulae of the dyestuffs in the description and in the examples are those of the free acids. In general, the dyestuffs are isolated and used in the form of their alkali metal salts, in particular the sodium salts or potassium salts.

EXAMPLE 1 A. 25.0 g of 1-amino-4-bromo-anthraquinone-2-sulphonic acid, 22.2 g of 1-amino-3-aminomethyl3,5,5-trimethylcyclohexane and 5.4 g of sodium hydroxide in 300 ml of water are warmed to 4550 under a nitrogen atmosphere. 1 g of copper-l chloride is added to the mixture, whereupon the mixture very rapidly becomes blue-coloured. It is stirred further at 4550 until the bromine compound employed has disappeared. The blue dyestuff components which have formed are precipitated from the blue solution by adding concentrated hydrochloric acid dropwise until the pH value is 2 and are filtered off, the filter cake is washed with dilute hydrochloric acid and the product is dried at 600 in a circulating air cabinet.

B. 12.0 g of 2-aminobenzene-1 ,4-disulphonic acid are dissolved in 60 ml of water by adding about 32 ml of 2N sodium carbonate solution until the pH value is 4.5. After cooling the mixture to 0--50, 7.0 g of 2,4,6-trifluorotriazine are added dropwise in the course of 10 minutes and the pH value is kept at 4.2-4.7 with 2N sodium carbonate solution.10 minutes after the the dropwise addition, the condensation reaction to give difluorotriazinylanilinedisulphonic acid has ended.

C. 15.0 g of the colour solid prepared according to paragraph A of this example are dissolved, at pH 12 by means of sodium hydroxide solution, in 350 ml of water, whilst warming to 600. After cooling the solution to 0--5 0, the pH value is carefully adjusted to 9.0-9.3 with hydrochloric acid and the solution, prepared in paragraph B, of the sodium salt of difluorotriazinylanilinedisulphonic acid is then allowed to run in immediately at 0--50 in the course of about 20 minutes. During this addition, the pH value of the reaction mixture is kept constant at 8.278.5 with 2N sodium hydroxide solution. The condensation reaction is brought to completion by subsequently stirring the mixture for several hours under the conditions indicated.

The resulting dyestuff solution is added dropwise, at 2030 , to a mixture of 200 ml of saturated potassium chloride solution and an amount of solid potassium chloride such that, after bringing the solutions together, the concentration of potassium chloride is about 2223%.

The dyestuff which has precipitated, which corresponds to an isomer mixture of the formula

is filtered off, washed with saturated potassium chloride solution and dried at 400 in vacuo.

D. 50 g of cotton hanks are dyed in 1 litre of dye liquor, which contains 1.5 g of the above dyestuff, by heating the bath to 400 in the course of 30 minutes, adding 50 g of sodium sulphate in several portions, then adding 20 g of sodium carbonate and treating the hanks at this temperature for 60 minutes. After rinsing, soaping at the boil and drying, a very brilliant, blue dyeing of excellent fastness to light and wet processing is obtained.

E. Cotton can also be dyed in the following manner: 100 g of cotton fabric are padded on a padder at room temperature with an aqueous solution which contains 30 g/litre of dyestuff and 20 g of sodium carbonate, in a manner such that the liquor pick-up of the fabric is 80% of its dry weight. The fabric is rolled up and stored at 250 for 24 hours in a manner such that no moisture can escape. The fabric is then rinsed, soaped at the boil and dried. A very brilliant blue dyeing which is fast to light and wet processing is likewise obtained.

F. A further variant for dyeing cellulose materials consists of the following procedure: 100 g of cotton of fabric are padded at room temperature with an aqueous solution which contains 3% of the dyestuff, 15 g/litre of sodium bicarbonate and 150 g/litre of urea, and are intermediately dried, heated to 1 400 for 2 minutes and then rinsed and soaped at the boil. The fabric is dyed in extremely brilliant blue shades which are very fast to light and wet processing.

Instead of heating the intermediately dried fabric to 1400, it is also possible to steam the fabric at 1020for2 minutes.

If, in accordance with the procedure of Example 1A, the diamines listed in Table 1, column (2), are reacted with 1 -amino-4-bromoanthraquinone-2-sulphonic acid in the molar ratio of 1:1 and the resulting blue intermediate products are subjected to condensation reactions with the reactive components in column (3), further reactive dyestuffs are obtained which dye cotton in brilliant blue shades, the combination possibilities between the anthraquinone intermediate products obtained and the reactive components not, of course, being restricted only to the examples listed in Table 1.

TABLE I

Example No.- [ Diamine (2) Reactive component (3) F 2 NHCH-NH NN FA1hl N 3 NHf oCHZ NH2 ssNH) S03H .4 H2- N: - F 5 CH3 F CHO FNNH OH3 T03H 6 CH3 F "I cH3 F NX1 NH3H OH3 7 NHZo CH2NHe ANHX NN 5tt3H 8 C -cH -NH 3H N" C-O-r -NH2 N fiq3H 9 NHz C a1gCH2NHz F as3 93 TABLE I (Continued)

Example No. Diamine (2) Reactive component (3) 10 CH3 F NH U-'z OH3 FN NH Q 11 F Q CH2 -012 -NH2 NH2 F ANHM 12 F NUN (CHPk I II I NN 13 2 F -NH F NNH 503H 14 oi F 3H NH FNH 3H CH3 CH3 15 oCH3 H3 I OhI3 16 -o CHZ' 3H NH,$3 503H 17 r } CHeCHeNHE 7 F S03H NH2-C/ CH-CHe -NH 3 503H TABLE I (Continued)

Example No. Diamine (2) Reactive component (3) 18 NH -cH F NN ,F N FN1 NH/ 19 NHZoO/ NH -NHz F NUN F N NH-CflC-SOH EXAMPLE 20 A. 9.7 g of 2-aminobenzene-1 ,4-disulphonic acid are dissolved in 60 ml of water by adding about 32 ml of 2N sodium carbonate solution until the pH value is 4.5. 7.1 g of finely ground cyanuric chloride are introduced at 200 in the course of 1 5 minutes and the pH value is kept at 4.5-5.0 with 2N sodium carbonate solution. The mixture is subsequently stirred for about a further 3 hours under these conditions, until the condensation reaction to give dichlorotriazinylanilinedisulphonic acid has ended.

B. 1 5.0 g of the colour solid prepared according to Example 1, paragraph A, are dissolved, at pH 12, in 350 ml of sodium hydroxide solution, whilst warming to 600. The solution is cooled to 200 and this solution is gradually brought together with the solution, prepared above, of the reactive component in a manner such that a pH value of 8.7-9.2 is always maintained in the reaction mixture. After bringing the two solutions together, the pH value is then kept further at 8.7-9.2 with 2N sodium hydroxide solution and the mixture is subsequently stirred at 200 until the condensation reaction between the colour solid and the reactive component has ended. The resulting dyestuff of the formula

is salted out with potassium chloride, filtered off, washed with saturated potassium chloride solution and dried at 500 in vacuo.

C. Cellulose fabric is printed with a printing paste which contains, per kilogram, 40 g of the above dyestuff, 1 00 g of urea, 300 ml of water, 500 g of alginate thickener and 20 g of sodium carbonate and which has been made up to 1 kilogram with water, and the fabric is dried, steamed at 1 050C for 8 minutes, rinsed with hot water and then soaped at the boil, rinsed and dried.

A brilliant blue print of very good fastness to wet processing and light is obtained.

Using the dyestuff obtained, it is also possible to achieve brilliant blue dyeings on cellulose materials in accordance with the procedure described in Example 1 E.

If, in accordance with the procedure of Example 1 A, the diamines listed in Table II, column (2) are reacted with 1-amino-4-bromoanthraquinone-2-sulphonic acid in the molar ratio 1:1 and the intermediate products obtained are subjected to condensation reactions with the reactive components in column (3), similar reactive dyestuffs which give brilliant blue prints on cotton are obtained.

TABLE II

Example No. Diamine (2) Reactive component (3) 21 3 Cl .CXCHeNHz ctAN NHX CH3 CL NH 503H 22 CM3 a CL Nne CLNNH CH3 fO3H 23 NH2oCH2 alz CL 503H NN -NH2 soli 24 NH2vCH2~NHz Br 503H II N s; 50D,H 25 NHz eCHzNHz A NH SO3!1 CL 26 NH2 {}01Z ~ NH ClXN NH Ja tIN CL NNH 503H 27 / \ . a S03H 27 C)CH2-CH,-NH\NH 509 5o 28 NHz < > t NH NAN 503H CLtt1NMN 503H 29 CH3 Br S03H t -N NN NH2- II ~~~~~~~ 503H TABLE II (Continued)

Example No. Diamine (2) Reactive component (3) 30 XCHz NHzA ) CH3 OH3 31 CL 5O NN a N NH 503H 32 ., Ct 503H ci %3M"' 33 a NN a N NHCHCH-5O3H 34 CL a N NH S03H 35 CH3 a 503H NH}NH ci \NH EXAMPLE 36 A. 30.0 g of 1 -amino-4-bromoanthraquinone-2-sulphonic acid, 1 5.0 g of 1 -amino-3- methylaminopropane and 10.0 g of sodium carbonate in 300 ml of water are warmed to 5560 under a nitrogen atmosphere. 1 g of copper-l chloride is added to this mixture, whereupon the reaction rapidly begins, the mixture becoming blue-coloured. The mixture is stirred further until the bromine compound employed has disappeared, the resulting solution is then clarified with 1 g of charcoal and 1 g of kieselguhr and the dyestuff is separated out from the filtrate by adjusting the pH value of the solution to pH 1 with hydrochloric acid. The needles which have precipitated are filtered off, washed with water and dried at 600 in a circulating air cabinet.

B. 13.7 g of 2-aminobenzene-1 ,4-disulphonic acid are suspended in 70 ml of water and the pH value is adjusted to 4.5 with 2N sodium carbonate solution. The resulting solution is cooled to 0--5 0 and 8.0 g of 2,4,6-trifluorotriazine are added dropwise in the course of 10 minutes. During this addition, the pH value is kept at 4.5 with 2N sodium carbonate solution. Some minutes after the dropwise addition, the reaction has ended.

C. 1 5.0 g of 1 -amino-4-(3-methylamino-1 -propylamino)-anthraquinone-2-sulphonic acid, prepared according to paragraph A of this example, are dissolved, at pH 1 2, in 300 ml of water with sodium hydroxide solution at 55 . The solution, which has been cooled to 0--50, is added dropwise, at the same time as the solution of the reactive component from B, into 100 ml of initially introduced icewater in a manner such that a pH value of 8.2-8.7 is established. After the dropwise addition, the pH value is kept further at the required value with 2N sodium hydroxide solution. The mixture is subsequently stirred at 0--5 for some hours in order to bring the condensation reaction to completion.

The resulting dyestuff is salted out with sodium chloride, filtered off and washed with saturated sodium chloride solution. It corresponds to the formula

and is dried at 400 in vacuo.

Using the dyestuff, very brilliant, blue dyeings with excellent fastness properties are obtained on cotton by the exhaustion process or by the various padding processes.

Further dyestuffs which dye cotton in brilliant blue shades are obtained if, instead of the dyestuff component prepared in this example, paragraph A, the anthraquinone compounds listed in Table Ill, column (2), are subjected to condensation reactions with the reactive components in column (3).

TABLE III

Example No. Anthraquinone component (2) Reactive component (3) N 37 XS03H F N NI & 13 FNX1 NHN:5O5H CH-CH- NH and its isomer 38 C NH isomer 38 4503H ANK N - C1H N 0 NH-CH-CH - & -CH-NH O NH- ONH F 5H 39 O "I tm503H N o NH -(cH)5 I CHQ 40 ONM F 5OM 40 O NHz F S03H O Nh-(CH-NH o NH-(CHe)6-Hz 41 0 NH2 F iN Ch CH2 cM-CH-NH O NH CHZ - 0505H 42 XS03H I FlSNlNHX5o H CHz F N NHN5O3H O NHCHzCHzNH 43 N F O3H 0 CH2-CH2-CH2/ and its isomer CH2 and NH Q .NH O NH CH2-CH2'C S03H CMz -CH-CH . and its isomer and its isomer TABLE III (Continued)

Example No. Anthraquinone component (2) Reactive component (3) 45 (i̇NM)% o NH-CH-CH-Oie-NH CH3 46 o EPle F 3t F $FIHJ43 NH NH, 50BH 47 XS03H F N ?4N I H I FNNH o NH-a-ule-cH - NH 48 o NFle F S03H 6-0 WNH))'$I o NH-CH-CH-CH -N 503H I NH-CHCHz-CH-NHz I CH3 CH3 49 O NH F S03H 3i" x3 O NH- (CHz)4 NH2 w & NH?)$3H 50 - N F 50 3c3H NN Q NHz F < FtNHX3H N O NH-OH ~ | te -CH II CH3 CH3 51 < CH3 F F'b 013 O NH-aiai-o1Z- F $NH4 52 NHe F O NH-( F N NHJa50EjH - NM TABLE III (Continued)

Example No. Anthraquinone component (2) Reactive component (3) 53 O NHz F > g H3 f tNH)t H035 0 NH-CH,-CHz-CH2NH 54 CnZ F F$lNI3 o < NM CHOHCiiZ-NM CM5 CH3 55 O NH2 F S03H 'flOl 503M N" N 0-CMZ fi$-N 56 O NHz F NN 1)3M F,NNH"" o NM-(CM3-NM 57 0 NH F T03 CHg503H ,NHS03H cHl F O NH-CHe-CH2-NH 58 o F 58 Cl2MS 2H5 F1$ NHJX O NH-CH'CH -- CH -- NH 593H 59 0 "12 /S03n CH3 F H I I N 1 NH NM -CM -CHCH -CH-NH and its isomer 60 1S1 W NM F N Z CeM5 I F N NM O NHCHz < rCH2NH COOM TABLE III (Continued)

Example No. Anthraquinone component (2) Reactive component (3) 61 Q NH2 F 303H F N N 0115 FNNH .CH2- CHo -CH-CHe -C -CH- NHZ S03H I I CH3 CH5 and its isomer 62 < Sn2 F S03H 0 NHCH2 CH2 *E 503H 63 O NHe F ",I0IN f N O NH - (CHz)4NHz 64 0 NM F NIN/I N 5H HO3"i~ FH O (CH-NH eO3h F 3H 65 0NH 65 O ';;'Hz N FNN1 503H 0 NH-CH2-CH,Z-CHZNH NM F NH 66 W50311 FENHJ? o NlHcHCHZNM F 67 0 NHe l"'i O NH-012--CH2-NH O NH ~CH2CH2 - F N NH NH 68 H035 H2 F O%MH 3CM iI tSC3H FtNXNH) N I-CHzOcFleNHz 903H TABLE Ill (Continued)

Example No. Anthraquinone component (2) Reactive component (3) 69 O NH2 F N" N XS03H CH3 A O NH -C71z-CHz-CHz- NH NH reactive mixture of 2,6- and 2,7 disulphonic acid 70 o C H N""' N NI) F NH N CM NH-cHz n zNHz 93H EXAMPLE 71 A. 1 0.0 g of 3-aminobenzenesulphonic acid are suspended in 90 ml of water. The pH value of the suspension is adjusted to 3.5 and the suspension is cooled to 0--50. 8.2 g of 2,4,6-trifluorotriazine are added dropwise in the course of 1 0 minutes.During this addition, the pH value of the reaction mixture is kept at 3.2-3.5 with 2N sodium carbonate solution. 1 5 minutes after the dropwise addition, the reaction has ended and a clear solution has formed. The pH value is now adjusted to 4.5-5.0.

B. 15.0 g of 1 -a mino-4-(3-methyla mino-l -propylamino)-anthraquinone-2-sulphonic acid are dissolved, at pH 12, in 300 ml of water at 600. The solution, which has been cooled to 0--5 0, is carefully adjusted to pH 9.5-1 0 and the solution of the reactive component prepared in section A is now added dropwise, during which the pH value is allowed to fall to 8.5-8.8 and is then kept in this range with 2N sodium hydroxide solution. The condensation reaction is brought to completion by subsequently stirring the mixture for several hours. The dyestuff formed, of the formula

is salted out with sodium chloride, filtered off, washed with 1 5% strength sodium chloride solution and dried at 400 in vacuo.

The dyestuff dyes cotton, by the dyeing processes of Example 1, in very clear blue shades which are fast to light and wet processing.

EXAMPLE 72 A. 30.0 g of 1-amino-4-bromoanthraquinone-2,6-disulphonic acid, 25.0 g of 1-amino-3aminomethyl-3,5,5-trimethylcyclohexane and 5.9 g of sodium hydroxide in 300 ml of water are warmed to 4045 under a nitrogen atmosphere. 1.1 g of copper-l chloride are added to the solution, whereupon the reaction starts, the mixture rapidly becoming blue-coloured. When the reaction has ended, 1 g of charcoal and 1 g of kieselguhr are added to the solution, the resulting solution is clarified, the pH value of the filtrate is adjusted to 7 with hydrochloric acid and the dyestuff is salted out with potassium chloride. It is filtered off, washed with 10% strength potassium chloride solution and dried at 600 in a circulating air cabinet.

B. 10.0 g of 4-aminobenzene-1 ,3-disulphonic acid are dissolved in 90 ml of water at 200 and the pH value is adjusted to 5.0. 7.3 of finely ground cyanuric chloride are now introduced and the pH value is kept at 4.5-5.0 with 2N sodium carbonate solution. After some hours, the condensation reaction has ended.

C. 15.0 g of the anthraquinone compound prepared in paragraph A are dissolved, at pH 12, in 300 mi of water. This solution and, at the same time, the solution of the reactive component B are now added dropwise into 80 ml of initially introduced water in a manner such that a pH value of 8.5-9.0 is established in the reaction mixture. The pH value is further kept at this value with 2N sodium hydroxide solution until the reaction has ended, that is to say after some hours. The dyestuff of the formula

is salted out with potassium chloride, filtered off, washed with 25% strength potassium chloride solution and dried at 500 in vacuo.

On cellulose materials, the dyestuff gives, by the process of Example 20C, prints in a brilliant blue shade which are very fast to light and wet processing and, in comparison to those of Example 20, somewhat more greenish-tinged.

EXAMPLE 73 A. 11.9 g of 4-aminobenzene-1 3-disuiphonic acid are dissolved in 100 ml of water at 200 and the pH value of the solution is adjusted to 5.0. 8.7 g of finely ground cyanuric chloride are now introduced and the pH value is kept at 4.5-5.0 with 2N sodium carbonate solution. After some hours, the condensation reaction has ended and the cyanuric chloride has disappeared.

B. 1 5.0 g of 1 -amino-4-(3'-methylamino-1 -propylamino)-anthraquinone-2-sulphonic acid are dissolved, at pH 12, in 300 mi of water at 55 . The solution is cooled to 200 and the solutions of the anthraquinone compound and the reactive component prepared according to A are now added dropwise, at the same time, into 100 ml of initially introduced water in a manner such that a pH value of 8.5-9.0 is established in the reaction mixture.After adding the dyestuff component, the pH value is maintained further by adding 2N sodium hydroxide solution dropwise, and the mixture is further stirred at 200 until the condensation reaction has ended;The resulting dyestuff of the formula

is salted out with sodium chloride, filtered off, washed with 25% strength sodium chloride solution and dried at 600 in vacuo.

On cellulose materials, the dyestuff gives brilliant, blue prints with very good fastness properties by the process of Example 20C.

Further analogous reactive dyestuffs are obtained by reacting the anthraquinone compounds in column (2) of Table IV with the reactive components in column (3).

The resulting dyestuffs likewise give, on cellulose materials, very clear blue prints with excellent fastness properties.

TABLE IV

Example Example No. Anthraquinone compound (2) Reactive component (3) 74 O CL a SO3H I 505H NN I",CHl5 CHl3 '1NH CL atNlNH N o NH-CH-CHZ-CH-th soy 75 O NM XS%H a NH-CHe-CH - 3 H O NH -CH - CH -NHE Z o NM-OH-CH-NM II CH3 CH3 76 0 NHe Cl S03H < 593H adNHJtJ O NH(CM+ZNH 77 o NHZ CL 0: 9" O NH (CH2)4 NH2 503H 78 O NH CL so3n vS03H N;N > o -NH cHH3 1{LNH) 79 0 NH I CH3 Cl N N -CHz 3HN N-CH-5O3H O rJ1 -CHe-O-12 CH3 013 80 O Nvig CL X c03H CL Ct;N1SHX O NH-(CM)3-NH 5oH 81 < ,C03H CL 81 503H IN/ -NH CL N O NH- CH2 TABLE IV (Continued)

Example No. Anthraquinone compound (2) Reactive component (3) 82 XSOsH Ct;NH Ct P CHZ N NM O NH-OM-CM-CH-NH 83 O NH2 0 SjP" -C"J 4" czns c 'NH o NM-CHCHCHZ-NM wi NH.%f3M 84 off ct a N"'N N NMN 3M O NH I-NH 505H 85 0 NH CM & a 5oaM N CHzOH Cl 1KN1 NHJa505H N CM CHZ NH-CHzCHzNH 86 Q NH; a NN S03H c1H-O5O3M CMz O NH-Q-12-U12-NH NCHCMZ1 O NHCHzCHZNH 87 N""0} I Cltss M-CMe-CH-NM ati3 CHi3 88 O NH2 a 505M $II)3MCM3 so,r c O NM-CH-OM-Nh SO311 and its isomer 89 o NFq! a sO3M NA < "Cs gNFt Ct N NHS O NHCH2CHzCHz N SQ3H and its isomer TABLE IV (Continued)

Example No. l Anthraquinone compound (2) Reactive component (3) 90 Q~4 CH ",, I 503M OHS N1 I I O NH-CH-C-CH NH 91 Q a CL -a-12''e a zcs 013 OHS CH3 CH3 and its isomer CL 503M 92 ; O NHZ NN O NH-CH2-CHz CH94-CHz-NHz 5 3!1 I I 013 OHS and its isomer 93 O NFt a u S03H d cne- u' O '01N$i-CHZ'mCH-NI CL'2INM)$I$I so 94 CL NHz a 503H CHz- 1W NXNH) O NHCH so3# 95 O NHCtmCHgNHz 0 503H N1 N0 NH-CHZ-31CH2 96 0 NM CL NN \N 503H < arizsNHz CL N NHX O NH-CHg > t) So3H TABLE IV (Continued)

Example No. Anthraquinone compound (2) Reactive component (3) 97 o ule CL 97 < g}flNHz Ct o S03H and its isomer 98 O NH a 50311 "I NO < 503H a N NH t1 O M- SOH EXAMPLE 99 16.0 g of the anthraquinone compound prepared in Example 1 A are dissolved, at pH 12, in 380 ml of water at 600. After cooling the solution to 200, 320 ml of acetone are added and the pH value is adjusted to 10.

7.8 g of cyanuric chloride are dissolved in 80 ml of acetone and the solution is poured onto 80 g of ice. The dyestuff solution is added dropwise to the resulting suspension at 0--50 in the course of 30 minutes and the pH value of the reaction mixture is kept at 8.0-8.5. The mixture is further stirred under the same conditions for a short time, until the reaction has ended.

A solution of 2-methylamino-ethanesulphonic acid is now added to the resulting solution of the dichlorotriazinyl dyestuff. The mixture is warmed to 200, the pH value is kept at 7.5 and the temperature is increased to 400 in the course of one hour. When the condensation reaction has ended, the resulting dyestuff of the formula

is salted out with sodium chloride, filtered off, washed with 10% strength sodium chloride solution and dried at 600 in vacuo.

Similar dyestuffs are obtained if, instead of 2-methylamino-ethanesulphonic acid, equivalent amounts of 2-aminoethanesulphonic acid or methylaminomethanesulphonic acid are employed.

EXAMPLE 100 9.7 g of 2-aminobenzene-1 ,4-disulphonic acid are reacted with 7.1 g of cyanuric chloride according to the instructions in Example 20A. 12.4 g of 1 -amino-4-(4-amino-1 -butylamino)anthraquinone-2-sulphonic acids are dissolved, at pH 12, in 300 ml of water at 600. The solution which has been cooled to 200, is now added dropwise, at the same time as the solution of the reactive component, to 100 ml of initially introduced water and the pH value of the reaction mixture formed is kept at 8.5-9.0. After the dropwise addition of the solutions, this pH value is maintained further using 2N sodium hydroxide solution. After subsequently stirring the mixture at 200 for several hours, the condensation reaction has ended.The dyestuff of the formula

is salted out with potassium chloride, filtered off, washed with 25% strength potassium chloride solution and dried at 600 in vacuo.

On cellulose materials, it gives, by the printing process of Example 20C, brilliant blue prints with excellent fastness to wet processing.

EXAMPLE 101 A. 8.5 g of 2-aminobenzenesulphonic acid are dissolved, at pH 4.5, in 100 ml of water. The solution is cooled to 0--50 and 6.6 g of 2,4,6-trifluorotriazine are added dropwise in the course of 10 minutes; during this addition the pH value is kept at 4.2-4.5 with 2N sodium carbonate solution.

B. 19.0 g of the colour solid prepared in Example 72A are dissolved, at pH 11.5, in 300 ml of water.

The solution is cooled to 0---50 and the pH value is carefully adjusted down to 9.5 with hydrochloric acid. The reactive component prepared under A is then added dropwise in the course of 20 minutes and the pH value is kept at 8.2-8.7 with 2N sodium hydroxide solution. The mixture is subsequently stirred at 0--50 under these conditions for some hours, until the condensation reaction has ended. The resulting dyestuff of the formula

is salted out with sodium chloride, filtered off, washed with 20% strength chloride solution and dried at 40 in vacuo.

The resulting product dyes cotton, from a long liquor or by the padding process of Example 1, in brilliant blue shades which are fast to light and wet processing.

Claims (14)

CLAIMS:

1. A reactive dyestuff of the general formula

in which Q denotes a substituent, nisO, 1,or2, A denotes an aliphatic bridge member, X denotes a fluorine, chlorine or bromine atom, R1 and R2 independently denote a hydrogen atom or an optionally substituted alkyl group and R3 denotes a radical of the benzene or naphthalene series or optionally substituted alkyl group, with the proviso that at least one of the radicals R2 and R3 contains at least one group conferring solubility in water.

2. A reactive dyestuff according to Claim 1, in which Q denotes a chlorine or bromine atom or a hydroxyl group.

3. A reactive dyestuff according to Claim 1, in which Q denotes an SO3H group.

4. A reactive dyestuff according to any of the foregoing claims in which the group conferring solubility in water is an SO3H or COOH group.

5. A reactive dyestuff according to any of the foregoing claims, in which A denotes a straight-chain or branched C2 to C8 alkylene group or a radical of the formula

6. A reactive dyestuff according to any of the foregoing claims, in which R2 denotes a hydrogen atom or a methyl group and R3 denotes a sulphophenyl, disulphophenyl, sulphocarboxyphenyl, dissulphonaphthyl or trisulphonaphthyl radical.

7. A reactive dyestuff according to Claim 1 as hereinbefore specifically identified.

8. A process for the production of a reactive dyestuff as claimed in Claim 1, in which an anthraquinone compound of the general formula

in which A, Q, n and R, have the same meaning as in Claim 1, is subjected to a condensation reaction with a dihalogenotriazinylamino compound of the general formula

in which R2, R3 and X have the same meanings as in Claim 1.

9. A process for the production of a reactive dyestuff as claimed in Claim 1, in which an anthraquinone compound of formula (IV), as defined in Claim 8, is reacted with a 2,4,6 trifluoro-, trichloro- or -tribromotriazine and the product is reacted with an amine of the general formula

in which R2 and R3 have the same meanings as in Claim 1.

10. A process for the production of a reactive dyestuff as claimed in Claim 1, when carried out substantially as described in any one of the Examples.

11. A reactive dyestuff as claimed in Claim 1, when produced by the process of any of Claims 8 to 10.

1 2. A process for dyeing or printing an OH-- containing or N-- containing fibre material comprising treating the material with a dyestuff as claimed in any of Claims 1 to 7 and 11.

1 3. A process according to Claim 12, when carried out substantially as described in any one of Examples 1,20,71 to 73,100 and 101.

14. An OH-- containing or N-- containing material when dyed or printed by the process of Claim 12 or 13.