Reactive dyestuff containing triazinyl and halopyrimidine moieties

The invention relates to new reactive dyestuffs, their preparation and their use.
Reactive dyestuffs are disclosed, for example, in EP-A-97 119. However, the reactive dyestuffs mentioned there still have disadvantages, for example in the fastness properties.
The present invention relates to reactive dyestuffs of the formula (1) ##STR3## in which D denotes the radical of an organic dyestuff,
R, R.sub.1 and R.sub.2, independently of one another, denote hydrogen or substituted or unsubstituted C.sub.1-4 -alkyl,
A denotes a substituted or unsubstituted aliphatic, aromatic or aromatic-aliphatic bridging member,
Pym denotes the radicals ##STR4## X denotes Cl, F n denotes 1 or 2.
Particularly preferred reactive dyestuffs have the following formulae (1a) and (1b) ##STR5## in which D, R, R.sub.1, R.sub.2, A, X and n have the abovementioned meaning.
The radical D is in particular the radical of a sulpho-containing organic dyestuff from the mono- or polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan, azomethine, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone, nitroaryl, naphthoquinone, pyrenequinone or perylenetetracarboximide series.
1 or 2 bireactive fluorotriazinylfluoropyrimidine groupings can be bound to the dyestuff radical D in formula (1). If the dyestuff 2 contains groupings of this type (where n is 2), they are independent of one another and can thus be identical or different with respect to the radicals R, R.sub.1, R.sub.2 or A.
The radical D in formula (1) can be substituted in the usual manner and contains in particular one or more sulpho groups. Examples of further substituents on the radical D are: alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl and butyl, alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy and butoxy, acylamino groups having 1 to 6 carbon atoms, such as acetylamino and propionylamino, benzoylamino, amino, alkylamino having 1 to 4 carbon atoms, phenylamino, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy radical, nitro, cyano, trifluoromethyl, halogen, such as fluorine, chlorine and bromine, sulphamoyl, carbamoyl, ureido, hydroxyl, carboxyl, sulphomethyl and sulpho. Those reactive dyestuffs in which D is the radical of an azo dyestuff contain as substituents in particular methyl, ethyl, methoxy, benzoylamino, amino, acetylamino, ureido, sulphomethyl, hydroxyl, carboxyl, halogen and sulpho.
A suitable alkyl radical for R, R.sub.1 and R.sub.2 in formula (1) is a straight-chain or branched alkyl radical which may also be substituted, for example by halogen, sulphato, carboxyl, hydroxyl, cyano or sulpho. Examples of R are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec.-butyl, tert.-butyl, .beta.-chloroethyl, .beta.-hydroxyethyl, .beta.-hydroxybutyl, .beta.-cyanoethyl, .beta.-sulphatoethyl, carboxymethyl and sulphomethyl. Preferred groups R.sub.1 and R.sub.2 are: hydrogen, methyl, ethyl, .beta.-hydroxyethyl and .beta.-sulphatoethyl.
A is preferably an alkylene, arylene or aralkyl radical. The term aliphatic bridging member also includes cycloaliphatic radicals. Thus, A can be a long (for example having 10 or more carbon atoms) or relatively short, straight-chain or branched alkylene radical; in particular, an alkylene radical having 2 to 6 carbon atoms is suitable, for example ethylene, propylene, butylene, hexylene or cyclohexylene. As an arylene radical, A is, for example, a naphthylene radical, the radical of a diphenyl or stilbene or in particular a phenylene radical. The radical A can contain further substituents, for example halogen atoms, such as fluorine, chlorine and bromine, alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl and propyl, alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy, propyloxy and isopropyloxy, carboxyl, hydroxyl or sulpho. A is preferably C.sub.2-6 -alkylene or substituted or unsubstituted phenylene. Preference is given to the ethylene, propylene, phenylene and sulphophenylene radical.
Preferred subgroups of the reactive dyestuffs of the formula (1) are:
a) reactive dyestuffs of the formula (1) in which
D is the radical of a sulpho-containing organic dyestuff from the mono- or polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan or dioxazine series,
Pym has the abovementioned meaning,
n is 1 or 2,
X is Cl or F and
R represents hydrogen, methyl or ethyl,
R.sub.1, R.sub.2, independently of one another, represent H or C.sub.1 -C.sub.4 -alkyl which may be substituted by OR, OSO.sub.3 H, SO.sub.3 H, COOR or halogen,
A represents a substituted or unsubstituted phenylene or a substituted or unsubstituted aromatic-aliphatic bridging member or a straight-chain or branched C.sub.1 -C.sub.6 -alkylene which may be interrupted by hetero atoms or groupings containing hetero atoms such as NR, O or S and which may be substituted by OR, OSO.sub.3 H, SO.sub.3 H, COOR or halogen.
Within the bridging member A, NR together with NR.sub.1 or NR.sub.2 can also form a heterocyclic, aliphatic ring.
b) Dyestuffs of the formula (1) in which
A, D, n, R, R.sub.1 and R.sub.2 have the meaning as in a) and
X is F.
c) Reactive dyestuffs of the formula ##STR6## in which D, X, R and Pym have the same meanings as in a) and
R.sub.3 and R.sub.4, independently of one another, are hydrogen, methyl, ethyl, methoxy, ethoxy, chlorine, carboxyl or sulpho.
d) Reactive dyestuffs according to c), in which
D, X, R and Pym have the same meanings as in c) and
R.sub.3 and R.sub.4, independently of one another, are hydrogen or sulpho.
e) Reactive dyestuffs of the formulae ##STR7## in which D, X and R have the same meanings as in a) and
A.sub.1 represents an aliphatic, straight-chain or branched C.sub.1 -C.sub.6 -diaminoalkylene which may be interrupted by hetero atoms or groupings containing hetero atoms such as NR.sub.1, O or S and which may be substituted by OR, OSO.sub.3 H, SO.sub.3 H, COOR or halogen. This also includes hetero- and carbocyclic aliphatic diamines.
R.sub.1 has the same meaning as in a).
Preferred aliphatic diamines are: ##STR8## f) Reactive dyestuffs of the formulae ##STR9## in which D, X and R have the same meanings as in a) and
R.sub.3 and R.sub.4, independently of one another, are H, methyl, ethyl or sulpho and
A.sub.2 represents an aliphatic, straight-chain or branched C.sub.1 -C.sub.6 bridging member which may be interrupted by hetero atoms or groupings containing hetero atoms such as NR.sub.1, O or S and which may be substituted by OR, OSO.sub.3 H, SO.sub.3 H, COOR or halogen.
They also include hetero- and carbocyclic aliphatic linking members.
g) Reactive dyestuffs according to c), d), e) and f), in which
X represents F.
The reactive dyestuffs of the formula (1) are preferably prepared by condensing an organic dyestuff of the formula ##STR10## or a dyestuff precursor,
2,4,6-trifluoro-s-triazine or 2,4,6-trichloro-s-triazine, a compound of the formula ##STR11## and 2,4,6-trifluoropyrimidine or 4,6-difluoro-5-chloropyrimidine with one another, in which D, R, R.sub.1, R.sub.2 and A have the meanings given in the abovementioned formulae under formula (1) and, if dyestuff precursors are used, by converting the intermediates obtained into the desired final dyestuffs.
In the process described above, the individual process steps can be carried out in a different order, if desired some of them may also be carried out simultaneously. For this, various process variants are possible. In general, the reaction is carried out stepwise in succession.
Which of the possible process variants gives the best results or under which special conditions, for example at which condensation temperature, it is most advantageous to carry out the reaction depends on the structure of the starting materials.
Important process variants are characterised in that:
1. an organic dyestuff of the formula (5) is condensed with 2,4,6-trifluoro-s-triazine or 2,4,6-trichloro-s-triazine, furthermore a compound of the formula (6) is condensed with 2,4,6-trifluoropyrimidine or 4,6-difluoro-5-chloropyrimidine, and both intermediates are condensed with one another;
2. an organic dyestuff of the formula (5) is condensed with 2,4,6-trifluoro-s-triazine or 2,4,6-trichloro-2-triazine, the primary condensation product is condensed with a compound of the formula (6), and the secondary condensation product obtained is condensed with 2,4,6-trifluoropyrimidine or 4,6-difluoro-5-chloropyrimidine;
3. a compound of the formula (6) is condensed with 2,4,6-trifluoropyrimidine or 4,6-difluoro-5-chloropyrimidine, the primary condensation product is condensed with 2,4,6-trifluoro-s-triazine or 2,4,6-trichloro-s-triazine, and the resulting intermediate is condensed with an organic dyestuff of the formula (5);
4. 2,4,6-trifluoro-s-triazine or 2,4,6-trichloro-s-triazine is condensed with a compound of the formula (6), the primary condensation product is condensed with an organic dyestuff of the formula (5), and the secondary condensation product obtained is condensed in a last step with 2,4,6-trifluoropyrimidine or 4,6-difluoro-5-chloropyrimidine.
The condensation reactions of organic dyestuffs (5), dyestuff precursors and diamines (6) with 2,4,6-trifluoro-s-triazine, 2,4,6-trichloro-s-triazine, 2,4,6-trifluoropyrimidine or 4,6-difluoro-5-chloropyrimidine or their primary condensation products are carried out by known processes, preferably in aqueous or aqueous-organic media in the presence of acid-binding agents.
The formulae given are those of the free acids. The preparation in general gives the salts, in particular the alkali metal salts such as sodium salts, potassium salts or lithium salts. The dyestuffs can also be used as concentrated solutions.
The dyestuffs according to the invention are highly suitable for the dyeing and printing of natural and synthetic OH-- or amido-containing materials, in particular those made of cellulose and polyamides. They are particularly suitable for the dyeing of cellulose materials by the exhaust and cold pad-batch methods, and for the printing of cotton and staple viscose.
Dyeings having good general fastness properties, in particular wet fastness properties, in combination with good build-up properties and high fixation yields are obtained.
Below, possible starting materials which can be used for the preparation of the reactive dyestuffs of the formula (1) are mentioned individually.
Suitable dyestuffs of the formula (5) are in particular dyestuffs of the following structural types: ##STR12## where Sa is H.sub.5 C.sub.2 --O-- or H.sub.3 C--O-- ##STR13## in which acyl is, for example, acetyl or substituted or unsubstituted benzoyl,
R is H, CH.sub.3 or C.sub.2 H.sub.5,
R.sub.5 is H, CH.sub.3, OCH.sub.3 or Cl,
R.sub.6 is H, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, Cl, Br, COOH, SO.sub.3 H.
Metal complexes of dyestuffs of the formulae: ##STR14## in which R.sub.7 is H, OH, NH.sub.2, NHCOCH.sub.3, NHCOPh, Cl, C.sub.1 -C.sub.4 -alkoxy or C.sub.1 -C.sub.4 -alkyl.
Preferred metal atoms are Cu (1:1 complex) or Cr and Co (1:2 complex). Cr complexes and Co complexes can contain the azo compound of the abovementioned formula once or twice, i.e. they can have a symmetrical structure or, together with any other ligand groups, an unsymmetrical structure. ##STR15## in which R.sub.8 is H, SO.sub.3 H, CH.sub.2 SO.sub.3 H, Cl, C.sub.1 -C.sub.4 -alkylsulphonyl, CN, carboxamide, in particular CONH.sub.2,
R.sub.9 is H, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, acylamino, in particular C.sub.1 -C.sub.4 -alkylcarbonylamino or arylcarbonylamino, such as, for example, substituted or unsubstituted phenylcarbonylamino, C.sub.1 -C.sub.4 -alkylsulphonylamino, Cl, Br, aminocarbonylamino, C.sub.1 -C.sub.4 -alkylsulphonylamino, arylsulphonylamino,
R.sub.10 is H, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, OH, SO.sub.3 H.
The fused rings indicated by dashed lines represent naphthalene systems which are possible as an alternative. ##STR16## in which R.sub.5 is H, methyl, methoxy, chlorine
R.sub.11 is H, SO.sub.3 H and
R is H, methyl, ethyl. ##STR17## in which Y is ##STR18## O and T.sub.1, T.sub.2 are H, Cl, Br, C.sub.1 -C.sub.2 -alkyl, OCH.sub.3, OC.sub.2 H.sub.5, acylamino C.sub.1 -C.sub.2 -alkoxycarbonyl. ##STR19## in which Me is Cu, Ni,
u+v+w is 3.4-4.0, with the proviso that
u is 0.8-2.0,
v is 0-1.0,
w is 1.0-3.0 and
R.sub.1, R.sub.2 and A have the abovementioned meanings,
R.sub.12 and R.sub.13 are H, C.sub.1 -C.sub.2 -alkyl, which is substituted or unsubstituted by OH, OSO.sub.3 H, SO.sub.3 H or COOH. ##STR20## v, w are 0 or 1, where w is not equal to v, ##STR21## R.sub.14 is H, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, OH, halogen, COOH, NO.sub.2, SO.sub.3 H, sulphonamido, C.sub.1 -C.sub.4 -alkylcarbonylamino, substituted or unsubstituted phenylcarbonylamino, C.sub.1 -C.sub.4 -alkylsulphonylamino, substituted or unsubstituted phenylsulphonylamino,
Me is a divalent metal atom, preferably Fe, Cu, Zn, Co, Ni, ##STR22## in which R.sub.15 is C.sub.1 -C.sub.4 -alkyl, halogen, in particular chlorine, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -alkylcarbonylamino, arylcarbonylamino, aralkylcarbonylamino,
R.sub.16 is C.sub.1 -C.sub.4 -alkoxy, or R.sub.15 and R.sub.16 form a ring and have the following meaning: ##STR23##

EXAMPLE 1
1.1 18.8 g of 2,4-diaminobenzenesulphonic acid are dissolved in 80 ml of water by neutralisation with 10% strength lithium hydroxide solution, and the solution is condensed at 20.degree. to 30.degree. C. with 15.4 g of 4,6-difluoro-5-chloropyrimidine at a pH of 5.5 to 6.0. After consumption of lithium hydroxide has ended, 19.3 g of cyanuric chloride are added to the solution of the condensation product, the temperature is maintained at 20.degree. to 25.degree. C. and the pH at 5.0 using lithium hydroxide. When no more diazotisable amino group can be detected, the second condensation step is complete and the solution or viscous suspension of the compound ##STR24## in the form of its lithium salt has been formed.
1.2 46.5 g of 1-amino-4-(2'-aminomethyl-4'-methyl-6'-sulphophenylamino)-anthraquinone-2-sulphonic acid are dissolved in 300 ml of water and 10 g of caprolactam with neutralisation at a pH of 7.degree. and 70.degree. C. After cooling to room temperature, the solution is added to the condensation product from Example 1.1, and the pH in the reaction mixture is maintained at 6.0 to 6.5 with 10% sodium carbonate solution or lithium hydroxide solution. When consumption of the alkaline condensating agent has come to a standstill after several hours and a chromatographic sample indicates the disappearance of the coloured educt, the solution is salted out with 20% of sodium chloride, the dyestuff is filtered off with suction and washed with 20% strength sodium chloride solution and dried at 50.degree. C. in vacuo. The dyestuff of the formula ##STR25## dyes cotton and staple viscose by the known printing and continuous processes in a high fixation yield in brilliant reddish blue shades having excellent wet fastness properties. .lambda..sub.max =621 nm, 583 nm in H.sub.2 O.
EXAMPLE 2
If the condensation product obtained from 2,4-diaminobenzene and 4,6-difluoro-5-chloropyrimidine in Example 1.1 is reacted with 14.2 g of cyanuric fluoride instead of cyanuric chloride at 0.degree. to 5.degree. C. and a pH of 4.5 to 5.0 and the difluorotriazinyl product obtained is then condensed with the dyestuff from Example 1.2 at 0.degree. to 10.degree. C. and a pH of 6.0, a dyestuff of the formula ##STR26## is obtained, which after a suitable work-up likewise dyes cellulose fibres in high fixation yields in brilliant blue shades. .lambda..sub.max =621 nm, 583 nm in H.sub.2 O.
EXAMPLE 3
The condensation product mentioned in Example 2 and prepared from 18.8 g of 2,4-diaminobenzenesulphonic acid, 15.4 g of 4,6-difluoro-5-chloropyrimidine and 14.2 g of cyanuric fluoride is introduced into a neutralised solution of 41.9 g of 1-amino-4-(3'-amino-2'-methyl-5'-sulphophenylamino)-anthraquinone-2-sulphonic acid in 500 ml of water at 10.degree. to 15.degree. C. and the pH is maintained at 5.5 to 6.0 using 10% strength sodium carbonate solution. After the reaction is complete, the dyestuff is salted out with sodium chloride, filtered off with suction and washed with 10% strength sodium chloride solution. The blue powder obtained after drying at 40.degree. C. in vacuo has the formula ##STR27## and dyes cotton in neutral blue shades. .lambda..sub.max =611 nm in H.sub.2 O.
EXAMPLE 4
39.9 g of 4-amino-6-(4'-fluoro-5'-chloro-6'-pyrimidinylamino)-benzene-1,3-disulphonic acid (prepared by sulphonation of the condensation product from 2,4-diaminobenzenesulphonic acid with 4,6-difluoro-5-chloropyrimidine in 4.5 times the amount of 20 to 30% strength oleum, pouring the oleum solution onto ice-water and removing the sulphuric acid by precipitation with calcium carbonate) are condensed in 250 ml of water with 19.4 g of cyanuric chloride at 15.degree. C. and a pH of 4.5 to 5.0. After condensation is complete, the pH is brought to 7 and the temperature to 20.degree. C.
A solution of 34.8 g of 1-amino-4-(4'-aminocyclohexylamino)-anthraquinone-2-sulphonic acid in 380 ml of water brought to a pH of 11.5 is then run in at such a rate that a pH of 8.5 to 9.8 is maintained in the reaction mixture by simultaneous metering-in of 2N sodium hydroxide solution. The solid obtained is salted out with potassium chloride, filtered off with suction, washed and dried at 50.degree. C. in vacuo. It has the formula ##STR28## and dyes and prints cellulose fibres by the known techniques in very high fixation yields in bright blue shades. .lambda..sub.max =634 nm, 592 nm in H.sub.2 O.
EXAMPLE 5
53.1 g of 1-amino-4-(3'-amino-5'-sulpho-2',4',6'-trimethylphenylamino)-anthraquinone-2-sulphonic acid are dissolved in 530 parts of water at a pH of 6.
12.4 g of cyanuric chloride are dissolved in 100 ml of methyl ethyl ketone, and the solution is poured onto 100 g of ice. The dyestuff solution is then added dropwise to the cyanuric chloride suspension at 0.degree. to 10.degree. C., and the pH in the reaction mixture is maintained at 4.5 with 10% strength sodium carbonate solution. After reaction is complete, 41.8 g of the condensation product obtained from 2,5-diaminobenzene-1,4-disulphonic acid and 4,6-difluoro-5-chloropyrimidine are added in the form of an aqueous sodium salt solution, the pH is maintained at 6.0, the temperature at 25.degree. C. for 3 hours, and later at 35.degree. to 40.degree. C. After condensation is complete, the product is salted out and dried.
The dyestuff obtained of the formula ##STR29## produces on cellulose fibres by the known continuous and printing processes in very high fixation yields brilliant reddish blue dyeings.
EXAMPLE 6
6.1 18.8 g of 2,5-diaminobenzenesulphonic acid are condensed in 150 ml of water with 15.4 g of 4,6-difluoro-5-chloropyrimidine analogously to Example 1.1. 14.2 g of cyanuric fluoride are added dropwise to the solution of the condensation product at 0.degree. to 5.degree. C., and the pH is maintained at 4.5 to 5.0 during this addition. A neutralised solution of 45 g of 1-amino-4-(4'-N-methylamino-methyl-2'-sulpho-phenylamino)-anthraquinone-2-sulphonic acid in 600 ml of water is added to the product formed of the formula ##STR30## the pH is maintained at 5.5 to 6.0 and the temperature is allowed to rise gradually to 15.degree. C. over a period of 3 hours. After reaction is complete, the dyestuff is isolated by salting out, buffered at a pH of 6.0 by adding 3% of primary and secondary sodium phosphate and dried. The product of the formula ##STR31## dyes cellulose fibres by the dyeing techniques customary for reactive dyestuffs in neutral blue shades. .lambda..sub.max =600 nm in H.sub.2 O.
EXAMPLE 7
The condensation product prepared by the procedure of Example 1.1 from 9.4 g of 2,4-diaminobenzenesulphonic acid, 7.7 g of 4,6-difluoro-5-chloropyrimidine and 9.65 g of cyanuric chloride is introduced into a neutralised solution of 21 g of 1-amino-4-(3'-amino-4'-sulpho-phenylamino)-anthraquinone-2-sulphonic acid in 250 ml of water, the temperature is maintained at 25.degree. C. and the pH at 6.0 to 6.5 using 20% strength sodium carbonate solution or 10% strength lithium hydroxide solution. Isolation of the product by salting out, followed by drying, gives a dyestuff of the formula ##STR32## which dyes cotton in high fixation yields in blue shades. .lambda..sub.max =596 nm in H.sub.2 O.
In analogy to Examples 1 to 7, the following dyestuffs of the general formula ##STR33## in which the substituents have the meanings given in the table below, can also be prepared.
TABLE 1______________________________________No. A' R X A"______________________________________ 8 ##STR34## H F ##STR35## 9 ##STR36## H F ##STR37##10 ##STR38## H Cl ##STR39##11 ##STR40## H F ##STR41##12 ##STR42## H Cl ##STR43##13 ##STR44## H Cl ##STR45##14 ##STR46## H F ##STR47##15 ##STR48## H F ##STR49##16 ##STR50## H F ##STR51##17 ##STR52## H F ##STR53##18 ##STR54## H Cl ##STR55##19 ##STR56## CH.sub.3 F ##STR57##20 ##STR58## CH.sub.3 Cl ##STR59##21 ##STR60## CH.sub.3 Cl ##STR61##22 ##STR62## H F ##STR63##23 ##STR64## CH.sub.3 F ##STR65##24 ##STR66## H F ##STR67##______________________________________
EXAMPLE 25
17.6 g of the triphendioxazine compound of the formula ##STR68## are dissolved in 600 ml of water by bringing the pH to 9 with 2N sodium hydroxide solution. The condensation product of the formula ##STR69## prepared from 9.8 g of 2,4-diaminobenzenesulphonic acid, 8.0 g of 4,6-difluoro-5-chloropyrimidine and 7.2 g of cyanuric fluoride is added to the solution at 0.degree. to 10.degree. C., and the pH of the reaction mixture is maintained at 8.5 to 9.0. After reaction is complete, the dyestuff of the formula ##STR70## is isolated by salting out and dried at 50.degree. C. in vacuo.
EXAMPLE 26
47.3 g of 4-amino-6-(4'-fluoro-5'-chloro-6'-pyrimidinylamino)-benzenesulphonic acid are condensed in 350 ml of water with 22.4 g of cyanuric chloride by the procedure of Example 4.
30.0 g of the triphendioxazine compound of the formula ##STR71## are dissolved in 500 ml by addition of 70 ml of 2N sodium hydroxide solution.
Both products are added evenly at 20.degree. C. to 80 ml of previously introduced water at such a rate that a pH of 9.0 to 9.5 is established in the resulting reaction mixture. After the components have been combined, the pH is further maintained at this value using 2N sodium hydroxide solution until condensation is complete.
The resulting solid of the formula ##STR72## is salted out and dried at 50.degree. C. in vacuo. It dyes cotton in strong blue shades. .lambda..sub.max =623 nm in H.sub.2 O.
Analogously to Examples 25 and 26, further triphendioxazine reactive dyestuffs of the general formula ##STR73## in which the substituents have the meanings given in the table, can be prepared. (Colour indicator numbers according to Colour Index Hue Indication Chart).
TABLE 2__________________________________________________________________________ Colour indicatorNo. A.sub.2 R X B number__________________________________________________________________________27 (CH.sub.2).sub.3 H F ##STR74## 1428 (CH.sub.2).sub.2 H F ##STR75## 1429 (CH.sub.2).sub.4 H Cl ##STR76## 1430 (CH.sub.2).sub.3 CH.sub.3 F ##STR77## 1431 (CH.sub.2).sub.2 CH.sub.2CH.sub.2OSO.sub.3 H F ##STR78## 1432 (CH.sub.2).sub.3 H F ##STR79## 14__________________________________________________________________________
EXAMPLE 33
48.2 g of the copper phthalocyanine component of the formula ##STR80## prepared by the procedure given in European Patent 0,073,267 are dissolved in 450 ml of water at a pH of 7. A suspension of the condensation product which was previously prepared by the procedure of Example 1 from 12.5 g of 2,4-diaminobenzenesulphonic acid, 10.3 g of 4,6-difluoro-5-chloropyrimidine and 12.9 g of cyanuric chloride is then added at 20.degree. to 25.degree. C., and the pH of the reaction mixture is maintained at 7.0 to 7.5 by addition of 2N sodium hydroxide solution. When the consumption of the sodium hydroxide solution has come to a standstill, the dyestuff formed of the formula ##STR81## is salted out with sodium chloride and dried. The bluegreen powder produces on cotton and staple viscose in high fixation yield clear greenish blue prints and dyeings having excellent wet fastness properties. .lambda..sub.max =669 nm, 627 nm in H.sub.2 O.
EXAMPLE 34
If equimolar amounts of a nickel phthalocyanine component of the formula ##STR82## prepared by the procedure given in German Offenlegungsschrift 3,405,204 are used in Example 33 instead of the copper phthalocyanine component, a nickel phthalocyanine dyestuff of the formula ##STR83## is obtained. .lambda..sub.max =662 nm in H.sub.2 O.
The dyestuff produces on cotton and staple viscose clear bluish green dyeings having excellent wet fastness properties in a high fixation yield.
Analogously, further metal phthalocyanine reactive dyestuffs of the general formula ##STR84## in which the meanings of the substituents and the indices are given in Examples No. 35 to 50 in the table below, can be synthesised.
TABLE 3__________________________________________________________________________Phthalocyanine reactive dyestuffs of the formula IIINo. Me R.sub.1 R.sub.2 R.sub.3 R.sub.4 A.sub.3 X B u v w__________________________________________________________________________35 Cu H H CH.sub.3 CH.sub.3 (CH.sub.2).sub.2 Cl ##STR85## 1,9 0,8 1,136 Cu -- -- H H (CH.sub.2).sub.2 Cl ##STR86## 2,6 0 1,337 Cu H CH.sub.2CH.sub.2SO.sub.3 H H H (CH.sub.2).sub.2 Cl ##STR87## 2,0 0,6 1,338 Cu CH.sub.3 CH.sub.2CH.sub.2SO.sub.3 H H H CH.sub.2).sub.2 F ##STR88## 1,9 0,6 1,339 Cu H H H H (CH.sub.2).sub.2 F ##STR89## 1,9 0,6 1,340 Cu H H H H ##STR90## Cl ##STR91## 2,6 0 1,341 Cu H CH.sub.2CH.sub.2OSO.sub.3 H H CH.sub.3 (CH.sub.2).sub.3 Cl ##STR92## 2,4 0,5 1,042 Cu H H H H (CH.sub.2).sub.2 Cl ##STR93## 1,9 0,5 1,043 Cu H H H H (CH.sub.2).sub.3 Cl ##STR94## 2,4 0,4 1,544 Ni H H H H (CH.sub.2).sub.2 Cl ##STR95## 2,1 0,4 1,345 Ni H H CH.sub. 3 CH.sub.3 (CH.sub.2).sub.2 F ##STR96## 2,7 0 1,246 Cu H H R.sub.3 + R.sub.4 = CH.sub.2CH.sub.2(CH.sub.2).sub.2 Cl ##STR97## 2,1 0,5 1,347 Cu H H H H ##STR98## Cl ##STR99## 2,2 0,5 1,248 Cu H H CH.sub.3 CH.sub.3 (CH.sub.2).sub.2 F ##STR100## 2,2 0,5 1,349 Ni -- -- R.sub.3 -R.sub.4 = CH.sub.2CH.sub.2 (CH.sub.2).sub.2 Cl ##STR101## 2,5 0 1,350 Ni -- -- H H (CH.sub.2).sub.2 Cl ##STR102## 2,4 0 1,4__________________________________________________________________________
EXAMPLE 51
40 g of 1-amino-4-(2'-aminomethyl-4'-methyl-6'-sulphophenylamino)-anthraquinone-2-sulphonic acid are dissolved in 800 ml of water and 100 ml of acetone by neutralisation with about 45 ml of 2N sodium hydroxide solution at pH 7. The solution is cooled to 10.degree. C., and a solution of 17.5 g of cyanuric chloride in 100 ml of acetone is added dropwise over a period of 15 to 20 minutes. During the dropwise addition, the pH of the reaction mixture is maintained at 6.0 to 7.0 with 2N sodium carbonate solution. When consumption of sodium carbonate has come to a standstill about 1 hour after the addition of the cyanuric chloride, a solution of 40 g of 2-(2-aminoethyl)-aminoethanol in 100 ml of water brought to a pH of 6 with concentrated hydrochloric acid is added, the temperature is raised to 20.degree. to 25.degree. C., and the pH is maintained at 5.5 to 6.0 with 2N sodium hydroxide solution. After condensation is complete, the dyestuff, which essentially has the formula ##STR103## is salted out, filtered off with suction, washed amine-free with saturated sodium chloride solution and dissolved again in 500 ml of water.
14.6 g of 4,6-difluoro-5-chloropyrimidine are added to the solution at 25.degree. C., and the pH is maintained at 7.5 to 8.0 with 2N sodium hydroxide solution. When consumption of sodium hydroxide solution has come to a standstill and the above intermediate can no longer be detected, the resulting product of the formula ##STR104## is salted out and dried at 50.degree. C. in vacuo.
The dyestuff produces on cellulose fibres brilliant reddish blue prints having excellent wet fastness properties. .lambda..sub.max =624 nm, 587 nm in H.sub.2 O.
EXAMPLE 52
If the corresponding sulphuric acid monoester is used in Example 51 instead of the 2-(2-aminoethyl)-aminoethanol, a dyestuff of the formula ##STR105## is obtained which, in printing and continuous processes on cotton, has similar fastness properties as the dyestuff from Example 51. .lambda..sub.max =624 nm, 587 nm in H.sub.2 O.
Further anthraquinone dyestuffs containing an alkylenediamine bridging member between the halogenotriazinyl and 6-fluoro-5-chloro-4-pyrimidinyl radical are obtained if the following components are used:
TABLE 4__________________________________________________________________________53 ##STR106## ##STR107## ##STR108## ##STR109##54 ##STR110## ##STR111## ##STR112## ##STR113##55 ##STR114## ##STR115## ##STR116## ##STR117##56 ##STR118## ##STR119## ##STR120## ##STR121##57 ##STR122## ##STR123## ##STR124## ##STR125##58 ##STR126## ##STR127## NH.sub.2CH.sub.2CH.sub.2NH.sub.2 ##STR128##59 ##STR129## ##STR130## ##STR131## ##STR132##60 ##STR133## ##STR134## ##STR135## ##STR136##61 ##STR137## ##STR138## ##STR139## ##STR140##62 ##STR141## ##STR142## ##STR143## ##STR144##63 ##STR145## ##STR146## ##STR147## ##STR148##__________________________________________________________________________
EXAMPLE 64
39.7 g of the copper phthalocyanine compound of the formula ##STR149## prepared by condensation of copper phthalocyanine (tetrasulphochloride/sulphonic acid) with 3-aminoacetanilide and ammonia, followed by hydrolysis of the acteylamino group with dilute sodium hydroxide solution are dissolved in 450 ml of water at pH 7.
The solution is run into a cyanuric chloride suspension prepared by dissolving 7.6 g of cyanuric chloride in 40 ml of methyl ethyl ketone and pouring the solution onto 60 g of ice. While the dyestuff base is run in, the temperature in the reaction mixture is maintained at 0.degree. to 5.degree. C. by external cooling and the pH at 4.5 to 5.0 using 10% strength sodium carbonate solution. After condensation is complete, a solution of 4.2 g of 2-(2-aminoethyl)-aminoethanol in 40 ml of water brought to a pH of 5.0 is added to the solution obtained.
The temperature is raised to 20.degree. to 25.degree. C. and the pH of the reaction mixture from 5.0 to 6.0 to 6.5 over a period of one hour using 2N sodium hydroxide solution. When consumption of sodium hydroxide solution has come to a standstill, indicating that condensation is complete, 7.2 g of 4,6-difluoro-5-chloropyrimidine are added to the reaction mixture, the temperature is maintained at 25.degree. to 28.degree. C. and the pH at 6.5 to 7.0 by addition of further sodium hydroxide solution. After several hours, condensation is complete. The dyestuff is salted out, filtered off with suction and dried in vacuo. It has the formula ##STR150##
It dyes cotton in a clear greenish blue shade having excellent wet fastness properties and in high fixation yields. .lambda..sub.max =668 nm in H.sub.2 O.
Further metal phthalocyanine reactive dyestuffs of the general formula ##STR151## in which the meanings of the substituents and indices can be seen from the table below, can be synthesised analogously.
TABLE 5__________________________________________________________________________No. Me R.sub.12 R.sub.13 R.sub.1 R.sub.2 A' B.sub.1 X u v w__________________________________________________________________________65 Cu H H H C.sub.2 H.sub.5 ##STR152## (CH.sub.2).sub.3 F 1,1 0,5 2,366 Cu -- -- H H ##STR153## ##STR154## Cl 1,4 0 2,567 Ni H H H CH.sub.2 CH.sub.2 OH ##STR155## (CH.sub.2).sub.2 Cl 1,3 0 2,568 Cu CH.sub.3 CH.sub.2 CH.sub.2 SO.sub.3 H H CH.sub.3 ##STR156## (CH.sub.2).sub.3 Cl 1,1 0,4 2,569 Ni H H H H ##STR157## ##STR158## F 1,1 0,5 2,3__________________________________________________________________________
EXAMPLE 70
26 g of the sodium salt of the compound of the formula ##STR159## are dissolved in 200 ml of water at pH 7.5. The solution is cooled to 0.degree. C., and 9 g of cyanuric chloride are added, during which the pH is maintained at 5.5 by addition of sodium carbonate solution. After reaction is complete, a neutralised solution of 9.5 g of 2,5-diaminobenzene-1,4-disulphonic acid in 100 ml of water is added dropwise. During this addition, the pH is maintained at 7 with sodium carbonate solution. The temperature is allowed to rise to 25.degree. C. over a period of 2 hours. After condensation is complete, the dyestuff formed is salted out and filtered off with suction.
The dyestuff obtained of the formula ##STR160## is suspended as a paste in 300 ml of water; the pH of the mixture is brought to 8 to 9 with 10% strength sodium hydroxide solution. 7 g of 5-chloro-4,6-difluoropyrimidine are then added at 40.degree. to 50.degree. C. over a period of 30 minutes, during which the pH is maintained at 8 to 9 with 10% strength sodium hydroxide solution.
After reaction is complete, the dyestuff is salted out, isolated, dried and milled.
The dyestuff thus obtained of the formula ##STR161## dyes cotton in blue hues having good fastness properties.
EXAMPLE 71
20 g of 2,5-diaminobenzenesulphonic acid are dissolved in 200 ml of water at a pH of 6.5 to 7.5. 12 g of 5-chloro-4,6-difluoropyrimidine are added at 20.degree. C., and the pH is maintained at 6 to 7. Condensation is completed by heating the mixture to 35.degree. to 45.degree. C. The resulting cloudy solution of the intermediate of the formula ##STR162## is filtered to give a clear filtrate, which is then cooled to -5.degree. C., followed by addition of 9 ml of cyanuric fluoride. During this, the pH is maintained at 6 with 10% strength sodium hydroxide solution.
35 g of the sodium salt of the compound of the formula ##STR163## are dissolved in 200 ml of water at pH 7 to 8 and added in portions to the solution of the component of the formula ##STR164## prepared above. During this addition, the pH is maintained at 7 with 10% strength sodium hydroxide solution. The temperature is allowed to rise to 20.degree. C. over a period of 2 hours. The resulting dyestuff of the formula ##STR165## is salted out, filtered off and dried. It dyes cotton from a long liquor in very high fixation yields in blue hues.
EXAMPLE 72
Further valuable blue formazan dyestuffs according to the invention are obtained by the procedure of Examples 70 or 71 by reacting the components listed in Table 6.
In the bridge --A.sub.4 --, the N atom designated by * is bound to the C atom of the triazine rings.
The dyestuffs obtained have very good fibre-reactive dyestuff properties and produce, by the dyeing and printing processes customary for cellulose fibres, dyeings and prints of high colour strength and good fastness properties in very high fixation yields.
TABLE 6__________________________________________________________________________ ##STR166##No. D Trihalogenotriazine A.sub.4 .lambda..sub.max__________________________________________________________________________73 N-(2-carboxy-4-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR167## ##STR168## 624 nm74 N-(2-carboxy-4-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR169## ##STR170## 616 nm75 N-(2-carboxy-4-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR171## ##STR172## 626 nm76 N-(2-carboxy-4-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR173## ##STR174## 620 nm77 N-(2-carboxy-4-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR175## ##STR176## 622 nm78 N-(2-carboxy-5-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR177## ##STR178## 610 nm79 N-(2-carboxy-5-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR179## ##STR180## 616 nm80 N-(2-carboxy-5-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR181## ##STR182## 618 nm81 N-(2-carboxy-5-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR183## ##STR184## 620 nm82 N-(2-carboxy-5-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR185## ##STR186## 622 nm83 N-(2-carboxy-5-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR187## ##STR188## 614 nm84 N-(2-carboxy-5-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR189## ##STR190## 616 nm85 N-(2-carboxy-5-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR191## ##STR192## 614 nm86 N-(2-carboxy-5-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR193## ##STR194## 610 nm87 N-(2-carboxy-5-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR195## ##STR196## 612 nm88 N-(2-carboxy-5-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR197## ##STR198## 615 nm89 N-(2-carboxy-4-aminophenyl)-N'- (2'-hydroxy-5'-sulphophenyl)- ms-(2"-su lphophenyl)-formazan, Cu complex ##STR199## ##STR200## 600 nm90 N-(2-carboxy-4-aminophenyl)-N'- (2'-hydroxy-5'-sulphophenyl)- ms-(2"-su lphophenyl)-formazan, Cu complex ##STR201## ##STR202## 600 nm91 N-(2-carboxy-5-aminophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-(2"-sulphophenyl)- formazan, Cu complex ##STR203## ##STR204## 592 nm92 N-(2-carboxy-4-aminophenyl)-N'- (2'-hydroxy-3',5'-disulpho- phenyl)-ms- (2"-sulphophenyl)- formazan, Cu complex ##STR205## ##STR206## 608 nm93 N-(2-carboxy-5-sulphophenyl)-N'- (2'-hydroxy-5'-amino-3'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR207## ##STR208## 634 nm94 N-(2-carboxy-5-sulphophenyl)-N'- (2'-hydroxy-5'-amino-3'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR209## ##STR210## 636 nm95 N-(2-carboxy-4-sulphophenyl)-N'- (2'-hydroxy-5'-amino-3'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR211## ##STR212## 638 nm96 N-(2-carboxy-4-sulphophenyl)- N'-(2'-hydroxy-5'-sulphophenyl)- ms-(3"-aminophenyl)-formazan, Cu complex ##STR213## ##STR214## 622 nm__________________________________________________________________________
EXAMPLE 97
97.1 9.9 g of 2,4-diaminobenzenesulphonic acid are dissolved in 100 ml of water together with LiOH at pH 6.5. 7.6 g of 4,6-difluoro-5-chloropyrimidine are added dropwise to this solution at 35.degree. to 40.degree. C. over a period of 30 minutes and the pH is simultaneously maintained at 6.5 with Li.sub.2 CO.sub.3. After 2 hours, 100 g of ice and 1 g of NaF are added. 6.6 g of cyanuric fluoride are added at 0.degree. C., and the pH drops to about 3.7 to 3.8. After 5 minutes, the 2nd condensation is complete and, after filtration, a dark solution of the compound ##STR215## is obtained in the form of its lithium salt.
97.2 10.4 g of 7-amino-4-hydroxy-2-naphthalenesulphonic acid are dissolved in 150 ml of water together with LiOH at pH 7, and the condensation solution from Example 97.1 is added. During this addition, the pH is maintained at 5.5 with Na.sub.2 CO.sub.3 solution. After 20 minutes, the pH is raised to 6.5 and, after a further 20 minutes, a suspension of diazotised 1,5-naphthalenedisulphonic acid (14.1 g) is added, and the pH is raised to 6.5.
After 1 hour, the azo coupling is complete, and the dyestuff is salted out, isolated and dried; it has the formula ##STR216## and dyes cotton in brilliant orange shades which have very good wet fastness properties.
97.3 A further method of preparing the dyestuff from Example 97.2 consists in condensing the azo dyestuff of the formula ##STR217## with the reactive component from Example 97.1 at pH 7 to 7.5.
By varying the diazo component (D), coupling component (K) and diamines (W), it is possible to prepare the dyestuffs of the general formula ##STR218## analogously to Examples 1 and 97; they dye cotton in the hues given.
TABLE 7__________________________________________________________________________ Hue .lambda..sub.max 8No.XD K W (H.sub.2__________________________________________________________________________ O) ##STR219## ##STR220## ##STR221## bluish red 544 nm ##STR222## ##STR223## ##STR224## yellowish red ##STR225## ##STR226## ##STR227## bluish red ##STR228## ##STR229## ##STR230## red ##STR231## ##STR232## ##STR233## red ##STR234## ##STR235## ##STR236## red 515 nm ##STR237## ##STR238## ##STR239## red ##STR240## ##STR241## ##STR242## yellowish red ##STR243## ##STR244## ##STR245## bluish red 514 nm ##STR246## ##STR247## ##STR248## red 504, 526 nm ##STR249## ##STR250## ##STR251## orange ##STR252## ##STR253## ##STR254## scarlet 503 nm ##STR255## ##STR256## ##STR257## orange 498 nm ##STR258## ##STR259## ##STR260## red ##STR261## ##STR262## ##STR263## orange ##STR264## ##STR265## ##STR266## scarlet 504 nm ##STR267## ##STR268## ##STR269## scarlet 504 nm ##STR270## ##STR271## ##STR272## scarlet ##STR273## ##STR274## ##STR275## scarlet ##STR276## ##STR277## ##STR278## orange ##STR279## ##STR280## ##STR281## orange 488 nm ##STR282## ##STR283## ##STR284## bluish red ##STR285## ##STR286## ##STR287## bluish red ##STR288## ##STR289## ##STR290## golden yellow .lambda..sub.max = 448__________________________________________________________________________ nm .sup.+) The N atoms designated by * are connected to the triazinyl radical.
EXAMPLE 122
23.6 g of 7-amino-1,3-naphthalenedisulphonic acid monosodium salt were stirred in 150 ml of water/30 g of ice and 20 ml of concentrated hydrochloric acid, and 17 ml of an aqueous sodium nitrite solution (300 g of NaNO.sub.2 /l) were added dropwise at 5.degree. to 10.degree. C. After stirring at 5.degree. to 10.degree. C. for one hour, excess nitrous acid was removed using sulphamic acid.
This cream-coloured suspension was metered into a neutral solution of the coupling component prepared from 13.5 g of N-(3-aminophenyl)-acetamide hydrochloride, 50 ml of water, 50 g of ice and about 30 ml of a 10% strength aqueous lithium hydroxide solution over a period of 30 minutes. During this addition, the pH of the reaction mixture was kept constant at 6.0 to 6.5 using 20% strength aqueous potassium bicarbonate solution. If possible, the temperature should not exceed 10.degree. C. After addition had been completed, stirring was continued for 30 minutes, during which the pH was further kept constant.
15.2 g of 2,4-diaminobenzenesulphonic acid monosodium salt were stirred in 100 ml of water and dissolved at pH 6 using 10% strength lithium hydroxide solution. The solution was heated to 40.degree. C., and 12 g of 5-chloro-4,6-difluoropyrimidine were added. During this condensation reaction, the pH was kept constant at 5.8 to 6.2 using lithium hydroxide solution. After 2 hours at 40.degree. C., hardly any more change in pH could be observed, and condensation was complete according to HPLC analysis. The precipitated lithium fluoride was separated off by filtration. The mixture was then cooled to 0.degree. C. with about 200 g of ice and reacted at this temperature with 10 g of trifluoro-s-triazine. The pH of the second condensation was kept constant between 6.0 and 6.5 by simultaneously metering in 10% strength lithium hydroxide solution. After 15 minutes at 0.degree. to 2.degree. C., the reaction was complete.
The warm red-brown coupling solution of 8.degree. C. prepared above was metered into this colourless condensation solution at 0.degree. C. over a period of 20 minutes, during which the pH was kept constant between 7.0 and 7.2 using 20% sodium carbonate solution. The mixture was heated to 25.degree. C. at a constant pH of 7.0 to 7.2 over a period of 3 hours. After an additional stirring phase of one hour, the reaction was complete. The dyestuff solution was clarified in order to separate off insoluble components, such as lithium fluoride, and salted out with 50 g of sodium chloride. The precipitated dyestuff was filtered off with suction and dried, giving 61 g of an orange-red powder (.lambda..sub.max =406 nm (H.sub.2 O)), which has the structure ##STR291## and dyes cotton in golden yellow dyeings having excellent fastness properties.
By varying the diazo component D-NH.sub.2, the coupling component containing R.sup.1 and R.sup.2 and the diamino compound, further valuable golden yellow reactive dyestuffs of the formula ##STR292## were available in analogy to Example 122, for example those listed in Table 8 below.
TABLE 8__________________________________________________________________________Ex. D R.sup.1 R.sup.2 B*) .lambda..sub.max (H.sub.2 O)__________________________________________________________________________123 ##STR293## CH.sub.3 H ##STR294##124 ##STR295## H OCH.sub.3 ##STR296##125 ##STR297## NHCONH.sub.2 H ##STR298##126 ##STR299## NHCOCH.sub.2 OH H ##STR300## 408 nm127 ##STR301## NHCOCH.sub.2 OSO.sub.3 H H ##STR302## 412 nm128 ##STR303## CH.sub.3 H ##STR304##129 ##STR305## H OCH.sub.3 ##STR306##130 ##STR307## OCH.sub.3 CH.sub.3 ##STR308##131 ##STR309## NHCOCH.sub.3 H ##STR310##132 ##STR311## NHCOCH.sub.3 H ##STR312##133 ##STR313## NHCONH.sub.2 H ##STR314##134 ##STR315## NHCOCH.sub.3 H ##STR316##135 ##STR317## NHCOCH.sub.3 H ##STR318## 408 nm136 ##STR319## NHCONH.sub.2 H ##STR320## 426 nm137 ##STR321## NHCOCH.sub.3 H ##STR322## 410 nm138 ##STR323## NHCONH.sub.2 H ##STR324## 429 nm139 ##STR325## NHCOCH.sub.3 H ##STR326##140 ##STR327## NHCONH.sub.2 H ##STR328##141 ##STR329## NHCONH.sub.2 H ##STR330##142 ##STR331## NHCOCH.sub.3 H ##STR332##143 ##STR333## NHCONH.sub.2 H ##STR334##144 ##STR335## NHCOCH.sub.3 H ##STR336## 391 nm145 ##STR337## NHCONH.sub.2 H ##STR338## 395 nm146 ##STR339## NHCOCH.sub.2 OH H ##STR340## 392 nm147 ##STR341## NHCOCH.sub.3 H ##STR342## 394 nm148 ##STR343## NHCONH.sub.2 H ##STR344##149 ##STR345## NHCOCH.sub.3 H ##STR346## 392 nm150 ##STR347## NHCOCH.sub.3 H ##STR348##151 ##STR349## NHCONH.sub.2 H ##STR350##152 ##STR351## NHCONH.sub.2 H ##STR352##153 ##STR353## NHCOCH.sub.2 OSO.sub.3 H H ##STR354##__________________________________________________________________________ *)The pyrimidinyl radical is always bound to the N atom of B.
If trifluorotriazine in Example 122 and the examples of Table 8 is replaced by cyanuric chloride, comparable golden yellow bifunctional reactive dyestuffs having excellent fastness properties are obtained which only differ in the dyeing temperature which is 20.degree. C. higher.
EXAMPLE 154
A neutral aqueous solution of 30.9 g of 2-amino-3,6,8-naphthalenetrisulphonic acid disodium salt and 6 g of sodium nitrite in 200 ml of water was metered into a mixture of 40 ml of concentrated hydrochloric acid, 50 g of ice and 50 ml of water over a period of 15 minutes. After stirring at 5.degree. to 10.degree. C. for another 30 minutes, diazotisation was complete. The nitrite excess was removed using sulphamic acid.
This suspension was added to a neutral suspension of the coupling component prepared from 13.5 g of N-(3-aminophenyl)-urea and 100 ml of water over a period of 30 minutes. During this addition, the pH of the reaction mixture was kept constant at 6.0 to 6.5 using 20% strength aqueous potassium bicarbonate solution. If possible, the temperature should not exceed 15.degree. C. After addition had been completed, stirring was continued for 15 minutes, during which the pH of the orange-red solution was further kept constant.
Ice was added to this red-brown coupling solution until a temperature of 0.degree. C. was reached. 12 g of cyanuric fluoride was swiftly added and the pH was simultaneously kept constant at 6.0 to 6.2 by addition of a 20% strength potassium bicarbonate solution. Condensation was complete after 10 minutes. The pH was brought to 5.8 with a few drops of hydrochloric acid, and a solution of 5.8 g of 1,2-diaminopropane in 10 ml of water which was likewise brought to a pH of 5.8 with hydrochloric acid was added to this solution. The red reaction mixture was then heated to 20.degree. C. over a period of 2 hours, during which the pH was maintained at 5.8 to 5.9 with potassium bicarbonate solution. For a short period, this resulted in a solution from which, during an additional stirring phase of one hour, an orange-red precipitate was formed at a pH of 6.0 to 6.1. This dyestuff intermediate was filtered off with suction, and the isolated moist paste was stirred in 200 ml of water at pH 6.0. 12 g of 5-chloro-4,6-difluoropyrimidine were then added, the mixture was heated to 45.degree. C. and condensed at pH 7.5 to 8.0. pH control was carried out by means of sodium carbonate solution. Condensation was complete after about 2 hours. The dyestuff solution was filtered until clear, and the dyestuff was salted out with 25 g of common salt. Filtering off with suction and drying gave 58 g of an orange-red powder (.lambda..sub.max =428 nm (H.sub.2 O)), which has the structure ##STR355## and dyes cotton in reddish yellow hues.
By varying the diazo component D--NH.sub.2, the coupling component containing R.sup.1 and the aliphatic diamino compound, further valuable yellow to golden yellow hues of the following structure could be prepared analogously to Example 154. ##STR356##
TABLE 9__________________________________________________________________________Ex. D R.sup.1 B*) .lambda..sub.max (H.sub.2 O)__________________________________________________________________________155 CH.sub.3 ##STR357##156 ##STR358## OCH.sub.3 ##STR359##157 ##STR360## NHCOCH.sub.3 ##STR361##158 ##STR362## NHCOCH.sub.2 OSO.sub.3 H ##STR363## 408 nm159 ##STR364## NHCOCH.sub.3 ##STR365##160 ##STR366## NHCOCH.sub.3 ##STR367##161 ##STR368## NHCOCH.sub.3 ##STR369##162 ##STR370## NHCONH.sub.2 ##STR371##163 ##STR372## NHCOCH.sub.3 ##STR373## 412 nm164 ##STR374## NHCOCH.sub. 2 OH ##STR375## 410 nm165 ##STR376## NHCOCH.sub.3 ##STR377## 412 nm166 ##STR378## NHCOCH.sub.3 ##STR379## 416 nm167 ##STR380## NHCOCH.sub.3 ##STR381## 410 nm168 ##STR382## NHCOCH.sub.3 ##STR383##169 ##STR384## NHCOCH.sub.3 ##STR385## 412 nm170 ##STR386## NHCOCH.sub.3 ##STR387##171 ##STR388## NHCONH.sub.2 ##STR389## 426 nm172 ##STR390## NHCONH.sub.2 ##STR391## 428 nm173 ##STR392## NHCONH.sub.2 ##STR393## 432 nm174 ##STR394## NHCONH.sub.2 ##STR395## 416 nm175 ##STR396## NHCOCH.sub.3 ##STR397##176 ##STR398## NHCONH.sub.2 ##STR399##177 ##STR400## NHCOCH.sub.3 ##STR401## 396 nm178 ##STR402## NHCOCH.sub.3 ##STR403## 397 nm179 ##STR404## NHCONH.sub.2 ##STR405## 410 nm180 ##STR406## NHCOCH.sub.3 ##STR407##181 ##STR408## NHCONH.sub.2 ##STR409##182 ##STR410## NHCONH.sub.2 ##STR411##__________________________________________________________________________ *)The pyrimidinyl radical is always bound to the N atom marked with *.
If trifluorotriazine in Example 154 and the examples of Table 9 is replaced by cyanuric chloride, golden yellow reactive dyestuffs are obtained which have comparably excellent fastness properties, such as
EXAMPLE 183 ##STR412##
EXAMPLE 184
As described in Example 122, 15.2 g of sodium 2,4-diaminobenzenesulphonate was first condensed with 12 g of 5-chloro-4,6-difluoropyrimidine and then with 10 g of trifluoro-s-triazine (cyanuric fluoride).
30 g of the dyestuff base of the formula ##STR413## were added to this solution at 0.degree. C. and pH 6.0 to 6.2, and the pH was then kept constant at 7.0 with 20% strength sodium carbonate solution. The mixture was heated to 25.degree. C. at pH 7.0 to 7.2 over a period of 3 hours. The dyestuff solution was clarified by filtration, and 50 g of sodium chloride were added. The mixture was stirred for 1 hour, and the precipitated dyestuff was isolated by filtering it off with suction.
Drying and milling gave about 60 g of a yellow powder (.lambda..sub.max =424 nm (H.sub.2 O)) which has the structure ##STR414## and dyes cotton in brilliant greenish yellow shades.
By varying the pyridine coupling component and the diamino compound, the following further greenish yellow dyestuffs can be prepared analogously to Example 122 and 154; ##STR415##
TABLE 10__________________________________________________________________________Ex. B R.sup.1 R.sup.2__________________________________________________________________________184 C.sub.2 H.sub.5 CH.sub.2 SO.sub.3 H185 ##STR416## CH.sub.2 CH.sub.2 SO.sub.3 H H186 ##STR417## CH.sub.2 CH.sub.2 SO.sub.3 H CONH.sub.2187 ##STR418## CH.sub.3 CH.sub.2 SO.sub.3 H188 ##STR419## C.sub.2 H.sub.5 CH.sub.2 SO.sub.3 H189 ##STR420## C.sub.2 H.sub.5 CH.sub.2 SO.sub.3 H190 ##STR421## CH.sub.3 CH.sub.2 SO.sub.3 H191 ##STR422## CH.sub.3 CH.sub.2 SO.sub.3 H192 ##STR423## CH.sub.2 CH.sub.2 SO.sub.3 H H__________________________________________________________________________ The N atoms designated by * are bound to the pyrimidinyl radical.
If the dyestuff base in Example 184 is replaced by a comparable pyrazolone chromophore, dyestuffs such as
EXAMPLE 193 ##STR424## which dyes cotton in clear yellow shades (.lambda..sub.max =448 nm (H.sub.2 O)) can also be prepared.
If the aminoazo compounds listed in Table 11 below are reacted analogously to Example 97.3 under suitable conditions with the reactive component from Example 97.1, dyestuffs are obtained which dye cotton in the hues mentioned.
TABLE 11__________________________________________________________________________Ex. Aminoazo compound Hue__________________________________________________________________________194 ##STR425## dark red195 ##STR426## dark red196 ##STR427## dark red197 ##STR428## dark red198 ##STR429## dark red199 ##STR430## dark red200 ##STR431## dark red201 ##STR432## dark red202 ##STR433## dark red203 ##STR434## dark red204 ##STR435## dark red205 ##STR436## dark red206 ##STR437## dark red207 ##STR438## dark red208 ##STR439## red-violet209 ##STR440## dark red210 ##STR441## dark red1:2 Cr complex of211 ##STR442## grey-blue (black)1:2 Co complex of212 ##STR443## yellow-brown213 ##STR444## blue214 ##STR445## blue215 ##STR446## blue216 ##STR447## blue217 ##STR448## navy__________________________________________________________________________
If the condensation products obtained according to Example 97.2 or 97.3 from the aminoazo compounds listed in Table 12 below with the reactive component from Example 97.1 are reacted in a known manner at pH 5 to 7 and 20.degree. C. to 60.degree. C. in aqueous solution with equimolar amounts of hydrogen peroxide, copper complex dyestuffs are obtained which dye cotton in the hues mentioned, for example from the aminoazo compound from Example 218 the dyestuff of the formula ##STR449##
TABLE 12__________________________________________________________________________Ex. Aminoazo compound Hue__________________________________________________________________________218 dark red219 ##STR450## dark red220 ##STR451## dark red221 ##STR452## dark red222 ##STR453## blue223 ##STR454## blue224 ##STR455## blue225 ##STR456## blue226 ##STR457## navy__________________________________________________________________________
If aminodisazo dyestuffs of the general formula ##STR458## are reacted with the reactive component from Example 97.1 analogously to Example 97, dyestuffs of the general formula from Table 13 ##STR459## are obtained which dye cotton in the hues mentioned.
TABLE 13__________________________________________________________________________No. Y D K D' W Hue__________________________________________________________________________227 F ##STR460## ##STR461## ##STR462## ##STR463## Black228 F ##STR464## ##STR465## ##STR466## ##STR467## Navy Black229 F ##STR468## ##STR469## ##STR470## ##STR471## Navy Black230 F ##STR472## ##STR473## ##STR474## ##STR475## Black231 F ##STR476## ##STR477## ##STR478## ##STR479## Navy232 F ##STR480## ##STR481## ##STR482## ##STR483## Navy233 F ##STR484## ##STR485## ##STR486## ##STR487## Navy__________________________________________________________________________ .sup.+) The N atoms designated by * are linked to the triazinyl radical
The following dyestuffs which dye cotton in the hues mentioned ##STR488## can be prepared analogously to Example 97.3.
EXAMPLE 236
18.8 g of 2,4-diaminobenzenesulphonic acid are dissolved in 80 ml of water by neutralisation with 10% strength lithium hydroxide solution and condensed at 25.degree. to 40.degree. C. with 15.4 g of 2,4,6-trifluoropyrimidine at pH 5.5 to 6.0. After consumption of lithium hydroxide is complete, 19.3 g of cyanuric chloride are added to the solution of the condensation product, the temperature is maintained at 20.degree. to 25.degree. C. and the pH at 5.0 using lithium hydroxide. When no more diazotisable amino group can be detected, the second condensation step is concluded, and a solution or viscous suspension of the compound ##STR489## in the form of its lithium salt has been formed.
46.5 g of 1-amino-4-(2'-aminomethyl-4'-methyl-6'-sulphophenylamino)-anthraquinone-2-sulphonic acid are dissolved in 300 ml of water and 10 g of caprolactam with neutralisation at pH at 7.degree. and 70.degree. C. After cooling to room temperature, the solution is added to the condensation product from Example 1.1, and the pH in the reaction mixture is maintained at 6.0 to 6.5 with 10% strength sodium carbonate solution or lithium hydroxide solution. When consumption of the alkaline condensating agent has come to a standstill after several hours, and a chromatographic sample indicates that the coloured educt has disappeared, the solution is salted out with 20% sodium chloride, the dyestuff is filtered off with suction and washed with 20% strength sodium chloride solution and dried at 50.degree. C. in vacuo. The dyestuff of the formula ##STR490## dyes cotton and staple viscose by the known printing and continuous processes in a high fixation yield in brilliant reddish blue shades having excellent wet fastness properties. .lambda..sub.max =621 nm, 583 nm in H.sub.2 O.
EXAMPLE 237
If the condensation product obtained from 2,4-diaminobenzene and 2,4,6-trifluoropyrimidine in Example 236 is reacted with 14.2 g of cyanuric fluoride instead of cyanuric chloride at 0.degree. to 5.degree. C. and pH 4.5 to 5.0, and the difluorotriazinyl product obtained is then condensed with the dyestuff from Example 1.2 at 0.degree. to 10.degree. C. and pH 6.0, a dyestuff of the formula ##STR491## is obtained, which after suitable work-up likewise dyes cellulose fibres in high fixation yields in brilliant blue shades. .lambda..sub.max =621 nm, 583 nm in H.sub.2 O.
EXAMPLE 238
The condensation product obtained from 18.8 g of 2,4-diaminobenzenesulphonic acid, 15.4 g of 2,4,6-trifluoropyrimidine and 14.2 g of cyanuric fluoride as mentioned in Example 237 is introduced into a neutralised solution of 41.9 g of 1-amino-4-(3'-amino-2'-methyl-5'-sulphophenylamino)-anthraquinone-2-sulphonic acid in 500 ml of water at 10.degree. to 15.degree. C., and the pH is maintained at 5.5 to 6.0 with 10% strength sodium carbonate solution. After reaction is complete, the dyestuff is salted out with sodium chloride, filtered off with suction and washed with 10% strength sodium chloride solution. The blue powder obtained after drying at 40.degree. C. in vacuo has the formula ##STR492## and dyes cotton in neutral blue shades. .lambda..sub.max =611 nm in H.sub.2 O.
EXAMPLE 239
39.9 g of 4-amino-6-(2',4'-difluoro-6'-pyrimidinylamino)-benzene-1,3-disulphonic acid (prepared by sulphonation of the condensation product of 2,4-diaminobenzenesulphonic acid with 2,4,6-trifluoropyrimidine in 4.5 times the amount of 20 to 30% strength oleum, pouring the oleum solution onto ice-water and removing the sulphuric acid by precipitation with calcium carbonate) are condensed in 250 ml of water with 19.4 g of cyanuric chloride at 15.degree. C. and pH 4.5 to 5.0. After condensation is complete, the pH is brought to 7 and the temperature to 20.degree. C.
A solution of 34.8 g of 1-amino-4-(4'-aminocyclohexylamino)-anthraquinone-2-sulphonic acid in 380 ml of water, which has been brought to a pH of 11.5, is then run in at such a rate that a pH of 8.5 to 9.0 is maintained in the reaction mixture by simultaneous metering-in of 2N sodium hydroxide solution. The solid obtained is salted out with potassium chloride, filtered off with suction, washed and dried at 50.degree. C. in vacuo. It has the formula ##STR493## and dyes and prints cellulose fibres by the known techniques in very high fixation yields in bright blue shades. .lambda..sub.max =634 nm, 592 nm in H.sub.2 O.
EXAMPLE 240
53.1 g of 1-amino-4-(3'-amino-5'-sulpho-2',4',6'-trimethylphenylamino)-anthraquinone-2-sulphonic acid are dissolved in 530 parts of water at pH 6.
12.4 g of cyanuric chloride are dissolved in 100 ml of methyl ethyl ketone, and the solution is poured onto 100 g of ice. The dyestuff solution is then added dropwise to the cyanuric chloride suspension at 0.degree. to 10.degree. C., and the pH in the reaction mixture is maintained at 4.5 using 10% strength sodium carbonate solution. After reaction is complete, 41.8 g of the condensation product obtained from 2,5-diaminobenzene-1,4-disulphonic acid and 2,4,6-trifluoro-pyrimidine are added in the form of an aqueous sodium salt solution, the pH is maintained at 6.0, the temperature at 25.degree. C. for 3 hours, and later at 35.degree. to 40.degree. C. After condensation is complete, the product is salted out and dried.
The dyestuff obtained of the formula ##STR494## produces on cellulose fibres by the known continuous and printing processes brilliant reddish blue dyeings in very high fixation yields.
EXAMPLE 241
18.8 g of 2,5-diaminobenzenesulphonic acid are condensed in 150 ml of water analogously to Example 236 with 15.4 g of 2,4,6-trifluoropyrimidine. 14.2 g of cyanuric fluoride are added dropwise to the solution of the condensation product at 0.degree. to 5.degree. C., and the pH is maintained during this addition at 4.5 to 5.0. A neutralised solution of 45 g of 1-amino-4-(4'-N-methylaminomethyl-2'-sulpho-phenylamino)anthraquinone-2-sulphonic acid in 600 ml of water is added to the product formed of the formula ##STR495## the pH is maintained at 5.5 to 6.0, and the temperature is allowed to rise gradually to 15.degree. C. over a period of 3 hours. After reaction is complete, the dyestuff is isolated by salting out, buffered at pH 6.0 by addition of 3% of primary and secondary sodium phosphate and dried. The product of the formula ##STR496## dyes cellulose fibres by the dyeing techniques customary for reactive dyestuffs in neutral blue hues. .lambda..sub.max =600 nm in H.sub.2 O.
EXAMPLE 242
The condensation product prepared by the procedure of Example 236 from 9.4 g of 2,4-diaminobenzenesulphonic acid, 7.7 g of 2,4,6-trifluoropyrimidine and 9.65 g of cyanuric chloride is introduced into a neutralised solution of 21 g of 1-amino-4-(3'-amino-4'-sulpho-phenylamino)-anthraquinone-2-sulphonic acid in 250 ml of water, the temperature is maintained at 25.degree. C. and the pH at 6.0 to 6.5 using 20% strength sodium carbonate solution or 10% strength lithium hydroxide solution. Isolation of the product by salting out, followed by drying, gives a dyestuff of the formula ##STR497## which dyes cotton in blue hues and high fixation yields. .lambda..sub.max =596 nm in H.sub.2 O.
Analogously to Examples 236 to 242, the following dyestuffs of the general formula ##STR498## in which the substituents have the meanings given in the table below, can also be prepared.
TABLE 14______________________________________No. A' R X A"______________________________________243 ##STR499## H F ##STR500##244 ##STR501## H F ##STR502##245 ##STR503## H Cl ##STR504##246 ##STR505## H F ##STR506##247 ##STR507## H Cl ##STR508##248 ##STR509## H Cl ##STR510##249 ##STR511## H F ##STR512##250 ##STR513## H F ##STR514##251 ##STR515## H F ##STR516##252 ##STR517## H F ##STR518##253 ##STR519## H Cl ##STR520##254 ##STR521## CH.sub.3 F ##STR522##255 ##STR523## CH.sub.3 Cl ##STR524##256 ##STR525## CH.sub.3 Cl ##STR526##257 ##STR527## H F ##STR528##258 ##STR529## CH.sub.3 F ##STR530##259 ##STR531## H F ##STR532##______________________________________
Example 260
17.6 g of the triphendioxazine compound of the formula ##STR533## are dissolved in 600 ml of water by bringing the pH to 9 with 2N sodium hydroxide solution. The condensation product of the formula ##STR534## prepared from 9.8 g of 2,4-diaminobenzenesulphonic acid, 8.0 g of 2,4,6-trifluoropyrimidine and 7.2 g of cyanuric fluoride is added to the solution at 0.degree. to 10.degree. C., and the pH of the reaction mixture is maintained at 8.5 to 9.0. After reaction is complete, the dyestuff of the formula ##STR535## is isolated by salting out and dried at 50.degree. C. in vacuo.
EXAMPLE 261
47.3 g of 4-amino-6-(2',4'-difluoro-6'-pyrimidinylamino)benzenesulphonic acid are condensed in 350 ml of water with 22.4 g of cyanuric chloride by the procedure of Example 239.
30.0 g of the triphendioxazine compound of the formula ##STR536## are dissolved in 500 ml by addition of 70 ml of 2N sodium hydroxide solution.
Both products are added evenly at 20.degree. C. to 80 ml of previously introduced water at such a rate that a pH of 9.0 to 9.5 is established in the resulting reaction mixture. After the components have been combined, the pH is further maintained at this value using 2N sodium hydroxide solution until condensation is complete.
The resulting solid of the formula ##STR537## is salted out and dried at 50.degree. C. in vacuo. It dyes cotton in strong blue shades. .lambda..sub.max =623 nm in H.sub.2 O.
Analogously to Examples 260 and 261, further triphendioxazine reactive dyestuffs of the general formula ##STR538## in which the substituents have the meanings given in the table, can be prepared. (Colour indicator numbers according to Colour Index Hue Indication Chart).
TABLE 15__________________________________________________________________________ Colour indicatorNo. A.sub.2 R X B number__________________________________________________________________________262 (CH.sub.2).sub.3 H F ##STR539## 14263 (CH.sub.2).sub.2 H F ##STR540## 14264 (CH.sub.2).sub.4 H Cl ##STR541## 14265 (CH.sub.2).sub.3 CH.sub.3 F ##STR542## 14266 (CH.sub.2).sub.2 CH.sub.2CH.sub.2OSO.sub.3 H F ##STR543## 14267 (CH.sub.2).sub.3 H F ##STR544## 14__________________________________________________________________________
EXAMPLE 268
48.2 g of the copper phthalocyanine component of the formula ##STR545## prepared by the procedure given in European Patent 0,073,267 are dissolved in 450 ml of water at a pH of 7. A suspension of the condensation product which was previously prepared by the procedure of Example 236 from 12.5 g of 2,4-diaminobenzenesulphonic acid, 10.3 g of 2,4,6-trifluoropyrimidine and 12.9 g of cyanuric chloride is then added at 20.degree. to 25.degree. C., and the pH in the reaction mixture is maintained at 7.0 to 7.5 by addition of 2N sodium hydroxide solution. When the consumption of the sodium hydroxide solution has come to a standstill, the dyestuff formed of the formula ##STR546## is salted out with sodium chloride and dried. The blue-green powder produces on cotton and staple viscose in high fixation yield clear greenish blue prints and dyeings having excellent wet fastness properties. .lambda..sub.max =669 nm, 627 nm in H.sub.2 O.
EXAMPLE 269
If equimolar amounts of a nickel phthalocyanine component of the formula ##STR547## prepared by the procedure given in German Offenlegungsschrift 3,405,204 are used in Example 268 instead of the copper phthalocyanine component, a nickel phthalocyanine dyestuff of the formula ##STR548## is obtained. .lambda..sub.max =662 nm in H.sub.2 O.
The dyestuff produces on cotton and staple viscose clear bluish green dyeings having excellent wet fastness properties in a high fixation yield.
Analogously, further metal phthalocyanine reactive dyestuffs of the general formula ##STR549## in which the meanings of the substituents and the indices are given in Examples No. 270 to 285 in the table below, can be synthesised.
TABLE 16__________________________________________________________________________Phthalocyanine reactive dyestuffs of the formula IIINo. Me R.sub.1 R.sub.2 R.sub.3 R.sub.4 A.sub.3 X B u v w__________________________________________________________________________270 Cu H H CH.sub.3 CH.sub.3 (CH.sub.2).sub.2 Cl ##STR550## 1,9 0,8 1,1271 Cu -- -- H H (CH.sub.2).sub.2 Cl ##STR551## 2,6 0 1,3272 Cu H CH.sub.2CH.sub.2SO.sub.3 H H H (CH.sub.2).sub.2 Cl ##STR552## 2,0 0,6 1,3273 Cu CH.sub.3 CH.sub.2CH.sub.2SO.sub.3 H H H CH.sub.2).sub.2 F ##STR553## 1,9 0,6 1,3274 Cu H H H H (CH.sub.2).sub.2 F ##STR554## 1,9 0,6 1,3275 Cu H H H H ##STR555## Cl ##STR556## 2,6 0 1,3276 Cu H CH.sub.2CH.sub.2OSO.sub.3 H H CH.sub.3 (CH.sub.2).sub.3 Cl ##STR557## 2,4 0,5 1,0277 Cu H H H H (CH.sub.2).sub.2 Cl ##STR558## 1,9 0,5 1,0278 Cu H H H H (CH.sub.2).sub.3 Cl ##STR559## 2,4 0,4 1,5279 Ni H H H H (CH.sub.2).sub.2 Cl ##STR560## 2,1 0,4 1,3280 Ni H H CH.sub. 3 CH.sub.3 (CH.sub.2).sub.2 F ##STR561## 2,7 0 1,2281 Cu H H R.sub.3 + R.sub.4 = CH.sub.2CH.sub.2(CH.sub.2).sub.2 Cl ##STR562## 2,1 0,5 1,3282 Cu H H H H ##STR563## Cl ##STR564## 2,2 0,5 1,2283 Cu H H CH.sub.3 CH.sub.3 (CH.sub.2).sub.2 F ##STR565## 2,2 0,5 1,3284 Ni -- -- R.sub.3 -R.sub.4 = CH.sub.2CH.sub.2 (CH.sub.2).sub.2 Cl ##STR566## 2,5 0 1,3285 Ni -- -- H H (CH.sub.2).sub.2 Cl ##STR567## 2,4 0 1,4__________________________________________________________________________
EXAMPLE 286
40 g of 1-amino-4-(2'-aminomethyl-4'-methyl-6'-sulphophenylamino)-anthraquinone-2-sulphonic acid are dissolved in 800 ml of water and 100 ml of acetone by neutralisation with about 45 ml of 2N sodium hydroxide solution at pH 7. The solution is cooled to 10.degree. C., and a solution of 17.5 g of cyanuric chloride in 100 ml of acetone is added dropwise over a period of 15 to 20 minutes. During the dropwise addition, the pH of the reaction mixture is maintained at 6.0 to 7.0 with 2N sodium carbonate solution. When consumption of sodium carbonate has come to a standstill about 1 hour after the addition of the cyanuric chloride, a solution of 40 g of 2-(2-aminoethyl)-aminoethanol in 100 ml of water brought to a pH of 6 with concentrated hydrochloric acid is added, the temperature is raised to 20.degree. to 25.degree. C., and the pH is maintained at 5.5 to 6.0 with 2N sodium hydroxide solution. After condensation is complete, the dyestuff, which essentially has the formula ##STR568## is salted out, filtered off with suction, washed amine-free with saturated sodium chloride solution and dissolved again in 500 ml of water.
14.6 g of 2,4,6-trifluoropyrimidine is added to the solution at 25.degree. C., and the pH is maintained at 7.5 to 8.0 with 2N sodium hydroxide solution. When consumption of sodium hydroxide solution has come to a standstill and the above intermediate can no longer be detected, the resulting product of the formula ##STR569## is salted out and dried at 50.degree. C. in vacuo.
The dyestuff produces on cellulose fibres brilliant reddish blue prints having excellent wet fastness properties. .lambda..sub.max =624 nm, 587 nm in H.sub.2 O.
EXAMPLE 287
If the corresponding sulphuric acid monoester is used in Example 286 instead of the 2-(2-aminoethyl)-aminoethanol, a dyestuff of the formula ##STR570## is obtained which, in printing and continuous processes on cotton, has similar fastness properties as the dyestuff from Example 51. .lambda..sub.max =624 nm, 587 nm in H.sub.2 O.
Further anthraquinone dyestuffs containing an alkylene-diamine bridging member between the halogenotriazinyl and 2,6-difluoro-4-pyrimidinyl radical are obtained if the following components are used:
TABLE 17__________________________________________________________________________288 ##STR571## ##STR572## ##STR573## ##STR574##289 ##STR575## ##STR576## ##STR577## ##STR578##290 ##STR579## ##STR580## ##STR581## ##STR582##291 ##STR583## ##STR584## ##STR585## ##STR586##292 ##STR587## ##STR588## ##STR589## ##STR590##293 ##STR591## ##STR592## NH.sub.2CH.sub.2CH.sub.2NH.sub.2 ##STR593##294 ##STR594## ##STR595## ##STR596## ##STR597##295 ##STR598## ##STR599## ##STR600## ##STR601##296 ##STR602## ##STR603## ##STR604## ##STR605##297 ##STR606## ##STR607## ##STR608## ##STR609##298 ##STR610## ##STR611## ##STR612## ##STR613##__________________________________________________________________________
EXAMPLE 299
39.7 g of the copper phthalocyanine compound of the formula ##STR614## prepared by condensation of copper phthalocyanine (tetrasulphochloride/sulphonic acid) with 3-aminoacetanilide and ammonia, followed by hydrolysis of the acetylamino group with dilute sodium hydroxide solution are dissolved in 450 ml of water at pH 7.
The solution is run into a cyanuric chloride suspension prepared by dissolving 7.6 g of cyanuric chloride in 40 ml of methyl ethyl ketone and pouring the solution onto 60 g of ice. While the dyestuff base is run in, the temperature in the reaction mixture is maintained at 0.degree. to 5.degree. C. by external cooling and the pH at 4.5 to 5.0 using 10% strength sodium carbonate solution. After condensation is complete, a solution of 4.2 g of 2-(2-aminoethyl)-aminoethanol in 40 ml of water brought to a pH of 5.0 is added to the solution obtained.
The temperature is raised to 20.degree. to 25.degree. C. and the pH of the reaction mixture from 5.0 to 6.0 to 6.5 over a period of one hour using 2N sodium hydroxide solution. When consumption of sodium hydroxide solution has come to a standstill indicating that condensation is complete, 7.2 g of 2,4,6-trifluoropyrimidine are added to the reaction mixture, the temperature is maintained at 25.degree. to 28.degree. C. and the pH at 6.5 to 7.0 by addition of further sodium hydroxide solution. After several hours, condensation is complete. The dyestuff is salted out, filtered off with suction and dried in vacuo. It has the formula ##STR615##
It dyes cotton in a clear greenish blue shade having excellent wet fastness properties and in high fixation yields. .lambda..sub.max =668 nm in H.sub.2 O.
Further metal phthalocyanine reactive dyestuffs of the general formula ##STR616## in which the meanings of the substituents and indices can be seen from the table below, can be synthesised analogously.
TABLE 18__________________________________________________________________________No. Me R.sub.12 R.sub.13 R.sub.1 R.sub.2 A' B.sub.1 X u v w__________________________________________________________________________300 Cu H H H C.sub.2 H.sub.5 ##STR617## (CH.sub.2).sub.3 F 1,1 0,5 2,3301 Cu -- -- H H ##STR618## ##STR619## Cl 1,4 0 2,5302 Ni H H H CH.sub.2 CH.sub.2 OH ##STR620## (CH.sub.2).sub.2 Cl 1,3 0 2,5303 Cu CH.sub.3 CH.sub.2 CH.sub.2 SO.sub.3 H H CH.sub.3 ##STR621## (CH.sub.2).sub.3 Cl 1,1 0,4 2,5304 Ni H H H H ##STR622## ##STR623## F 1,1 0,5 2,3__________________________________________________________________________
EXAMPLE 305
26 g of the sodium salt of the compound of the formula ##STR624## are dissolved in 200 ml of water at pH 7.5. The solution is cooled to 0.degree. C., and 9 g of cyanuric chloride are added, during which the pH is maintained at 5.5 by addition of sodium carbonate solution. After reaction is complete, a neutralised solution of 9.5 g of 2,5-diaminobenzene-1,4-disulphonic acid in 100 ml of water is added dropwise. During this addition, the pH is maintained at 7 with sodium carbonate solution. The temperature is allowed to rise to 25.degree. C. over a period of 2 hours. After condensation is complete, the dyestuff formed is salted out and filtered off with suction.
The dyestuff obtained of the formula ##STR625## is suspended as a paste in 300 ml of water; the pH of the mixture is brought to 8 to 9 with 10% strength sodium hydroxide solution. 7 g of 2,4,6-trifluoropyrimidine are then added at 40.degree.to 50.degree. C. over a period of 30 minutes, during which the pH is maintained at 8 to 9 with 10% strength sodium hydroxide solution.
After reaction is complete, the dyestuff is salted out, isolated, dried and milled.
The dyestuff thus obtained of the formula ##STR626## dyes cotton in blue hues having good fastness properties.
EXAMPLE 306
20 g of 2,5-diaminobenzenesulphonic acid are dissolved in 200 ml of water at a pH of 6.5 to 7.5. 12 g of 2,4,6-trifluoropyrimidine are added at 20.degree. C., and the pH is maintained at 6 to 7. Condensation is completed by heating the mixture to 35.degree.to 45.degree. C. The resulting cloudy solution of the intermediate of the formula ##STR627## is filtered to give a clear filtrate, which is then cooled to -5.degree. C., followed by addition of 9 ml of cyanuric fluoride. During this, the pH is maintained at 6 with 10% strength sodium hydroxide solution.
35 g of the sodium salt of the compound of the formula ##STR628## are dissolved in 200 ml of water at pH 7 to 8 and added in portions to the solution of the component of the formula ##STR629## prepared above. During this addition, the pH is maintained at 7 with 10% strength sodium hydroxide solution. The temperature is allowed to rise to 20.degree. C. over a period of 2 hours. The resulting dyestuff of the formula ##STR630## is salted out, filtered off and dried. It dyes cotton from a long liquor in very high fixation yields in blue hues.
EXAMPLE 307
Further valuable blue formazan dyestuffs according to the invention are obtained by the procedure of Examples 305 or 306 by reacting the components listed in Table 6.
In the bridge --A.sub.4 --, the N atom designated by * is bound to the C atom of the triazine rings.
The dyestuffs obtained have very good fibre-reactive dyestuff properties and produce, by the dyeing and printing processes customary for cellulose fibres, dyeings and prints of high colour strength and good fastness properties in very high fixation yields.
TABLE 19__________________________________________________________________________ ##STR631##No. D Trihalogenotriazine A.sub.4 .lambda..sub.max__________________________________________________________________________308 N-(2-carboxy-4-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR632## ##STR633## 624 nm309 N-(2-carboxy-4-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR634## ##STR635## 616 nm310 N-(2-carboxy-4-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR636## ##STR637## 626 nm311 N-(2-carboxy-4-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR638## ##STR639## 620 nm312 N-(2-carboxy-4-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR640## ##STR641## 622 nm313 N-(2-carboxy-5-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR642## ##STR643## 610 nm314 N-(2-carboxy-5-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR644## ##STR645## 616 nm315 N-(2-carboxy-5-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR646## ##STR647## 618 nm316 N-(2-carboxy-5-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR648## ##STR649## 620 nm317 N-(2-carboxy-5-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR650## ##STR651## 622 nm318 N-(2-carboxy-5-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR652## ##STR653## 614 nm319 N-(2-carboxy-5-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR654## ##STR655## 616 nm320 N-(2-carboxy-5-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR656## ##STR657## 614 nm321 N-(2-carboxy-5-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR658## ##STR659## 610 nm322 N-(2-carboxy-5-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR660## ##STR661## 612 nm323 N-(2-carboxy-5-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR662## ##STR663## 615 nm324 N-(2-carboxy-4-aminophenyl)-N'- (2'-hydroxy-5'-sulphophenyl)-ms- (2"-sulphophenyl)-formazan, Cu complex ##STR664## ##STR665## 600 nm325 N-(2-carboxy-4-aminophenyl)-N'- (2'-hydroxy-5'-sulphophenyl)- ms-(2"-su lphophenyl)-formazan, Cu complex ##STR666## ##STR667## 600 nm326 N-(2-carboxy-5-aminophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho- phenyl)-ms-(2"-sulphophenyl)- formazan, Cu complex ##STR668## ##STR669## 592 nm327 N-(2-carboxy-4-aminophenyl)-N'- (2'-hydroxy-3',5'-disulpho- phenyl)-ms- (2"-sulphophenyl)- formazan, Cu complex ##STR670## ##STR671## 608 nm328 N-(2-carboxy-5-sulphophenyl)-N'- (2'-hydroxy-5'-amino-3'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR672## ##STR673## 634 nm329 N-(2-carboxy-5-sulphophenyl)-N'- (2'-hydroxy-5'-amino-3'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR674## ##STR675## 636 nm330 N-(2-carboxy-4-sulphophenyl)-N'- (2'-hydroxy-5'-amino-3'-sulpho- phenyl)-ms-phenylformazan, Cu complex ##STR676## ##STR677## 638 nm331 N-(2-carboxy-4-sulphophenyl)- N'-(2'-hydroxy-5'-sulpho- phenyl)-ms-(3"- aminophenyl)- formazan, Cu complex ##STR678## ##STR679## 622 nm__________________________________________________________________________
EXAMPLE 332
332.1
9.9 g of 2,4-diaminobenzenesulphonic acid are dissolved in 100 ml of water together with LiOH at pH 6.5. 7.6 g of 2,4,6-trifluoropyrimidine are added dropwise to this solution at 35.degree. to 40.degree. C. over a period of 30 minutes and the pH is simultaneously maintained at 6.5 with Li.sub.2 CO.sub.3. After 2 hours, 100 g of ice and 1 g of NaF are added. 6.6 g of cyanuric fluoride are added at 0.degree. C., and the pH drops to about 3.7 to 3.8. After 5 minutes, the 2nd condensation is complete and, after filtration, a dark solution of the compound ##STR680## is obtained in the form of its lithium salt.
332.1
10.4 g of 7-amino-4-hydroxy-2-naphthalenesulphonic acid are dissolved in 150 ml of water together with LiOH at pH 7, and the condensation solution from Example 332.1 is added. During this addition, the pH is maintained at 5.5 with Na.sub.2 CO.sub.3 solution. After 20 minutes, the pH is raised to 6.5 and, after a further 20 minutes, a suspension of diazotised 1,5-naphthalenedisulphonic acid (14.1 g) is added, and the pH is raised to 6.5.
After 1 hour, the azo coupling is complete, and the dyestuff is salted out, isolated and dried; it has the formula ##STR681## and dyes cotton in brilliant orange shades which have very good wet fastness properties.
332.3
A further method of preparing the dyestuff from Example 332.2 consists in condensing the azo dyestuff of the formula ##STR682## with the reactive component from Example 332.1 at pH 7 to 7.5.
By varying the diazo component (D), coupling component (K) and diamines (W), it is possible to prepare the dyestuff of the general formula ##STR683## analogously to Examples 236 and 332; they dye cotton in the hues given.
TABLE 20__________________________________________________________________________ Hue .lambda..sub.max NNo.XD K W (H.sub.2__________________________________________________________________________ O) ##STR684## ##STR685## ##STR686## bluish red 544 nm ##STR687## ##STR688## ##STR689## yellowish red ##STR690## ##STR691## ##STR692## bluish red ##STR693## ##STR694## ##STR695## red ##STR696## ##STR697## ##STR698## red ##STR699## ##STR700## ##STR701## red 515 nm ##STR702## ##STR703## ##STR704## red ##STR705## ##STR706## ##STR707## yellowish red ##STR708## ##STR709## ##STR710## bluish red 514 nm ##STR711## ##STR712## ##STR713## red 504, 526 nm ##STR714## ##STR715## ##STR716## orange ##STR717## ##STR718## ##STR719## scarlet 503 nm ##STR720## ##STR721## ##STR722## orange 498 nm ##STR723## ##STR724## ##STR725## red ##STR726## ##STR727## ##STR728## orange ##STR729## ##STR730## ##STR731## scarlet 504 nm ##STR732## ##STR733## ##STR734## scarlet 504 nm ##STR735## ##STR736## ##STR737## scarlet ##STR738## ##STR739## ##STR740## scarlet ##STR741## ##STR742## ##STR743## orange ##STR744## ##STR745## ##STR746## orange 488 nm ##STR747## ##STR748## ##STR749## bluish red ##STR750## ##STR751## ##STR752## bluish red ##STR753## ##STR754## ##STR755## golden yellow .lambda..sub.max = 448__________________________________________________________________________ nm .sup.+) The N atoms designated by * are connected to the triazinyl radical.
EXAMPLE 357
23.6 g of 7-amino-1,3-naphthalenedisulphonic acid monosodium salt were stirred in 150 ml of water/30 g of ice and 20 ml of concentrated hydrochloric acid, and 17 ml of an aqueous sodium nitrite solution (300 g of NaNO.sub.2 /l) were added dropwise at 5.degree. to 10.degree. C. After stirring at 5.degree. to 10.degree. C. for one hour, excess nitrous acid was removed using sulphamic acid.
This cream-coloured suspension was metered into a nuetral solution of the coupling component prepared from 13.5 g of N-(3-aminophenyl)-acetamide hydrochloride, 50 ml of water, 50 g of ice and about 30 ml of a 10% strength aqueous lithium hydroxide solution over a period of 30 minutes. During this addition, the pH of the reaction mixture is kept constant at 6.0 to 6.5 using 20% strength aqueous potassium bicarbonate solution. If possible, the temperature should not exceed 10.degree. C. After addition had been completed, stirring was continued for 30 minutes, during which the pH was further kept constant.
15.2 g of 2,4-diaminobenzenesulphonic acid monosodium salt were stirred in 100 ml of water and dissolved at pH 6 using 10% strength lithium hydroxide solution. The solution was heated to 40.degree. C., and 12 g of 2,4,6-trifluoropyrimidine were added. During this condensation reaction, the pH was kept constant at 5.8 to 6.2 using lithium hydroxide solution. After 2 hours at 40.degree. C., hardly any more change in pH could be observed, and condensation was complete according to HPLC analysis. The precipitated lithium fluoride was separated off by filtration. The mixture was then cooled to 0.degree. C. with about 200 g of ice and reacted at this temperature with 10 g of trifluoro-s-triazine. The pH of the second condensation was kept constant between 6.0 and 6.5 by simultaneously metering in 10% strength lithium hydroxide solution. After 15 minutes at 0.degree. to 2.degree. C., the reaction was complete.
The warm red-brown coupling solution of 8.degree. C. prepared above was metered into this colourless condensation solution at 0.degree. C. over a period of 20 minutes, during which the pH was kept constant between 7.0 and 7.2 using 20% sodium carbonate solution. The mixture was heated to 25.degree. C. at a constant pH of 7.0 to 7.2 over a period of 3 hours. After an additional stirring phase of one hour, the reaction was complete. The dyestuff solution was clarified, in order to separate off insoluble components, such as lithium fluoride, and salted out with 50 g of sodium chloride. The precipitated dyestuff was filtered off with suction and dried, giving 61 g of an orange-red powder (.lambda..sub.max =406 nm (H.sub.2 O)), which has the structure ##STR756## and dyes cotton in golden yellow dyeings having excellent fastness properties.
By varying the diazo component D--NH.sub.2, the coupling component containing R.sup.1 and R.sup.2 and the diamino compound, further valuable golden yellow reactive dyestuffs of the formula ##STR757## were available in analogy to Example 357, for example those listed in Table 21 below.
TABLE 21__________________________________________________________________________Ex. D R.sup.1 R.sup.2 B*) .lambda..sub.max (H.sub.2 O)__________________________________________________________________________358 ##STR758## CH.sub.3 H ##STR759##359 ##STR760## H OCH.sub.3 ##STR761##360 ##STR762## NHCONH.sub.2 H ##STR763##361 ##STR764## NHCOCH.sub.2 OH H ##STR765## 408 nm362 ##STR766## NHCOCH.sub.2 OSO.sub.3 H H ##STR767## 412 nm363 ##STR768## CH.sub.3 H ##STR769##364 ##STR770## H OCH.sub.3 ##STR771##365 ##STR772## OCH.sub.3 CH.sub.3 ##STR773##366 ##STR774## NHCOCH.sub.3 H ##STR775##367 ##STR776## NHCOCH.sub.3 H ##STR777##368 ##STR778## NHCONH.sub.2 H ##STR779##369 ##STR780## NHCOCH.sub.3 H ##STR781##370 ##STR782## NHCOCH.sub.3 H ##STR783## 408 nm371 ##STR784## NHCONH.sub.2 H ##STR785## 426 nm372 ##STR786## NHCOCH.sub.3 H ##STR787## 410 nm373 ##STR788## NHCONH.sub.2 H ##STR789## 429 nm374 ##STR790## NHCOCH.sub.3 H ##STR791##375 ##STR792## NHCONH.sub.2 H ##STR793##376 ##STR794## NHCONH.sub.2 H ##STR795##377 ##STR796## NHCOCH.sub.3 H ##STR797##378 ##STR798## NHCONH.sub.2 H ##STR799##379 ##STR800## NHCOCH.sub.3 H ##STR801## 391 nm380 ##STR802## NHCONH.sub.2 H ##STR803## 395 nm381 ##STR804## NHCOCH.sub.2 OH H ##STR805## 392 nm382 ##STR806## NHCOCH.sub.3 H ##STR807## 394 nm383 ##STR808## NHCONH.sub.2 H ##STR809##384 ##STR810## NHCOCH.sub.3 H ##STR811## 392 nm385 ##STR812## NHCOCH.sub.3 H ##STR813##386 ##STR814## NHCONH.sub.2 H ##STR815##387 ##STR816## NHCONH.sub.2 H ##STR817##388 ##STR818## NHCOCH.sub.2 OSO.sub.3 H H ##STR819##__________________________________________________________________________ *)The pyrimidinyl radical is always bound to the N atom of B.
If trifluorotriazine in Example 357 and the examples of Table 21 is replaced by cyanuric chloride, comparable golden yellow bifunctional reactive dyestuffs having excellent fastness properties are obtained which only differ in the dyeing temperature which is 20.degree. C. higher.
EXAMPLE 389
A neutral aqueous solution of 30.9 g of 2-amino-3,6,8-naphthalenetrisulphonic acid disodium salt and 6 g of sodium nitrite in 200 ml of water was metered into a mixture of 40 ml of concentrated hydrochloric acid, 50 g of ice and 50 ml of water over a period of 15 minutes. After stirring at 5.degree. to 10.degree. C. for another 30 minutes, diazotisation was complete. The nitrite excess was removed using sulphamic acid.
This suspension was added to a neutral suspension of the coupling component prepared from 13.5 g of N-(3-aminophenyl)-urea and 100 ml of water over a period of 30 minutes. During this addition, the pH of the reaction mixture was kept constant at 6.0 to 6.5 using 20% strength aqueous potassium bicarbonate solution. If possible, the temperature should not exceed 15.degree. C. After addition had been completed, stirring was continued for 15 minutes, during which the pH of the orange-red solution was further kept constant.
Ice was added to this red-brown coupling solution until a temperature of 0.degree. C. was reached. 12 g of cyanuric fluoride was swiftly added and the pH was simultaneously kept constant at 6.0 to 6.2 by addition of a 20% strength potassium bicarbonate solution. Condensation was complete after 10 minutes. The pH was brought to 5.8 with a few drops of hydrochloric acid, and a solution of 5.8 g of 1,2-diaminopropane in 10 ml of water which was likewise brought to a pH of 5.8 with hydrochloric acid was added to this solution. The red reaction mixture was then heated to 20.degree. C. over a period of 2 hours, during which the pH was maintained at 5.8 to 5.9 with potassium bicarbonate solution. For a short period, this resulted in a solution from which, during an additional stirring phase of one hour, an orange-red precipitate was formed at a pH of 6.0 to 6.1. This dyestuff intermediate was filtered off with suction, and the isolated moist paste was stirred in 200 ml of water at pH 6.0. 12 g of 2,4,6-trifluoropyrimidine were added, the mixture was heated to 45.degree. C. and condensed at pH 7.5 to 8.0. pH control was carried out by means of sodium carbonate solution. Condensation was complete after about 2 hours. The dyestuff solution was filtered until clear, and the dyestuff was salted out with 25 g of common salt. Filtering off with suction and drying gave 58 g of an orange-red powder (.lambda..sub.max =428 nm (H.sub.2 O)), which has the structure ##STR820## and dyes cotton in reddish yellow hues.
By varying the diazo component D--NH.sub.2, the coupling component containing R.sup.1 and the aliphatic diamino compound, further valuable yellow to golden yellow hues of the following structure could be prepared analogously to
Example 389. ##STR821##
TABLE 22__________________________________________________________________________Ex. D R.sup.1 B*) .lambda..sub.max (H.sub.2 O)__________________________________________________________________________390 CH.sub.3 ##STR822##391 ##STR823## OCH.sub.3 ##STR824##392 ##STR825## NHCOCH.sub.3 ##STR826##393 ##STR827## NHCOCH.sub.2 OSO.sub.3 H ##STR828## 408 nm394 ##STR829## NHCOCH.sub.3 ##STR830##395 ##STR831## NHCOCH.sub.3 ##STR832##396 ##STR833## NHCOCH.sub.3 ##STR834##397 ##STR835## NHCONH.sub.2 ##STR836##398 ##STR837## NHCOCH.sub.3 ##STR838## 412 nm399 ##STR839## NHCOCH.sub. 2 OH ##STR840## 410 nm400 ##STR841## NHCOCH.sub.3 ##STR842## 412 nm401 ##STR843## NHCOCH.sub.3 ##STR844## 416 nm402 ##STR845## NHCOCH.sub.3 ##STR846## 410 nm403 ##STR847## NHCOCH.sub.3 ##STR848##404 ##STR849## NHCOCH.sub.3 ##STR850## 412 nm405 ##STR851## NHCOCH.sub.3 ##STR852##406 ##STR853## NHCONH.sub.2 ##STR854## 426 nm407 ##STR855## NHCONH.sub.2 ##STR856## 428 nm408 ##STR857## NHCONH.sub.2 ##STR858## 432 nm409 ##STR859## NHCONH.sub.2 ##STR860## 416 nm410 ##STR861## NHCOCH.sub.3 ##STR862##411 ##STR863## NHCONH.sub.2 ##STR864##412 ##STR865## NHCOCH.sub.3 ##STR866## 396 nm413 ##STR867## NHCOCH.sub.3 ##STR868## 397 nm414 ##STR869## NHCONH.sub.2 ##STR870## 410 nm415 ##STR871## NHCOCH.sub.3 ##STR872##416 ##STR873## NHCONH.sub.2 ##STR874##417 ##STR875## NHCONH.sub.2 ##STR876##__________________________________________________________________________ *)The pyrimidinyl radical is always bound to the N atom marked with *.
If trifluorotriazine in Example 389 and the examples of Table 22 is replaced by cyanuric chloride, golden yellow reactive dyestuffs which have comparably excellent fastness properties, such as
EXAMPLE 418 ##STR877##
EXAMPLE 419
As described in Example 357, 15.2 g of monosodium 2,4-diaminobenzenesulphonate were first condensed with 12 g of 2,4,6-trifluoropyrimidine and then with 10 g of trifluoro-s-triazine (cyanuric fluoride).
30 g of the dyestuff base of the formula ##STR878## were added to this solution at 0.degree. C. and pH 6.0 to 6.2, and the pH was then kept constant at 7.0 with 20% strength sodium carbonate solution. The mixture was heated to 25.degree. C. at pH 7.0 to 7.2 over a period of 3 hours. The dyestuff solution was clarified by filtration, and 50 g of sodium chloride were added. The mixture was stirred for 1 hour, and the precipitated dyestuff was isolated by filtering it off with suction.
Drying and milling gave about 60 g of a yellow powder (.lambda..sub.max =424 nm (H.sub.2 O)) which has the structure ##STR879## and dyes cotton in brilliant greenish yellow shades.
By varying the pyridone coupling component and the diamino compound, the following further greenish yellow dyestuffs can be prepared analogously to Example 357 and 389: ##STR880##
TABLE 23__________________________________________________________________________Ex. B R.sup.1 R.sup.2__________________________________________________________________________419 C.sub.2 H.sub.5 CH.sub.2 SO.sub.3 H420 ##STR881## CH.sub.2 CH.sub.2 SO.sub.3 H H421 ##STR882## CH.sub.2 CH.sub.2 SO.sub.3 H CONH.sub.2422 ##STR883## CH.sub.3 CH.sub.2 SO.sub.3 H423 ##STR884## C.sub.2 H.sub.5 CH.sub.2 SO.sub.3 H424 ##STR885## C.sub.2 H.sub.5 CH.sub.2 SO.sub.3 H425 ##STR886## CH.sub.3 CH.sub.2 SO.sub.3 H426 ##STR887## CH.sub.3 CH.sub.2 SO.sub.3 H427 ##STR888## CH.sub.2 CH.sub.2 SO.sub.3 H H__________________________________________________________________________ The N atoms designated by * are bound to the pyrimidinyl radical.
If the dyestuff base in Example 419 is replaced by a comparable pyrazolone chromophore, dyestuffs such as
EXAMPLE 428 ##STR889## which dyes cotton in clear yellow shades (.lambda..sub.max =448 nm (H.sub.2 O)) can also be prepared.
If the aminoazo compounds listed in Table 24 below are reacted analogously to Example 332.3 under suitable conditions with the reactive component from Example 332.1, dyestuffs are obtained which dye cotton in the hues mentioned.
TABLE 24__________________________________________________________________________Ex. Aminoazo compound Hue__________________________________________________________________________429 ##STR890## dark red430 ##STR891## dark red431 ##STR892## dark red432 ##STR893## dark red433 ##STR894## dark red434 ##STR895## dark red435 ##STR896## dark red436 ##STR897## dark red437 ##STR898## dark red438 ##STR899## dark red439 ##STR900## dark red440 ##STR901## dark red441 ##STR902## dark red442 ##STR903## dark red443 ##STR904## red-violet444 ##STR905## dark red445 ##STR906## dark red1:2 Cr complex of446 ##STR907## grey-blue (black)1:2 Co complex of447 ##STR908## yellow-brown448 ##STR909## blue449 ##STR910## blue450 ##STR911## blue451 ##STR912## blue452 ##STR913## navy__________________________________________________________________________
If the condensation products obtained according to Example 332.2 or 332.3 from the aminoazo compounds listed in Table 25 below are reacted with the reactive component from Example 332.1 in a known manner at pH 5 to 7 and 20.degree. C. to 60.degree. C. in aqueous solution with equimolar amounts of hydrogen peroxide, copper complex dyestuffs are obtained which dye cotton in the hues mentioned, for example from the aminoazo compound from Example 453 the dyestuff of the formula ##STR914##
TABLE 25__________________________________________________________________________Ex. Aminoazo compound Hue__________________________________________________________________________453 dark red454 ##STR915## dark red455 ##STR916## dark red456 ##STR917## dark red457 ##STR918## blue458 ##STR919## blue459 ##STR920## blue460 ##STR921## blue461 ##STR922## navy__________________________________________________________________________
If aminodisazo dyestuffs of the general formula ##STR923## are reacted with the reactive component from Example 332.1 analogously to Example 332, dyestuffs of the general formula of Table 26 ##STR924## are obtained which dye cotton in the hues mentioned.
TABLE 26__________________________________________________________________________No. Y D K D' W Hue__________________________________________________________________________462 F ##STR925## ##STR926## ##STR927## ##STR928## Black463 F ##STR929## ##STR930## ##STR931## ##STR932## Navy/Black464 F ##STR933## ##STR934## ##STR935## ##STR936## Navy/Black465 F ##STR937## ##STR938## ##STR939## ##STR940## Black466 F ##STR941## ##STR942## ##STR943## ##STR944## Navy467 F ##STR945## ##STR946## ##STR947## ##STR948## Navy468 F ##STR949## ##STR950## ##STR951## ##STR952## Navy__________________________________________________________________________ .sup.+) The N atoms designated by * are linked to the triazinyl radical
The following dyestuffs which dye cotton in the hues mentioned ##STR953## can be prepared analogously to Example 332.3.

Number	Date	Country	Kind
4115833	May 1991	DEX
4117387	May 1991	DEX

Number	Name	Date
4248771	Scholl et al.	Feb 1981
4330469	Gati et al.	May 1982
4806640	Harms et al.	Feb 1989

Number	Date	Country
97119	Dec 1983	EPX
345577	Dec 1989	EPX
1450102	Oct 1965	FRX
2341626	Sep 1977	FRX
2417532	Sep 1979	FRX
1115778	May 1968	GBX
1530104	Oct 1978	GBX
2200131	Jul 1988	GBX
2039289	Aug 1988	GBX

Reactive dyestuff containing triazinyl and halopyrimidine moieties

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Entry
84-1001470/01, "Dyes cont'g fluoro-triazinyl and tri:halo . . . ", Chem.Ab.J-5, Textiles;Paper;Cellulose, p. 14 (J5-F). (1984).
100:122758g, K. Seitz, "Reactive Dyes", Chem. Ab., V100, (1984) pp. 81-82.