CH627206A5 - - Google Patents

Description

The invention relates to reactive dyes of the form

d - n - c c -

f I II

r-, n n

1 ^

I.

f wherein D is the residue of an organic dye, Ri is hydrogen or Ci_4-alkyl, R2 is hydrogen, methyl or ethyl, X is a residue of the formula -SO2CH2CH2CI, -SC> 2CH = CH2, -SO2CH2CH2OSO3H, -SO2CH2CH2OPO3H or -N (R3) S02CH2CH20S03H and R3 is hydrogen, methyl or ethyl and the benzene or naphthalene radical may contain other substituents besides X.

In the reactive dyes of the formula (1), the radical D is in particular the radical of a dye of the mono- or polyazo, metal complex azo, anthraquinone, phthalocyanine, formazane, nitroaryl, dioxazine, phenazine or stilbene series.

The radical D preferably contains water-solubilizing groups, in particular sulfonic acid groups.

Reactive dyes of the formula (1) in which D is the remainder of a mono- or disazo dye are preferred.

The substituent Ri in formula (1) is as alkyl with 1 to 4 carbon atoms: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl.

If the radical bonded to the s-triazine ring via the -N (R2) bridge member is a naphthalene radical, it can be bonded in the a or β position.

30th

35

45

(D,

The rest of an organic dye D in formula (1) may contain further substituents, examples being: alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl and butyl, alkoxy groups with 1 to 4 carbon atoms, such as methoxy, ethoxy , Propoxy, iso-propoxy and butoxy, acylamino groups with 1 to 6 carbon atoms, such as acetylamino, propionylamino and benzoyl-amino, halogen, such as fluorine, chlorine and bromine, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, ureido, hydroxy, Carboxy, sulfomethyl and sulfo. In particular, the radical D contains sulfonic acid groups as substituents.

The benzene or naphthalene radical in formula (1) can be used as further substituents in addition to X z. B. contain the following: Ci_4-alkyl, Ct_4-alkoxy, halogen such as fluorine, chlorine and bromine, nitro, hydroxy, carboxy and sulfo.

Reactive dyes of the formula (1) in which R 1 is hydrogen, methyl or ethyl and R 2 and R 3 are each a hydrogen atom are preferred.

The reactive dyes of the formula a-n = n form an important class

(so3h)

m

(2),

wherein A is a benzene or naphthalene radical, m 1 or 2, n 0 or 1 and p 0 or 1, where the benzene or naphthalene radical A and the benzene radical B may contain further substituents and X has the meaning given under formula (1) .

The other substituents in the benzene or naphthalene radical A and in the benzene radical B are the same as those mentioned above in the explanation of the formula (1) as possible substituents in the radical D.

If the radical D or A contains complex-forming groups, such as hydroxyl, carboxy, amino and sulfo, the heavy metal complexes of the reactive dyes of the formulas (1) and (2) can also be used.

627206

4th

A valuable reactive dye of the class characterized by formula (2) is the reactive dye of the formula nh—

(3).

s02ch2ch20s03h

The reactive dyes of the formula (1) can be prepared by adding 2,4,6-trifluoro-s-triazine of the formula

v f - c c - f

IN THE

n n * C '

i f

an organic dye of the formula d - nh i

r-,

(4);

or a precursor of the formula D'-N (Ri) H (5b) which can be coupled to an azo dye of the formula (5a)

and an amine of the formula

(6)

condensed in any order, and that if a dye precursor of the formula (5b) is used, D 'is converted into D by coupling.

The organic dyes of the formula (5a) used are, in particular, those in which the radical D is the residue of a dye of the mono- or polyazo, metal complex azo, anthraquinone, phthalocyanine, formazane, azomethine, nitroaryl, dioxazine, Phenazine or stilbene series.

Organic dyes of the formula (5a) in which the radical D contains water-solubilizing groups or dye precursors of organic dyes of the formula (5b) which contain water-solubilizing groups are preferably used as starting materials.

The sulfonic acid group is particularly suitable as a water-solubilizing group.

Organic dyes of the formula (5a) in which D is the remainder of a mono- or disazo dye are preferably used as starting materials.

Since the individual method steps specified above can be carried out in different orders, if necessary partially also simultaneously, different method variants are possible.

In general, the reaction is carried out step by step, the order of the simple reactions between the individual reaction components of the

15

Formulas (4), (5a) and (6) can be chosen freely.

Important process variants for the preparation of the reactive dyes of the formula (1) are characterized in that

20 1) 2,4,6-trifluoro-s-triazine of the formula (4) is condensed with an organic dye of the formula (5a) and the primary condensation product is condensed with an amine of the formula (6); 2) 2,4,6-trifluoro-s-triazine of the formula (4) is condensed with an amine of the formula (6) and the primary condensation product 25 is condensed with an organic dye of the formula (5a).

After a modification of the process described above, the reactive dyes of the formula (1), in which D is the residue of an organic dye composed of two or more than two components, can be prepared in such a way that one component of the dye of the formula (5a), which contains a -N (Ri) H group, a 2,4,6-tri-fluoro-s-triazine of the formula (4) and an aminobenzene of the formula (6), and in any stage of the process with the other (or the remaining) component (s) of the dye of the formula (5a) to form a reactive dye of the formula (1).

Examples of such organic dyes composed of two or more than two components are: monoazo, disazo, trisazo, tetrazo, metal complex azo and 40 formazan dyes.

The process modification described above is particularly important for the production of reactive dyes of the formula (1), in which D is the remainder of an azo dye containing sulfo groups. In these the part of the azo dye residue to which the s-triazine residue is attached can be either the rest of the di-azo component or the rest of the coupling component. This results in two variants of the process modification described above.

One of the two variants is characterized in that a diazo component containing an -N (Ri) H group is condensed with a 2,4,6-trifluoro-s-triazine of the formula (4), the resultant Condensation product diazotized and coupled to a coupling component, and before or after reacting with an amine of formula (6).

55 The second variant is characterized in that a coupling component which contains an -N (Ri) H group is condensed with a 2,4,6-trifluoro-s-triazine of the formula (4) and onto the condensation product thus obtained couples a diazotized diazo component and reacts before or after with a 60 amine of the formula (6).

According to this production variant, reactive dyes of the formula (1) which contain 2 reactive s-triazine radicals can be prepared by mixing a diazo component which contains an -N (Ri) -H group with a 2,4,6-trifluoro- s-tria-65 in the formula (4) is condensed, that further a coupling component which contains an -N (Ri) -H group with a 2,4,6-trifluoro-s-triazine of the formula (4) condensed, and that the condensation product of the diazo component

5

627206

diazotized and coupled to the condensation product of the coupling component and reacted before or after with an amine of formula (6).

Reactive dyes of the formula (1) which contain two or more than 2 reactive s-triazine radicals can also be prepared in such a way that organic dyes of the formula (5b) which are further D -N (Ri) -H Contain groups, condensed with a corresponding amount of 2,4,6-trifluoro-s-triazine of the formula (4), so that two or more than two s-triazine residues are introduced into the dye molecule. 10th

A preferred embodiment of the process for the preparation of the reactive dyes of the formula (1) is characterized in that organic dyes of the formula (5a), in which D is the remainder of a mono- or disazo dye, are used as starting materials, or that disazokompo 15 nenten and / or coupling components containing an -N (Ri) -H group condensed with the 2,4,6-trifluoro-s-triazine of the formula (4), and after or after the other

Condensation with the amine of formula (6) completes the dye by coupling with the other component or the other components of the mono- or disazo dye.

A further preferred embodiment is characterized in that organic dyes of the formula (5a), in which R 1 is hydrogen, methyl or ethyl, and amines of the formula (66), in which R 2 and R 3 are each a hydrogen atom, are used as starting materials.

The preferred reactive dyes of the formula (2) are prepared by using a diazotized amino compound of the formula a - nh2 (7),

a coupling component of the formula

- nh-

(8th)

H

-TI

2,4,6-trifluoro-s-triazine of the formula (4) and an amine of the formula 30 a reactive dye of the formula (2).

h2n-

<0

(9)

x by coupling and condensation in any order to ho a-n = n

The most important process variants for the preparation of the reactive dyes of the formula (2) are characterized in that

1) a diazotized amino compound of the formula (7) with a coupling component of the formula (8) to an azo compound of the formula

(10)

- nh -

H

-TI

couples, this condenses with 2,4,6-trifluoro-1,3,5-triazine of the formula (4) and the primary condensation product obtained is condensed with an amine of the formula (9) to form a reactive dye of the formula (2);

2) a coupling component of the formula (8) is condensed with 2,4,6-tri-fluoro-1,3,5-triazine of the formula (4), the primary condensation product obtained is condensed with an amine of the formula (9) and the resulting product couples secondary condensation product with a diazotized amino compound of formula (7) to a reactive dye of formula (2);

3) a coupling component of the formula (8) is condensed with 2,4,6-tri-fluoro-1,3,5-triazine of the formula (4), a diazotized amino compound of the formula (7) is coupled to the primary condensation product obtained and the obtained azo compound with an amine of formula (9) condensed to a reactive dye of formula (2).

If the finished reactive dyes of the formula (1) or (2)

oh contain complex-forming groups, they can be subsequently implemented with heavy metal donating agents. The particularly valuable reactive dye of the formula (3) 50 is preferably prepared according to the process variant listed under (2) by condensing l-amino-8-hydroxynaphthalene-3,6-disulfonic acid with cyanuric fluoride, the primary condensation product with l-aminobenzene-3 -ß-sulfatoäthylsul-fon condensed and coupled to the secondary condensation product 55-diazotized 2-aminonaphthalene-l, 5-disulfonic acid.

The following may be mentioned as starting materials for the preparation of the reactive dyes of the formula (1):

60 a) 2,4,6-trifluoro-s-triazine (cyanuric fluoride) of the formula (4) b) organic dyes of the formula (5) 1. monoazo compounds of the formula nhr,

(11)

627206

6

wherein Di is an at most bicyclic aryl radical free of azo and -NHRi groups, Ri is hydrogen or Ci_4-alkyl, and the -NHRi group is preferably attached to the 5-, 6-, 7- or 8-position of the naphthalene nucleus and which may contain a sulfonic acid group in the 5- or 6-position of the naphthalene nucleus.

Di can mean a radical of the naphthalene or benzene series which contains no azo substituents, for example a stilbene, diphenyl, benzthiazolylphenyl or diphenylamine radical. In this class, the related dyes should also be noted, in which the -NHRi group, instead of being bound to the naphthalene nucleus, to a benzoyl-amino- bonded to the 5-, 6-, 7- or 8-position of the naphthalene nucleus or anilino group.

Particularly valuable starting dyes are those in which Di is a sulfonated phenyl or naphthyl radical, in particular those which contain an -SChH group ortho to the azo bond; the phenyl radical can be further substituted, for example by halogen atoms such as chlorine, alkyl radicals such as methyl, acylamino groups such as acetylamino and alkoxy radicals such as methoxy.

2. Disazo compounds of the formula (11), in which Di denotes a radical of the azobenzene, azonaphthalene or phenylazonaphthalene series and the naphthalene nucleus is substituted by the -NHRi group and, if desired, by sulfonic acid, as in class 1.

3. Monoazo compounds of the formula dx - n = n— (12) »

wherein Di is an at most bicyclic aryl radical, as described in class 1 and preferably a disulfonaphthyl or stilbene radical, Ri has the meaning given above and the benzene nucleus has further substituents, such as halogen atoms or alkyl, alkoxy, carboxylic acid, ureido and acylamino groups may contain.

4. Mono- or diazo compounds of the formula

H-N-Di-N = N-K (13),

I.

Ri wherein Di is an arylene radical, e.g. B. a residue of the azobenzene, azonaphthalene or phenylazonaphthalene series, or preferably an at most bicyclic arylene residue of the benzene or naphthalene series and K the residue of a naphtholsulfonic acid or the residue of an enolized or enolizable ketomethylene compound (such as an acetoacetarylide or a 5-pyrazolone) with the OH group in the ortho position to the azo group, and Ri has the meaning given above. Di preferably denotes a residue of the benzene series which contains a sulfonic acid group.

5. Mono- or diazo compounds of the formula

D! -N = N-Ki-NHRi (14),

wherein Di is a radical of the types defined for Di in classes 1 and 2 above and Ki is the radical of an enolizable ketomethylene compound (such as an acetoacetarylide or a 5-pyrazolone) with the OH group ortho to the azo group.

6. The metal complex compounds, e.g. B. the copper, chromium and cobalt complexes, the dyes of the formulas (11) to (14), wherein Di, K and Ki have the meanings given in each case and also a metallizable group (for example a hydroxyl, lower alkoxy or carboxylic acid group ) is present in the ortho position to the azo group in Di:

Examples class 1:

6-amino-1-hydroxy-2- (2'-sulfophenylazo) naphthalene-3-sulphonic acid,

6-methylamino-l-hydroxy-2- (4'-acetylamino-2'-sulfophe-nyIazo) -naphthalene-3-sulfonic acid,

8-amino-l-hydroxy-2- (2'-sulfophenylazo) naphthalene-3,6-disulfonic acid,

8-amino-l-hydroxy-2- (4'-chloro-2'-sulfophenylazo) -naphtha-lin-3,5-disulfonic acid,

7-amino-2- (2 ', 5'-disulfophenylazo) -l-hydroxynaphthalene-3-sulfonic acid,

7-methylamino-2- (2'-sulfophenylazo) -l-hydroxynaphthalene-3-sulfonic acid,

7-methylamino-2- (4'-methoxy-2'-sulfophenylazo) -l-hydro-xynaphthalene-3-sulfonic acid,

8- (3'-aminobenzoylamino) -l-hydroxy-2- (2'-sulfophenyl-azo) -naphthalene-3,6-disulfonic acid,

8-amino-l-hydroxy-2,2'-azonaphthalene-l ', 3,5', 6-tetrasulfonic acid,

8-amino-l-hydroxy-2,2'-azonaphthalene-l ', 3,5'-trisulfonic acid,

6-amino-l-hydroxy-2,2'-azonaphthalene-l ', 3,5'-trisulfonic acid,

6-methylamino-l-hydroxy-2,2'-azonaphthalene-l ', 3,5'-trisulfonic acid,

7-amino-l-hydroxy-2,2 '-azonaphthalene-1', 3-disulfonic acid,

8-amino-l-hydroxy-2- (4'-methyl-2'-sulfophenylazo) -naphthalin-3,6-disulfonic acid,

6-amino-l-hydroxy-2- (2'-sulfophenylazo) naphthalene-3,5-disulfonic acid,

2nd grade:

8-amino-l-hydroxy-2- [4 '- (2 "-sulfophenylazo) -2'-methoxy-5'-methylphenylazo] -naphthalene-3,6-disulfonic acid,

8-amino-l-hydroxy-2- [4 '- (4 "-methoxyphenylazo) -2'-carboxyphenylazo] naphthalene-3,6-disulfonic acid,

8-amino-l-hydroxy-2- [4 '- (2 "-hydroxy-3", 6 "-disulfo-l" -naphthylazo) -2'-carboxyphenylazo] -naphthalene-3,6-disulfonic acid, 4,4'-bis (8 "-amino-1" -hydroxy-3 ", 6" -disulfo-2 "-naphthyl-azo) -3,3'-dimethoxydiphenyl,

6-Amino-l-hydroxy-2- [4, - (2 "-sulfophenylazo) -2'-methoxy-5'-methylphenylazo] -naphthalene-3,5-disulfonic acid.

Class 3:

2- (4'-amino-2'-methylphenylazo) -naphthalene-4,8-disulfonic acid,

2 <4'-amino-2'-acetyIaminophenylazo) -naphthalene-5,7-disulphonic acid,

4-nitro-4 '- (4 "-methylaminophenylazo) -stilbene-2,2'-disulfonic acid,

4-nitro-4 '- (4 "-amino-2" -methyl 1-5 "-methoxy-phenylazo) -stil-ben-2,2'-disulfonic acid,

4-amino-2-methylazobenzene-2 ', 5'-disulfonic acid.

Class 4:

1- (2 ', 5'-dichloro-4'-sulfophenyl) -3-methyl-4- (3 "-amino-6" -sul-fophenylazo) -5-pyrazolone,

1- (4'-sulfophenyl) -3-carboxy-4- (4 "-amino-2" -sulfophenyl-azo) -5-pyrazolone,

H2 '-methyl-5' -sulfophenyl) -3-methyl-4- (4 "-amino-2" -sulfo-phenylazo> 5-pyrazolone,

1- (2'-sulfophenyl) -3-methyl-4- (3 "-amino-6" -sulfophenylazo) -5-pyrazolone,

4-amino-4 '- (3 "-methyl-1" -phenyl-4 "-pyrazole-5" -onylazo) -stilbene-2,2'-disulfonic acid,

5

10th

IS

20th

25th

30th

35

40

45

50

55

60

65

627206

4-Amino4 '- (2 "-hydroxy-3", 6 "-disulfo-l" -naphthyl-azo> stiIben-2,2-disulfonic acid

8-acetylamino-l-hydroxy-2- (3 '-amino-6' -sulfophenylazo) -naphthalene-3,6-disulfonic acid,

7- (3'-sulfophenylamino) -l-hydroxy-2- (4 "-amino-2" -carboxy-phenylazo) -naphthalene-3-sulfonic acid,

8-phenylamino-l-hydroxy-2- (4'-amino-2 '-sulfophenylazo) -naphthalene-3,6-disulfonic acid,

6-acetylamino-l-hydroxy-2- (3'-amino-6'-sulfophenylazo) -naphthalene-3-sulfonic acid.

Class 5:

l- (3'-aminophenyl) -3-methyl4- (2 ", 5" -disulfophenylazo) -5-pyrazolone,

1- (3'-aminophenyl) -3-carboxy-4- (2 "-carboxy-4" -sulfophenyl-azo) -5-pyrazoIon,

4-Amino4 '- [3 "-methyl4" - {2 "', 5" '-disulfophenylazo) -l "-pyrazoI-5" -onyl] -stilbene-2,2'-disulfonic acid,

1- (3'-aminophenyl) -3-carboxy4- [4 "- (2" ', 5 "' disulfophenyl-azo) -2" -methoxy-5 "-methylphenylazo] -5-pyrazolone.

Class 6:

The copper complex of 8-amino-l-hydroxy-2- (2'-hydroxy-5 '-sulfophenylazo) -naphthalene-3,6-disulfonic acid,

the copper complex of 6-amino-l-hydroxy-2- (2'-hydroxy-5 '-sulfophenylazo) -naphthalene-3-sulfonic acid,

the copper complex of 6-amino-l-hydroxy-2- (2'-hydroxy-5'-sulfophenylazo) -naphthalene-3,5-disulfonic acid,

the copper complex of 8-amino-l-hydroxy-2- (2'-hydroxy-3 '-chloro-5' -sulfophenylazo) -naphthalene-3,6-disulfonic acid,

the copper complex of 6-methylamino-l-hydroxy-2- (2'-carboxy-5'-sulfophenylazo) -naphthalene-3-sulfonic acid,

the copper complex of 8-amino-l-hydroxy-2- [4 '- (2 "-sulfo-phenylazo) -2' -methoxy-5 '-methylphenylazo] -naphthalene-3,6-disulfonic acid,

the copper complex of 6-amino-l-hydroxy-2- [4 '- (2 ", 5" -5 disulfophenylazo) -2'-methoxy-5'-methylphenylazo] -naphthalene-3,5-disulfonic acid,

the copper complex of l- (3'-amino4'-sulfophenyl) -3-methyl-4- [4 "- (2" ', 5 "' disulfophenylazo) -2" -methoxy-5 "-methyl-phenylazo] - 5-pyrazolone,

io the copper complex of

7- (4'-Amino-3'-sulfoanilino) -l-hydroxy-2- [4 "- (2" ', 5 "' - disulfo-phenylazo) -2" -methoxy-5 "-methylphenylazoj-naphthalene 3-sulfonic acid,

the copper complex of 6- (4'-amino-3'-sulfoanilino) -l-15 hydroxy-2- (2 "-carboxyphenylazo) -naphthalene-3-sulfonic acid, the 1: 2 chromium complex of 7-amino-6 ' -nitro-l, 2'-dihydroxy-2,1 '-azonaphthalene-3,4'-disulfonic acid,

the 1: 2 chromium complex of 6-amino-l-hydroxy-2- (2'-carboxyphenylazo) naphthalene-3-sulfonic acid, 20 the 1: 2 chromium complex of 8-amino-l-hydroxy-2- (4'-nitro-2'-hydroxyphenylazo) -naphthalene-3,6-disulfonic acid,

the 1: 2 cobalt complex of 6- (4'-amino-3'-sulfoanilino> l-hydroxy-2- (5 "-chloro-2" -hydroxyphenylazo) -naphthalene-3-sulfonic acid,

25 the 1: 2 chromium complex of l- (3'-amino4'-sulfophenyl) -3-methyl4- (2 "-hydroxy4" -sulfo-l "-naphthylazo) -5-pyrazolone,

the 1: 2 chromium complex of 7- (4'-sulfoanilino) -l-hydroxy-2- (4 "-amino-2" -carboxyphenylazo) -naphthalene-3-sulfonic acid, the 1: 2 chromium complex of l- ( 3'-aminophenyl) -3-methyl4-3o (4 "-nitro-2" -carboxyphenylazo) -5-pyrazolone.

Particularly important azo dyes that can be used to prepare the reactive dyes of the formula (1) are the azo dyes of the formulas

(S03H) 0_3

//

'i

N = N - K

\

/ N / / /

H; OCH ^; NH-acyl mn q ï ï- [| i H— N = N

(H03S) 0_3 ^

and

(15),

N (Rn) H

(16)

(S03H) 1_3

H; CHo; OCHo; NH-acyl 7N (Ri) h <H03S) l-3 i'CÖ N = N (S ° 3H) 0-3

(17)

H3; NH-acyl where K is the rest of a coupling component the benzene-containing aromatic radical, and Ri is the one explained in the

Naphthalene or the heterocyclic series, acyl has a lowering of the formula (1), and the molecular ali-metal complex azo dyes containing a maximum of 3 carbon atoms of the formulas phatic acyl radical or a maximum of 8 carbon atoms

627206

8th

<H03s) Ö ^ T:

- Me

N = N

H ; Oli; H; Cl; NC> 2

N (R-,) H

(S03H) 1_3

(18)

NO,

and

(S03H) 0_2

p Cu

N = N

N (R1) H

wherein Ri and acyl have the meanings given in the explanation of the formulas (15), (16) and (17) and Me stands for Cu, Cr or Co.

7. Anthraquinone compounds which contain a group of the formula -NHRi, in which Ri has the meaning given above, to an alkylamino or arylamino group which is itself bound to the a-position of the anthraquinone nucleus, in particular of the formula

NH2 (or NH-acyl)

(so3h) 1_3

(19)

25th

(20),

NH-Z1-NHR,

wherein the anthraquinone nucleus can contain an additional sulfonic acid group in the 5-, 6-, 7- or 8-position and Z 'is a bridge member which is preferably a divalent radical of the benzene series, for example a phenylene, diphenylene or 4 , 4'-stilbene or azobenzene residue. Preferably Z 'should contain a sulfonic acid group for each benzene ring present.

45

Examples

1-Amino-4- (4 '-aminoanilino) -anthraquinone-2,3' -disulfonic acid and the corresponding 2,3 ', 5-, 2,3', 6- and 2,3 ', 7-trisulfone Acid, 1-amino-4- (4 "-amino-4 '-benzoylaminoaniline) -anthrachi-non-2,3'-disulfonic acid and the corresponding -2,3', 5-trisulfonic acid, l-amino -4- [4 ', (4 "-aminophenylazo) anilino] anthrachi-non-2,2", 5-trisulfonic acid, 1-amino-4- (4' -amino-3 '-carboxyanilino) - anthraquinone-2,5-disulfonic acid, 1-amino-4- (3 '-aminoani-lino) -anthraquinone-2,4', 5-trisulfonic acid and the corresponding 2,4'-disulfonic acid, 1-amino-4- [ 4 '- (4 "-aminophenyl) anilino] - 55 anthraquinone-2,3", 5-trisulfonic acid, 1-amino-4- (4' -methylamino) anilinoanthraquinone-2,3'-disulfonic acid and the corresponding 2,3 ', 5-trisulfonic acid, 1-amino-4- (4' -n-butylamino) -anili-noanthraquinone-2,3'-disulfonic acid, 1-amino-4- (4'-methylamino-3 ' -carboxyanilino) -anthraquinone-2-sulfonic acid, l- (4'-aminoani- 60 lino) -anthraquinone-2,3'-disulfonic acid and l-amino-4- (4'-amino-2'-methoxyanilino) -anthraquinone -2.3 'disulfonic acid.

8. Phthalocyanine compounds of the formula wherein Pc is a phthalocyanine nucleus, preferably copper phthalocyanine, <a-OH and / or -NH2, Z 'is a bridge member, preferably an aliphatic, cycloaliphatic or aromatic bridge, and n and m are each 1, 2 or 3 mean and can be the same or different, provided that n + m is not greater than 4.

The dye compounds of the phthalocyanine series which can be used as starting materials are preferably metal-containing phthalocyanines, such as copper phthalocyanine, which contain at least one water-solubilizing group, such as a sulfonic acid group, and at least one group of the formula -NHRi, in which Ri has the meaning given. The -NHRi group or groups can be bonded directly or via a divalent bridge to the benzene rings of the phthalocyanine nucleus, for example via a -phenylene-, -CO-phenylene, -SO2-phenylene, -NH-phenylene -, -S-Phe-nylene, -O-phenylene, -CH2S-phenylene, -CHìO-phenylene, -CH2-phenylene, -SCHî-phenylene, -SChCHz-phenylene, -S02NR-Phe-nylene- , -CH2-, -SChNR-arylene, -NR-CO-phenylene, -NR-SO2-phenylene, -S020-phenylene, -CH2NR-phenylene, -CH2NH-CO-phenylene, -SChNR alkylene -, -CH2NR-alkylene, -CONR-phenylene, -CONR-arylene, -SO2 or a -CO bridge. In the above-mentioned divalent bridge members, R is hydrogen, alkyl or cycloalkyl, arylene is a divalent aromatic, optionally z. B. by halogen, alkyl or alkoxy substituted radical, in which the terminal bonds may be bound to the same or different nuclei, and alkylene a divalent aliphatic radical, which may include heteroatoms, such as nitrogen, in the atomic chain, for example the radical -CH2CH2-NH -CH2CH2-.

Examples of such divalent aromatic radicals, which are denoted by arylene, are: aromatic nuclei, for example a benzene, naphthalene, acridine and carbazole nucleus, which can carry further substituents, and radicals of the formula

(22)

in which the benzene rings can carry further substituents and -D- denotes a bridging group, for example -CH = CH-, -NH-, -S-, -O-, -SO2-, -NO = N-, -N = N- , -NH-CO-NH-CO-NH-, -O-CH2CH2O- or

(so2-u) n

(S02NH-Z'-NHR.)

(21),

65

m

N N

ii ii -C c-

(23)

9

627 206

Examples

3- (3'-amino4'sulfophenyl) sulfamyl copper phthalocyanine tri-3 sulfonic acid,

Di-4- (3'-amino-4'-sulfophenyl) sulfamyl copper phthalocyanine di-4-sulfonic acid,

3- (3'-aminophenylsulfamyl) -3-sulfamyl copper phthalocyanine-di-3-sulfonic acid,

KupferphthaIocyanin4-N- (4-amino-3-sulfophenyl) sulfonamide 4 ', 4 ", 4"' - trisulfonic acid,

Cobalt phthalocyanine 4,4'-di-N- (4'-amino-4'-sulfophenyl) carbonamide4 ", 4" '- dicarboxylic acid and

Copper 4- (4'-amino-3'-sulfobenzoyl) phthalocyanine. Mixtures of phthalocyanines can also be used. For example, a mixture of approximately equal parts of copper phthalocyanine-N- (4-amino-3-sulfophenyl) sulfonamide trisulfonic acid and copper phthalocyanine di-N- (4-amino-3-sulfophenyl) sulfonamide disulfonic acid can be used.

9. nitro dyes of the formula z

I.

02n-d-n-q (24),

where D is a naphthalene or benzene nucleus, which may be further substituted, the nitrogen atom N is ortho to the nitro group, Z is hydrogen or an optionally substituted hydrocarbon radical and Q is hydrogen 5 or an organic radical bonded to the nitrogen by a carbon atom, and wherein Q and Z are not both hydrogen, and Q may be attached to Z when Z is hydrocarbon or to D ortho to the nitrogen atom N to form a heterocyclic ring, and which is at least one group of the formula -NHRi, in which Ri has the meaning given above, contain; especially nitro dyes of the formula y-nh-b-nhr ^ (25)>

no2

where V and B are monocyclic aryl nuclei and the nitro group in V is ortho to the NH group.

20th

example

4-amino-2'-nitro-diphenylamine-3,4'-disulfonic acid. 9. Metal complexes of formazan dyes of the formula n = n-a-y

1

q-ch

Ri

I.

-nh

(n = 1 or 2) (26),

n where Q is an organic radical, a nitro or cyano group 35, A and B are residues of diazo components of the benzene, naphthalene or heterocyclic series and Y1 and Y2 each have an o-position to the azo group and are capable of complexing with a heavy metal Mean substituents and Ri has the meaning given. The radical Q is especially a radical of the benzene series, such as phenyl or sulfophenyl, or a low molecular weight alkyl radical, such as methyl, a low molecular weight alkanoyl group, a low molecular weight carbalkoxy group, preferably containing 1 to 4 carbon atoms, a benzoyl group or a heterocyclic radical, and A and B 45 are preferably phenyl radicals substituted by sulfo, sulfonamido or alkylsulfonyl groups. The hydroxyl and carboxyl groups are particularly suitable as substituents Yi and Y2. Suitable heavy metals are copper, chromium,

Cobalt and nickel. 50

Examples

Copper complex of 2'-carboxy-2 "-hydroxy-3" -amino-l, 3,5-triphenylformazan4 ', 5 ", 3"' - trisulfonic acid,

Copper complex of 2 ', 2 "-dihydroxy-3'-amino-5'-methyl-55 sulfonyl-l, 3,5-triphenylformazan-3", 5 ", 4"' - trisulfonic acid,

Copper complex of 2'-carboxy-4'-amino-2 "-hydroxy-l, 3,5-triphenylformazan-3", 5 ", 2" '- trisulfonic acid,

Copper complex of 2'-hydroxy-2 "carboxy-4" 'amino-l, 3,5-triphenylformazan-4', 4 "disulfonic acid, 60

Copper complex of 2 ', 2 "-dihydroxy-5" -amino-l, 5-diphenyl-3-methylformazan-5', 3 "-disulfonic acid,

Copper complex of 2 ', 2 "-dihydroxy-5'-amino-l, 3,5-triphenylformazan-3', 3", 5 "-trisulfonic acid,

Copper complex of 2'-carboxy-3'-amino-2 "-hydroxy-65 3" '(1 "" -phenyl-3 "" -methyl-pyrazole-5 "" -onyl-4 "" -azo) -l , 3,5-tri-phenylformazan-3 ", 5", 2 "", 5 "" -tetrasulfonic acid,

Nickel complex of 2 ', 2 "-dicarboxy-l, 5-diphenyl-3- (m-ami-

nobenzoyl) -formazan4 ', 4 "-disulfonic acid.

The following diazo and coupling components are particularly suitable for the preparation of the preferred reactive dyes of the formula (1), in which D is the remainder of an azo dye:

Diazo components:

Aminobenzene, l-amino-2-, -3- or 4-methylbenzene, 1-amino-2-, -3- or 4-methoxybenzene,

1-amino-2-, -3- or -4-chlorobenzene, 1-amino-2,5-dichlorobenzene, 1-amino-2,5-dimethylbenzene, l-amino-3-methyl-6-methoxybenzene, 1 - Amino-2-methoxy-4-nitrobenzene, 4-aminodiphenyl,

1-aminobenzene-2-, -3- or -4-carboxylic acid,

2-aminodiphenyl ether, l-aminobenzene-2 -, - 3- or 4-sulfonic acid amide, -N-methylamide, -N-ethylamide, -N, N-dimethylamide or -N, N-diethylamide, dehydrothio-p- toluidine sulfonic acid, l-amino-3-trifluoromethyl-6-sulfonic acid, l-amino-3-or -4-nitrobenzene, l-amino-3- or 4-acetylaminobenzene, 1-amino-benzene-2-, -3 - or-4-sulfonic acid, l-aminobenzene-2,4- and -2,5-disulfonic acid, l-amino-4-methylbenzene-2-sulfonic acid, 1-amino-3-methylbenzene-6-sulfonic acid, 1-amino -6-methylbenzene-3- or -4-sulfonic acid, l-amino-2-carboxybenzene-4-sulfonic acid, l-amino-4-carboxybenzene-2-sulfonic acid, l-amino-4- or -5-chlorobenzene-2 sulfonic acid, l-amino-6-chlorobenzene-3- or -4-sulfonic acid, 1-amino-3,4-dichlorobenzene-6-sulfonic acid,

1 - amino-2,5-dichlorobenzene-6-sulfonic acid, 1-amino-2,5-dichlorobenzene-4-sulfonic acid, 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid, 1-amino- 5-methyl4-chlorobenzene-2-sulfonic acid, l-amino4- or -5-methoxybenzene-2-sulfonic acid, l-amino-6-methoxybenzene-3- or 4-sulfonic acid, l-amino-6-ethoxybenzene-3 - or 4-sulfonic acid, 1-amino-2,4-dimethoxybenzene-6-sulfonic acid, 1-amino-2,5-dimethoxybenzene-4-sulfonic acid, 1-amino-3-acetylaminobenzene-6-sulfonic acid, 1 - Amino-4-acetyl-aminobenzene-2-sulfonic acid, l-amino-3-acetylamino-4-methyl-

627206] (

benzene-6-sulfonic acid, 2-amino-l-methylbenzene-3,5-disulfonic acid, l-amino-4-methoxybenzene-2,5-disulfonic acid, 1,4-diaminobenzene-2,5-disulfonic acid, 1-amino-2- or -4-nitrobenzene-6-sulfonic acid, 1-aminonaphthalene, 2-aminonaphthalene, 1-amino-naphthalene-2-, -4-, -5-, -6-, -7- or - 8-sulfonic acid, 2-aminonaphthalene-3,6-or-5,7-disulfonic acid, l-aminonaphthalene-3,6-or -5,7-disulfonic acid, 2-aminonaphthalene-l, 5-, -1 , 7-, -3,6-, -5,7-, 4,8-or-6,8-disulfonic acid, l-aminonaphthalene-2,5,7-trisulfonic acid, 2-aminonaphthalene-l, 5,7- , -3,6,8- or -4,6,8-trisulfonic acid l-hydroxy-2-aminobenzene-4-sulfonic acid, l-hydroxy-2-amino-io benzene-5-sulfonic acid, l-hydroxy-2-aminobenzene- 4,6-disulfonic acid, l-hydroxy-2-amino-4-acetyIaminobenzoI-6-sulfonic acid, l-hydroxy-2-amino-6-acetylaminobenzene-4-sulfonic acid,

1-hydroxy-2-amino-4-chlorobenzene-5-sulfonic acid, l-hydroxy-2-amino4-methylsulfonylbenzene, l-amino-2-hydroxy-6-nitronaph-15 thalin4-sulfonic acid, 2-amino-l-hydroxynaphthalene4 , 8-disulfonic acid, 4-aminoazobenzene-3.4 'disulfonic acid, 3-methoxy-4-amino-6-methylazobenzene-2', 4'-disulfonic acid, 3-methoxy-4-amino-6-methylazobenzene-2 ' , 5'-disulfonic acid.

20th

Coupling components:

Phenol, l-hydroxy-3-or-4-methylbenzene, 1-hydroxybenzene-4-sulfonic acid, 1-hydroxynaphthalene, 2-hydroxynaphthalene,

2-hydroxynaphthalene-6- or -7-sulfonic acid, 2-hydroxynaphthalene-3,6- or -6,8-disulfonic acid, l-hydroxynaphthalene-4-sulfonic acid, l-hydroxynaphthalene-4,6- or -4,7-disulfonic acid, l-amino-3-methylbenzene, l-amino-2-methoxy-5-methylbenzene,

1-amino-2,5-dimethylbenzene, 3-aminophenylurea, 1-amino-3-acetylaminobenzene, 1-amino-3-hydroxyacetylamino-benzene, 1,3-diaminobenzene-4-sulfonic acid, l-aminonaphthalene-6- 30 or -8 -sulfonic acid, l-amino-2-methoxynaphthalene-6-sulfonic acid, 2-aminonaphthalene-5,7-disulfonic acid, l-amino-8-hydro-xynaphthalene-6-sulfonic acid, 1-amino-8-hydroxynaphthalene-2 , 4-disulfonic acid, 2-hydroxy-3-aminonaphthalene-5,7-disulfonic acid,

1-amino-8-hydroxynaphthalene-2,4,6-trisulfonic acid, l-hydroxy-8- 35 acetylamirionaphthalene-3-sulfonic acid, l-benzoylamino-8-hydro-xynaphthalene-3,6- or 4,6-disulfonic acid, 2-benzoylamino-5-hydroxynaphthalene-7-sulfonic acid, 2-amino-5-hydroxynaphthalene-7-sulfonic acid, 2-methyl- or 2-ethylamino-5-hydroxynaphthalene-7-sulfonic acid, 2- (N AcetyI-N-methylamino) -5-hydroxy-40-naphthalene-7-sulfonic acid, 2-acetylamino-5-hydroxynaphthalene-7-sulfonic acid, 2-amino-5-hydroxynaphthalene-l, 7-disulfonic acid,

2-amino-8-hydroxynaphthalene-6-sulfonic acid, 2-methyl- or -ethylamino-8-hydroxynaphthalene-6-sulfonic acid, 2 - (, N-acetyl-N-methylamino) -8-hydroxynaphthalene-6-sulfonic acid, 2-acetyl-45 amino-8-hydroxynaphthalene-6-sulfonic acid, 2-amino-8-hydroxy-naphthalene-3,6-disulfonic acid, 2-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid, l-amino -5-hydroxynaphthalene-7-sulfonic acid, l-amino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, l-acetylamino-8-hydroxynaphthalene-3,6-or4, 6-disul-50-fonic acid, l- (4'-aminobenzoylamino) -8-hydroxynaphthalene-3,6-or 4,6-disulfonic acid, l- (4'-nitrobenzoylamino) -8-hydroxy-naphthalene-3,6 -respectively. 4,6-disulfonic acid, l- (3'-aminobenzoyl-amino) -8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, l- (3'-nitrobenzoylamino) -8-hydroxynaphthalene-3,6 - or -4,6- 55 disulfonic acid, 2- (4'-amino-3'-sulfophenylamino) -5-hydroxy-naphthalene-7-sulfonic acid, 3-methylpyrazolone- (5), l-phenyl-3-methyI -5-pyrazolone, 1 - (4'-sulfophenyl) -3-methyl-5-pyrazolone, l- (4'-sulfophenyl) pyrazolone- (5) -3-carboxylic acid, l- (3'-aminophenyl ) -3-methyl-5-pyrazolone, l- (2 ', 5'-disulfophenyl) -3-methyl-' 6o 5-pyrazolone, l- (2'-methyl-4'-sulfophenyl) -5-pyrazolone- 3-carboxylic acid, l- (4 ', 8'-disulfonaphthal- [2'] - 3-methyl-5-pyrazolone, l- (5 ', 7'-disulfonaphthyl- [2'] - 3-methyl- 5-pyrazolone, l- (2 ', 5'-dichlor4'-sulfophenyl) -3-methyl-5-pyrazolone, 3-aminocarbo-nyl4-methyl-6-hydroxypyridone-2,1-ethyl-3-cyan- or -3-chloro-65 4-methyl-6-hydroxypyridone-2,1-ethyl-3-sulfomethy! -4-methyl 1-6-hydroxypyridone-2,2,4,6-triamino-3-cyanopyridine, 2- (3'-sulfophenylamino) 4,6-diamino-3-cyanopyridine, 2- (2'-hydroxyethylamino)

10th

3-cyan-4-methyl-6-aminopyridine, 2,6-bis (2 '-hydroxyethylamino) -3-cyan-4-methylpyridine, l-ethyl-3-carbamoyl4-methyl-6-hydroxypyridone - (2), 1-ethyl-3-sulfomethyl-4-methyl-5-carbamoyl-6-hydroxypyridone- (2), N-acetoacetylaminobenzene,

5 1 - (N-acetoacetylamino) -2-methoxybenzene-5-sulfonic acid,

4-hydroxyquinolone- (2), l-amino-8-hydroxy-7- (phenylazo) -naphthalin-3,6-disulfonic acid, l-amino-8-hydroxy-7) -4'-sulfophenyl-azo) -naphathalin-3,6-disulfonic acid, l-amino-8-hydroxy-7- (2 ', 5'-disulfophenylazo) -naphthalene-3,6-disulfonic acid.

10 c) amines of the formula (6)

l-aminobenzene-2 -, - 3- or-4-ß-sulfatoethylsulfone, 1-amino-bcnzol-3-ß-phosphatoethylsulfone, l-amino-4-methylbenzene-3-ß-sulfatoethylsulfone, l-aminobenzene-3- ß-chloroethylsulfone, l-amino4-methoxybenzene-3-ß-sulfatoethylsulfone, 1-aminoben-15 zol-4-ß-sulfatoethylsulfone-2-sulfonic acid, l-aminobenzene-5-ß-sul-fatoethylsulfone-2-sulfonic acid, l Aminobenzene-5-β-sulfatoethyl-sulfone-2,4-disulfonic acid,

l-aminonaphthalene-4-ß-sulfatoethylsulfone, l-amino-2,5-dimethoxybenzene4-ß-sulfatoethylsulfone, 20 1 -aminobenzene4-ß-sulfatoethylsulfone-2-carboxylic acid, i-aminobenzene-5-ß-sulfatoethylsulfone-2-carboxylic acid , l-Amino-2-methoxybenzene-4-ß-sulfatoethylsulfone, l-amino-2-chlorobenzene4-ß-sulfatoethylsulfone,

1-amino-2-methoxybenzene-5-ß-sulfatoethylsulfone, 25 2-aminonaphthalene-8-ß-sulfatoethylsulfone,

2-aminonaphthalene-8-ß-sulfatoethylsulfone-6-sulfonic acid, l-amino-2,5-dimethoxybenzene-4-vinyl sulfone, l-amino-2-methoxy-5-methylbenzene4-ß-sulfatoethylsulfone, l-amino-2,5- diethoxybenzene-4-ß-sulfatoethylsulfone,

30 1 -Amino-2-bromobenzene4-ß-sulfatoethylsulfone, l-amino-2-bromobenzene4-vinylsulfone, l-aminobenzene-5-vinylsulfone-2,4-disulfonic acid, l-aminobenzene-5-ß-phosphatoethylsulfone-2,4 -disulfonic acid,

1-aminobenzene-5-ß-chloroethylsulfone-2,4-disulfonic acid,

35 2-aminonaphthalene-8-β-phosphatoethylsulfone-6-sulfonic acid,

2-aminonaphthalene-8-vinylsulfone-6-sulfonic acid,

1-amino-2-methoxy-5-methylbenzene-4-ß-chloroethylsulfone,

2-aminophenol4-ß-sulfatoethylsulfone,

l-aminobenzene-3 or 4-vinyl sulfone,

40 l-amino-2-hydroxybenzene4-β-sulfatoethylsulfone, l-aminobenzene-5-vinylsulfone-2-sulfonic acid.

In the preparation of the preferred reactive dyes of the formula (1), in which D is the residue of an azo dye, in particular a mono- or disazo dye, the intermediate products containing a diazotizable amino group are generally diazo-treated by the action of nitrous acid in aqueous mineral acid Solution at low temperature, the coupling at weakly acidic, neutral to weakly alkaline pH values.

50 The condensation of the 2,4,6-trifluoro-s-triazine of the formula (4) with the organic dyes of the formula (5a) or with the precursors of the formula (5b) and the amines of the formula (6) are preferably carried out in aqueous solution or suspension, at low temperature and with a weakly acidic, neutral 55 to weakly alkaline pH value, and so that in the finished dye of the formula (1) a fluorine atom remains as a detachable residue. The hydrogen fluoride liberated during the condensation is advantageously continuously neutralized by adding aqueous alkali metal hydroxides, carbonates or bicarbonates. 60 If the reactive dyes of the formula (1), wherein D is the remainder of an azo dye in the ortho-ortho 'position to the azo group, complex-forming groups, eg. B. hydroxyl or carboxy groups, metal complexes of the azo dyes of the formula (1) can also be prepared by the 65 azo compounds obtained according to the invention, which contain complex-forming groups in the ortho-ortho 'position to the azo group, before or optionally after condensation with the 2,4,6-trifluoro-s-triazine of the formula (4) with metal

11

627206

donating funds treated.

Copper complexes of azo dyes of the formula (1) are of particular interest. In addition to the abovementioned, metallization and, for the production of copper complexes, oxidative coppering also come into consideration as the method of metallization.

The dyes of the formula (1) are fiber-reactive since they contain a releasable fluorine atom in the s-triazine radical.

Fiber-reactive compounds are to be understood as those which are able to react with the hydroxyl groups of cellulose or with the amino groups of natural or synthetic polyamides to form covalent chemical bonds.

The reactive dyes of formula (1) are new. They are characterized by high reactivity and they give dyeings with good wet and light fastness. They also have good fixability and give colorations of remarkably high color strength. Of particular note is the good build-up of the red azo dyes of the formula (1), especially those of the formula (2), on bleached cotton yarn.

The reactive dyes of the formula (1) are suitable for dyeing and printing a wide variety of materials, such as silk, leather, wool, superpolyamide fibers and superpolyamide urethanes, but in particular fibrous materials containing cellulose

Structure such as linen, cellulose, regenerated cellulose and especially cotton. They are suitable both for the exhaust process and for dyeing according to the pad dyeing process, according to which the goods are impregnated with aqueous and, if appropriate, also salt-containing dye solutions, and the dyes are fixed after an alkali treatment or in the presence of alkali, if appropriate with the action of heat.

They are also suitable for printing, especially on cotton, but also for printing on nitrogen-containing io fibers, e.g. B. of wool, silk or wool containing blended fabrics.

It is advisable to subject the dyeings and prints to a thorough rinsing with cold and hot water, if appropriate with the addition of a dispersing agent and promoting the diffusion 15 of the non-fixed portions.

The production of the monoazo or disazo intermediate compounds is not described in all cases in the following exemplary embodiments, but it results readily from what has been said above.

20 In the examples below, the parts are parts by weight and the temperatures are given in degrees Celsius.

example 1

25 24.5 parts of the dye of the formula r \ CHi w o3sch2. 1

0 '

isr SH5

2 well

0

are dissolved neutral in 400 parts of water. The mixture is cooled to 0 ° to 5 ° C. by adding ice and 7.1 parts of 2,4,6-trifluoro-l, 3,5-triazine are added dropwise at this temperature in the course of 15 minutes, while adding 2N sodium hydroxide solution keeps the pH of the reaction mixture at 5 to 6.

As soon as no starting dye can be detected chromatographically, 14.8 parts of 1-aminobenzene-3-β-sulfatoethyl-45 sulfone are added. A pH of 6 to 6.5 is maintained with constant blunting of the hydrogen fluoride liberated with 2N sodium hydroxide solution and raising the temperature to 20 ° C. When the reaction is complete, the formed

Salt out reactive dye by sprinkling in sodium chloride, filter, wash and dry in vacuo. It is a yellow powder and dyes cotton and regenerated cellulose in clear yellow tones.

Dyes with similar properties are obtained if the amino dyes listed in column 1 below in column 2 with equivalent parts of 2,4,6-tri-fluoro-1,3,5-triazine and immediately afterwards with those mentioned in column 3 Amines condensed according to the information in Example 1.

627206 12

Table 1

No amino dye amine hue on

cotton

1

2-aminonaphthalene-l, 5-disulfonic acid - l-amino-3-acetylaminobenzene

1-aminobenzene-3-ß-sulfa-

reddish

ethylsulfone yellow

2nd

2-aminonaphthalene-1,5-disulfonic acid - 3-aminophenylurea same as above

3rd

2-aminonaphthalene-l, 5-disulfonic acid - l-amino-3-hydroxyacetylaminobenzene

1-aminobenzene-3-ß-phos-

dito

phatoethyl sulfone

4th

2-aminonaphthalene-5,7-disulfonic acid - l-amino-3-acetylaminobenzene l-aminobenzene-2-ß-sulfa-

dito

ethyl sulfone

5

2-aminonaphthalene-5,7-disulfonic acid - 3-aminophenylurea l-aminobenzene4-ß-sulfa-

dito

ethyl sulfone

6

2-aminonaphthalene-4,8-disulfonic acid - l-amino-3-methylbenzene

1-aminobenzene-3-ß-sulf a-

yellow

ethyl sulfone

7

2-aminonaphthalene-4,8-disulfonic acid - 1-amino-3-acetylaminobenzene same as above

8th

2-aminonaphthalene-3,6-disulfonic acid - l-amino-3-acetylaminobenzoI

ditto reddish

9

2-aminonaphthalene-3,6-disulfonic acid - 3-aminophenylurea ditto yellow ditto

10th

2-aminonaphthalene-6,8-disulfonic acid - • 1-amino-3-acetylaminobenzene same as above

11

2-aminonaphthalene-6,8-disulfonic acid same as above

l-amino-2-methoxynaphthalene-6-sulfonic acid

12

2-aminonaphthalene-3,6,8-trisulfonic acid - ■ l-amino-3-acetylaminobenzene same as above

13

2-aminonaphthalene-3,6,8-trisulfonic acid - 3-aminophenylurea same as above

14

2-aminonaphthalene-3,6,8-trisulfonic acid - l-amino-3-methylbenzene same as above

15

2-aminonaphthalene4,6,8-trisulfonic acid - l-amino-3-methylbenzene same as above

16

2-aminonaphthalene4,6,8-trisulfonic acid - 1-amino-3-acetylaminobenzene same as above

17th

1-aminobenzo I-2,5-disulfonic acid - 1-aminonaphthalene-6-sulfonic acid same as above

18th

l-aminobenzene-2,5-disulfonic acid - • l-aminonaphthalene-6-sulfonic acid - •

ditto reddish

1-aminonaphthalene-8-sulfonic acid

brown

19th

l-aminonaphthalene-2,5,7-trisulfonic acid - l-aminonaphthalene-6-sulfonic acid -

ditto violet style

1-aminonaphthalene-8-sulfonic acid

cheeky brown

20th

l-aminonaphthalene-2,5,7-trisulfonic acid ^ l-amino-2,5-dimethylbenzene -

ditto reddish

l-aminonaphthalene-6-sulfonic acid

brown

21st

4-aminoazobenzene-3,4'-disulfonic acid - l-aminonaphthalene-6-sulfonic acid ditto yellow-brown

22

1,4-diaminobenzene-2,5-disulfonic acid -

l-amino4-methylbenzene

yellow

l-Ethyl-3-sulfomethyl4-methyl-6-hydroxypyridone- (2) -5-carboxamide

3-ß-sulfatoethylsulfone

23

l-amino-3-acetylaminobenzene-6-sulfonic acid -

l-aminobenzene-3-ß-sulfa-

dito

l-ethyl-3-sulfomethyl4-methyl-6-hydroxypyridone- (2> 5-carboxamide (saponified)

ethyl sulfone

24th

l-amino-3-acetylaminobenzene-6-sulfonic acid —-

ditto ditto

l-ethyl-3-aminocarbonyl4-methyl-6-hydroxypyridon- (2) (saponified)

25th

1-amino-3-acetylaminobenzo I-6-sulfonic acid -

ditto ditto

l- (2 ', 5'-Dichlor4'-sulfophenyl) -3-methyl-5-pyrazolone (saponified)

26

l-amino-3-acetylaminobenzene-6-sulfonic acid same as above

1- (2 ', 5' disulfophenyl) -3-methyl-5-pyrazolone (saponified)

27th

l-amino-3-acetylaminobenzene-6-sulfonic acid -

ditto ditto

1- (4'-sulfophenyl) -5-pyrazolone-3-carboxylic acid (saponified)

28

1-amino-3-acetylaminobenzene-6-sulfonic acid - *

ditto ditto

1- (2'-Methyl4'-sulfophenyl) -5-pyrazolone-3-carboxylic acid (saponified)

29

1-amino-3-acetylaminobenzene-6-sulfonic acid -

ditto ditto

l- (4 ', 8'-disulfonaphthyl- [2']) - 3-methyl-5-pyrazolone (saponified)

30th

l-aminobenzene-2,5-disulfonic acid - l- (3'-aminophenyl) -3-methyl-5-pyrazolone same as above

31

1-aminobenzene-2,5-disulfonic acid - •

ditto orange

2-acetylamino-5-hydroxynaphthalene-7-sulfonic acid (saponified)

32

l-aminobenzene-2-sulfonic acid - 2-amino-5-hydroxynaphthalene-l, 7-disulfonic acid same as above

33

2-aminonaphthalene-1,5-disulfonic acid -

ditto ditto

2-acetylamino-5-hydroxynaphthalene-7-sulfonic acid (saponified)

34

2-aminonaphthalene-3,6,8-trisulfonic acid -

ditto ditto

2-acetylamino-5-hydroxynaphthalene-7-sulfonic acid (saponified)

35

2-aminonaphthalene-l, 5,7-trisulfonic acid -

ditto ditto

l-acetylamino-5-hydroxynaphthalene-7-sulfonic acid (saponified)

36

l-amino4-methoxybenzene-2,5-disulfonic acid -

dito

Scarlet fever

2-amino-5-hydroxynaphthalene-7-sulfonic acid

37

l-amino4-methoxybenzene-2-sulfonic acid -

ditto ditto

2-amino-5-hydroxynaphthalene-7-sulfonic acid

38

l-aminobenzene-2-sulfonic acid -

ditto red

l- (4'-nitrobenzoylamino) -8-hydroxynaphthalene-3,6-disulfonic acid (reduced)

39

l-aminobenzene-2,5-disulfonic acid -

ditto ditto

l- (3'-Nitrobenzoylamino) -8-hydroxynaphthalene-4,6-disulfonic acid (reduced)

No.

40

41

42

43

44

45

46

47

48

49

50

51

52

53

54

55

56

57

58

59

60

61

62

63

64

65

66

67

68

69

70

71

72

73

74

75

13

Amino dye amine

2-aminonaphthalene-1,5-disulfonic acid -

ditto l- (4'-nitrobenzoylamino) -8-hydroxynaphthalene-3,6-disulfonic acid (reduced)

1-hydroxy-2-aminobenzene-4-sulfonic acid - *

dito

2-amino-5-hydroxynaphthalene-7-sulfonic acid (Cu complex)

l-hydroxy-2-aminobenzene-4,6-disulfonic acid -

1-aminobenzene-3-ß-chloro-

2-amino-5-hydroxynaphthalene-7-sulfonic acid (Cu complex)

ethyl sulfone l-hydroxy-2-aminobenzene-4,6-disulfonic acid • -

1-amino-4-methoxyben-

2-ethylamino-5-hydroxynaphthalene-7-sulfonic acid (Cu complex)

zol-3-ß-sulfatoethyl sulfone

1-hydroxy-2-aminobenzene-4,6-disulfonic acid -

l-aminobenzene-3-ß-sulfa-

2-amino-8-hydroxynaphthalene-3,6-disulfonic acid (Cu complex)

ethyl sulfone

1-hydroxy-2-aminobenzene-4,6-disulfonic acid -

dito

1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (Cu complex)

1-hydroxy-2-aminobenzene-4,6-disulfonic acid —-

dito

1-amino-8-hydroxynaphthalene-4,6-disulfonic acid (Cu complex)

1-hydroxy-2-amino4-acetylaminobenzene-6-sulfonic acid -

ditto l-amino-8-hydroxynaphthalene-2,4-disulfonic acid (Cu complex) (saponified)

l-hydroxy-2-amino-6-acetylaminobenzene-4-sulfonic acid —-

ditto l-amino-8-hydroxynaphthalene-2,4-disulfonic acid, saponified (Cu complex)

1-amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid -

ditto l-amino-8-hydroxynaphthalene-2,4-disulfonic acid, reduced (Cu complex)

1-amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid -

ditto l-amino-8-hydroxynaphthalene-2,4,6-trisulfonic acid, reduced (Cu complex)

2-amino-1-hydroxynaphthalene-4,8-disulfonic acid ditto

1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (Cu complex)

2-aminonaphthalene-4,8-disulfonic acid ditto

2-hydroxy-3-aminonaphthalene-5,7-disulfonic acid (copper oxidized)

3-methoxy-4-amino-6-methylazobenzene-2 ', 5'-disulfonic acid -

dito

2-methylamino-5-hydroxynaphthalene-7-sulfonic acid (demethylated copper)

3-methoxy-4-amino-6-methylazobenzene-2 ', 4'-disulfonic acid -

dito

2-amino-5-hydroxynaphthalene-l, 7-disulfonic acid (demethylated copper)

l-amino-3-acetylaminobenzene-6-sulfonic acid ^

ditto l-amino-8-hydroxy-7- (4'-sulfophenylazo) -naphthalene-3,6-disulfonic acid (saponified)

l-Amino4- (3 '-amino-2', 4 '.6' -trimethylphenyl-

ditto amino) -anthraquinone-2,5'-disulfonic acid

1 -Amino4- (2 ', 6' -dimethyl-3 '-aminomethyl-phenylamino) -anthraquinone-2,5' -disul ditto fonic acid

1 -Amino4- (4 '-methyl-2' -aminomethyl-phenyl-

ditto amino) -anthraquinone-2,6'-disulfonic acid

1 -Amino4- (5'-amino-phenylamino) -anthraquinone-2,2 ', 4' -trisulfonic acid ditto l-amino4- (4'-amino-phenylamino) -anthraquinone-2,3'-disulfonic acid ditto l-amino4 - (4'-amino-phenylamino) -anthraquinone-2,2'-disulfonic acid ditto l-amino4- (3'-aminophenylamino) -anthraquinone-2,4'-disulfonic acid ditto l-amino4- (2'-methyl -3'-amino-phenylamino) -anthraquinone-2,5'-disulfonic acid ditto l-amino4- (2'-methyl-3'-ammo-phenylamino) -anthraquinone-2,6,5'-trisulfonic acid ditto l-amino4 - (4'-amino-cyclohexylamino) -anthraquinone-2-sulfonic acid ditto

N- (2-carboxy4-sulfophenyl) -N '- (2' -hydroxy-3 '-amino-5' -sulfophenyl) -ms-phenyl-

ditto formazan (Cu complex)

N- (2-carboxy-5-sulfophenyl) -N '- (2' -hydroxy-3 '-amino-5' -sulfophenyl) -ms-phenyl-

ditto formazan

N- (2-Carboxy4-sulfophenyl) -N '- (2' -hydroxy-3 '-amino-5' -sulfophenyl) -ms- (2 "-chloro-

dito

5 "sulfophenyl) formazan (Cu complex)

N- (2-carboxy-4-aminophenyl) -N '- (2' -hydroxy-3 ', 5' -disulfophenyl) -ms- (3 "-sulfophe-

ditto nyl) formazan (Cu complex)

N- (2-carboxy-5-sulfophenyl) -N '- (2' -hydroxy-3 ', 5' -disulfophenyl) -ms- (3 "-aminophe-

ditto nyl) formazan (Cu complex)

N- (2-Hydroxy-3-amino-5-sulfophenyl) -N '- (2' -hydroxy-4 '-sulfophenyl) -ms- (2 "-sulfo-

ditto phenyl) formazan (Cu complex)

N- (2-Hydroxy-5-sulfophenyl) -N '- (2' -hydroxy-3 ', 5' -disulfophenyl) -ms- (4 "-aminophe-

ditto nyl) formazan (Cu complex)

N- (2-Hydroxy-5-amino-3-sulfophenyl) -N '- (2', 5'-disulfophenyl) ms-phenylformazane ditto

(Cu complex)

N- (2-Hydroxy4,6-disulfophenyl) -N '- (2', 4 '-disulfophenyl) -ms- (3 "-aminophenyl) -for-

ditto mazan (Cu complex)

N- (2-Hydroxy4-sulfophenyl) -N '- (4' -amino-2 '-sulfophenyl) -ms- (4 "-chlor-3" -sulfo-

ditto phenyl) formazan (Cu complex)

N °

Amino dye

Amine

Color on cotton

75

N- (2-Hydroxy-4-sulfophenyl) -N '- (41-amino-21-sulfophenyl) -ms- (4 "-chloro-3M-suifophenyl) formazan l-aminobenzene-3-ß-suifatoethylsulfone blue

(Cu complex)

76

CuPc- (3) -

- (see "h) 2

NH

- so9m? / 2nd

\ - so, ».- ®

- (so3h) 2

do turquoise blue

77

NiPc- (3) -

- S02NH2 rJRl

- S02NH—

- (S03H) 2

do do

78

CuPc- (3) -

- S02NH2

- S02NH - ^^ - NH2

do do

79

CuPc (3)

- (S03H) 2, 7

(so2kh ^ Q) j3 ™ 2

do do

n °

Amino dye

Amine

Color on cotton

80

CuPc- (3) -

- \ s02nh2 / / 2 X (S02nh - ^> - S03HJl.j3

l-aminobenzene-3-0-sulfatoethylsulfone turquoise blue

81

CuPc- (4) -

~ YS03H V2) 6

- \ s02nh2 /

- (so9m - ^ "V-so, h \

^ HH2 V-1-4

do do

82

CuPc- (4) -

- (sooh) p

NH

- s02nh2, nh2

- s02NH-f ^>

do ^

\

! 1

do

83

NiPc- (4)

- (SO3H) 3 ^ NH2

- so2nh- ^ 0

do do

84

CuPc- (3)

(S ° 3H) 2} 5

- (so2nhch2ch2nh2) 1 5

do do

N °

Amino dye

Amine

Color on cotton

85

-4- (so3h) 2

CuPc- (3) S02N112

—J- so2nhch2ch2nh2

l-aminobenzene-3-ß-sulfatoethylsulfone turquoise blue

86

so3h cl

H9NCH0CH0HN XTTÎ „tT XTTT 2 2 1 il —NHCH0CH0NH0

y ^ Cr T 12 2

ci so3h do blue

87

so3h so3h Cl so3h

,!, ^^ s3dCP- ™ A '"2

■ 13H il lo3 H ^ ° 3H

do blue

17th

627206

Example 2

22 parts 2 of the aminoazo dye obtained in 500 parts of water 5 are added to the neutral solution of 30.5 parts of the trisodium salt of the aminoazo dye obtained by coupling diazotized 2-aminonaphthalene-3,6,8-trisulfonic acid with 3-aminophenylurea in acetic acid medium, at 20 ° C. 4-difluoro-6- (4'-ß-sulfatoethyl-sulfo-

nylphenylamino) -s-triazine, a pH of 6 to 6.5 being maintained by constant addition of 2N sodium hydroxide solution. The condensation is continued until no starting dye can be detected chromatographically. The resulting dye of the formula

(/ Nxc - NH - ^^ - S02CH2CH20S03H N N

^ C /

I.

F

is salted out with sodium chloride, suction filtered, washed and dried in vacuo. It dyes cellulose materials in very real reddish yellow tones.

Dyes with similar properties are obtained analogously to 20

the procedure described above by reacting the amino dyes listed in column 2 of the table below with the primary condensation products of 2,4,6-trifluoro-l, 3,5-triazine and amine mentioned in column 3.

Table 2

No amino dye

Condensation product

Hue on

Trifluorotriazine and

cotton

1-aminobenzene 4-ß-sulf a-

Yellow ethylsulfone-2-sulfone-

acid

1-aminobenzene-5-ß-sulfa-

Reddish toethylsulfone-2-sulfone-

yellow acid

ditto ditto ditto

yellow

1-aminobenzene-4-ß-sulf a-

ditto toethylsulfone-2-carbon

acid

1-aminobenzene-5-ß-sulfa-

Reddish toethylsulfone-2-carbon

yellow acid

l-aminobenzene-2-ß-sulfa-

Reddish brown ethyl sulfone l-amino-2-methoxyben-

Yellow zol4-ß-sulfatoethylsulfone

l-aminobenzene4-ß-suifa-

ditto ethyl sulfone

ditto ditto

1-amino-2-chlorobenzene4-

dito

ß-sulfatoethylsulfone

1-amino-2-methoxyben-

Orange zol-5-ß-sulfatoethylsulfone

1 - amino-2-methoxyb en-

ditto zol-5-ß-sulfatoethylsulfone

1-aminobenzene-5-ß-sulfa-

Scarlet toethylsulfone-2,4-disulfone-

acid

l-aminobenzene4-ß-sulfa-

Yellowish toethylsulfone-2-sulfone-

red acid

dito

Red l-aminobenzene-5-ß-sulfa-

ditto toethylsulfone-2-sulfone-

acid

l-aminobenzene-2-ß-sulfa-

Ruby ethyl sulfone

1 2-aminonaphthalene-l, 5-disulfonic acid - l-amino-3-methylbenzene

2-aminonaphthalene-l, 5-disulfonic acid - l-amino-3-methyl-6-methoxybenzene

3rd

4th

5

10th

11

12

13

14

15

16

17th

18th

2-aminonaphthalene-5,7-disulfonic acid ■ 2-aminonaphthalene-4,8-disulfonic acid • 2-aminonaphthalene-4,8-disulfonic acid ■

l-amino-3-methylbenzene

N-methylaminobenzene 1-N-ethylamino-3-methylbenzene

2-aminonaphthalene-3,6,8-trisulfonic acid - 1-aminobenzene l-aminonaphthaiine-2,5,7-trisulfonic acid - l-amino-3-methyl-6-methoxybenzene - ■ 1-aminonaphthalene-8-sulfonic acid 1-amino -3-acetylaminobenzene-6-sulfonic acid —-

l-ethyl-3-sulfomethyl-4-methyl-6-hydroxypyridone- (2) -5-carboxamide (saponified) 1-amino-3-acetylaminobenzene-6-sulfonic acid - l-ethyl-3-aminocarbonyl-4-methyl- 6-hydroxypyridone- (2) (saponified) l-amino-3-acetylaminobenzene-6-sulfonic acid - l- (4'-sulfophenyl) -3-methyl-5-pyrazolone (saponified) l-amino-3-acetylaminobenzene-6 -sulfonic acid - l- (5 ', 7'-disulfonaphthyl- [2']) - 3-methyl-5-pyrazolone (saponified)

1-aminobenzene-2,4-disulfonic acid

2-acetylamino-5-hydroxynaphthalene-7-sulfonic acid (saponified) 2-aminonaphthalene-1,5-disulfonic acid - 2-acetylamino-5-hydroxynaphthalene-7-sulfonic acid (saponified) 1-amino-methoxybenzene-2-sulfonic acid - 2- Amino-5-hydroxynaphthalene-7-sulfonic acid

2-aminonaphthalene-1,5-disulfonic acid - 2-acetylamino-8-hydroxynaphthalene-6-sulfonic acid (saponified)

1-aminobenzo 1-2,4-disulfonic acid -

1- (4'-nitrobenzoylamino) -8-hydroxynaphthalene-3,6-disulfonic acid (reduced)

2-aminonaphthalene-1,5-disulfonic acid -

1- (4'-nitrobenzoylamino) -8-hydroxynaphthalene4,6-disulfonic acid (reduced)

1-hydroxy-2-aminobenzene4,6-disulfonic acid -

2-amino-8-hydroxynaphthalene-6-sulfonic acid (Cu complex)

627 206

18th

No amino dye

Condensation product from color on trifluorotriazine and cotton

19 l-hydroxy-2-aminobenzene-5-sulfonic acid - l-amino-8-hydroxynaphthalene-3,6-disulfonic acid (Cu complex)

20 l-amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid - l-amino-8-hydroxynaphthalene-2,4-disulfonic acid (Cu complex)

21 l-hydroxy-2-amino-4-acetylaminobenzene-6-sulfonic acid - l-amino-8-hydroxynaphthalene-2,4,6-trisulfonic acid (saponified, Cu complex)

22 2-Amino-l-methylbenzene-3,5-disulfonic acid - l-amino-2-methoxy-5-methylbenzene - 2-amino-5-hydroxynaphthalene-7-sulfonic acid (demethylated copper)

23 l-Amino-3-acetylaminobenzene-6-sulfonic acid - • l-Amino-8-hydroxy-7- (phenylazo) -naphthalene-3,6-disulfonic acid (saponified)

24 l-Amino-3-acetylaminobenzene-6-sulfonic acid - l-amino-8-hydroxy-7- (2 ', 5'-disulfophenylazo) -naphthalene-3,6-disulfonic acid l-aminobenzene 4-ß-sulfa violet toethylsulfone l-aminobenzene-5-ß-sulfa- blue toethylsulfone-2,4-disulfonic acid l-aminonaphthalene4-ß-dito sulfatoethylsulfone l-aminobenzene-5-ß-sulfa- navy blue toäthyIsulfon-2-sulfone-

acid l-aminobenzene-5-ß-sulfa-blue ethylsulfone-2,4-disulfonic acid l-amino-2,5-dimethoxy-dito benzene4-ß-sulfoethylsul-

hairdryer

No.

Amino dye

Condensation product from trif luortriazine and

Color on cotton

25th

so3h fa »f1

cl s03h 3

l-amino-2} 5-dimethoxy-

benzene-4-ß-sulfato-

ethyl sulfone blue

26

NH2

do blue

27th

v-t ^ jaîCLa ^ r

C ^ -s03®

och3

reddish blue

28

Q o3s

NH— <f ~ ^ —NH9 hn | j- *

ò O

do do

627206

20th

Example 3

16 parts of l-amino-8-hydroxynaphthalene-3,6-disulfonic acid are dissolved in 400 parts of water until neutral. The reaction solution is adjusted to a pH of 4.5 and 7.0 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise at 0 to 3 ° C. while stirring well. The hydrogen fluoride released is neutralized by the metered addition of 2N sodium hydroxide solution. As soon as free l-amino-8-hydroxynaphthalene-3,6-disulfonic acid can no longer be detected, 10.6 parts of l-aminobenzene-3-ß-sul-fatoethylsulfone in 50 parts of water are added. The temperature is allowed to rise to 20 to 25 ° C. and the pH of the reaction solution is kept at 4 to 4.5. After the condensation has ended, the dye intermediate is coupled at 0 to 10 ° C. with 15 parts of diazotized 2-aminonaphthalene-1,5-disulfonic acid. At a final pH of 6.5 to 7, the dye becomes the formula

* Nn c c

I ff n n

- nh

02CH2CH20S03H

Salted out with sodium chloride, filtered, washed and dried in a vacuum. It is a dark red powder and dyes cotton and regenerated cellulose in bluish red tones of good wet, rub and light fastness.

Diazo components, the coupling energy of which is sufficient,

in order to couple in a pH range from 4 to 5.5, the primary condensation product of coupling component and 2,4,6-trifluoro-1,3,5-triazine can be coupled to 25, whereupon the reaction with the amine in the last stage.

Table 3 below contains further dyes which are obtained by reacting 2,4,6-trifluoro-l, 3,5-triazine with the coupling components listed in column 2, then with the amines mentioned in column 3 and finally by coupling with the Diazo components mentioned in column 4 can be obtained.

Table 3

No. coupling component amine diazo component color tone

cotton

1

1-amino-8-hydroxynaphthalene

1-aminobenzene-3-ß-sulf atoethyl-

l-aminobenzene-2-sulfonic acid

red

3,6-disulfonic acid sulfone

2nd

l-amino-8-hydroxynaphthalene

l-aminobenzene-3-ß-phosphato-

ditto ditto

4,6-disulfonic acid

ethyl sulfone

3rd

1-amino-8-hydroxynaphthalene

2-aminonaphthalene-8-ß-sulfato-

l-amino-4-carboxybenzene-2-sul

dito

3,6-disulfonic acid

ethyl sulfone fonic acid

4th

dito

1-aminobenzene-4-ß-sulfatoethyl-

1 -Amino4-methylbenzene-2-sulfone-

dito

sulfonic acid

5

dito

1-aminobenzene-3-ß-sulf atoethyl-

l-aminobenzene-2,5-disulfonic acid ditto

sulfone

6

dito

2-aminonaphthalene-8-ß-sulfato-

2-aminonaphthalene-l-sulfonic acid ditto

äthvlsulfon-6-sulfonic acid

7

1-amino-8-hydroxynaphthalene

1-aminobenzene-3-ß-sulfatoethyl-

2-aminonaphthalene-l, 5-disulfone ditto

4,6-disulfonic acid sulfonic acid

8th

1-amino-8-hydroxynaphthalene-6-

dito

2-aminonaphthalene-l, 5,7-trisul-

dito

sulfonic acid

fonic

Dyeing Instructions I

2 parts of the dye obtained in Example 1 are dissolved in 100 parts of water with the addition of 0.5 part of m-nitrobenzenesulfonic acid 55 sodium. A cotton fabric is impregnated with the solution obtained so that it increases by 75% of its weight, and then dried.

Then the fabric is impregnated with a 20 ° C warm solution, which contains 5 grams of sodium hydroxide and 300 grams of sodium chloride per liter, squeezed to 75% weight gain, steaming the dyeing for 30 seconds at 100 to 101 ° C, rinsing, soaping during one Quarter of an hour in a 0.3% boiling solution of an ion-free detergent, rinsing and drying.

Staining instructions II

2 parts of the dye obtainable according to Example 1 are dissolved in 100 parts of water.

The solution is added to 1900 parts of cold water, 60 parts of sodium chloride are added and 100 parts of a cotton fabric are added to this dye bath.

The temperature is raised to 40 ° C., after 30 minutes 40 parts of soda ash and another 60 parts of sodium chloride are added. The temperature is kept at 40 ° C. for 30 minutes, rinsed and the soap is then soaped for 15 minutes in a 0.3% boiling solution of an ion-free detergent, rinsed and dried.

60

65

Claims (8)

627206 2nd PATENT CLAIMS 1. Reactive dyes of formula d - n - c i Rn c I I » n n ✓ I. f a), wherein D is the radical of an organic dye, Ri is hydrogen or Ci_4-alkyl, R2 is hydrogen, methyl or ethyl, X is a radical of the formula -SO2CH2CH2CI, -S02CH = CH2, -S02CH2CH20S03H, -SO2CH2CH2OPO3H or -N (R3) S02CH2CH20SC> 3H and R3 is hydrogen, methyl or ethyl and the benzene or naphthalene radical may contain other substituents besides X. 2. reactive dyes according to claim 1, wherein D is the rest of a dye of the mono- or polyazo, metal complex azo, Anthraquinone, phthalocyanine, formazan, nitroaryl, dioxazin, phenazine or stilbene series. 3. A reactive dye according to claim 2, wherein D is the residue 15 of a mono- or disazo dye. 4. Reactive dyes according to claim 3, wherein Ri is hydrogen, methyl or ethyl and R2 and R3 are each a hydrogen atom. 5. Reactive dyes according to claim 4, the formula 20th a-n = n <- c0-> p1lB - nh 11 (2), c-nh If n n wherein A is a benzene or naphthalene radical, m 1 or 2, n 0 or 1 35 X has the meaning given in claim 1. and p is 0 or 1, where the benzene or naphthalene radical A and 6. The reactive dye according to claim 5, the formula of the benzene radical B may contain further substituents and s02ch2ch20s03h 7. Heavy metal complexes of complexable reactive dyes according to claims 1 to 5. 8. A process for the preparation of reactive dyes according to claim 1, characterized in that 2,4,6-trifluoro-s-triazine of the formula * NN f - c c - f 1 11 n n 1 f an organic dye of the formula d - nh 1 R-, (4) (5a) 50 and an amine of the formula (6) condensed in any order. 60 9. A process for the preparation of reactive dyes according to claim 1, wherein D is the remainder of an azo dye, characterized in that 2,4,6-trifluoro-s-triazine of the formula jg ^ \ f - c c - f 1 M n n f f (4) 3rd 627 206 one to an azo dye of the formula D - nh i Ri detachable intermediate of formula d! - nh i Ri and an amine of the formula (5a) (5b) (6) condensed in any order and D 'converted to D by coupling. 10. The method according to claim 8, characterized in that one uses organic dyes of the formula (5a), wherein D is the rest of a dye of the mono- or polyazo, metal complex azo, anthraquinone, phthalocyanine, formazane, nitroaryl, dioxazine -, phenazine or stilbene series. 10th 15 mei